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Search Results (5,893)

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Keywords = high-temperature oxidation

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23 pages, 10957 KiB  
Article
Thermodynamic Justification for the Effectiveness of the Oxidation—Soda Conversion of Ilmenite Concentrates
by Kuralay Akhmetova, Nesipbay Tusupbayev, Bagdaulet Kenzhaliyev, Sergey Gladyshev, Nazym Akhmadiyeva and Leila Imangaliyeva
Processes 2024, 12(10), 2276; https://doi.org/10.3390/pr12102276 (registering DOI) - 18 Oct 2024
Abstract
This article presents the results of a thermodynamic analysis of the oxidation soda conversion reactions of minerals in ilmenite concentrates in the temperature range of 373–2273 K. The thermodynamic parameters of pseudorutile, pseudobrukite, and the new minerals, zhikinite and spessartine, were calculated for [...] Read more.
This article presents the results of a thermodynamic analysis of the oxidation soda conversion reactions of minerals in ilmenite concentrates in the temperature range of 373–2273 K. The thermodynamic parameters of pseudorutile, pseudobrukite, and the new minerals, zhikinite and spessartine, were calculated for the first time. It has been established that the most important criterion relating to the stability of titanium minerals and related elements, as well as the reaction properties of the structural oxides of metals and silicon, is their degree of oxidation. Oxides of silicon (IV) and manganese have the best reactivity in solid-phase oxidizing alkaline environments (VI). Modeling this process scientifically substantiates the mechanism involved in the destruction of minerals in ilmenite concentrates in the low-temperature region in the presence of atmospheric oxygen and sodium oxide of soda ash, which are decomposed through the absorption of heat and the evaporation of moisture during the dehydration of hydrated minerals of iron and manganese and the dehydration of the soda–ilmenite batch. Tests conducted during pilot metallurgical production at the Institute of Metallurgy and Enrichment (PMP of JSC) confirmed the feasibility of processing high-chromium and siliceous rutile leucoxene ilmenite concentrates, which are unsuitable for traditional pyro- and hydro-metallurgical enrichment methods, through single-stage oxidation soda roasting, followed by the leaching of easily soluble sodium salts of iron and associated impurities with water and a dilute hydrochloric acid solution. The proposed energy-saving method ensures the production of high-purity (>98%) synthetic rutile while eliminating the formation of strong deposits on the lining of roasting units. Full article
(This article belongs to the Special Issue Biochemical Processes for Sustainability, 2nd Edition)
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Figure 1
<p>Horizontal roasting tube furnace (<b>a</b>) and reaction zone of the furnace with briquette in an alunda boat (<b>b</b>).</p>
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<p>Tray with briquettes cooled in an alunda boat in the air (<b>a</b>) and boat containing the cooled briquettes (<b>b</b>).</p>
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<p>X-ray phase analysis of fractional samples of ilmenite concentrate with grain sizes of −0.071 +0.063 (<b>a</b>), −0.063 +0.044 (<b>b</b>), and −0.044 +0 (<b>c</b>).</p>
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<p>Thermograms of samples of ilmenite concentrate with grain sizes of −0.071 +0.063 (<b>a</b>), −0.063 +0.044 (<b>b</b>), and +0.071 −0 (<b>c</b>).</p>
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<p>Thermograms of samples of ilmenite concentrate with grain sizes of −0.071 +0.063 (<b>a</b>), −0.063 +0.044 (<b>b</b>), and +0.071 −0 (<b>c</b>).</p>
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<p>Monocrystals of chromite (<b>left</b>) and aluminochromite (<b>center</b>,<b>right</b>).</p>
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<p>Deformation of chromite crystal lattice.</p>
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<p>Dependence of ∆G°<sub>T</sub> (<b>a</b>) and lg K<sub>eq</sub> (<b>b</b>) changes on the temperature of reactions of the oxidative decomposition of ilmenite by soda ash.</p>
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<p>Dependence of ∆G°<sub>T</sub> (<b>a</b>) and lg K<sub>eq</sub> (<b>b</b>) changes on the temperature of oxidative decomposition reactions of ilmenite by sodium oxide with soda ash.</p>
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<p>Dependence of ∆G°<sub>T</sub> (<b>a</b>) and lg K<sub>eq</sub> (<b>b</b>) on the temperature of decomposition reactions of pseudorutile by sodium oxide and soda ash.</p>
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<p>Dependence of ∆G°<sub>T</sub> (<b>a</b>) and lg K<sub>eq</sub> (<b>b</b>) change on the temperature of the decomposition reaction of pseudobrookite by sodium oxide of soda ash.</p>
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<p>Dependence of ∆G°<sub>T</sub> (<b>a</b>) and lg K<sub>eq</sub> (<b>b</b>) change on the reaction temperature oxidative decomposition of titanium disilicide by sodium oxide of soda ash.</p>
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<p>Dependence of ∆G°<sub>T</sub> (<b>a</b>) and lg K<sub>eq</sub> (<b>b</b>) on the temperature of reactions of oxidative decomposition of chromite by sodium oxide with soda ash.</p>
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<p>Dependence of change in ∆G°<sub>T</sub> (<b>a</b>) and lg K<sub>eq</sub> (<b>b</b>) on the temperature of oxidative decomposition reactions of spessartine by sodium oxide of soda ash.</p>
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<p>Dependence of change in ∆G°<sub>T</sub> (<b>a</b>) and lg K<sub>eq</sub> (<b>b</b>) on the temperature of reactions of zircon decomposition by sodium oxide of soda ash.</p>
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<p>X-ray diffraction of a representative sample of synthetic rutile.</p>
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14 pages, 15081 KiB  
Article
Implementation of Regenerative Thermal Oxidation Device Based on High-Heating Device for Low-Emission Combustion
by Hoon-Min Park, Dal-Hwan Yoon, Joon-Seong Lee, Hyun-Min Jung, Dae-Hee Lee, Dong-Hwan Jeon and Tae-Yeung Lim
Energies 2024, 17(20), 5182; https://doi.org/10.3390/en17205182 (registering DOI) - 17 Oct 2024
Viewed by 289
Abstract
In this paper, a heating device is implemented by considering two large factors in a 100 cmm RTO design. First, when the combustion chamber is used for a long time with a high temperature of 750–1100 °C depending on the high concentration VOC [...] Read more.
In this paper, a heating device is implemented by considering two large factors in a 100 cmm RTO design. First, when the combustion chamber is used for a long time with a high temperature of 750–1100 °C depending on the high concentration VOC gas capacity, there is a problem that the combustion chamber explodes or the function of the rotary is stopped due to the fatigue and load of the device. To prevent this, the 100 cmm RTO design with a changed rotary position is improved. Second, an RTO design with a high-heating element is implemented to combust VOC gas discharged from the duct at a stable temperature. Through this, low-emission combustion emissions and energy consumption are reduced. By implementing a high heat generation device, the heat storage combustion oxidation function is improved through the preservation of renewable heat. Over 177 h of demonstration time, we improved the function of 100 cm by discharging 99% of VOC’s removal efficiency, 95.78% of waste heat recovery rate, 21.95% of fuel consumption, and 3.9 ppm of nitrogen oxide concentration. Full article
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<p>Various RTO accident examples.</p>
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<p>The 3D configuration in the combustion chamber and rotary part.</p>
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<p>The energy index flow according to the 100 cmm RTO design.</p>
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<p>Improved RTO according to rotary distributor side design.</p>
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<p>VOCs gas streamline analysis at rotary distributor inlet and outlet.</p>
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<p>Design of the combustion chamber with a high-heating element applied.</p>
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<p>Design of the ceramic heat storage in the chamber.</p>
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<p>Air flowability and temperature characteristics by burner and high-heating element. (<b>a</b>) Analysis with only burner. (<b>b</b>) Analysis with high-heating element.</p>
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<p>Characteristics analysis of rotary distributor by inlet and outlet.</p>
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<p>Integration of experimental RTO configuration.</p>
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<p>VOCs concentration change rate of dry and printing part.</p>
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<p>Combustion chamber operation characteristics with only burner.</p>
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<p>Combustion chamber characteristics with the burner and the high-heating element.</p>
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12 pages, 4891 KiB  
Article
Theoretical Analysis of Landfill Gas Migration in Capillary Barrier Covers Considering Effects of Waste Temperature
by Tao Wu, Huaning Yang, Jiankang Cheng, Guannian Chen, Haoqing Xu and Lei Zhang
Appl. Sci. 2024, 14(20), 9473; https://doi.org/10.3390/app14209473 - 17 Oct 2024
Viewed by 268
Abstract
The high-temperature and high-humidity conditions arising from the biochemical degradation of landfill waste result in significant temperature gradients within the landfill cover. The effects of waste temperature on landfill gas transport and microbial aerobic methane oxidation are not fully understood. In this study, [...] Read more.
