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14 pages, 565 KiB  
Article
A Parameter Study of 1D Atmospheric Models of Pulsating AGB Stars
by Henry A. Prager, Lee Anne M. Willson, Joyce A. Guzik, Michelle J. Creech-Eakman and Qian Wang
Galaxies 2024, 12(6), 81; https://doi.org/10.3390/galaxies12060081 (registering DOI) - 29 Nov 2024
Viewed by 129
Abstract
Using the atmospheric pulsation code written by George Bowen, we have performed a parameter study examining the effects of modifying various parameters of models of oxygen-rich AGB atmospheres pulsating in the fundamental and first-overtone modes. For each pulsation mode, we have examined the [...] Read more.
Using the atmospheric pulsation code written by George Bowen, we have performed a parameter study examining the effects of modifying various parameters of models of oxygen-rich AGB atmospheres pulsating in the fundamental and first-overtone modes. For each pulsation mode, we have examined the effects of adjusting the dust condensation temperature, dust condensation temperature range, pulsation amplitude, dust opacity, and metallicity. Our model grids are generated with the constraint that their luminosities are chosen to span the range of observed mass loss rates at a chosen mass. The dust condensation temperature, pulsation amplitude, and dust opacity have strong effects on the ultimate location and shape of the final model grids in the mass luminosity plane. The mass loss rate evolution of the fundamental and first-overtone mode models show a significant difference in behavior. While the fundamental mode models exhibit the typically assumed power–law relation with mass and luminosity, the first-overtone mode models show significant non-power law behavior at observed mass loss rates. Effectively, models in the first-overtone mode require somewhat higher luminosities to reach the same mass loss rates seen in fundamental mode models of the same mass, consistent with observed AGB stars. Full article
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Figure 1

Figure 1
<p>This diagram depicts the location of observed AGB stars (contours) and models generated using reference values (markers) in <math display="inline"><semantics> <mrow> <mo form="prefix">log</mo> <mi>M</mi> </mrow> </semantics></math> vs. <math display="inline"><semantics> <mrow> <mo form="prefix">log</mo> <mi>L</mi> </mrow> </semantics></math> in solar units. Solid blue contours depict the location of fundamental mode M-type stars in the LMC and dashed red contours depict the location of first-overtone mode M-type stars in the LMC from Riebel et al. [<a href="#B14-galaxies-12-00081" class="html-bibr">14</a>]; contours are the percentile of stars included in steps of 20, starting from 90 working inward. Blue dots are fundamental mode M-type star models and red crosses are first-overtone-mode M-type star models within the established mass loss rate ranges.</p>
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<p>These figures depict the effects of adjusting model parameters on the ratio of the power law exponents |B/C|, and thus the orientation of the model grid. Shifts due to the maximum dust opacity <math display="inline"><semantics> <msub> <mi>κ</mi> <mrow> <mi mathvariant="normal">D</mi> <mo>,</mo> <mi>max</mi> <mo>.</mo> </mrow> </msub> </semantics></math> are found in (<b>a</b>), the dust condensation temperature <math display="inline"><semantics> <msub> <mi>T</mi> <mrow> <mi>con</mi> <mo>.</mo> </mrow> </msub> </semantics></math> in (<b>b</b>), a constant piston amplitude <math display="inline"><semantics> <msub> <mi>u</mi> <mrow> <mi>amp</mi> <mo>.</mo> </mrow> </msub> </semantics></math> in (<b>c</b>), the factor <math display="inline"><semantics> <mi>ϵ</mi> </semantics></math> from Equation (<a href="#FD3-galaxies-12-00081" class="html-disp-formula">3</a>) in (<b>d</b>), and the range of condensation and evaporation temperatures <math display="inline"><semantics> <msub> <mi>δ</mi> <mi>T</mi> </msub> </semantics></math> in (<b>e</b>). The fundamental mode fit line can be seen in solid blue with individual grids marked by blue dots, and the first-overtone mode fit line can be seen in dashed red with individual model grids marked by red crosses.</p>
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<p>These figures depict the effects of adjusting model parameters on the position of the death line, and thus the position of the model grid. Shifts due to the maximum dust opacity <math display="inline"><semantics> <msub> <mi>κ</mi> <mrow> <mi mathvariant="normal">D</mi> <mo>,</mo> <mi>max</mi> <mo>.</mo> </mrow> </msub> </semantics></math> are found in (<b>a</b>), the dust condensation temperature <math display="inline"><semantics> <msub> <mi>T</mi> <mrow> <mi>con</mi> <mo>.</mo> </mrow> </msub> </semantics></math> in (<b>b</b>), a constant piston amplitude <math display="inline"><semantics> <msub> <mi>u</mi> <mrow> <mi>amp</mi> <mo>.</mo> </mrow> </msub> </semantics></math> in (<b>c</b>), the factor <math display="inline"><semantics> <mi>ϵ</mi> </semantics></math> from Equation (<a href="#FD3-galaxies-12-00081" class="html-disp-formula">3</a>) in (<b>d</b>), and the range of condensation and evaporation temperatures <math display="inline"><semantics> <msub> <mi>δ</mi> <mi>T</mi> </msub> </semantics></math> in (<b>e</b>). The fundamental mode fit line can be seen in solid blue with individual grids marked by blue dots, and the first-overtone mode fit line can be seen in dashed red with individual model grids marked by red crosses.</p>
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<p>This figure depicts the necessary change in energy factor <math display="inline"><semantics> <mi>ϵ</mi> </semantics></math> or maximum dust opacity <math display="inline"><semantics> <msub> <mi>κ</mi> <mrow> <mi mathvariant="normal">D</mi> <mo>,</mo> <mi>max</mi> <mo>.</mo> </mrow> </msub> </semantics></math> necessary for a grid of models generated using the Bowen atmospheric pulsation code to match the observed population of AGB stars in the LMC. The blue shaded region spans the shifts for the fundamental mode, with the solid curve being the shift, assuming no error in Prager et al. [<a href="#B18-galaxies-12-00081" class="html-bibr">18</a>], and the dashed lines bounding the maximum spread, as described by Equation (<a href="#FD5-galaxies-12-00081" class="html-disp-formula">5</a>). The red shaded region and corresponding curves show the same for the first-overtone mode. Note that this figure extends beyond the bounds discussed in <a href="#sec2-galaxies-12-00081" class="html-sec">Section 2</a> to show which combination of parameters is implied to replicate the observed range of AGB stars.</p>
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<p>This figure depicts an extreme (<span class="html-italic">not physical</span>) combination of the explored parameters chosen to shift the death line position as close to observations as possible, <math display="inline"><semantics> <mrow> <mi>ϵ</mi> <mo>=</mo> <mn>0.05</mn> </mrow> </semantics></math> and <math display="inline"><semantics> <mrow> <msub> <mi>κ</mi> <mrow> <mi>D</mi> <mo>,</mo> <mi>max</mi> <mo>.</mo> </mrow> </msub> <mo>=</mo> <mn>50</mn> <mspace width="4pt"/> <msup> <mi>cm</mi> <mn>2</mn> </msup> <mo>/</mo> <mi mathvariant="normal">g</mi> </mrow> </semantics></math>. The contours depict the same data as in <a href="#galaxies-12-00081-f001" class="html-fig">Figure 1</a>. Fundamental-mode models are represented by blue dots and first-overtone models are represented by red crosses. The fundamental-mode models have moved closer to the observed population, but are not yet in agreement. While the first-overtone mode models are within error bounds, neither they nor the fundamental mode are as extensive as expected, implying the mass loss rate increases too quickly with luminosity.</p>
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<p>Comparisons of pulsation period <span class="html-italic">P</span> to acoustic cut-off period <math display="inline"><semantics> <msub> <mi>P</mi> <mi>ac</mi> </msub> </semantics></math> in AGB atmospheres of a 1 <math display="inline"><semantics> <msub> <mi>M</mi> <mo>⊙</mo> </msub> </semantics></math> star, as a function of luminosity. Blue compares these in the fundamental mode while red compares these in the first-overtone mode. Dots track the pulsation period of the modeled stars, and triangles track the acoustic cut-off period at the photosphere for the modeled stars. The acoustic cut-off period varies between modes due to differences in the effective scale height—the initial <span class="html-italic">e</span>-folding distance in the dynamic atmosphere—between the different pulsation modes.</p>
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<p>These figures depict locations of shock fronts relative to the stellar radius (<math display="inline"><semantics> <mrow> <mi>R</mi> <mo>/</mo> <msub> <mi>R</mi> <mo>★</mo> </msub> </mrow> </semantics></math>) in <math display="inline"><semantics> <mrow> <mi>M</mi> <mo>=</mo> <mn>1</mn> <mspace width="4pt"/> <msub> <mi mathvariant="normal">M</mi> <mo>⊙</mo> </msub> </mrow> </semantics></math>, <math display="inline"><semantics> <mrow> <mi>L</mi> <mo>=</mo> <mn>6309</mn> <mspace width="4pt"/> <msub> <mi mathvariant="normal">L</mi> <mo>⊙</mo> </msub> </mrow> </semantics></math> AGB atmospheres. (<b>a</b>) displays these in the fundamental mode, (<b>b</b>) displays these in the first-overtone mode. Note that these models share an RML relation (see <a href="#sec2-galaxies-12-00081" class="html-sec">Section 2</a>) and are thus the same mean radius, but have different cycle time scales due to differences in their pulsation period. These models are evaluated to a distance of over 80 stellar radii, with some variation as models are rezoned (see Bowen [<a href="#B10-galaxies-12-00081" class="html-bibr">10</a>] for details).</p>
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<p>This figure demonstrate the inverse correlation between the mass loss rate <math display="inline"><semantics> <mover accent="true"> <mi>M</mi> <mo>˙</mo> </mover> </semantics></math> (y-axis) and <math display="inline"><semantics> <mrow> <mi>P</mi> <mo>/</mo> <msub> <mi>P</mi> <mi>ac</mi> </msub> </mrow> </semantics></math> (x-axis) in AGB atmospheres of 1 <math display="inline"><semantics> <msub> <mi>M</mi> <mo>⊙</mo> </msub> </semantics></math> models assuming the reference parameters in <a href="#galaxies-12-00081-t001" class="html-table">Table 1</a>. Blue dots are the fundamental mode models and red crosses are the first-overtone mode models. This plot is limited to models that fall within the observed mass loss rate range (see <a href="#sec2-galaxies-12-00081" class="html-sec">Section 2</a>). The luminosity of each model in solar units is included in the plot; (4466, 4731, 5011, 5308, 5623, 5956, 6309, 6683, 7079, 7498, 7943) is the fundamental mode set and (4731, 5011, 5308, 5623, 5956, 6309, 6683, 7079, 7498, 7943, 8413, 8912, 9440, 9999, 10,592) is the first-overtone mode set.</p>
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15 pages, 1651 KiB  
Article
Proteomic Analysis Unveils the Protective Mechanism of Active Modified Atmosphere Packaging Against Senescence Decay and Respiration in Postharvest Loose-Leaf Lettuce
by Lili Weng, Jiyuan Han, Runyan Wu, Wei Liu, Jing Zhou, Xiangning Chen and Huijuan Zhang
Agriculture 2024, 14(12), 2156; https://doi.org/10.3390/agriculture14122156 - 27 Nov 2024
Viewed by 256
Abstract
In this study, physicochemical and proteomic analyses were performed to investigate the effect of modified atmosphere packaging (MAP) on the quality of postharvest loose-leaf lettuce. The results showed that MAP enhanced the sensory characteristics of loose-leaf lettuce and delayed the incidence of postharvest [...] Read more.
