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26 pages, 14835 KiB  
Article
Mechanical and Tribological Properties of (AlCrNbSiTiMo)N High-Entropy Alloy Films Prepared Using Single Multiple-Element Powder Hot-Pressed Sintered Target and Their Practical Application in Nickel-Based Alloy Milling
by Jeng-Haur Horng, Wen-Hsien Kao, Wei-Chen Lin and Ren-Hao Chang
Lubricants 2024, 12(11), 391; https://doi.org/10.3390/lubricants12110391 - 14 Nov 2024
Viewed by 310
Abstract
(AlCrNbSiTiMo)N high-entropy alloy films with different nitrogen contents were deposited on tungsten carbide substrates using a radio-frequency magnetron sputtering system. Two different types of targets were used in the sputtering process: a hot-pressing sintered AlCrNbSiTi target fabricated using a single powder containing multiple [...] Read more.
(AlCrNbSiTiMo)N high-entropy alloy films with different nitrogen contents were deposited on tungsten carbide substrates using a radio-frequency magnetron sputtering system. Two different types of targets were used in the sputtering process: a hot-pressing sintered AlCrNbSiTi target fabricated using a single powder containing multiple elements and a vacuum arc melting Mo target. The deposited films were denoted as RN0, RN33, RN43, RN50, and RN56, where RN indicates the nitrogen flow ratio relative to the total nitrogen and argon flow rate (RN = (N2/(N2 + Ar)) × 100%). The as-sputtered films were vacuum annealed, with the resulting films denoted as HRN0, HRN33, HRN43, HRN50, and HRN56, respectively. The effects of the nitrogen content on the composition, microstructure, mechanical properties, and tribological properties of the films, in both as-sputtered and annealed states, underwent thorough analysis. The RN0 and RN33 films displayed non-crystalline structures. However, with an increase in nitrogen content, the RN43, RN50, and RN56 films transitioned to FCC structures. Among the as-deposited films, the RN43 film exhibited the best mechanical and tribological properties. All of the annealed films, except for the HRN0 film, displayed an FCC structure. In addition, they all formed an MoO3 solid lubricating phase, which reduced the coefficient of friction and improved the anti-wear performance. The heat treatment HRN43 film displayed the supreme hardness, H/E ratio, and adhesion strength. It also demonstrated excellent thermal stability and the best wear resistance. As a result, in milling tests on Inconel 718, the RN43-coated tool demonstrated a significantly lower flank wear and notch wear, indicating an improved machining performance and extended tool life. Thus, the application of the RN43 film in aerospace manufacturing can effectively reduce the tool replacement cost. Full article
(This article belongs to the Special Issue Recent Advances in Tribological Properties of Machine Tools)
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Figure 1

Figure 1
<p>(<b>a</b>) Diagrammatic sketch of sputtering target configuration, and (<b>b</b>) diagrammatic sketch of film design.</p>
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<p>Morphology and elemental composition of new AlCrNbSiTi powder for hot-pressing sintering targets.</p>
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<p>Schematic showing tool wear and notch wear measurement positions.</p>
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<p>Element content of (<b>a</b>) as-sputtered and (<b>b</b>) heat-treated (AlCrNbSiTiMo)N films.</p>