The high-temperature and high-humidity conditions arising from the biochemical degradation of landfill waste result in significant temperature gradients within the landfill cover. The effects of waste temperature on landfill gas transport and microbial aerobic methane oxidation are not fully understood. In this study, a fully coupled theoretical model was developed to simulate the interactions of moisture, heat, and gas transport within a capillary barrier cover. A series of parametric studies were carried out to investigate the influence of the combined effects of temperature gradient, initial soil moisture content, and landfill gas generation rate on methane transport, oxidation, and emissions. The simulated results indicated that increasing waste temperature intensified the temperature gradient, leading to higher surface evaporation rates and variations in methane oxidation efficiencies. Additionally, variations in initial soil moisture content and landfill gas generation rates were found to significantly impact gas migration and methane oxidation in the cover. This study demonstrates the critical role of waste temperature in landfill gas migration within landfill cover systems, providing technical methodologies for the optimized design of soil cover systems. Full article
(This article belongs to the Section Civil Engineering)
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Figure 1
<p>Field loess–gravel capillary barrier cover (<b>a</b>) and schematic of the model (<b>b</b>).</p>
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<p>Influence of temperature gradient on (<b>a</b>) temperature, (<b>b</b>) volumetric water content, and (<b>c</b>) evaporation.</p>
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<p>Influence of temperature gradient on CH<sub>4</sub> oxidation efficiency.</p>
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<p>Effects of initial moisture content on (<b>a</b>) evaporation at surface and (<b>b</b>) water storage of the cover.</p>
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<p>Effects of initial moisture content on (<b>a</b>) distribution of O<sub>2</sub> concentration and (<b>b</b>) CH<sub>4</sub> oxidation rate.</p>
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<p>Influence of LFG generation rate on (<b>a</b>) evaporation and (<b>b</b>) MAMO.</p>
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15 pages, 3323 KiB  
Article
Chemistry of Reduced Graphene Oxide: Implications for the Electrophysical Properties of Segregated Graphene–Polymer Composites
by Maxim K. Rabchinskii, Kseniya A. Shiyanova, Maria Brzhezinskaya, Maksim V. Gudkov, Sviatoslav D. Saveliev, Dina Yu. Stolyarova, Mikhail K. Torkunov, Ratibor G. Chumakov, Artem Yu. Vdovichenko, Polina D. Cherviakova, Nikolai I. Novosadov, Diana Z. Nguen, Natalia G. Ryvkina, Alexander V. Shvidchenko, Nikita D. Prasolov and Valery P. Melnikov
Nanomaterials 2024, 14(20), 1664; https://doi.org/10.3390/nano14201664 - 16 Oct 2024
Viewed by 406
Abstract
Conductive polymer composites (CPCs) with nanocarbon fillers are at the high end of modern materials science, advancing current electronic applications. Herein, we establish the interplay between the chemistry and electrophysical properties of reduced graphene oxide (rGO), separately and as a filler for CPCs [...] Read more.
Conductive polymer composites (CPCs) with nanocarbon fillers are at the high end of modern materials science, advancing current electronic applications. Herein, we establish the interplay between the chemistry and electrophysical properties of reduced graphene oxide (rGO), separately and as a filler for CPCs with the segregated structure conferred by the chemical composition of the initial graphene oxide (GO). A set of experimental methods, namely X-ray photoelectron spectroscopy (XPS), ultraviolet-visible spectroscopy, van der Paw and temperature-dependent sheet resistance measurements, along with dielectric spectroscopy, are employed to thoroughly examine the derived materials. The alterations in the composition of oxygen groups along with their beneficial effect on nitrogen doping upon GO reduction by hydrazine are tracked with the help of XPS. The slight defectiveness of the graphene network is found to boost the conductivity of the material due to facilitating the impact of the nitrogen lone-pair electrons in charge transport. In turn, a sharp drop in material conductivity is indicated upon further disruption of the π-conjugated network, predominantly governing the charge transport. Particularly, the transition from the Mott variable hopping transport mechanism to the Efros–Shklovsky one is signified. Finally, the impact of rGO chemistry and physics on the electrophysical properties of CPCs with the segregated structure is evaluated. Taken together, our results give a hint at how GO chemistry manifests the properties of rGO and the CPC derived from it, offering compelling opportunities for their practical applications. Full article
(This article belongs to the Section 2D and Carbon Nanomaterials)
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<p>(<b>a</b>) Survey and (<b>b</b>) C 1<span class="html-italic">s</span> X-ray photoelectron spectra of the MC#1–MC#3 samples.</p>
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<p>(<b>a</b>) Survey and (<b>b</b>) C 1<span class="html-italic">s</span> X-ray photoelectron spectra of the MC#4–MC#6 samples.</p>
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<p>(<b>a</b>) UV-Vis spectra of the materials under study in the form of thin films on the quartz substrates. The spectra are vertically offset for clarity. (<b>b</b>) Bar chart exhibiting the assessed conductivity values for the MC#1–MC#6 samples.</p>
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<p>(<b>a</b>,<b>b</b>) Semi-log scale temperature-dependent sheet resistance for MC#1–MC#6 samples. (<b>c</b>,<b>d</b>) The resistivity <span class="html-italic">LnR</span> versus <span class="html-italic">T<sup>−1/3</sup></span> graphs for the materials under study. The symbols are the experimental data, and the solid lines are a fit to <span class="html-italic">T<sup>−1/3</sup></span> behavior. (<b>e</b>) Reduced activation energy (<span class="html-italic">W</span>) plotted vs. temperature (<span class="html-italic">T</span>) in a log–log scale. For eye guidance, lines with <span class="html-italic">p</span> = 1/2 (ES-VRH) and <span class="html-italic">p</span> = 1/3 (2D Mott-VRH) are shown.</p>
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<p>SEM images of the polymer powder particles (<b>a</b>) FPC-MC#1, (<b>b</b>) FPC-MC#2, (<b>c</b>) FPC-MC#3, (<b>d</b>) FPC-MC#4, (<b>e</b>) FPC-MC#5, and (<b>f</b>) FPC-MC#6 coated with 1 wt.% of the corresponding MC#1-MC#6 rGO.</p>
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<p>(<b>a</b>) Electrical conductivity versus frequency plot for the derived composites. Insets—visualization of Jonscher’s power law and compliance of the MC#5 data to it. (<b>b</b>) Dependence of electrical conductivity on the mass fraction of KMnO<sub>4</sub> in a mixture of oxidizing agents KMnO<sub>4</sub>/K<sub>2</sub>Cr<sub>2</sub>O<sub>7.</sub></p>
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18 pages, 7530 KiB  
Article
Investigating the Synergistic Effect of Decoration and Doping in Silver/Strontium Titanate for Air Remediation
by Marcela Frías Ordóñez, Elisabetta Sacco, Marco Scavini, Giuseppina Cerrato, Alessia Giordana, Ermelinda Falletta and Claudia Letizia Bianchi
Nanomaterials 2024, 14(20), 1663; https://doi.org/10.3390/nano14201663 - 16 Oct 2024
Viewed by 298
Abstract
Strontium titanate (STO) and its variants have emerged as leading materials in photocatalysis, particularly for degrading nitrogen oxides (NOx), due to their non-toxic nature, structural adaptability, and exceptional thermal stability. Although the one-pot sol-gel method leads to high-quality photocatalysts, areas remain for improvement. [...] Read more.