In this study, physicochemical and proteomic analyses were performed to investigate the effect of modified atmosphere packaging (MAP) on the quality of postharvest loose-leaf lettuce. The results showed that MAP enhanced the sensory characteristics of loose-leaf lettuce and delayed the incidence of postharvest deterioration by suppressing weight loss, electrolyte leakage, and reactive oxygen species levels. MAP-inhibited storage-induced programmed cell death may be attributed to a lower expression of protein disulfide isomerase and a higher expression of oligonucleotide/oligosaccharide binding fold nucleic acid binding site protein and reducing glutamine synthase levels. Also, we explore the potential of MAP to protect against oxidative damage in loose-leaf lettuce by potentially modulating the expression levels of NAC family proteins, which may enhance signaling and the expression of cytochrome c oxidase and membrane-bound pyrophosphate in the oxidative phosphorylation pathway. In addition, MAP potentially delayed postharvest senescence and extended the shelf life of lettuce by regulating key protein metabolic pathways that may reduce respiration rates. These include the NAC family of proteins, enzymes in the oxidative phosphorylation pathway, glutamine synthetize, and other crucial metabolic routes. These findings provide a scientific basis for enhancing the postharvest preservation of leafy vegetables, such as loose-leaf lettuce, through MAP technology. Full article
(This article belongs to the Special Issue Nutritional Quality and Health of Vegetables)
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Figure 1
<p>Effects of MAP on the sensory state (<b>A</b>), overall visual quality score (<b>B</b>), and chlorophyll content (<b>C</b>) in postharvest loose-leaf lettuce stored at 4 °C for 6 d. The asterisk (*) denotes a significant difference between MAP treatment and the control (<span class="html-italic">p</span> &lt; 0.05), the asterisk (***) denotes a significant difference between MAP treatment and the control (<span class="html-italic">p</span> &lt; 0.001).</p>
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<p>Effect of MAP on weight loss (<b>A</b>) and gas percentage (<b>B</b>) in postharvest lettuces during storage at 4 °C. The asterisk (***) denotes a significant difference between MAP treatment and the control (<span class="html-italic">p</span> &lt; 0.001).</p>
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<p>Effect of MAP on electrolyte leakage (<b>A</b>), hydroxyl radical superoxide radical (<b>B</b>), and superoxide radical (<b>C</b>) contents in postharvest lettuces during storage at 4 °C. The asterisk (***) denotes a significant difference between MAP treatment and the control (<span class="html-italic">p</span> &lt; 0.001).</p>
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<p>Differentially expressed genes of loose-leaf lettuce at the end of the storage period (control vs. MAP-treated). Enrichment of differentially expressed proteins for cellular components (<b>A</b>), molecular function (<b>B</b>), and biological processes (<b>C</b>).</p>
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16 pages, 6046 KiB  
Article
Investigation on Mechanical Shock Wave Protective and Thermodynamic Properties of SiO2-Aerogel-Modified Polyurea
by Chuanyi Liu, Wenlong Xu, Tonghui Yang, Dong Ma, Shiyu Jia and Zehao Li
Materials 2024, 17(23), 5817; https://doi.org/10.3390/ma17235817 - 27 Nov 2024
Viewed by 241
Abstract
In recent years, industrial explosion accidents are frequent, causing serious negative influences on society. Mechanical shock waves, as a typical destructive factor in explosion accidents, can cause serious personal injury and building damage. In addition, actual explosion accidents usually involve heat sources, harming [...] Read more.
In recent years, industrial explosion accidents are frequent, causing serious negative influences on society. Mechanical shock waves, as a typical destructive factor in explosion accidents, can cause serious personal injury and building damage. In addition, actual explosion accidents usually involve heat sources, harming protective materials and personnel. In this study, we designed SiO2-aerogel-modified polyurea and studied the effects of manufacturing pressure process and the concentration of SiO2 aerogel on the mechanical shock wave mitigation and thermodynamic properties of the modified polyurea. The results show that the addition of SiO2 aerogel can improve the mechanical shock wave mitigation performance of polyurea. The maximum peak overpressure and acceleration mitigation rate of the material has reached 17.84% and 62.21%, respectively. The addition of SiO2 aerogel helps to reduce the thermal conductivity of materials and improve the thermal insulation performance, and the atmospheric pressure process is more conducive to improving the thermal insulation performance of materials. The minimum thermal conductivity of the material has reached 0.14174 W/m·K, which is 45.65% lower than that of pure polyurea. The addition of SiO2 aerogel has different effects on the limiting oxygen index (LOI) of polyurea. Using a vacuum process, the LOI value increased with the increase in the SiO2 aerogel concentration, while using atmospheric pressure, the LOI value increased but is always lower than 21% and lower than pure polyurea. Thermogravimetric analysis showed that the addition of SiO2 aerogel under the vacuum process was helpful to improve the thermal stability of materials. However, atmospheric pressure would disrupt the thermal stability, manifested in a decrease in peak degradation temperature, an increase in peak degradation rate, and a decrease in residual mass. Full article
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<p>Material preparation process.</p>
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<p>Mechanical shock wave experimental setup.</p>
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<p>Peak overpressure baseline model and peak acceleration baseline model.</p>
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<p>Microscopic morphology of SiO<sub>2</sub>-aerogel-modified polyurea composites.</p>
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<p>Mechanical shock wave experiment overpressure results.</p>
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<p>Overpressure mitigation trend of polyurea composites with different filler concentrations. (<b>a</b>) Overpressure mitigation trend rates of PAV polyurea composites. (<b>b</b>) Overpressure mitigation trend rates of PAN polyurea composites.</p>
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<p>Mechanical shock wave experiment acceleration results.</p>
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<p>Mechanical shock wave experiment acceleration results.</p>
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<p>Overpressure mitigation trend of polyurea with different filler concentration. (<b>a</b>) Overpressure mitigation trend rates of PAV polyurea composites. (<b>b</b>) Overpressure mitigation trend rates of PAN polyurea composites.</p>
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<p>Trend in LOI and thermal conductivity of polyurea composites with different filler concentration.</p>
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<p>Thermogravimetric experiments results.</p>
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<p>Thermogravimetric experiments results.</p>
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12 pages, 10800 KiB  
Article
Transparent Zinc Oxide Memristor Structures: Magnetron Sputtering of Thin Films, Resistive Switching Investigation, and Crossbar Array Fabrication
by Alexander V. Saenko, Roman V. Tominov, Igor L. Jityaev, Zakhar E. Vakulov, Vadim I. Avilov, Nikita V. Polupanov and Vladimir A. Smirnov
Nanomaterials 2024, 14(23), 1901; https://doi.org/10.3390/nano14231901 - 27 Nov 2024
Viewed by 334
Abstract
This paper presents the results of experimental studies of the influence of high-frequency magnetron sputtering power on the structural and electrophysical properties of nanocrystalline ZnO films. It is shown that at a magnetron sputtering power of 75 W in an argon atmosphere at [...] Read more.