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<p>X-ray diffraction patterns of (<b>a</b>) as-sputtered and (<b>b</b>) heat-treated (AlCrNbSiTiMo)N films.</p>
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<p>Cross-section SEM graphics of (AlCrNbSiTiMo)N films: (<b>a</b>) R<sub>N0</sub>, (<b>b</b>) HR<sub>N0</sub>, (<b>c</b>) R<sub>N33</sub>, (<b>d</b>) HR<sub>N33</sub>, (<b>e</b>) R<sub>N43</sub>, (<b>f</b>) HR<sub>N43</sub>, (<b>g</b>) R<sub>N50</sub>, (<b>h</b>) HR<sub>N50</sub>, (<b>i</b>) R<sub>N56</sub>, and (<b>j</b>) HR<sub>N56</sub>.</p>
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<p>SEM surface graphics of (AlCrNbSiTiMo)N films: (<b>a</b>) R<sub>N0</sub>, (<b>b</b>) HR<sub>N0</sub>, (<b>c</b>) R<sub>N33</sub>, (<b>d</b>) HR<sub>N33</sub>, (<b>e</b>) R<sub>N43</sub>, (<b>f</b>) HR<sub>N43</sub>, (<b>g</b>) R<sub>N50</sub>, (<b>h</b>) HR<sub>N50</sub>, (<b>i</b>) R<sub>N56</sub>, and (<b>j</b>) HR<sub>N56</sub>.</p>
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<p>OM graphics of scratch track on R<sub>N33</sub> film.</p>
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<p>Curves of COF for (<b>a</b>) as-deposited (AlCrNbSiTiMo)N films and substrate (WC), and (<b>b</b>) annealed (AlCrNbSiTiMo)N films and substrate (WC).</p>
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<p>SEM graphics and EDS results of worn traces on (<b>a</b>) R<sub>N0</sub> and (<b>b</b>) R<sub>N43</sub> films and (<b>c</b>) R<sub>N43</sub> film enlarged image and (Note: For comparative analysis, the originally existed elemental compositions of the R<sub>N0</sub>, R<sub>N43</sub> films are also shown).</p>
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<p>SEM graphics and EDS results for worn traces on (<b>a</b>) HR<sub>N0</sub> film, (<b>b</b>) HR<sub>N43</sub> film (regular magnification), and (<b>c</b>) HR<sub>N43</sub> film (high magnification). (Note: For comparative analysis, the originally existed elemental compositions of the HR<sub>N0</sub> and HR<sub>N43</sub> films are also provided).</p>
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<p>OM graphics showing the flank wear and notch wear on (<b>a</b>) bare WC cutting tool and (<b>b</b>) R<sub>N43</sub> coated WC cutting tool completing a total processing distance of 18 m.</p>
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<p>(<b>a</b>) Flank wear and (<b>b</b>) Notch wear of bare WC cutting tool and R<sub>N43</sub> coated WC cutting tool compared with other coated tools after completing three processing distances of 6, 12, and 18 m, individually.</p>
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13 pages, 8022 KiB  
Article
On the Effect of Randomly Oriented Grain Growth on the Structure of Aluminum Thin Films Deposited via Magnetron Sputtering
by Vagelis Karoutsos, Nikoletta Florini, Nikolaos C. Diamantopoulos, Christina Balourda, George P. Dimitrakopulos, Nikolaos Bouropoulos and Panagiotis Poulopoulos
Coatings 2024, 14(11), 1441; https://doi.org/10.3390/coatings14111441 - 13 Nov 2024
Viewed by 287
Abstract
The microstructure of aluminum thin films, including the grain morphology and surface roughness, are key parameters for improving the thermal or electrical properties and optical reflectance of films. The first step in optimizing these parameters is a thorough understanding of the grain growth [...] Read more.