Strontium titanate (STO) and its variants have emerged as leading materials in photocatalysis, particularly for degrading nitrogen oxides (NOx), due to their non-toxic nature, structural adaptability, and exceptional thermal stability. Although the one-pot sol-gel method leads to high-quality photocatalysts, areas remain for improvement. This study examines the impact of ethanol as a cosolvent in STO synthesis, focusing on optimizing the water-to-ethanol volume ratio. The findings reveal that a 1:3 ratio significantly enhances macropore formation and photocatalytic efficiency, achieving 42% NOx degradation under LED within three hours. Furthermore, incorporating 8.0 wt.% Ag into STO substantially improves visible light absorption and enables complete NOx elimination, thanks to enhanced charge separation and localized surface plasmon resonance. Even at high temperatures (1100 °C), the Ag-STO photocatalyst maintains partial activity, despite exceeding silver’s melting point. These results highlight the potential of STO-based materials for industrial applications, positioning them as a promising solution for effective NOx mitigation. Full article
(This article belongs to the Special Issue Advanced Nanomaterials for Photocatalysis)
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<p>Schematic representation of the experimental set-up employed for the NOx photodegradation.</p>
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<p>Experimental patterns of STO (black curve), 2.5% Ag-STO (red curve), 5.8% Ag-STO (blue curve), and 8.0% Ag-STO (pink curve).</p>
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<p>Panel (<b>A</b>): Complete experimental XRD pattern of 8.0 wt.% Ag-STO sample (black symbol) together with its Rietveld refinement (red curve) and the difference curve (blue curve). The inset highlights the high-angle data and refined curve. Panel (<b>B</b>): Details of the same pattern corresponding to the (111) reflection of Ag phase(s). Black symbols are the experimental data; blue and green curves show the contribution of “Ag-broad” and “Ag-sharp” phases to the peak while the red curve is their sum. See the main text for details. Panel (<b>C</b>): Williamson–Hall plot for the Ag-broad phase.</p>
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<p>FE-SEM images of 8 wt.% Ag-STO_1100C with (<b>a</b>) 2 h, (<b>b</b>) 10 h, and (<b>c</b>) 15 h of heat treatment.</p>
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<p>FE-SEM images of (<b>a</b>) STO (1:3), (<b>b</b>) STO (1:5), and (<b>c</b>) 8 wt.% Ag-STO.</p>
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<p>SEM image (<b>a</b>), elemental mapping of strontium (<b>b</b>), titanium (<b>c</b>), oxygen (<b>d</b>), carbon (<b>e</b>), and EDX spectrum (<b>f</b>) of STO (1:3) photocatalyst.</p>
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<p>SEM image (<b>a</b>), elemental mapping of strontium (<b>b</b>), titanium (<b>c</b>), oxygen (<b>d</b>), silver (<b>e</b>), carbon (<b>f</b>), and EDX spectrum (<b>g</b>) of 8 wt.% Ag-STO photocatalyst.</p>
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<p>HR-TEM images of 8 wt.% Ag-STO calcined at increasing temperatures and for different times. Section (<b>a</b>): sample calcined at 900 °C; Section (<b>b</b>): sample calcined at 1100 °C for 2 h; Section (<b>c</b>): sample calcined at 1100 °C for 15 h.</p>
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<p>N<sub>2</sub> adsorption/desorption isotherms at −196 °C.</p>
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<p>UV-DRS spectra of (<b>a</b>) Ag-STO photocatalysts at 900 °C and (<b>b</b>) 8 wt.% Ag-STO_1100C treated at different time conditions (2, 10, 15 h).</p>
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<p>(<b>a</b>) NOx photocatalytic removal efficiency reported as C/Co as a function of time, (<b>b</b>) photocatalytic kinetic studies of the synthesized STO and Ag-STO photocatalysts, (<b>c</b>) reusability of 8.0 wt.% Ag-STO photocatalyst for NOx degradation under LED irradiation.</p>
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20 pages, 5211 KiB  
Article
Perspectives of Hydrogen Generation in Cavitation–Jet Hydrodynamic Reactor
by G. K. Mamytbekov, I. V. Danko, Zh. I. Beksultanov, Y. R. Nurtazin and A. Rakhimbayev
Appl. Sci. 2024, 14(20), 9415; https://doi.org/10.3390/app14209415 - 15 Oct 2024
Viewed by 356
Abstract
The article investigates the potential for producing hydrogen by combining the methods of water splitting under cavitation and the chemical activation of aluminum in a high-speed cavitation–jet flow generated by a specialized hydrodynamic reactor. The process of cavitation and water spraying causes the [...] Read more.
The article investigates the potential for producing hydrogen by combining the methods of water splitting under cavitation and the chemical activation of aluminum in a high-speed cavitation–jet flow generated by a specialized hydrodynamic reactor. The process of cavitation and water spraying causes the liquid heating itself until it reaches saturated vapor pressure, resulting in the creation of vapor–gaseous products from the splitting of water molecules. The producing of vapor–gaseous products can be explained through the theory of non-equilibrium low-temperature plasma formation within a high-speed cavitation–jet flow of fluid. Special focus is also given to the interactions occurring at the interface boundary phase of aluminum and liquid under cavitation condition. The primary solid products formed on aluminum surfaces are bayerite, copper oxides (I and II), iron carbide, and a compound of magnesium oxides and aluminum hydroxide. A high hydrogen yield of 60% was achieved when using a 0.1% sodium hydroxide solution as a working liquid compared to demineralized water. Moreover, hydrogen methane was also detected in the volume of the vapor–gas mixture, which could be utilized to address the challenges of decarbonization and the recycling of aluminum-containing solid industrial and domestic waste. This work provides a contribution to the study of the mechanism of hydrogen generation by cavitation–jet processing of water and aqueous alkali solutions, in which conditions are created for double cavitation in the cavitation–jet chamber of the hydrodynamic reactor. Full article
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<p>General view of the cavitation–jet reactor: 1—cavitation–jet chamber; 2—liquid receiver vessel; 3—frequency converter; 4—centrifugal pump; 5, 6, 7, and 8—digital manometers.</p>
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<p>Schematic Diagram of the Mass Spectrum Analysis Stand for Residual Gases: MS—mass spectrometer, TP—turbomolecular pump, SP—spiral dry pump, V—vacuum valves, P—pressure sensor, BO—storage tank, and R—gas containing chamber.</p>
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<p>The sections of cavitation–jet chamber.</p>
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<p>Dependence of pH and temperature of water on of cavitation–jet processing time (<b>a</b>) and the increase in water temperature in relation to the frequency of the current supplied to the centrifugal pump via the frequency converter (<b>b</b>).</p>
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<p>Dependence of concentration of four metals on temperature and time of cavitation–jet processing of demineralized water (<b>a</b>) and aqueous solution of 0.1 wet % NaOH (<b>b</b>).</p>
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<p>Accumulation of gaseous products as a function of temperature during cavitation–jet processing of a 0.1% solution in a cavitation–jet reactor.</p>
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<p>Hydrogen accumulation data from gas chromatography during the cavitation–jet processing of 0.1% solution of NaOH in CJR.</p>
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<p>XRD (<b>a</b>), SEM (<b>bI</b>,<b>bII</b>) and EDA (<b>bIII</b>) data of the suspension formed during the cavitation–jet treatment of demineralized water. The colors of the lines indicate the element: calcium—brown line, carbon—turquoise line, oxygen—green line.</p>
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<p>XRD data of the powder formed during the cavitation–jet treatment of 0.1% NaOH solution on the surface of Al<sub>disc/foil</sub> and working part (Screw, Reflector and Splitter) of the cavitation–jet chamber.</p>
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<p>SEM data of the powder formed during the cavitation–jet treatment of 0.1% NaOH solution on the surface of working parts of cavitation–jet chamber, * means an increase in the scale of particle size measurement.</p>
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<p>Hydrogen generation on the reflector surface of the CJR.</p>
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11 pages, 4324 KiB  
Article
Revisiting Atmospheric Oxidation Kinetics of Nitrogen Oxides: The Use of Low-Cost Electrochemical Sensors to Measure Reaction Kinetics
by Steven M. Owen, Lachlan H. Yee and Damien T. Maher
Reactions 2024, 5(4), 789-799; https://doi.org/10.3390/reactions5040040 - 15 Oct 2024
Viewed by 212
Abstract
The high cost of equipment is a significant entry barrier to research for smaller organisations in developing solutions to air pollution problems. Low-cost electrochemical sensors have shown sensitivity at parts-per-billion by volume (ppbV) mixing ratios but are subject to variations due to changing [...] Read more.