This paper presents the results of experimental studies of the influence of high-frequency magnetron sputtering power on the structural and electrophysical properties of nanocrystalline ZnO films. It is shown that at a magnetron sputtering power of 75 W in an argon atmosphere at room temperature, ZnO films have a relatively smooth surface and a uniform nanocrystalline structure. Based on the results obtained, the formation and study of resistive switching of transparent ITO/ZnO/ITO memristor structures as well as a crossbar array based on them were performed. It is demonstrated that memristor structures based on ZnO films obtained at a magnetron sputtering power of 75 W exhibit stable resistive switching for 1000 cycles between high resistance states (HRS = 537.4 ± 26.7 Ω) and low resistance states (LRS = 291.4 ± 38.5 Ω), while the resistance ratio in HRS/LRS is ~1.8. On the basis of the experimental findings, we carried out mathematical modeling of the resistive switching of this structure, and it demonstrated that the regions with an increase in the electric field strength along the edge of the upper electrode become the main sources of oxygen vacancy generation in ZnO film. A crossbar array of 16 transparent ITO/ZnO/ITO memristor structures was also fabricated, demonstrating 20,000 resistive switching cycles between LRS = 13.8 ± 1.4 kΩ and HRS = 34.8 ± 2.6 kΩ for all devices, with a resistance ratio of HRS/LRS of ~2.5. The obtained results can be used in the development of technological processes for the manufacturing of transparent memristor crossbars for neuromorphic structures of machine vision, robotics, and artificial intelligence systems. Full article
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Figure 1
<p>Experimental transparent ITO/ZnO/ITO memristor on glass substrate: (<b>a</b>) schematic structure; (<b>b</b>) appearance and transmission spectrum.</p>
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<p>SEM and AFM images of the surface of ZnO nanocrystalline films obtained at RF magnetron sputtering power: (<b>a</b>,<b>e</b>) 25 W; (<b>b</b>,<b>f</b>) 50 W; (<b>c</b>,<b>g</b>) 75 W; (<b>d</b>,<b>h</b>) 100 W.</p>
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<p>Structure of ZnO films and electrophysical properties of ZnO films: (<b>a</b>) transverse cleavage with a thickness of about 60 nm; (<b>b</b>) dependence of surface roughness on sputtering power; (<b>c</b>) dependence of charge carrier concentration on sputtering power; (<b>d</b>) charge carrier mobility on sputtering power.</p>
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<p>Structural properties of ZnO films obtained at different RF magnetron sputtering powers: (<b>a</b>) 25 W; (<b>b</b>) 50 W; (<b>c</b>) 75 W; (<b>d</b>) 100 W; (<b>e</b>) overview XPS spectrum of the film at 75 W; (<b>f</b>) high-resolution XPS spectrum of the zinc level; (<b>g</b>) high-resolution XPS spectrum of the oxygen level.</p>
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<p>Investigation of resistive switching and modeling of transparent ITO/ZnO/ITO memristor: (<b>a</b>) experimental current-voltage characteristic; (<b>b</b>) dependence of resistance on the number of switching cycles; (<b>c</b>) cumulative probability; (<b>d</b>) general view of the memristor structure model; (<b>e</b>) initial distribution of electric field strength with equipotential lines in the upper electrode region; (<b>f</b>) distribution of electric field strength with equipotential lines in the upper electrode region, taking into account the generation/recombination and migration of vacancies; (<b>g</b>) initial distribution of vacancy concentration in the upper electrode region; (<b>h</b>) distribution of vacancy concentration in the upper electrode region, taking into account their generation/recombination and migration; (<b>i</b>) theoretical current-voltage characteristics of the memristor structure based on ZnO film obtained at different powers of RF magnetron sputtering.</p>
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<p>Study of resistive switching of crossbar array of 16 transparent memristor structures: (<b>a</b>) optical image of one memristor structure; (<b>b</b>) current-voltage characteristic for one memristor structure; (<b>c</b>) dependence of resistance on the number of switching cycles for one memristor structure; (<b>d</b>) cumulative probability for one memristor structure; (<b>e</b>) optical image of crossbar; (<b>f</b>) current-voltage characteristics for crossbar array; (<b>g</b>) average statistical dependence of resistance on the number of switching cycles for crossbar array; (<b>h</b>) average statistical cumulative probability for crossbar array.</p>
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13 pages, 4072 KiB  
Article
Electrochemical Reactions at the Boundary Areas Between Cold Atmospheric Pressure Plasma, Air, and Water
by Jamiah Thomas and Alexander G. Volkov
Plasma 2024, 7(4), 891-903; https://doi.org/10.3390/plasma7040049 - 25 Nov 2024
Viewed by 379
Abstract
A cold atmospheric-pressure He-plasma jet (CAPPJ) interacts with air and water, producing reactive oxygen and nitrogen species (RONS), including biologically active ions, radicals, and molecules such as NOx, H2O2, HNO3, HNO2, and O [...] Read more.
A cold atmospheric-pressure He-plasma jet (CAPPJ) interacts with air and water, producing reactive oxygen and nitrogen species (RONS), including biologically active ions, radicals, and molecules such as NOx, H2O2, HNO3, HNO2, and O3. These compounds can activate interfacial redox processes in biological tissues. The CAPPJ can oxidize N2 to HNO3 and water to H2O2 at the interface between plasma and water. It can also induce the oxidation of water-soluble redox compounds in various organisms and in vitro. This includes salicylic acid, hydroquinone, and mixtures of antioxidants such as L (+)-ascorbic acid sodium salt with NADPH. It can react with redox indicators, such as ferroin, in a three-phase system consisting of air, CAPPJ, and water. Without reducing agents in the water, the CAPPJ will oxidize the water and decrease the pH of the solution. When antioxidants such as ascorbate, 1,4-hydroquinone, or NADPH are present in the aqueous phase, the CAPPJ oxidizes these substances first and then oxidizes water to H2O2. The multielectron mechanisms of the redox reactions in the plasma-air/water interfacial area are discussed and analyzed. Full article
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Figure 1
<p>Redox chemicals between cold atmospheric pressure He-plasma jet, air, and water. Asterics (*) indicate radicals.</p>
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<p>Cold atmospheric pressure He-plasma jet.</p>
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<p>(<b>A</b>): Absorbance of the aqueous phase after treatment with cold He-plasma jet. (<b>B</b>): Time dependence of adsorption of aqueous phase at the wavelength of 204 nm. (<b>C</b>): Absorbance of aqueous solutions of HNO<sub>3</sub>.</p>
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<p>Detection with test strips H<sub>2</sub>O<sub>2</sub> production during the treatment of water (<b>A</b>), 0.25 mM sodium ascorbate (<b>B</b>), and 50 μM 1,4-hydroquinone aqueous solution (<b>C</b>), with cold atmospheric pressure He-plasma jet. These strips were used for the detection of H<sub>2</sub>O<sub>2</sub> in water after the treatment with cold atmospheric pressure He-plasma jet. The plasma treatment time of the aqueous solution in experiments (<b>A</b>–<b>C</b>) is indicated for each detection strip case (<b>A</b>–<b>C</b>). The test strips acquire the specific color only in the presence of specific substrates, such as H<sub>2</sub>O<sub>2</sub>.</p>
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<p>Gibbs energy and redox potentials scheme for the water oxidation at pH 7 are shown. The number of involved electrons is n<sub>e</sub>. Redox potentials were taken from the Handbooks of Chemistry and Physics. The Gibbs energy was calculated as ∆G = −n<sub>e</sub>FE, where n<sub>e</sub> is the number of electrons, F is the Faraday constant, and E is the redox potential at pH = 7.</p>
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<p>Absorption spectra of an aqueous solution containing 50 μM of salicylic acid after treatment with CAPPJ. Lines: black 0 min, blue 15 min, grey 30 min, green 45 min, red 60 min. Figure (<b>B</b>) shows an enlarged portion of the upper graph (<b>A</b>). The dependence of the absorption at 296 nm on the treatment time of the aqueous solution with CAPPJ is shown in Figure (<b>C</b>).</p>
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<p>Absorption spectra of an aqueous solution containing ferroin at a concentration of 50 μM ferroin before (1) and after (2,3) treatment with cold atmospheric pressure He-plasma jet. Time of treatment: 1—0 min, 2—1 h, 3—5 h.</p>
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<p>(<b>A</b>): Absorption spectra of aqueous solution containing 50 μM AgNO<sub>3</sub> before and after treatment with cold atmospheric pressure He-plasma jet. (<b>B</b>): Standard redox potentials scheme for silver redox reactions at pH 7; n<sub>e</sub> is the number of electrons.</p>
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<p>Absorption spectra of 50 μM NADP<sup>+</sup> aqueous solution before (black) and after treatment with CAPPJ for 15 min (green), 30 min (red), and 45 min (blue).</p>
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<p>(<b>A</b>) Absorption spectra of 25 μM NADPH and 0.125 mM sodium ascorbate aqueous solution before (1) and after treatment with cold atmospheric pressure He-plasma jet for 15 min (2), 30 min (3), 45 min (4), and 60 min (5). (<b>B</b>) A magnified part of the upper graph (<b>A</b>).</p>
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15 pages, 10215 KiB  
Article
Study on the Repair of Irregular and Deep Cracks Induced by Thermal Shock Using Al-Cu-O Reactions in Al2O3 Ceramics
by Fuhai Bao, Seiji Yamashita and Hideki Kita
Processes 2024, 12(11), 2606; https://doi.org/10.3390/pr12112606 - 20 Nov 2024
Viewed by 364
Abstract
The irregular and deep cracks induced by thermal shock in Al2O3 ceramics were repaired by applying Cu powder layer on their surface and heating at 1200 °C under an atmosphere of air. The Al-Cu-O liquid phase formed at 1200 °C [...] Read more.