The microstructure of aluminum thin films, including the grain morphology and surface roughness, are key parameters for improving the thermal or electrical properties and optical reflectance of films. The first step in optimizing these parameters is a thorough understanding of the grain growth mechanisms and film structure. To investigate these issues, thin aluminum films with thicknesses ranging from 25 to 280 nm were coated on SiOx/Si substrates at ambient temperature under high-vacuum conditions and a low argon pressure of 3 × 10−3 mbar (0.3 Pa) using the radio frequency magnetron sputtering method. Quantitative analyses of the surface roughness and nanograin characteristics were conducted using atomic force microscopy (AFM), transmission electron microscopy (TEM), and X-ray diffraction. Changes in specular reflectance were measured using ultraviolet–visible and near-infrared spectroscopy. The low roughness values obtained from the AFM images resulted in high film reflectivity, even for thicker films. TEM and AFM results indicate monomodal, randomly oriented grain growth without a distinct columnar or spherical morphology. Using TEM cross-sectional images and the dependence of the grain size on the film thickness, we propose a grain growth mechanism based on the diffusion mobility of aluminum atoms through grain boundaries. Full article
(This article belongs to the Section Thin Films)
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Figure 1

Figure 1
<p>XRD pattern of the 280 nm thick Al film deposited on SiO<sub>x</sub>/Si.</p>
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<p>(<b>a</b>) Cross-sectional high-angle annular dark-field (HAADF) STEM image of the Al/Si heterostructure. (<b>b</b>) Corresponding layered image of EDS maps. The inset illustrates the interfacial region with the oxygen signal due to the SiO<sub>x</sub> interlayer.</p>
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<p>AFM images of the deposited Al films for the following samples: (<b>a</b>) ALM1, (<b>b</b>) ALM2, (<b>c</b>) ALM3, (<b>d</b>) ALM4, (<b>e</b>) ALM5, and (<b>f</b>) ALM6. All image dimensions are 1 × 1 μm<sup>2</sup>, except for image (<b>a</b>), whose dimensions are 500 × 500 nm<sup>2</sup>.</p>
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<p>Grain size distribution histograms corresponding to each AFM image in <a href="#coatings-14-01441-f003" class="html-fig">Figure 3</a>; d<sub>g</sub> denotes the mean grain size obtained by the Gaussian function fitted to each histogram.</p>
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<p>Measured average RMS roughness for the six film surfaces (<a href="#coatings-14-01441-t002" class="html-table">Table 2</a>) plotted as a function of film thickness.</p>
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<p>Reflectance spectra of two Al thin films with different thicknesses deposited on glass substrate.</p>
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<p>(<b>a</b>) Cross-sectional bright-field TEM image of a region of the Al/Si heterostructure obtained along the [1<math display="inline"><semantics> <mrow> <mover accent="true"> <mrow> <mn>1</mn> </mrow> <mo>¯</mo> </mover> </mrow> </semantics></math>0]Si zone axis of the substrate. SAED patterns obtained from the substrate and the Al film are given as insets. Reflections from diffracting planes are denoted on the SAED patterns. In the case of the Al film, its polycrystalline character yields a ring-type SAED pattern. (<b>b</b>) The 3D AFM surface image of the same film.</p>
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<p>(<b>a</b>) Cross-sectional bright field TEM image showing another region of the Al/Si heterostructure. (<b>b</b>,<b>c</b>) Corresponding dark field TEM images obtained with different reflections of the film, showing diffraction contrast from different crystallites. In (<b>b</b>), the arrows indicate smaller-sized crystallites near the heterointerface.</p>
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<p>(<b>a</b>) HRTEM image along the [1<math display="inline"><semantics> <mrow> <mover accent="true"> <mrow> <mn>1</mn> </mrow> <mo>¯</mo> </mover> </mrow> </semantics></math>0] zone axis of Si, showing in atomic resolution the polycrystalline Al epilayer grown on the Si substrate. Moiré fringes in the Al film are due to the overlap of grains along the projection direction. (<b>b</b>) GPA phase map illustrating the phase changes in the epilayer due to its polycrystalline structure. The inset is the corresponding diffractogram indicating the selected spatial periodicities close to 220 Si that were employed for creating the phase map.</p>
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<p>Measured average grain diameter obtained by distribution histograms of <a href="#coatings-14-01441-f003" class="html-fig">Figure 3</a> plotted as a function of film thickness.</p>
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15 pages, 3369 KiB  
Article
Nanocrystalline Lanthanum Oxide Layers on Tubes Synthesized Using the Metalorganic Chemical Vapor Deposition Technique
by Agata Sawka
Materials 2024, 17(22), 5539; https://doi.org/10.3390/ma17225539 - 13 Nov 2024
Viewed by 238
Abstract
Lanthanum oxide (La2O3) layers are widely used in electronics, optics, and optoelectronics due to their properties. Lanthanum oxide is also used as a dopant, modifying and improving the properties of other materials in the form of layers, as well [...] Read more.