The high cost of equipment is a significant entry barrier to research for smaller organisations in developing solutions to air pollution problems. Low-cost electrochemical sensors have shown sensitivity at parts-per-billion by volume (ppbV) mixing ratios but are subject to variations due to changing environmental conditions, particularly temperature. We have previously demonstrated that under isothermal/isohume conditions such as those found in kinetic studies, very stable electrochemical responses occur. In this paper, we demonstrate the utility of a low-cost IoT-based sensor system that employs four-electrode electrochemical sensors under isothermal/isohume conditions for studying the kinetics of the atmospheric oxidation of nitrogen oxides. The results suggest that reproducible results for NO and NO2 kinetics can be achieved. The method produced oxidation rates of 7.95 × 103 L2 mol−2 s−1 (±1.3%), for NO and 7.99 × 10−4 s−1 (±2.1%) for NO2. This study suggests that the oxidation kinetics of nitrogen oxides can be assessed with low-cost sensors, which can support a wide range of industrial applications, such as designing biocatalytic coatings for air pollution remediation. Full article
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<p>Concentration of nitrogen oxides near a medium-sized semi-industrial city (Wollongong: 34.4248° S, 150.8931° E).</p>
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<p>LCES based on the design by Owen et al. [<a href="#B24-reactions-05-00040" class="html-bibr">24</a>] with modifications to isolate the electrochemical sensors from the bulk chamber environment.</p>
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<p>Depletion of target NO gas in measurement cell following shutdown of micropump (chamber conditions 25 °C/50% rH).</p>
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<p>(<b>a</b>) NO<sub>2</sub> formation from an initial nitric oxide concentration of 132 ppmV under anhydrous conditions (adapted from Skalska) [<a href="#B25-reactions-05-00040" class="html-bibr">25</a>]. (<b>b</b>) NO<sub>2</sub> undetected under the given measurement conditions for a humid environment (50% rH).</p>
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<p>Stepwise addition of target gases in a humid environment. Measurements were undertaken without an isolation hood.</p>
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<p>(<b>a</b>) Depletion of NO<sub>2</sub> in calibration hood following de-energising micropump. (<b>b</b>) Kinetics of NO<sub>2</sub> depletion following the de-energising micropump.</p>
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<p>(<b>a</b>) NO<sub>2</sub> depletion at varying starting concentrations with chamber conditions maintained at 25 °C/50% rH. (<b>b</b>) Reaction kinetics confirmed as the first order. (<b>c</b>) Rate constant measurements indicate a slight decrease with increasing NO<sub>2</sub> starting concentration.</p>
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<p>(<b>a</b>) Nitrogen dioxide depletion at varying relative humidities. (<b>b</b>) Reaction kinetics confirmed as the first order. (<b>c</b>) Rate constant measurements indicate a slight increase with increasing relative humidity.</p>
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<p>(<b>a</b>) NO kinetics for varying sampling times. (<b>b</b>) Rate constant for NO kinetics for varying sampling times.</p>
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<p>Kinetic study of nitric oxide oxidation under humid conditions (chamber conditions 25 °C/50%rH). (<b>a</b>) Depletion of nitric oxide at varying starting concentrations. (<b>b</b>) Confirmed as second-order reaction kinetics at varying starting concentrations. (<b>c</b>) Rate constant as a function of initial nitric oxide concentration.</p>
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15 pages, 3144 KiB  
Communication
Optimizing Ammonia Detection with a Polyaniline−Magnesia Nano Composite
by Sharanabasava V. Ganachari, Fatheali A. Shilar, Veerabhadragouda B. Patil, T. M. Yunus Khan, C. Ahamed Saleel and Mohammed Azam Ali
Polymers 2024, 16(20), 2892; https://doi.org/10.3390/polym16202892 - 14 Oct 2024
Viewed by 337
Abstract
Polyaniline−magnesia (PANI/MgO) composites with a fibrous nanostructure were synthesized via in situ oxidative polymerization, enabling uniform MgO integration into the polyaniline matrix. These composites were characterized using FTIR spectroscopy to analyze intermolecular bonding, XRD to assess crystallographic structure and phase purity, and SEM [...] Read more.
Polyaniline−magnesia (PANI/MgO) composites with a fibrous nanostructure were synthesized via in situ oxidative polymerization, enabling uniform MgO integration into the polyaniline matrix. These composites were characterized using FTIR spectroscopy to analyze intermolecular bonding, XRD to assess crystallographic structure and phase purity, and SEM to examine surface morphology and topological features. The resulting PANI/MgO nanofibers were utilized to develop ammonia (NH3) gas-sensing probes with evaluations conducted at room temperature. The study addresses the critical challenge of achieving high sensitivity and selectivity in ammonia detection at low concentrations, which is a problem that persists in many existing sensor technologies. The nanofibers demonstrated high selectivity and optimal sensitivity for ammonia detection, which was attributed to the synergistic effects between the polyaniline and MgO that enhance gas adsorption. Furthermore, the study revealed that the MgO content critically influences both the morphology and the sensing performance, with higher MgO concentrations improving sensor response. This work underscores the potential of PANI/MgO composites as efficient and selective ammonia sensors, highlighting the importance of MgO content in optimizing material properties for gas-sensing applications. Full article
(This article belongs to the Collection Progress in Polymer Composites and Nanocomposites)
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<p>Synthesis of the PANI–magnesium oxide composite. The formation of Mg(II)-doped PANI is illustrated, with Mg acting as the interlink between two polymeric chains during polymerization. However, in a broader context, the resulting structure is referred to as a MgO/PANI composite, Reproduced with permission from ref. [<a href="#B21-polymers-16-02892" class="html-bibr">21</a>], Patil, V.B et al., Polymers. Adv. Technol, Wiley Publisher, 2021.</p>
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<p>FTIR curve of sample PANI/MgO nanocomposites.</p>
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<p>(<b>a</b>) SEM image and surface studies of PANI/MgO (0.1%), (<b>b</b>) PANI/MgO (0.2%), (<b>c</b>) PANI/MgO (0.3%) composites; (<b>d</b>) pure MgO nanoparticles; and (<b>e</b>) EDS of the MgO nanoparticles.</p>
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<p>XRD curves for the PANI/MgO nanocomposites.</p>
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<p>Sensor probe preparation: (<b>a</b>) Copper clad board (CCB), (<b>b</b>) sensor probe pattern printed on CCB, (<b>c</b>) sensor probe pattern etched using ferric chloride (FeCl₃), (<b>d</b>) sensor probe coated with PANI nanocomposite, (<b>e</b>) sensor dried at room temperature, (<b>f</b>) final prepared sensor probe.</p>
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<p>Results of sensing of ammonia vapors employing PANI/MgO composite with different concentrations of MgO (in %).</p>
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<p>(<b>a</b>) DC conductivity of PANI/MgO Composites (<b>b</b>) sensor setup.</p>
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15 pages, 5839 KiB  
Article
Electrochemical Behavior of Tantalum Nitride Protective Layers for PEMFC Application
by Aurélie Achille, Fabrice Mauvy, Sebastien Fourcade, Dominique Michau, Marjorie Cavarroc and Angéline Poulon-Quintin
Energies 2024, 17(20), 5099; https://doi.org/10.3390/en17205099 - 14 Oct 2024
Viewed by 387
Abstract
Proton Exchange Membrane Fuel Cells (PEMFCs) are promising technology to convert chemical energy from dihydrogen in electrical energy. HT-PEMFCs are working at high temperatures (above 120 °C) and with doped orthophosphoric acid H3PO4 PBI membranes. In such devices, bipolar metallic [...] Read more.