The irregular and deep cracks induced by thermal shock in Al2O3 ceramics were repaired by applying Cu powder layer on their surface and heating at 1200 °C under an atmosphere of air. The Al-Cu-O liquid phase formed at 1200 °C by the reaction of molten Cu, oxygen, and Al2O3 phases penetrate deep into the narrow cracks, and the precipitation phases of Cu2O and CuAlO2 densely fill the crack interior. Our observation and analysis of the filled cracks and the surrounding areas of the repaired cracks, as well as the microstructural analysis results obtained through SEM-EDS and TEM observation, suggested the aforementioned crack repair mechanism. The bending strength of the coated surface after repairing the cracks is 301.8 MPa (ΔT = 300 °C), which is twice as strong as the specimen after thermal shock and 10% higher than the original strength of the base material. Full article
(This article belongs to the Section Materials Processes)
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<p>Conceptual diagram of the four-point bending test.</p>
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<p>Optical microscopic images of Al<sub>2</sub>O<sub>3</sub> specimen stained with red ink (<b>a</b>,<b>b</b>) before and (<b>c</b>,<b>d</b>) after thermal shock (Δ<span class="html-italic">T</span> = 300 °C); (<b>a</b>,<b>c</b>) 4 × 40 mm surface and (<b>b</b>,<b>d</b>) cross-sectional face.</p>
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<p>Cracks observed on the cross-sectional surfaces of the Al<sub>2</sub>O<sub>3</sub> specimens that were heat-treated at 525 °C for 30 min in air and quenched in water at 25 °C (<b>a</b>–<b>c</b>). The white arrow indicates the region where cracks have formed due to thermal shock.</p>
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<p>Residual strength of sintered Al<sub>2</sub>O<sub>3</sub> under different thermal shock conditions.</p>
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<p>Cross-sectional surfaces of Al<sub>2</sub>O<sub>3</sub> specimens without thermal shock, following heating at 1200 °C for 1 h with a Cu coating (<b>a</b>–<b>c</b>).</p>
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<p>(<b>a</b>) The coated surface and opposite side of the Al<sub>2</sub>O<sub>3</sub> specimens subjected to thermal shock (Δ<span class="html-italic">T</span> = 500 °C) after heating at 1200 °C for 1 h. The arrow points to the crack. (<b>b</b>) Cross-sectional surfaces of the specimens. (<b>c</b>) A schematic of the mechanism of Cu penetrating the Al<sub>2</sub>O<sub>3</sub> specimen.</p>
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<p>Cross-section of Al<sub>2</sub>O<sub>3</sub> specimens subjected to thermal shock (Δ<span class="html-italic">T</span> = 500 °C) after heating at 1200 °C for 1 h (<b>a,b</b>).</p>
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<p>Various contrasts observed in Al<sub>2</sub>O<sub>3</sub> specimens subjected to thermal shock (Δ<span class="html-italic">T</span> = 500 °C) after heating at 1200 °C for 1 h.</p>
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<p>XRD patterns of Al<sub>2</sub>O<sub>3</sub> specimens subjected to thermal shock (Δ<span class="html-italic">T</span> = 500 °C) after heating at 1200 °C for 1 h with Cu.</p>
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<p>Average four-point bending strength of Al<sub>2</sub>O<sub>3</sub> subjected to thermal shock at different Δ<span class="html-italic">T</span> before and after heating with Cu at 1200 °C for 1 h. The dashed line represents the baseline strength of untreated Al<sub>2</sub>O<sub>3.</sub></p>
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<p>HAADF-STEM image of the cross-section of the specimen after thermal shock (Δ<span class="html-italic">T</span> = 500 °C). The red arrows represents the Cu<sub>2</sub>O region.</p>
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<p>FFT diffraction patterns of (<b>b</b>) the Cu<sub>2</sub>O phase, (<b>c</b>) the Cu<sub>2</sub>O phase near the interface, and (<b>d</b>) the Al<sub>2</sub>O<sub>3</sub> phase in (<b>a</b>) a TEM image of the Cu<sub>2</sub>O-Al<sub>2</sub>O<sub>3</sub> interface.</p>
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<p>FFT diffraction patterns of (<b>b</b>) the CuAlO<sub>2</sub> phase, (<b>c</b>) the Al<sub>2</sub>O<sub>3</sub> phase near the crystal interface, and (<b>d</b>) the Al<sub>2</sub>O<sub>3</sub> phase in (<b>a</b>) a TEM image of the CuAlO<sub>2</sub>-Al<sub>2</sub>O<sub>3</sub> interface.</p>
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<p>Phase diagram of the Cu<sub>2</sub>O-Al<sub>2</sub>O<sub>3</sub> system [<a href="#B31-processes-12-02606" class="html-bibr">31</a>].</p>
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<p>Relationship between different crack lengths and bending strengths.</p>
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14 pages, 4748 KiB  
Article
Growth and Characterization of High-Quality YTiO3 Single Crystals: Minimizing Ti4+ Containing Impurities and TiN Formation
by Yong Liu, David Wenhua Bi and Arnaud Magrez
Crystals 2024, 14(11), 989; https://doi.org/10.3390/cryst14110989 - 16 Nov 2024
Viewed by 378
Abstract
We report the growth of YTiO3 single crystals using different starting materials with the nominal compositions, (1) stoichiometric YTiO3; (2) oxygen deficient YTiO2.925; (3) oxygen deficient YTiO2.85, and different atmospheres, (1) 97%Ar/3%H2; (2) Ar; [...] Read more.
We report the growth of YTiO3 single crystals using different starting materials with the nominal compositions, (1) stoichiometric YTiO3; (2) oxygen deficient YTiO2.925; (3) oxygen deficient YTiO2.85, and different atmospheres, (1) 97%Ar/3%H2; (2) Ar; (3) forming gas 95%N2/5%H2, using the laser floating zone growth technique. The oxygen-deficient starting materials were prepared by mixing Y2O3, Ti2O3, and Ti powder according to the YTiO3-δ stoichiometry. The addition of Ti powder to the starting materials effectively reacts with the oxygen in the floating zone furnace chamber, reducing Ti4+ ion-containing impurities. High-quality YTiO3 single crystals with (2 0 0) facet were grown from the starting materials corresponding to the nominal composition YTiO2.925. YTiO3 single crystals grown from different starting materials are characteristic of oxygen content of 3 in both pure crystals and crystals containing impurities, revealed by the same oxygen occupancy in single crystal X-ray diffraction measurements. When forming gas was used, a golden TiN coating formed on the surface of rod. Full article
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<p>(<b>a</b>) Rods are wrapped in a tantalum foil and sealed in quartz ampoules. (<b>b</b>) The grey rods after sintering at 1100 °C for 24 h. (<b>c</b>) The XRD pattern shows three phases: YTiO<sub>3</sub>, Y<sub>2</sub>O<sub>3</sub>, and Ti<sub>2</sub>O<sub>3</sub>, in the sintered rod.</p>
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<p>(<b>a</b>) YTiO<sub>3</sub> single crystals grown from the starting materials YTiO<sub>3</sub> (growth rate 10 mm/h). (<b>b</b>) Laue X-ray diffraction pattern was performed on the surface of the rod after growth in the floating zone furnace. (<b>c</b>) The Laue pattern obtained from the surface of the rod. (<b>d</b>) The Laue X-ray diffraction measurement was performed on the cross-section of the rod. (<b>e</b>) The Laue pattern obtained from the cross-section of the rod. (<b>f</b>) The rod was titled until a symmetric Laue pattern was obtained. (<b>g</b>) The two-fold symmetric Laue pattern taken from the tilted rod.</p>
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<p>Profile fitting of powder XRD data from the crystal grown from the starting materials with nominal composition YTiO<sub>3</sub> at a growth rate of 10 mm/h. The insets highlight the peaks assigned to the Y<sub>2</sub>Ti<sub>2</sub>O<sub>7</sub> and Y<sub>2</sub>TiO<sub>5</sub> impurities, as indicated by the arrows. The red dotted line, Y<sub>obs</sub>, presents the raw data, the black solid line, Y<sub>calc</sub> by the Le Bail fitting using the HighScore plus program and ICDD PDF5+ data base, the red line Y<sub>obs</sub>-Y<sub>calc</sub>, <span class="html-italic">R</span><sub>wp</sub> and GOOF (goodness of fit) values indicate the quality of fitting. The blue vertical bars indicate the Bragg peak position in the calculated pattern.</p>
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<p>(<b>a</b>) Crystal structure of orthorhombic YTiO<sub>3</sub>. (<b>b</b>) Pyrochlore Y<sub>2</sub>Ti<sub>2</sub>O<sub>7</sub> structure with <math display="inline"><semantics> <mrow> <mi>F</mi> <mi mathvariant="normal">d</mi> <mover accent="true"> <mrow> <mn>3</mn> </mrow> <mo>¯</mo> </mover> <mi mathvariant="normal">m</mi> </mrow> </semantics></math> cubic space group. (<b>c</b>) Hexagonal Y<sub>2</sub>TiO<sub>5</sub> with space group <span class="html-italic">P</span>6<sub>3</sub>/mmc. The red, purple and grey spheres represent the O atoms, the Ti atoms, and the Y atoms, respectively.</p>
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<p>(<b>a</b>) YTiO<sub>3</sub> single crystals grown from the starting materials with nominal composition YTiO<sub>2.925</sub> at a growth rate of 4 mm/h. The rod has two parallel flat surfaces. The inset shows the flat surface after polishing. (<b>b</b>) The XRD measurement reveals that the flat surface corresponds to the (2 0 0) plane. (<b>c</b>) The Laue X-ray diffraction measurement performed on the flat surface. (<b>d</b>) The two-fold symmetric Laue pattern obtained from the flat surface. (<b>e</b>) View of the rod tilted to obtain a symmetric Laue pattern. (<b>f</b>) The two-fold symmetric Laue pattern taken from the tilted rod.</p>
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<p>Profile fitting of powder XRD data from the crystal grown from the starting materials with nominal composition YTiO<sub>2.925</sub> at a growth rate of 4 mm/h. The red dotted line, Y<sub>obs</sub>, presents the raw data, the black solid line, Y<sub>calc</sub> by the Le Bail fitting using the HighScore plus program and ICDD PDF5+ data base, the red line Y<sub>obs</sub>-Y<sub>calc</sub>, <span class="html-italic">R</span><sub>wp</sub> and GOOF (goodness of fit) values indicate the quality of fitting.</p>
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<p>(<b>a</b>) The temperature dependence of the magnetic susceptibility of single-crystal crushed powder samples from the single crystals grown from the starting materials YTiO<sub>3</sub>, YTiO<sub>2.925</sub> and YTiO<sub>2.85</sub>. (<b>b</b>) The magnetic field dependence of magnetization for the same powder samples as those in (<b>a</b>). (<b>c</b>) Heat capacity as a function of temperature for the crystals grown from rods with an oxygen-deficient YTiO<sub>2.925</sub> composition.</p>
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<p>(<b>a</b>) YTiO<sub>3</sub> single crystals grown from the starting materials YTiO<sub>2.85</sub> at 10 mm/h under Ar + H<sub>2</sub> atmosphere. A thin golden layer formed on the surface of the rod due to the air leak. (<b>b</b>) The XRD pattern shows the presence of TiN phase in the sample shown in (<b>a</b>). (<b>c</b>) A homogeneous gold-like coating on the YTiO<sub>3</sub> single crystal obtained when growth is performed under forming gas. (<b>d</b>) The XRD measurement was performed on the surface of the rod and TiN phase is identified.</p>
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<p>(<b>a</b>) The temperature dependence of magnetization reveals the superconducting transition at about 4 K in the powder obtained by grinding the rod grown under forming gas. (<b>b</b>) The magnetic hysteresis loop measured at <span class="html-italic">T</span> = 3 K also evidences the presence of the TiN superconducting phase in the powder.</p>
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10 pages, 5129 KiB  
Commentary
Challenging the Chemistry of Climate Change
by Bruce Peachey and Nobuo Maeda
Chemistry 2024, 6(6), 1439-1448; https://doi.org/10.3390/chemistry6060086 - 16 Nov 2024
Viewed by 2384
Abstract
As talk grows about billions or even trillions of dollars being directed toward potential “Net Zero” activities, it is imperative that the chemistry inherent in or driving those actions make scientific sense. The challenge is to close the mass and energy balances to [...] Read more.