Lanthanum oxide (La2O3) layers are widely used in electronics, optics, and optoelectronics due to their properties. Lanthanum oxide is also used as a dopant, modifying and improving the properties of other materials in the form of layers, as well as having a large volume. In this work, lanthanum oxide layers were obtained using MOCVD (Metalorganic Chemical Vapor Deposition) on the inner walls of tubular substrates at 600–750 °C. The basic reactant was La(tmhd)3 (tris(2,2,6,6-tetramethyl-3,5-heptanedionato)lanthanum(III)). The evaporation temperature of La(tmhd)3 amounted to 170–200 °C. Pure argon (99.9999%) and air were used as the carrier gases. The air was also intended to remove the carbon from the synthesized layers. Tubes of quartz glass were used as the substrates. La2O3 layers were found to be growing on their inner surfaces. The value of the extended Grx/Rex2 criterion, where Gr—Grashof’s number, Re—Reynolds’ number, x—the distance from the gas inflow point, was below 0.01. The microstructure of the deposited layers of lanthanum oxide was investigated using an electron scanning microscope (SEM). Their chemical composition was analyzed via energy-dispersive X-ray (EDS) analysis. Their phase composition was tested via X-ray diffraction. The transmittance of the layers of lanthanum oxide was determined with the use of UV-Vis spectroscopy. The obtained layers of lanthanum oxide were characterized by a nanocrystalline microstructure and stable cubic structure. They also exhibited good transparency in both ultraviolet (UV) and visible (Vis) light. Full article
(This article belongs to the Section Thin Films and Interfaces)
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Figure 1

Figure 1
<p>SEM microstructure of the La<sub>2</sub>O<sub>3</sub> layer at different magnifications (<b>a</b>,<b>b</b>). Results of X-ray analysis of this layer (<b>c</b>). Layer deposition temperature: 600 °C. Synthesis time: 20 min. Evaporation temperature of La(tmhd)<sub>3</sub>: 185 °C.</p>
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<p>SEM microstructure of the La<sub>2</sub>O<sub>3</sub> layer at different magnifications (<b>a</b>,<b>b</b>). Results of X-ray analysis of this layer (<b>c</b>). Layer deposition temperature: 600 °C. Synthesis time: 20 min. Evaporation temperature of La(tmhd)<sub>3</sub>: 185 °C.</p>
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<p>SEM microstructure of the La<sub>2</sub>O<sub>3</sub> layer at different magnifications (<b>a</b>,<b>b</b>). EDS spectra of the sample (<b>c</b>). Layer deposition temperature: 650 °C. Synthesis time: 10 min. Evaporation temperature of La(tmhd)<sub>3</sub>: 195 °C.</p>
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<p>SEM microstructure of the La<sub>2</sub>O<sub>3</sub> layer at different magnifications (<b>a</b>,<b>b</b>). Cross-section of the lanthanum oxide layer—quartz glass substrate (<b>b</b>) with linear EDS analysis along the marked line (<b>c</b>,<b>d</b>). Layer deposition temperature: 650 °C. Synthesis time: 15 min. Evaporation temperature of La(tmhd)<sub>3</sub>: 185 °C.</p>
Full article ">Figure 3 Cont.