Proton Exchange Membrane Fuel Cells (PEMFCs) are promising technology to convert chemical energy from dihydrogen in electrical energy. HT-PEMFCs are working at high temperatures (above 120 °C) and with doped orthophosphoric acid H3PO4 PBI membranes. In such devices, bipolar metallic plates are used to provide reactive gas inside the fuel cell and collect the electrical current. The metallic elements used as bipolar plates, end plates, and interconnectors in acid electrolyte and gaseous fuel cells are severely damaged by a combination of oxidation (due in particular to the use of oxygen, whether pure or contained in the air) and corrosion (due in particular to acid effluents from the electrolyte). This degradation rapidly leads to the loss of the electrical conductivity of the metallic elements and today requires the use of very specific alloys, possibly coated with pure gold. The solution investigated in the present study is the use of a protective coating based on single-phase nitrides obtained by reactive magnetron sputtering or reactive HiPIMS (High-Power Impulse Magnetron Sputtering). The influence of the microstructure on the physical–chemical properties was studied. The electrochemical properties were quantified following two approaches. First, the corrosion current of the developed coatings was measured at room temperature and at higher temperatures using the Linear Sweep Voltammetry (LSV) technique. Then, Electrochemical Impedance Spectroscopy (EIS) measurements were performed to better identify and evaluate their corrosion-resistance performances. Full article
(This article belongs to the Section A5: Hydrogen Energy)
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<p>Electrochemical cell designed at ICMCB: (<b>a</b>) cell overview and (<b>b</b>) face with the window enabling sample contact with the electrolyte. Contact surface 1.54 cm<sup>2</sup>.</p>
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<p>GIXD diffractograms (0.5°) of AlN substrate, h-TaN and fcc-TaN RF-MS coatings, and h-TaN and fcc-TaN HiPIMS coatings. DRX references data h-TaN (red lines): JCPDS 00-039-1485; fcc-TaN: JCPDS 00-049-1283 (blue lines).</p>
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<p>SEM surface images of h-TaN (<b>a</b>) MS and (<b>b</b>) HiPIMS deposited on mirror polished AlN substrate.</p>
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<p>SEM cross section images of h-TaN (<b>a</b>) MS and (<b>b</b>) HiPIMS deposited on mirror polished AlN substrate (similar deposition duration, 3 h).</p>
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<p>XPS Ta 4f and N 1s spectra obtained on TaN coatings after 30 s of etching (experimental curve in red; de-summed curve in blue). energie de liaison: binding energy.</p>
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<p>Evolution of the electrical conductivity of TaN coatings under different atmospheres as a function of temperature (from room temperature to 200 °C (vertical dashed line represents the HT-PEMFC temperature during operation).</p>
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<p>The 316L alloy corrosion behavior at room temperature: (<b>a</b>) polarization curve I–E and (<b>b</b>) Tafel (Log |i| = f(E) plot obtained from the polarization curve with red dashed line determine the E<sub>corr</sub> and i<sub>corr</sub> values.</p>
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<p>Example of the determination of the current densities for anodic and cathodic potentials at 120 °C for h-TaN MS.</p>
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<p>Typical Nyquist plots: experimental (black) and modeling (red) data obtained for gold and fcc and h-TaN HiPIMS coating. The associated equivalent circuit is reported inside the figure.</p>
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22 pages, 4104 KiB  
Article
Modeling and Performance Analysis of Solid Oxide Fuel Cell Power Generation System for Hypersonic Vehicles
by Yiming Liu, Jianguo Tan, Dongdong Zhang and Zihan Kuai
Aerospace 2024, 11(10), 846; https://doi.org/10.3390/aerospace11100846 - 14 Oct 2024
Viewed by 355
Abstract
Advanced airborne power generation technology represents one of the most effective solutions for meeting the electricity requirements of hypersonic vehicles during long-endurance flights. This paper proposes a power generation system that integrates a high-temperature fuel cell to tackle the challenges associated with power [...] Read more.
Advanced airborne power generation technology represents one of the most effective solutions for meeting the electricity requirements of hypersonic vehicles during long-endurance flights. This paper proposes a power generation system that integrates a high-temperature fuel cell to tackle the challenges associated with power generation in the hypersonic field, utilizing techniques such as inlet pressurization, autothermal reforming, and anode recirculation. Firstly, the power generation system is modeled modularly. Secondly, the influence of key parameters on the system’s performance is analyzed. Thirdly, the performance of the power generation system under the design conditions is simulated and evaluated. Finally, the weight distribution and exergy loss of the system’s components under the design conditions are calculated. The results indicate that the system’s electrical efficiency increases with fuel utilization, decreases with rising current density and steam-to-carbon ratio (SCR), and initially increases before declining with increasing fuel cell operating temperature. Under the design conditions, the system’s power output is 48.08 kW, with an electrical efficiency of 51.77%. The total weight of the power generation system is 77.09 kg, with the fuel cell comprising 69.60% of this weight, resulting in a power density of 0.62 kW/kg. The exergy efficiency of the system is 55.86%, with the solid oxide fuel cell (SOFC) exhibiting the highest exergy loss, while the mixer demonstrates the greatest exergy efficiency. This study supports the application of high-temperature fuel cells in the hypersonic field. Full article
(This article belongs to the Section Aeronautics)
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<p>The structure of the FCPS.</p>
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<p>The results of the SOFC model validation. (<b>a</b>) The different operating temperatures and (<b>b</b>) the different fuel concentrations. (Note: The “600 V” in the figure represents the SOFC operating voltage when the SOFC operating temperature is 600 °C).</p>
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<p>Diagram of computational logic.</p>
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<p>The effect of the fuel utilization on the FCPS performance.</p>
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<p>The effect of the current density on the FCPS performance.</p>
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<p>The effect of the SOFC operating temperature on the FCPS performance.</p>
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<p>The effect of the SCR on the FCPS performance.</p>
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<p>Effects of OCR on reformer performance. (<b>a</b>) Performance parameters; (<b>b</b>) outlet gas composition.</p>
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<p>Weight distribution of FCPS. (<b>a</b>) 0.9 kW/kg; (<b>b</b>) 1.2 kW/kg; (<b>c</b>) 2.5 kW/kg; (<b>d</b>) 4.6 kW/kg.</p>
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<p>Distribution of FCPS exergy loss.</p>
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<p>Exergy flow diagram of FCPS.</p>
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10 pages, 2515 KiB  
Article
Controlled Growth of ZIF-8 Membranes on GO-Coated α-Alumina Supports via ZnO Atomic Layer Deposition for Improved Gas Separation
by Nahyeon Lee, Yun-Ho Ahn, Jaheon Kim and Kiwon Eum
Membranes 2024, 14(10), 216; https://doi.org/10.3390/membranes14100216 - 14 Oct 2024
Viewed by 536
Abstract
This study presents a novel approach for fabricating ZIF-8 membranes supported on α-alumina hollow fibers through the introduction of a graphene oxide (GO) gutter layer and the application of zinc oxide (ZnO) Atomic Layer Deposition (ALD). The method successfully addressed key challenges, including [...] Read more.