As talk grows about billions or even trillions of dollars being directed toward potential “Net Zero” activities, it is imperative that the chemistry inherent in or driving those actions make scientific sense. The challenge is to close the mass and energy balances to the carbon and oxygen cycles in the Earth’s atmosphere and oceans. Several areas of climate science have been identified that chemists can investigate through methods that do not require a supercomputer or a climate model for investigation, most notably the following: (1) The carbon cycle, which still needs to be balanced, as many known streams, such as carbon to landfills, carbon in human-enhanced sewage and land runoff streams, and carbon stored in homes and other material, do not seem to have been accounted for in carbon balances used by the IPCC. (2) Ocean chemistry and balances are required to explain the causes of regional and local-scale salinity, pH, and anoxic conditions vs. global changes. For example, local anoxic conditions are known to be impacted by changes in nutrient discharges to oceans, while large-scale human diversions of fresh water streams for irrigation, power, and industrial cooling must have regional impacts on oceanic salinity and pH. (3) Carbon Capture and Storage (CCS) schemes, if adopted on the large scales being proposed (100s to 1000s of Gt net injection by 2100), should impact the composition of the atmosphere by reducing free oxygen, adding more water from combustion, and displacing saline water from subsurface aquifers. Data indicate that atmospheric oxygen is currently dropping at about twice the rate of CO2 concentrations increasing, which is consistent with combustion chemistry with 1.5 to 2 molecules of oxygen being converted through combustion to 1 molecule of CO2 and 1 to 2 molecules of H2O, with reverse reactions occurring as a result of oxygenic photosynthesis by increased plant growth. The CCS schemes will sabotage these reverse reactions of oxygenic photosynthesis by permanently sequestering the oxygen atoms in each CO2 molecule. Full article
(This article belongs to the Section Physical Chemistry and Chemical Physics)
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<p>Atmospheric CO<sub>2</sub> concentrations over geologic time range of 0–7000 ppmv (left image, reproduced from Ref. [<a href="#B9-chemistry-06-00086" class="html-bibr">9</a>]) and recent measurement range of 310–430 ppm (right image, reproduced from NOAA <a href="https://gml.noaa.gov/ccgg/trends/" target="_blank">https://gml.noaa.gov/ccgg/trends/</a> (accessed on 30 September 2024). The (<b>left</b>) panel shows that the atmospheric CO<sub>2</sub> concentration has varied considerably over time while the temperature has been falling steadily over the last 450 million years, which illustrates the difficulty in directly correlating CO<sub>2</sub> as being a driver of temperature. The (<b>right</b>) panel shows the steadily rising atmospheric CO<sub>2</sub> concentrations over the last 65 years, which are still at much lower concentrations than indicated by CO<sub>2</sub> proxies.</p>
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<p>Graph illustrating the impacts of carbon sinks on CO<sub>2</sub> buildup in the atmosphere (reproduced from [<a href="#B12-chemistry-06-00086" class="html-bibr">12</a>]). The atmospheric CO<sub>2</sub> concentration growth remained below the anthropogenic CO<sub>2</sub> emissions over the years because a fraction of the anthropogenic CO<sub>2</sub> emissions has been absorbed by natural or human-caused carbon sinks. As time went by, the anthropogenic CO<sub>2</sub> emissions increased/accelerated, but so did the absorption by the less-defined carbon sinks. This implies that to predict future change, a better understanding is needed of where the additional carbon added has gone and whether this has a net positive or negative effect.</p>
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<p>This diagram of the fast carbon cycle shows the movement of carbon between the land, atmosphere, and oceans. White numbers indicate stored carbon (stocks). Yellow numbers are natural fluxes (flows), and red is assumed human contributions in gigatons of carbon per year and assumed carbon masses moving into assumed sinks (adapted from <a href="https://earthobservatory.nasa.gov/features/CarbonCycle" target="_blank">https://earthobservatory.nasa.gov/features/CarbonCycle</a> (accessed on 30 September 2024). Blue arrows and boxes have been added by the authors to indicate carbon streams not shown in the original reference diagram. Focusing on the red numbers would show that an incremental 3Gt/yr of carbon is going to increased plant biomass or soil carbon, but the diagram does not split this out or show the impact of other human activities, which would remove and sequester that carbon. Similarly, 2 Gt/yr of carbon is shown going into the oceans with nothing returning, but the diagram does not specify if that carbon is in the form of CO<sub>2</sub>, which might cause acidification, or carbon, which may just increase sedimentation in the oceans.</p>
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<p>The change in the composition of the Earth’s atmosphere (left image, reproduced from Ref. [<a href="#B18-chemistry-06-00086" class="html-bibr">18</a>]) and the oxygen concentration in the Earth’s atmosphere over time (right image, reproduced from Ref. [<a href="#B19-chemistry-06-00086" class="html-bibr">19</a>]). The original atmosphere of the Earth contained very little free oxygen. All the oxygen in the atmosphere now came from oxygenic photosynthesis of plants over billions of years. While oxygen is currently a major component of the atmosphere, there are areas where anoxic conditions may be impacted and need to be better understood in the context of the past and potential future.</p>
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<p>Measured data on CO<sub>2</sub> and O<sub>2</sub> concentrations between 1991 and 2020 with correlations (reproduced from Ref. [<a href="#B21-chemistry-06-00086" class="html-bibr">21</a>]). The O<sub>2</sub> concentrations have been dropping by ~130 ppm, while the CO<sub>2</sub> concentrations have been increasing by about 50 ppm over 20 years. What does this potentially tell us about the availability of CO<sub>2</sub> for ocean acidification vs. the transfer of carbon to ocean sediments?</p>
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<p>Relative changes in the type and amount of fossil fuel consumption over time (reproduced from BP Statistical Review of World Energy 2019). The fuel consumption by humans has consistently been shifting from carbon-rich sources to progressively hydrogen-rich ones. The combustion of these fuels should have changed the relationship between the rate of CO<sub>2</sub> increase vs. the rate of O<sub>2</sub> decrease in the atmosphere in recent decades.</p>
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20 pages, 8835 KiB  
Article
Origin of Intercrystalline Brine Formation in the Balun Mahai Basin, Qaidam: Constraints from Geochemistry and H-O-Sr Isotopes
by Ning Feng, Xiwei Qin, Yuliang Ma, Tong Pan, Jianzhou Chen, Chengwang Ding, Ziwen Jiang, Dong Zhang, Chenglin Liu, Qingkuan Li, Erfeng Ren and Fan Zhang
Water 2024, 16(22), 3286; https://doi.org/10.3390/w16223286 - 15 Nov 2024
Viewed by 530
Abstract
The Balun Mahai Basin (BLMH), located in the northern Qaidam Basin (QB), is endowed with substantial brine resources; however, the genetic mechanisms and potential of these brine resources remain inadequately understood. This study investigated the intercrystalline brine (inter-brine) in BLMH, performing a comprehensive [...] Read more.