<p>SEM microstructure of the La<sub>2</sub>O<sub>3</sub> layer at different magnifications (<b>a</b>,<b>b</b>). Cross-section of the lanthanum oxide layer—quartz glass substrate (<b>b</b>) with linear EDS analysis along the marked line (<b>c</b>,<b>d</b>). Layer deposition temperature: 650 °C. Synthesis time: 15 min. Evaporation temperature of La(tmhd)<sub>3</sub>: 185 °C.</p>
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<p>SEM microstructure of the La<sub>2</sub>O<sub>3</sub> layer at different magnifications (<b>a</b>,<b>b</b>). EDS spectra of the sample (<b>c</b>). Layer deposition temperature: 650 °C. Synthesis time: 20 min. Evaporation temperature of La(tmhd)<sub>3</sub>: 185 °C.</p>
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<p>SEM microstructure of the La<sub>2</sub>O<sub>3</sub> layer (<b>a</b>) and the results of the X-ray analysis of this layer (<b>b</b>). Layer deposition temperature: 750 °C. Synthesis time: 20 min. Evaporation temperature of La(tmhd)<sub>3</sub>: 195 °C.</p>
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<p>Transmittance of quartz glass covered with La<sub>2</sub>O<sub>3</sub> layers under different conditions and without layers. 0—uncoated glass; 1—glass coated with La<sub>2</sub>O<sub>3</sub> at 650 °C, evaporation temperature of La(tmhd)<sub>3</sub>: 170 °C, and deposition time: 20 min; 2—glass coated with La<sub>2</sub>O<sub>3</sub> at 650 °C, evaporation temperature of La(tmhd)<sub>3</sub>: 185 °C, and deposition time: 20 min; 3—glass coated with La<sub>2</sub>O<sub>3</sub> at 650 °C, evaporation temperature of La(tmhd)<sub>3</sub>: 185 °C, and deposition time: 15 min; 4—glass coated with La<sub>2</sub>O<sub>3</sub> at 650 °C, evaporation temperature of La(tmhd)<sub>3</sub>: 190 °C, and deposition time: 20 min; 5—glass coated with La<sub>2</sub>O<sub>3</sub> at 650 °C, evaporation temperature of La(tmhd)<sub>3</sub>: 195 °C, and deposition time: 10 min; 6—glass coated with La<sub>2</sub>O<sub>3</sub> at 750 °C, evaporation temperature of La(tmhd)<sub>3</sub>: 185 °C, and deposition time: 20 min; 7—glass coated with La<sub>2</sub>O<sub>3</sub> at 750 °C, evaporation temperature of La(tmhd)<sub>3</sub>: 195 °C, and deposition time: 20 min; 8—glass coated with La<sub>2</sub>O<sub>3</sub> at 750 °C, evaporation temperature of La(tmhd)<sub>3</sub>: 195 °C, and deposition time: 15 min; 9—glass coated with La<sub>2</sub>O<sub>3</sub> at 650 °C, evaporation temperature of La(tmhd)<sub>3</sub>: 190 °C, and deposition time: 20 min.</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 329
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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Figure 1

Figure 1
<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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16 pages, 6912 KiB  
Article
Graphite Regeneration and NCM Cathode Type Synthesis from Retired LIBs by Closed-Loop Cycle Recycling Technology of Lithium-Ion Batteries
by Alexandra Kosenko, Konstantin Pushnitsa, Vladislav Chernyavsky, Pavel Novikov and Anatoliy A. Popovich
Energies 2024, 17(22), 5570; https://doi.org/10.3390/en17225570 - 7 Nov 2024
Viewed by 358
Abstract
A closed-loop regeneration process for spent LiCoO2 has been successfully designed with prior synthesis of LiNixCoyMnzO2, by the authors. This research applies the methodology to lithium-ion battery anodes, using spent graphite from a decommissioned [...] Read more.