This study presents a novel approach for fabricating ZIF-8 membranes supported on α-alumina hollow fibers through the introduction of a graphene oxide (GO) gutter layer and the application of zinc oxide (ZnO) Atomic Layer Deposition (ALD). The method successfully addressed key challenges, including excessive precursor penetration and membrane thickness. The introduction of the GO layer and subsequent ZnO ALD treatment significantly reduced membrane thickness to approximately 300 nm and eliminated delamination issues between the GO layer and the alumina support. The optimized membranes demonstrated enhanced propylene permeance, with values approximately three times higher than those of membranes without GO, and achieved higher separation factors, indicating minimal inter-crystalline defects. Notably, the GO layer influenced the microstructure, leading to an increase in permeance with rising temperatures. These findings highlight the potential of this strategy for developing high-performance ZIF-8 membranes for gas separation applications. Full article
(This article belongs to the Special Issue Thin-Film Composite Membranes for Gas and Vapor Separation)
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<p>Cross-sectional SEM images of (<b>A</b>) ZIF-8 membranes on bare α-alumina hollow fiber supports using RTD, and (<b>B</b>) deep penetration of ZIF-8 into the finger-like pores of the α-alumina support.</p>
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<p>(<b>A</b>) Photograph of GO solution and bare α-alumina hollow fibers before coating. (<b>B</b>–<b>F</b>) Cross-sectional SEM images of GO-coated α-alumina fibers with varying GO concentrations: (<b>B</b>) 0.5 mg/mL, (<b>C</b>) 1 mg/mL, (<b>D</b>) 5 mg/mL, (<b>E</b>) 10 mg/mL, and (<b>F</b>) 20 mg/mL.</p>
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<p>(<b>A</b>) pXRD patterns of the ZIF-8 membrane on GO-layered α-alumina support, bare α-alumina hollow fiber, and simulated ZIF-8 pattern. Cross-sectional SEM images showing (<b>B</b>) bare α-alumina support, (<b>C</b>) GO-coated α-alumina support, and (<b>D</b>) as-synthesized GO@ZIF-8 layer, with the delaminated interface between the GO layer and α-alumina. (<b>E</b>–<b>G</b>) Corresponding top-view SEM images of (<b>E</b>) bare α-alumina, (<b>F</b>) GO-coated support, and (<b>G</b>) GO@ZIF-8 layer.</p>
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<p>(<b>A</b>) GO layer surface before ALD treatment, showing surface wrinkles. (<b>B</b>) GO surface after 20-cycle ZnO ALD treatment. (<b>C</b>) EDX mapping of Zn showing uniform distribution on the GO surface after 20 ALD cycles. (<b>D</b>) GO surface after post-treatment with 2 mIm vapor. (<b>E</b>) EDX mapping of the nitrogen atom. The illustrations in each column were designed to facilitate understanding.</p>
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<p>(<b>A</b>) Cross-sectional and (<b>B</b>) top-view SEM image of ZIF-8 membrane grown on 2 mIm vapor-treated GO-layered α-alumina support, and (<b>C</b>) corresponding pXRD patterns.</p>
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<p>(<b>A</b>) Propane/propylene separation performance of ZIF-8 membranes on non-coated α-alumina (Case 1) and GO-coated α-alumina (Case 2). (<b>B</b>) Temperature dependence of propylene permeance and propylene/propane selectivity for the non-coated α-alumina (Case 1) and GO-coated α-alumina (Case 2).</p>
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26 pages, 35353 KiB  
Article
New Insights into the Understanding of High-Pressure Air Injection (HPAI): The Role of the Different Chemical Reactions
by Dubert Gutiérrez, Gord Moore, Don Mallory, Matt Ursenbach, Raj Mehta and Andrea Bernal
Geosciences 2024, 14(10), 270; https://doi.org/10.3390/geosciences14100270 - 13 Oct 2024
Viewed by 324
Abstract
High-pressure air injection (HPAI) is an enhanced oil recovery process in which compressed air is injected into deep, light oil reservoirs, with the expectation that the oxygen in the injected air will react with a fraction of the reservoir oil at an elevated [...] Read more.
High-pressure air injection (HPAI) is an enhanced oil recovery process in which compressed air is injected into deep, light oil reservoirs, with the expectation that the oxygen in the injected air will react with a fraction of the reservoir oil at an elevated temperature to produce carbon dioxide. The different chemical reactions taking place can be grouped into oxygen addition, thermal cracking, oxygen-induced cracking, and bond scission reactions. The latter reactions involve the combustion of a flammable vapor as well as the combustion of solid fuel, commonly known as “coke”. Since stable peak temperatures observed during HPAI experiments are typically below 300 °C, it has been suggested that thermal cracking and combustion of solid fuel may not be important reaction mechanisms for the process. The objective of this work is to assess the validity of that hypothesis. Therefore, this study makes use of different oxidation and combustion HPAI experiments, which were performed on two different light oil reservoir samples. Modeling of those tests indicate that thermal cracking is not an important reaction mechanism during HPAI and can potentially be ignored. The work also suggests that the main fuel consumed by the process is a flammable vapor generated by the chemical reactions. This represents a shift from the original in situ combustion paradigm, which is based on the combustion of coke. Full article
(This article belongs to the Topic Enhanced Oil Recovery Technologies, 3rd Volume)
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<p>Schematic flow diagram of ramped temperature system.</p>
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<p>Schematic view of high-pressure combustion tube.</p>
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<p>Photo of experimental core holder of high-pressure ramped temperature reactor along with its 3D simulation grid representation.</p>
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<p>Photo of experimental core holder of high-pressure combustion tube along with its 3D simulation grid representation.</p>
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<p>Simulated core temperatures–HPRTC Oil I.</p>
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<p>Simulated core temperatures–HPRTC Oil K.</p>
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<p>Simulated residual phases in post-test core and produced mole fraction of gas pseudo-component–HPRTC Oil I.</p>
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<p>Simulated residual phases in post-test core and produced mole fraction of gas pseudo-component–HPRTC Oil K.</p>
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<p>Simulated injection pressure–HPRTO Oil I without TCR and CSR.</p>
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<p>Simulated core temperatures–HPRTO Oil I without TCR and CSR.</p>
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<p>Simulated fluid production–HPRTO Oil I without TCR and CSR.</p>
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<p>Simulated gas concentrations of CO, CO<sub>2</sub>, and O<sub>2</sub>–HPRTO Oil I without TCR and CSR.</p>
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<p>Simulated gas concentrations of gas and nitrogen–HPRTO Oil I without TCR and CSR.</p>
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<p>Simulated produced oil properties–HPRTO Oil I without TCR and CSR.</p>
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<p>Simulated residual phases in post-test core–HPRTO Oil I without TCR and CSR.</p>
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<p>Simulated injection pressure–HPRTO Oil K without TCR and CSR.</p>
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<p>Simulated core temperatures–HPRTO Oil K without TCR and CSR.</p>
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<p>Simulated fluid production–HPRTO Oil K without TCR and CSR.</p>
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<p>Simulated gas concentrations of CO, CO<sub>2</sub>, and O<sub>2</sub>–HPRTO Oil K without TCR and CSR.</p>
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<p>Simulated gas concentrations of gas and nitrogen–HPRTO Oil K without TCR and CSR.</p>
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<p>Simulated produced oil properties–HPRTO Oil K without TCR and CSR.</p>
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<p>Simulated residual phases in post-test core–HPRTO Oil K without TCR and CSR.</p>
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<p>Simulated injection pressure–HPCT Oil I without TCR and CSR.</p>
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<p>Simulated core temperatures (Zones 1–11)–HPCT Oil I without TCR and CSR.</p>
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<p>Simulated core temperatures (Zones 12–22)–HPCT Oil I without TCR and CSR.</p>
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<p>Simulated core temperatures (Zones 23–33)–HPCT Oil I without TCR and CSR.</p>
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<p>Simulated fluid production–HPCT Oil I without TCR and CSR.</p>
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<p>Simulated gas composition (CO, CO<sub>2</sub>, and O<sub>2</sub>)–HPCT Oil I without TCR and CSR.</p>
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<p>Simulated gas composition (nitrogen and gas)–HPCT Oil I without TCR and CSR.</p>
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<p>Simulated produced oil properties–HPCT Oil I without TCR and CSR.</p>
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<p>Simulated residual phases in post-test core–HPCT Oil I without TCR and CSR.</p>
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<p>Simulated injection pressure–HPCT Oil K without TCR and CSR.</p>
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<p>Simulated core temperatures (Zones 1–11)–HPCT Oil K without TCR and CSR.</p>
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<p>Simulated core temperatures (Zones 12–22)–HPCT Oil K without TCR and CSR.</p>
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<p>Simulated core temperatures (Zones 23–33)–HPCT Oil K without TCR and CSR.</p>
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<p>Simulated fluid production–HPCT Oil K without TCR and CSR.</p>
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<p>Simulated gas composition (CO, CO<sub>2</sub>, and O<sub>2</sub>)–HPCT Oil K without TCR and CSR.</p>
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<p>Simulated gas composition (nitrogen and gas)–HPCT Oil K without TCR and CSR.</p>
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<p>Simulated produced oil properties–HPCT Oil K without TCR and CSR.</p>
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<p>Simulated residual phases in post-test core–HPCT Oil K without TCR and CSR.</p>
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12 pages, 2706 KiB  
Article
Chromium Immobilization as Cr-Spinel by Regulation of Fe(II) and Fe(III) Concentrations
by Tianci Hua, Yanzhang Li, Bingxu Hou, Yimei Du, Anhuai Lu and Yan Li
Minerals 2024, 14(10), 1024; https://doi.org/10.3390/min14101024 - 13 Oct 2024
Viewed by 422
Abstract
The complex environmental conditions at Cr-contaminated sites, characterized by uneven ion distribution, oxidants competition, and limited solid-phase mobility, lead to inadequate mixing of Fe-based reducing agents with Cr, posing significant challenges to the effectiveness of Cr remediation through Cr-spinel precipitation. This study investigates [...] Read more.