The Balun Mahai Basin (BLMH), located in the northern Qaidam Basin (QB), is endowed with substantial brine resources; however, the genetic mechanisms and potential of these brine resources remain inadequately understood. This study investigated the intercrystalline brine (inter-brine) in BLMH, performing a comprehensive geochemical analysis of elemental compositions and H-O-Sr isotopes. It evaluated the water source, solute origin, evolutionary process, and genetic model associated with this brine. Moreover, a mass balance equation based on the 87Sr/86Sr isotopic ratio was developed to quantitatively evaluate the contributions of Ca-Cl water and river water to the inter-brine in the study area. The results suggest that the hydrochemical type of inter-brine in the north part of BLMH is Cl-SO4-type and in the south part is Ca-Cl-type. The solutes in brine are mainly derived from the dissolution of minerals such as halite, sylvite, and gypsum. The hydrochemical process of brine is controlled by evaporation concentration, water–rock interaction, and ion exchange interaction. Hydrogen and oxygen isotopes suggest that the inter-brine originates from atmospheric precipitation or ice melt water and has experienced intense evaporation concentration and water–rock interaction. The strontium isotopes suggest that the inter-brine was affected by the recharge and mixing of Ca-Cl water and river water, which controlled the spatial distribution and formation of brine hydrochemical types. The analysis of ionic ratios suggest that the inter-brine is derived from salt dissolution and filtration, characterized by poor sealing and short sealing time in the salt-bearing formation. The differences in hydrochemical types and spatial distribution between the north and the south are fundamentally related to the replenishment and mixing of these two sources, which can be summarized as mixed origin model of “dissolution and filtration replenishment + deep replenishment” in BLMH. Full article
(This article belongs to the Special Issue Saline Water and Brine Geochemistry)
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<p>(<b>a</b>) The QB is located in the northeast of the Qinghai–Tibet Plateau. (<b>b</b>) Geologic structure schematic map of BLMH [<a href="#B20-water-16-03286" class="html-bibr">20</a>]. (<b>c</b>) Isopach map and sampling location of inter-brine in BLMH (F1—Tunan fault, F2—Quenan fault, F3—Qiannan fault, F4—Lengqi fault).</p>
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<p>Composite column map of Quaternary stratigraphy in BLMH [<a href="#B20-water-16-03286" class="html-bibr">20</a>,<a href="#B22-water-16-03286" class="html-bibr">22</a>].</p>
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<p>Piper plot showing the major ionic concentrations of different samples in MH.</p>
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<p>(<b>a</b>) The <sup>87</sup>Sr/<sup>86</sup>Sr ratios of different types of brine and salt layers in MH. (<b>b</b>) The <sup>87</sup>Sr/<sup>86</sup>Sr ratios of inter-brines in BLMH.</p>
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<p>Ternary Ca-SO<sub>4</sub>-HCO<sub>3</sub>-alkalinity plot showing the chemical composition of distinct waters in MH.</p>
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<p>logK (<b>a</b>), logNa (<b>b</b>), logCa (<b>c</b>), logMg (<b>d</b>), logSO<sub>4</sub> (<b>e</b>), logHCO<sub>3</sub> (<b>f</b>), logLi (<b>g</b>), logBr (<b>h</b>), logTDS (<b>i</b>), and logSr (<b>j</b>) vs. logCl plots showing the inter-brine in BLMH [<a href="#B35-water-16-03286" class="html-bibr">35</a>,<a href="#B36-water-16-03286" class="html-bibr">36</a>].</p>
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<p>(<b>a</b>) (Ca<sup>2+</sup>+Mg<sup>2+</sup>) − (SO<sub>4</sub><sup>2−</sup> + HCO<sub>3</sub><sup>−</sup>) vs. (Na<sup>+</sup> + K<sup>+</sup> − Cl<sup>−</sup>); (<b>b</b>) CAI1 vs. CAI2 plots showing the inter-brine in BLMH.</p>
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<p>Mineral saturation index plot showing the inter-brine in BLMH.</p>
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<p>TDS for sulfate (<b>a</b>) and halide (<b>b</b>) minerals plots showing the inter-brine in BLMH.</p>
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<p>(<b>a</b>) The Ca<sub>excess</sub> vs. Na<sub>deficit</sub>; (<b>b</b>) Ca/Mg vs. Ca/Sr plots showing the inter-brine in MH.</p>
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<p>(<b>a</b>) Hydrogen and oxygen isotopes of brines; (<b>b</b>) δ<sup>18</sup>O<sub>V-SMOW</sub> vs. d-Excess in MH.</p>
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<p>The relationship of <sup>87</sup>Sr/<sup>86</sup>Sr ratios and 1/Sr of waters in MH and its surrounding area. EM 1 (End member 1) is water in the Yuqia River; EM 2 (End member 2) is anticlinal brine in the LH. NLZV Lake: Niulang Zhinv Lake. (<b>a</b>) The high 87Sr/86Sr ratios; (<b>b</b>) high Sr concentrations; (<b>c</b>) low Sr concentrations.</p>
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<p>The relationship between Br × 10<sup>3</sup>/Cl density ratio and Na/Cl molar ratio of inter-brine in BLMH.</p>
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<p>The diagram of inter-brine source and origin in BLMH.</p>
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14 pages, 7281 KiB  
Article
Ti3+ Self-Doping of TiO2 Boosts Its Photocatalytic Performance: A Synergistic Mechanism
by Mingqing Zhang, Manyu Liu, Keyi Han, Yingbin Liang, Xinyu Zhao, Lin Han, Jinnong Wang, Shifeng Wang and Yong Li
Molecules 2024, 29(22), 5385; https://doi.org/10.3390/molecules29225385 - 15 Nov 2024
Viewed by 407
Abstract
Pollution remains one of the most significant global challenges. Photocatalysis consists of a new organic pollutant removal technology, with TiO2 widely studied as a photocatalyst in the photocatalytic removal of water pollution. However, intrinsic TiO2 has the disadvantages of weak visible [...] Read more.
Pollution remains one of the most significant global challenges. Photocatalysis consists of a new organic pollutant removal technology, with TiO2 widely studied as a photocatalyst in the photocatalytic removal of water pollution. However, intrinsic TiO2 has the disadvantages of weak visible light absorption, low electron separation, and transmission efficiency, as well as few active sites. In this study, anatase-phase Ti3+ self-doped TiO2 (B-TiO2) with a core-shell structure was successfully prepared by forming an amorphous layer rich in oxygen vacancies (OVs) and Ti3+ defects on the TiO2 surface under a nitrogen atmosphere using NaBH4 as a chemical-reducing agent. The visible light absorption performance of the catalyst was notably improved when exposed to light irradiation. The bending of surface energy bands facilitated the separation of photogenerated electron-hole pairs, and the core-shell structure allowed the electron-hole pairs to be transported to the surface of the catalyst and participate in the reaction faster. We observed that 92.86% of Rhodamine B (RhB) was degraded in only 5 min, an increase of 2.73 times that of the degradation rate observed in commercial P25. With extraordinary stability, the photocatalytic efficiency of the catalyst remained at 96.2% after five degradation cycles. Full article
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<p>(<b>a</b>) XRD image and (<b>b</b>) electron paramagnetic resonance (EPR) of anatase TiO<sub>2</sub> and B-TiO<sub>2</sub>.</p>
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<p>TiO<sub>2</sub> and B-TiO<sub>2</sub>-300 (<b>a</b>), XPS O1s mapping (<b>b</b>), and XPS Ti2p mapping.</p>
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<p>(<b>a</b>) SEM image, (<b>b</b>) TEM image, and (<b>c</b>,<b>d</b>) HRTEM of B-TiO<sub>2</sub>-300.</p>
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<p>(<b>a</b>) Photocatalytic degradation, (<b>b</b>) first-order kinetics, (<b>c</b>) 5 min degradation rate, and (<b>d</b>) 15 min cyclic degradation of RhB by P25, TiO<sub>2</sub>, and B-TiO<sub>2</sub>-300.</p>
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<p>Nitrogen adsorption/desorption isotherm curves.</p>
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<p>TiO<sub>2</sub> and B-TiO<sub>2</sub> (<b>a</b>) UV–visible diffuse reflectance (UDS), (<b>b</b>) TiO<sub>2</sub> bandgap, (<b>c</b>) TiO<sub>2</sub> DFT energy bands, and (<b>d</b>) B-TiO<sub>2</sub> DFT energy bands.</p>
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<p>(<b>a</b>) Ultraviolet photoelectron spectra (UPS) of TiO<sub>2</sub> and B-TiO<sub>2</sub>; (<b>b</b>) energy band diagrams.</p>
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<p>(<b>a</b>) Transient photocurrent response, and (<b>b</b>) electrochemical impedance Nyquist plots of TiO<sub>2</sub> and B-TiO<sub>2</sub>.</p>
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<p>EPR spectra of the DMPO trapping radicals on B-TiO<sub>2</sub>-300: (<b>a</b>) DMPO-·O<sub>2</sub><sup>−</sup>, (<b>b</b>) DMPO-·OH, and (<b>c</b>) degradation of RhB by B-TiO<sub>2</sub>-300 and the addition of different scavengers: p-benzoquinone (p-BQ), ammonium oxalate (AO), and isopropyl alcohol (IPA), after visible light irradiation (λ &gt; 300 nm, 30 s).</p>
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16 pages, 23580 KiB  
Article
Study on Surface Quality Analysis of an Uncoated Boron Steel and Its Oxide Layer Suppression Method for Hot Stamping
by Jiho Lee, Junghan Song and Gihyun Bae
Materials 2024, 17(22), 5563; https://doi.org/10.3390/ma17225563 - 14 Nov 2024
Viewed by 418
Abstract
This study investigates the effects of hot stamping on boron steel surface properties, comparing uncoated steel to Al–Si-coated steel, with a focus on developing atmosphere-controlled hot stamping technology. Experiments using a hat-shaped specimen revealed that uncoated steel formed a thick oxide layer due [...] Read more.