The complex environmental conditions at Cr-contaminated sites, characterized by uneven ion distribution, oxidants competition, and limited solid-phase mobility, lead to inadequate mixing of Fe-based reducing agents with Cr, posing significant challenges to the effectiveness of Cr remediation through Cr-spinel precipitation. This study investigates the distinct roles of Fe(II), Fe(III), and Cr(III) in Cr-spinel crystallization under ambient temperature and pressure. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray absorption near-edge structure spectroscopy, and Mössbauer spectroscopy were employed to elucidate the phase composition, microstructure, and ion coordination within the precipitates. Our findings indicate that Fe(II) acts as a catalyst in the formation of the spinel phase, occupying octahedral sites within the spinel structure. Under the catalytic influence of Fe(II), Fe(III) transitions into the spinel phase, occupying both the tetrahedral and the remaining octahedral sites. Meanwhile, Cr(III), due to its high octahedral site preference energy, preferentially occupies the octahedral sites. When Fe(II) or Fe(III) is present but does not meet the ideal stoichiometric ratio, a deficiency in Fe(II) leads to low yield and poor crystallinity of Cr-spinel, whereas a deficiency in Fe(III) can completely inhibit its formation. Conversely, when either Fe(II) or Fe(III) is in excess, the formation of Cr-spinel remains feasible. Furthermore, metastable Cr phases can be transformed into stable Cr-spinel by adjusting the Fe(II)/Fe(III)/Cr(III) ratio. These results highlight the broad range of conditions under which Cr-spinel mineralization can occur in environmental settings, enhancing our understanding of the mechanisms driving Cr-spinel formation in Cr-contaminated sites treated with Fe-based reducing agents. This research provides critical insights for optimizing Cr remediation strategies. Full article
(This article belongs to the Section Environmental Mineralogy and Biogeochemistry)
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<p>Synthesis of Cr-spinel with Fe(II) at non-ideal stoichiometric ratios. (<b>a</b>) Comparison of the reduction processes of Fe(III) and Cr(III) co-precipitate by <span class="html-italic">S.</span> MR-1. (<b>b</b>) XRD patterns of Fe(II) precipitate, co-precipitate of Fe(III) and Cr(III), reduction of Fe(III) and Cr(III) co-precipitate by <span class="html-italic">S.</span> MR-1, and the co-precipitation of Fe(II), Fe(III), and Cr(III) at stoichiometric ratios of 2:1.5:0.5 and 0.5:1.5:0.5, respectively. The symbols ♥ and ♦ represent spinel and goethite, respectively.</p>
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<p>XRD patterns of Fe(III) precipitate, co-precipitate of Fe(II) and Cr(III), the oxidation of Fe(II) and Cr(III) co-precipitate by O<sub>2</sub>, and the co-precipitation of Fe(II), Fe(III), and Cr(III) at stoichiometric ratios of 1:2:1 and 1:0.5:1, respectively. The symbols ♥ and ♦ represent spinel and goethite, respectively.</p>
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<p>XRD patterns of Cr(III) precipitate, co-precipitate of Fe(II) and Fe(III), and the co-precipitation of Fe(II), Fe(III), and Cr(III) at stoichiometric ratios of 1:1.5:0.25 and 1:1.5:2, respectively. The symbols ♥ and ♦ represent spinel and goethite, respectively.</p>
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<p>XRD patterns of precipitates formed from various mixing sequences of ion precipitates. The symbols ♥ and ♦ represent spinel and goethite, respectively.</p>
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<p>SEM-EDS and TEM patterns of (<b>a</b>) the mixed precipitate of Fe(III) and Cr(III) co-precipitate with Fe(II) precipitate, (<b>b</b>) the mixed precipitate of Fe(II) and Cr(III) co-precipitate with Fe(III) precipitate, and (<b>c</b>) the mixed precipitate of Fe(II) and Fe(III) co-precipitate with Cr(III) precipitate. The red plus sign indicates the detection position of EDS.</p>
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<p>Cr K-edge XANES of the precipitates.</p>
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<p>Mössbauer spectrum analysis of the mixed precipitate of Fe(II) and Cr(III) co-precipitate with Fe(III) precipitate.</p>
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11 pages, 19447 KiB  
Article
Microstructure Characteristics and Elevated-Temperature Wear Mechanism of FeCoCrNiAl High-Entropy Alloy Prepared by Laser Cladding
by Yali Gao, Sicheng Bai, Guangpeng Kou, Shan Jiang, Yu Liu and Dongdong Zhang
Processes 2024, 12(10), 2228; https://doi.org/10.3390/pr12102228 - 13 Oct 2024
Viewed by 554
Abstract
This paper investigated the FeCoCrNiAl high-entropy alloy on H13 steel, prepared using laser cladding, to improve the elevated-temperature wear resistance of the alloy. The results revealed that FCC and BCC phases, in terms of the coating, produced a large dislocation density. The coating [...] Read more.
This paper investigated the FeCoCrNiAl high-entropy alloy on H13 steel, prepared using laser cladding, to improve the elevated-temperature wear resistance of the alloy. The results revealed that FCC and BCC phases, in terms of the coating, produced a large dislocation density. The coating exhibited a columnar and equiaxed crystal microstructure. With the comprehensive effects of fine-grain strengthening, solid solution strengthening, and dislocation strengthening, the average hardness of the coating (500 HV0.1) was improved by 150% compared with that of H13 steel (200 HV0.1). The wear experiments were conducted at 623 K, 723 K, and 823 K. Compared with H13 steel, the wear volume of the coating decreased by 59.20%, 70.79%, and 78.20% under different temperatures. The wear forms impacting the coating were mainly abrasive wear and oxidation wear. However, H13 steel presented adhesive wear and fatigue wear, in addition to abrasive wear and oxidation wear. Full article
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<p>XRD results of FeCoCrNiAl high-entropy alloy coating.</p>
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<p>Microstructure of FeCoCrNiAl high-entropy alloy: (<b>a</b>) cross-section morphology and the EDS line scan results; (<b>b</b>) enlarged morphology of the interface; (<b>c</b>) enlarged morphology of the columnar crystal area; and (<b>d</b>) enlarged morphology of the equiaxed crystal area.</p>
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<p>Map scanning results of the equiaxed crystals: (<b>a</b>) SEM of equiaxed crystals; (<b>b</b>) Al distribution; (<b>c</b>) Cr distribution; (<b>d</b>) Fe distribution; (<b>e</b>) Co distribution; (<b>f</b>) Ni distribution.</p>
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<p>Point scanning results of the equiaxed crystals: (<b>a</b>) point scanning result of position 1; (<b>b</b>) point scanning result of position 2; (<b>c</b>) point scanning result of position 3; (<b>d</b>) point scanning result of position 4; (<b>e</b>) point scanning result of position 5; (<b>f</b>) point scanning result of position 6.</p>
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<p>The cross-sectional microhardness distribution of the coating.</p>
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<p>Wear scars on the coating and H13 steel at 623 K, 723 K, and 823 K: (<b>a</b>) wear scar on the coating at 623 K; (<b>b</b>) wear scar on the coating at 723 K; (<b>c</b>) wear scar on the coating at 823 K; (<b>d</b>) wear scar on H13 steel at 623 K [<a href="#B34-processes-12-02228" class="html-bibr">34</a>]; (<b>e</b>) wear scar on H13 steel at 723 K; (<b>f</b>) wear scar on H13 steel at 823 K [<a href="#B34-processes-12-02228" class="html-bibr">34</a>]; (<b>g</b>) EDS of the coating at 823 K; and (<b>h</b>) EDS of H13 steel at 823 K [<a href="#B34-processes-12-02228" class="html-bibr">34</a>].</p>
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<p>Wear volume of the coating and H13 steel at 623 K, 723 K, and 823 K.</p>
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17 pages, 5669 KiB  
Article
Stacking Fault Nucleation in Films of Vertically Oriented Multiwall Carbon Nanotubes by Pyrolysis of Ferrocene and Dimethyl Ferrocene at a Low Vapor Flow Rate
by Ayoub Taallah, Shanling Wang, Omololu Odunmbaku, Lin Zhang, Xilong Guo, Yixin Dai, Wenkang Li, Huanqing Ye, Hansong Wu, Jiaxin Song, Jian Guo, Jiqiu Wen, Yi He and Filippo S. Boi
C 2024, 10(4), 91; https://doi.org/10.3390/c10040091 - 12 Oct 2024
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Abstract
Recent observations of superconductivity in low-dimensional systems composed of twisted, untwisted, or rhombohedral graphene have attracted significant attention. One-dimensional moiré superlattices and flat bands have interestingly been identified in collapsed chiral carbon nanotubes (CNTs), opening up new avenues for the tunability of the [...] Read more.