This study investigates the effects of hot stamping on boron steel surface properties, comparing uncoated steel to Al–Si-coated steel, with a focus on developing atmosphere-controlled hot stamping technology. Experiments using a hat-shaped specimen revealed that uncoated steel formed a thick oxide layer due to exposure to atmospheric oxygen at high temperatures, negatively impacting surface quality and weldability. In contrast, the Al–Si-coated steel showed no oxide formation. Although uncoated steel exhibited higher average Vickers hardness, the detrimental effects of the oxide layer on weld quality necessitate advancements in process technology. A lab-scale hot stamping simulator was developed to control atmospheric oxygen levels, utilizing a donut-shaped induction heating coil to heat the material above 1000 °C, followed by rapid cooling in a forming die. Results demonstrated that maintaining oxygen concentrations below 6% significantly reduced oxide layer thickness, with near-vacuum conditions eliminating oxide formation altogether. These findings emphasize the critical role of oxygen control in enhancing the surface quality and weldability of uncoated boron steel for ultra-high-strength automotive applications, potentially reducing manufacturing costs while ensuring part performance. Full article
(This article belongs to the Special Issue Metal Additive Manufacturing: Design, Performance, and Applications)
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<p>Main test devices for the hot stamping test.</p>
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<p>Hot stamping test process of a hat-type specimen.</p>
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<p>Hat-type specimens before and after the hot stamping test: (<b>a</b>) uncoated material; (<b>b</b>) coated material.</p>
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<p>Oxide layer formation of the uncoated boron steel due to oxygen contact.</p>
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<p>Point EDS composition analysis of uncoated boron steel sheets after heat treatment.</p>
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<p>EDS mapping analysis of Al–Si-coated boron steel sheets before and after heat treatment.</p>
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<p>Sample-capturing locations of the hat-type specimen.</p>
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<p>SEM images at the top, wall, and flange locations to measure the oxide layer thickness of uncoated boron steel.</p>
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<p>SEM images of Al–Si-coated hat-type specimen at the top, wall, and flange locations.</p>
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<p>Vickers hardness of uncoated and coated boron steel sheets.</p>
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<p>Schematic diagram of an atmosphere-controllable hot stamping simulator.</p>
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<p>Lab-scale hot stamping simulator.</p>
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<p>Equipment configuration for the performance evaluation of the heating module.</p>
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<p>Locations of thermocouple attachment considering the heated area.</p>
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<p>Temperature distribution according to the heating module output.</p>
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<p>Installation of the oxygen analyzer inside the vacuum chamber.</p>
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<p>Atmosphere control test result according to the nitrogen gas pressure: (<b>a</b>) 5.0 kPa; (<b>b</b>) 7.2 kPa.</p>
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<p>Experimental results of simulated specimens through atmosphere control.</p>
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<p>Optical microscope measurements according to atmosphere conditions at the top area: (<b>a</b>) oxygen 0%; (<b>b</b>) oxygen 2%; (<b>c</b>) oxygen 4%; (<b>d</b>) oxygen 6%; (<b>e</b>) oxygen 8%.</p>
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15 pages, 7039 KiB  
Article
Fire Safety Characteristics of Pine Wood Under Low Pressure and Oxygen Enrichment
by Sijie Ding, Xuhong Jia, Junhao Ma, Jing Tang and Wenbing Li
Fire 2024, 7(11), 416; https://doi.org/10.3390/fire7110416 - 14 Nov 2024
Viewed by 489
Abstract
Oxygen enrichment at high altitudes indoors can be effective in meeting demand. However, the high oxygen environment inevitably brings about additional fire hazards, and the specific changes are still unclear. As pine wood is a common material in construction, this paper provides data [...] Read more.
Oxygen enrichment at high altitudes indoors can be effective in meeting demand. However, the high oxygen environment inevitably brings about additional fire hazards, and the specific changes are still unclear. As pine wood is a common material in construction, this paper provides data support for fire protection for buildings in highland areas by studying the combustion characteristics of pine wood at different oxygen concentration (21.0%, 23.0%, 30.0%, 27.0%, 33.0%) under different atmospheric pressures (50.0 kPa, 60.0 kPa, 70.0 kPa). The results show the relations of mass loss rate and the oxygen concentration with different pressures: mPYO2,21.84 (m is the mass loss rate; P is the pressure; and Yo2 is the oxygen concentration). The relation of flame spread rate and the oxygen concentration with different pressures is also shown: VfPYO24.51.2 (Vf is the flame spread rate). It was observed that the increase in pressure and oxygen concentration made the combustion reaction more complete, for burning time, flame area, flame propagation rate, MLR, flame temperature, and CO2 production increase, but CO shows an opposite trend. Oxygen enrichment will significantly increase the fire risk of pine wood within a low-pressure environment. Full article
(This article belongs to the Special Issue Fire Safety Management and Risk Assessment)
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<p>Low-pressure oxygen-enriched combustion platform.</p>
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<p>Diagram of the internal experimental setup.</p>
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<p>Burning time in different pressures and oxygen concentrations.</p>
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<p>Pine wood flame during stable combustion stages. (<b>a</b>) Pine wood flame morphology. (<b>b</b>) The flame edge image after image preprocessing. (<b>c</b>) The variation in flame area with oxygen concentration.</p>
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<p>Changes in pine wood quality under different environments: (<b>a</b>) 50.0 kPa; (<b>b</b>) 70.0 kPa. (<b>c</b>) Remaining mass percentage. (<b>d</b>) Mass burning rate as a function of pressure and oxygen concentration.</p>
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<p>Vertical flame propagation.</p>
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<p>The relationship of flame propagation rate with pressure and oxygen concentration.</p>
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<p>Flame propagation rate as a function of pressure and oxygen concentration.</p>
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<p>Relationship between surface and maximum flame temperature and pressure and oxygen concentration. (<b>a</b>) Surface temperature during ignition. (<b>b</b>) The maximum flame temperature in the vertical direction.</p>
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<p>Relationship between CO<sub>2</sub> and oxygen concentration. (<b>a</b>) The variation in CO<sub>2</sub> with time. (<b>b</b>) The relationship between CO<sub>2</sub> generation rate and oxygen concentration and pressure.</p>
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<p>Relationship between CO and oxygen concentration. (<b>a</b>) The variation in CO with time. (<b>b</b>) The relationship between CO generation rate and oxygen concentration and pressure.</p>
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14 pages, 3032 KiB  
Article
Recovery of Titanium from Red Mud Using Carbothermic Reduction and High Pressure Leaching of the Slag in an Autoclave
by Srecko Stopic, Duško Kostić, Richard Schneider, Magnus Sievers, Florian Wegmann, Elif Emil Kaya, Mitar Perušić and Bernd Friedrich
Minerals 2024, 14(11), 1151; https://doi.org/10.3390/min14111151 - 13 Nov 2024
Viewed by 472
Abstract
Red mud is a by-product of alumina production, which is largely stored in landfills that can endanger the environment. Red mud, or bauxite residue, is a mixture of inorganic compounds of iron, aluminum, sodium, titanium, calcium and silicon mostly, as well as a [...] Read more.
Red mud is a by-product of alumina production, which is largely stored in landfills that can endanger the environment. Red mud, or bauxite residue, is a mixture of inorganic compounds of iron, aluminum, sodium, titanium, calcium and silicon mostly, as well as a large number of rare earth elements in small quantities. Although certain methods of using red mud already exist, none of them have been widely implemented on a large scale. This paper proposes a combination of two methods for the utilization of red mud, first by carbothermic reduction and then, by leaching under high pressure in an autoclave in order to extract useful components from it with a focus on titanium. In the first part of the work, the red mud was reduced with carbon at 1600 °C in an electric arc furnace, with the aim of removing as much iron as possible using magnetic separation. After separation, the slag is leached in an autoclave at different parameters in order to obtain the highest possible yield of titanium, aiming for the formation of titanium oxysulfate and avoiding silica gel formation. A maximal leaching efficiency of titanium of 95% was reached at 150 °C using 5 mol/L sulfuric acid with 9 bar oxygen in 2 h. We found that high-pressure conditions enabled avoiding the formation of silica gel during leaching of the slag using 5 mol/L sulfuric acid, which is a big problem at atmospheric pressure. Previously silica gel formation was prevented using the dry digestion process with 12 mol/L sulfuric acid under atmospheric pressure. Full article
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<p>Design of research methodology.</p>
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<p>Dependence of the compound mass fractions on carbon content in slag.</p>
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<p>Composition of the metal phase depending on the reducing agent’s mass.</p>
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<p>Dependence of slag and titanium oxide masses in the slag from reducing agent’s mass.</p>
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<p>XRD Analysis of red mud.</p>
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<p>Electric arc furnace (<b>a</b>) and carbon-reduced red mud (<b>b</b>).</p>
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<p>Experimental setup for leaching and schematic diagram of the autoclave.</p>
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<p>Thermodynamic calculation reduction of red mud (T) and experimentally obtained results.</p>
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<p>Diffractograms for slag reduced at 1600 °C. Identified minerals (gehlenite, perovskite and magnetite) with positions of diffraction maxima are shown in the lower part. The position of intensive diffraction maxima which do not overlap with the other maxima of the other minerals are shown in colored bands and used for comparison in mineral abundance.</p>
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<p>Leaching efficiency for different parameters (150 °C, 6–9 bar O<sub>2</sub>, 0.5–5 mol/L H<sub>2</sub>SO<sub>4</sub>).</p>
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<p>XRD diffractogram for solid residue after the leaching process at 150 °C, 9 bar O<sub>2</sub>, 2 h (experiment nine).</p>
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<p>EDS analysis of solid residue (experiment nine).</p>
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9 pages, 6360 KiB  
Article
The Study of the Etching Resistance of YOF Coating Deposited by Atmospheric Plasma Spraying in HBr/O2 Plasma
by Zaifeng Tang, Bing Wang, Kaiqu Ang, Xiaojun Jiang, Yuwei Wang, Jin Xu, Hua Meng, Hongli Chen, Ying Shi and Linjun Wang
Coatings 2024, 14(11), 1442; https://doi.org/10.3390/coatings14111442 - 13 Nov 2024
Viewed by 457
Abstract
Yttrium oxyfluoride (YOF) coatings with different oxygen content were prepared using atmospheric plasma spraying (APS) technology. The etching resistance of the coatings in HBr/O2 plasma was investigated. Shifts in diffraction peaks of the X-ray diffraction, along with XPS analysis conducted before and [...] Read more.
Yttrium oxyfluoride (YOF) coatings with different oxygen content were prepared using atmospheric plasma spraying (APS) technology. The etching resistance of the coatings in HBr/O2 plasma was investigated. Shifts in diffraction peaks of the X-ray diffraction, along with XPS analysis conducted before and after etching, demonstrated that Br ions could replace O and F ions and fill the oxygen vacancies after exposure to HBr/O2 plasma, which is supported by the first-principles calculations. Br ions formed a protective layer on the surface of the YOF coating, slowing down further etching by Br ions. By adjusting the oxygen mass fraction in YOF powder, the oxygen vacancy concentration and Br ion filling were regulated to enhance etching resistance. YOF coatings with 6% oxygen content exhibited improved etching resistance compared to YOF coatings with 3% and 9% oxygen content. This improvement was primarily due to the increased Br ion concentration. These findings provide a new approach for developing coatings with enhanced etching resistance. Full article
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<p>Simple schematic illustration of the etching chamber system.</p>
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<p>SEM images of (<b>a</b>) YOF 3%, (<b>b</b>) YOF 6%, and (<b>c</b>) YOF 9% powders.</p>
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<p>XRD spectra of (<b>a</b>) YOF powders, (<b>b</b>) YOF 3% coatings as deposited and after plasma exposure, (<b>c</b>) YOF 6% coatings as deposited and after plasma exposure, and (<b>d</b>) YOF 9% coatings as deposited and after plasma exposure.</p>
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<p>SEM images of (<b>a</b>) YOF 3%, (<b>b</b>) YOF 6% and (<b>c</b>) YOF 9% coating before etching, and SEM images of (<b>d</b>) YOF 3%, (<b>e</b>) YOF 6% and (<b>f</b>) YOF 9% coating after etching.</p>
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<p>SEM images for etching depth of (<b>a</b>) YOF 3%, (<b>b</b>) YOF 6%, and (<b>c</b>) YOF 9% coatings.</p>
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<p>The XPS images of YOF 3%, YOF 6%, and YOF 9% coatings before (<b>a</b>–<b>c</b>) and after (<b>d</b>–<b>f</b>) HBr/O<sub>2</sub> plasma exposure.</p>
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<p>Oxygen vacancy concentration of YOF 3%, YOF 6%, and YOF 9% fitting by XPS (<b>a</b>) before and (<b>b</b>) after etching.</p>
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<p>(<b>a</b>) the Y<sub>5</sub>O<sub>4</sub>F<sub>7</sub> unit cell; (<b>b</b>) the filling of Br atoms for oxygen vacancy within the Y<sub>5</sub>O<sub>4</sub>F<sub>7</sub> unit cell; (<b>c</b>) the substitution of Br atoms for F atoms in the Y<sub>5</sub>O<sub>4</sub>F<sub>7</sub> unit cell; and (<b>d</b>) the substitution of Br atoms for O atoms in the Y<sub>5</sub>O<sub>4</sub>F<sub>7</sub> unit cell.</p>
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16 pages, 4586 KiB  
Article
Raising the Oxidation Resistance of Low-Alloyed Mg-Ca Alloys Through a Preheating Treatment in an Argon Atmosphere
by Siyuan Liu, Jonathan Apell, Zhihui Liu, Guojun Liu, Xingyou Lang, Yongfu Zhu and Qing Jiang
Materials 2024, 17(22), 5481; https://doi.org/10.3390/ma17225481 - 10 Nov 2024
Viewed by 415
Abstract
With the rise and development of aerospace, communications, electronics, medical, transportation and other fields, magnesium (Mg) and its alloys have attracted much attention for their high specific strength and stiffness, good electromagnetic shielding properties, excellent damping properties and other advantages. However, magnesium has [...] Read more.
With the rise and development of aerospace, communications, electronics, medical, transportation and other fields, magnesium (Mg) and its alloys have attracted much attention for their high specific strength and stiffness, good electromagnetic shielding properties, excellent damping properties and other advantages. However, magnesium has a high affinity for oxygen, producing magnesium oxide (MgO), and MgO’s Pilling–Bedworth ratio (PBR) of 0.81 is not protective. The occurrence of catastrophic oxidation is unavoidable with the increase of oxidation time and temperature. A promising approach is to perform an appropriate pretreatment in conjunction with alloying to obtain a dense and compact composite protective film. In this work, the effect of a preheating treatment on the oxidation resistance (OR) of Mg-xCa (x = 1, 3 and 5 wt. %) was investigated. The preheating was carried out in an Ar atmosphere at 400 °C for 8 h. Upon it, a dense and compact MgO/CaO composite protective film was formed on the surface, which is CaO-rich especially in the vicinity to the surface. The alloys’ oxidation resistance was strongly increased due to the composite protective film formed during the preheating treatment, in particular for Mg-3Ca. Relative to the Mg-hcp phase, the OR of the Mg2Ca phase was significantly raised. Full article
(This article belongs to the Special Issue Microstructures and Properties of Corrosion-Resistant Alloys)
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<p>Preheating treatment experimental installation diagram.</p>
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<p>Surface morphologies of uP-Mg-<span class="html-italic">x</span>Ca and P-Mg-<span class="html-italic">x</span>Ca alloys preheating at 400 °C for 8 h in Ar with uP-Mg-1Ca in (<b>a</b>), uP-Mg-3Ca in (<b>b</b>), uP-Mg-5Ca in (<b>c</b>), P-Mg-1Ca in (<b>d</b>), P-Mg-3Ca in (<b>e</b>) and P-Mg-5Ca in (<b>f</b>). The inserts in (<b>b</b>) uP-Mg-3Ca and (<b>e</b>) P-Mg-3Ca, respectively, are high magnification FESEM images of the Mg-hcp phase in (<b>b</b>)-1 and (<b>e</b>)-1 and the eutectic phase Mg<sub>2</sub>Ca in (<b>b</b>)-2 and (<b>e</b>)-2.</p>
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<p>XRD results of the uP-Mg-<span class="html-italic">x</span>Ca alloys. It shows the formation of Mg<sub>2</sub>Ca as eutectic phase together with Mg-hcp.</p>
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<p>EDS mapping results of uP-Mg-3Ca and P-Mg-3Ca preheating at 400 °C for 8 h. (<b>a</b>) uP-Mg-3Ca surface with element distribution of (<b>b</b>) Mg, (<b>c</b>) O and (<b>d</b>) Ca; (<b>e</b>) P-Mg-3Ca at 400 °C surface with element distribution of (<b>f</b>) Mg, (<b>g</b>) O and (<b>h</b>) Ca. It shows the preferential oxidation of the Ca-rich Mg<sub>2</sub>Ca phase.</p>
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<p>BF TEM images of cross section and element mappings of P-Mg-3Ca preheating at 400 °C for 8 h. (<b>a</b>) Cross section, (<b>b</b>) high-resolution image of red-boxed area in (<b>a</b>), (<b>c</b>) high-resolution image of the yellow-boxed area in (<b>a</b>), (<b>d</b>) STEM image with the corresponding EDS mapping of (<b>e</b>) Mg, (<b>f</b>) Ca and (<b>g</b>) O. Note that the tiny particles observed over the cross-section in (<b>a</b>–<b>c</b>) are composed of Pt induced by contamination during the continuous thinning process in the FIB sample preparation.</p>
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<p>XPS spectra of Mg-3Ca with preheating at 400 °C for 8 h. (<b>a</b>) C 1s, (<b>b</b>) Mg 1s, (<b>c</b>) Ca 2p and (<b>d</b>) O 1s.</p>
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<p>The XPS depth profiles of Mg, Ca and O atomic content along the depth direction in Mg-3Ca alloys preheated at 400 °C for 8 h.</p>
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<p>Mass gain curves of oxidation at 400 °C for 2 h for pure Mg, uP-Mg-<span class="html-italic">x</span>Ca alloys in dashed and P-Mg-<span class="html-italic">x</span>Ca alloys in Ar atmosphere at 400 °C for 8 h in solid.</p>
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<p>Surface morphology images of pure Mg and Mg-<span class="html-italic">x</span>Ca oxidized at 400 °C for 2 h, with SEM images of pure Mg after oxidation in (<b>a</b>), uP-Mg-3Ca in (<b>b</b>), P-Mg-1Ca in (<b>c</b>), P-Mg-3Ca in (<b>d</b>) and P-Mg-5Ca in (<b>e</b>). The inserts in (<b>b</b>–<b>e</b>), respectively, exhibit high magnification FESEM images of Mg-hcp of uP-Mg-3Ca in (<b>b</b>)-1, P-Mg-1Ca in (<b>c</b>)-1, P-Mg-3Ca in (<b>d</b>)-1 and P-Mg-5Ca in (<b>e</b>)-1, and also those of Mg<sub>2</sub>Ca of uP-Mg-3Ca in (<b>b</b>)-2 and P-Mg-3Ca in (<b>d</b>)-2.</p>
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<p>Cross-section STEM morphology of (<b>a</b>) uP-Mg-3Ca and (<b>b</b>) P-Mg-3Ca oxidized at 400 °C for 2 h with the EDS mapping of Mg in (<b>c</b>,<b>d</b>), Ca in (<b>e</b>,<b>f</b>) and O in (<b>g</b>,<b>h</b>).</p>
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<p>Schematic illustration of the formation of the MgO and CaO composite layer during preheating in Ar atmosphere with 0.1 Pa O<sub>2</sub> at 400 °C for 8 h.</p>
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