Recent observations of superconductivity in low-dimensional systems composed of twisted, untwisted, or rhombohedral graphene have attracted significant attention. One-dimensional moiré superlattices and flat bands have interestingly been identified in collapsed chiral carbon nanotubes (CNTs), opening up new avenues for the tunability of the electronic properties in these systems. The nucleation of hexagonal moiré superlattices and other types of stacking faults has also been demonstrated in partially collapsed and uncollapsed carbon nano-onions (CNOs). Here, we report a novel investigation on the dynamics of stacking fault nucleation within the multilayered lattices of micrometer-scale vertically oriented films of multiwall CNTs (MWCNTs), resulting from the pyrolysis of molecular precursors consisting of ferrocene or dimethyl ferrocene, at low vapor flow rates of ~5–20 mL/min. Interestingly, local nucleation of moiré-like superlattices (as stacking faults) was found when employing dimethyl ferrocene as the pyrolysis precursor. The morphological and structural properties of these systems were investigated with the aid of scanning and transmission electron microscopies, namely SEM, TEM, and HRTEM, as well as X-ray diffraction (XRD) and Raman point/mapping spectroscopy. Deconvolution analyses of the Raman spectra also demonstrated a local surface oxidation, possibly occurring on defect-rich interfaces, frequently identified within or in proximity of bamboo-like graphitic caps. By employing high-temperature Raman spectroscopy, we demonstrate a post-growth re-graphitization, which may also be visualized as an alternative way of depleting the oxygen content within the MWCNTs’ interfaces through recrystallization. Full article
(This article belongs to the Special Issue Characterization of Disorder in Carbons (2nd Edition))
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Figure 1

Figure 1
<p>Schematic of the CVD system employed for the nucleation and growth of VA-MWCNTs, employing ferrocene or dimethyl ferrocene as the molecular precursor.</p>
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<p>SEM micrographs (<b>A</b>–<b>F</b>) of typical flakes of free-standing films of MWCNTs obtained by pyrolysis of dimethyl ferrocene at a low Ar vapor flow rate of ~10 mL/min. In particular, the micrographs in (<b>C</b>–<b>E</b>) allow for a clear observation of the high degree of CNT alignment.</p>
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<p>Transmission electron micrographs (<b>A</b>–<b>F</b>) showing, with an increasing level of detail, the cross-sectional morphology of films comprising vertically aligned MWCNTs decorated with filled CNOs. The TEM micrographs in (<b>E</b>,<b>F</b>) show the fine details of the CNOs decorating the MWCNT (scale bar in green corresponds to 0.05 μm). These films were obtained through the pyrolysis of ferrocene at very low vapor flow rates of ~5 mL/min.</p>
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<p>Low-magnification TEM micrograph of as-grown VA-MWCNTs obtained through the pyrolysis of dimethyl ferrocene.</p>
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<p>HRTEM micrographs (<b>A</b>–<b>F</b>) exhibiting the structural arrangement of the CNT walls. Note the presence of structural stress and dislocation-rich interfaces, as shown in (<b>D</b>–<b>F</b>). The formation of graphitic caps on both sides of the encapsulated particle indicates a bamboo-like growth mechanism with a variable orientation. The presence of stacking faults and moiré-like super-periodicities is visible in the micrograph presented in (<b>D</b>).</p>
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<p>HRTEM (<b>A</b>–<b>C</b>) and profile analyses (<b>D</b>) revealing the presence of a transition in the stacking order of the CNT walls in proximity of partially nucleated graphite caps (see (<b>B</b>)).</p>
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<p>HRTEM micrograph revealing, with high detail, the nucleation of moiré-like stacking faults within the walls of the CNT, as a result of a variation in the orientation of the multilayered lattice. The nucleation of this type of stacking fault appears to be linked to the formation of graphitic bamboo-like caps with a variable orientation (see cyan arrow).</p>
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<p>HRTEM micrograph of the stacking fault shown in <a href="#carbon-10-00091-f007" class="html-fig">Figure 7</a> (cyan arrow) and profile analyses (<b>A</b>–<b>C</b>) performed with the aid of DigitalMicrograph software, revealing examples of super-periodicities D ranging from ~0.4 nm to ~0.6 nm.</p>
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<p>Typical XRD diffractogram (red line) and Rietveld refinement (green line) of the free-standing aligned MWCNT films, revealing the following phase abundances: 74.8% Fe<sub>3</sub>C, 18.6% α-Fe, and 6.6% γ-Fe. The magenta line corresponds to the difference between the XRD diffractogram (experimental data) and the Rietveld model (theoretical data). The extracted R<sub>p</sub> value was 0.0278. The following database cards were employed for the refinements: COD 1008725 (Fe<sub>3</sub>C with space group Pnma), COD 1100108 (α-Fe with space group Im-3m), and COD 1534888 (γ-Fe with space group Fm-3m). See ESI <a href="#app1-carbon-10-00091" class="html-app">Figure S3</a> for details on extracted unit cell parameters.</p>
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<p>Typical examples of Raman spectroscopy point/map analyses of the VA-MWCNT. The map analyses in (<b>A</b>–<b>D</b>) and the point analyses in (<b>E</b>,<b>F</b>) highlight a significant local variation in the amplitude of the D and G band components, with the appearance of D’ band features indicative of an enhancement in the relative abundance of defect-rich carbon within certain regions of the film.</p>
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<p>In (<b>A</b>,<b>B</b>) deconvolution analyses of the Raman spectra collected at T ~ 673 K after 1 min (<b>A</b>) and 2 min (<b>B</b>) of laser exposure, respectively, evidencing the presence of an enhanced 2D band in (<b>B</b>), deriving from a re-graphitization process.</p>
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<p>High-temperature Raman spectroscopy measurement showing the variation in the intensities of D, G, and 2D bands as a function of laser beam exposure time for a constant temperature (T ~ 673 K under N<sub>2</sub> flow). This is shown in a large frequency range in (<b>A</b>), from 1000 to 3000 cm<sup>−1</sup> and shorter frequency range in (<b>B</b>,<b>C</b>) from 1000 to 1800 and from 1800 to 3000 cm<sup>−1</sup> respectively.</p>
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<p>Evolution of the amplitude of the 2D band as a function of the laser beam exposure time, at T ~ 673 K.</p>
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