A closed-loop regeneration process for spent LiCoO2 has been successfully designed with prior synthesis of LiNixCoyMnzO2, by the authors. This research applies the methodology to lithium-ion battery anodes, using spent graphite from a decommissioned battery in a leaching process with 1.5 mol∙L−1 malic acid and 3% H2O2 alongside LiCoO2. The filtered graphite was separated, annealed in an argon atmosphere, and the filtrate was used to synthesize NCM cathode material. Characterization involved X-ray diffraction, EDX, and SEM techniques. The regenerated graphite (RG) showed a specific discharge capacity of 340.4 mAh/g at a 0.1C rate in the first cycle, dropping to 338.4 mAh/g after 55 cycles, with a Coulombic efficiency of 99.9%. CV and EIS methods provided further material assessment. In a related study, the SNCM111 synthesized from the leaching solution showed a specific discharge capacity of 131.68 mAh/g initially, decreasing to 115.71 mAh/g after 22 cycles. Full article
(This article belongs to the Special Issue Advances in Battery Degradation and Recycling)
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Figure 1

Figure 1
<p>The scheme of closed-loop regeneration process.</p>
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<p>The diffraction pattern of the preliminary electrodes.</p>
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<p>The SEM images of the spent materials in SE mode: (<b>a</b>)—spent anode material, (<b>b</b>)—spent cathode material.</p>
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<p>The diffraction patterns: (<b>a</b>) of spent graphite (SG), leached graphite (LG), and regenerated graphite (RG); (<b>b</b>) the same patterns with a large magnification in the angles 2θ.</p>
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<p>The SEM images of the recovered graphite material. (<b>a</b>)—LG, (<b>b</b>–<b>d</b>)—RG.</p>
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<p>The analysis of the RG electrochemical performance includes (<b>a</b>) charge/discharge curves for the first and tenth cycles, (<b>b</b>) cyclic testing, and (<b>c</b>) a study on varying current loads.</p>
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<p>CVA curves of RG (<b>a</b>) and CG (<b>b</b>).</p>
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<p>The impedance spectrum of the graphite layout and its equivalent circuit.</p>
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<p>SEM photographs of SNCM. (<b>a</b>) at magnification ×1.5 K; (<b>b</b>) at magnification ×5 K.</p>
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<p>XRD pattern of SNCM material.</p>
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<p>The electrochemical behavior of the SNCM. (<b>a</b>)—charge/discharge curves on 1st and 10th cycles, (<b>b</b>)—cyclic test, (<b>c</b>)—t current load study.</p>
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15 pages, 6393 KiB  
Article
Nanoporous Copper Films: How to Grow Porous Films by Magnetron Sputter Deposition
by Michał A. Borysiewicz, Patrycja Barańczyk, Jakub Zawadzki, Marek Wzorek, Rafał Zybała, Beata Synkiewicz-Musialska and Paweł Krzyściak
Crystals 2024, 14(11), 965; https://doi.org/10.3390/cryst14110965 - 7 Nov 2024
Viewed by 314
Abstract
Porous copper films used in current collectors have been shown to improve the stability of Li-ion batteries. They can be applied in Si-based photodiodes, sensors or as microradiators. Their fabrication, however, remains a challenge. In this work, we report on the direct deposition [...] Read more.
Porous copper films used in current collectors have been shown to improve the stability of Li-ion batteries. They can be applied in Si-based photodiodes, sensors or as microradiators. Their fabrication, however, remains a challenge. In this work, we report on the direct deposition of porous copper films using magnetron sputtering in regular chamber geometry. We show how by using appropriate process gases and substrate temperatures, it is possible to control the morphology of the deposited films. In particular, the optimization of the argon to oxygen flow ratios and flow values leads to small porosification of the deposited copper films. Further, heating the substrate during deposition enables the growth of pore sizes into mesoporous and macroporous ranges. This approach is scalable, and since it does not require glancing angle deposition enables the easy coverage of large surfaces with uniformly porous films. Full article
(This article belongs to the Section Crystalline Metals and Alloys)
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<p>Schematic of the sputtering setup. A Cu source, called a ‘target’ is sputtered in a vacuum chamber when argon gas is introduced into it (dark blue dots) and ionized under the voltage applied between the target and substrate. The ionized gas hits the target and ejects the material into the chamber, including on the substrate on which it is coated. The addition of a reactive gas such as oxygen (pale grey dots) enables changes in the growth of the material, either by oxidizing or by influencing the nucleation of the grains. The substrate is rotated during deposition about its axis and may be heated to modify the film growth conditions.</p>
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<p>SEM cross-section images of the samples deposited at 10:1 and 10:2 Ar:O<sub>2</sub> ratios. For sample names, please consult <a href="#crystals-14-00965-t001" class="html-table">Table 1</a>.</p>
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<p>XRD patterns of the samples deposited at room temperature in the flow ratios 10:1 (<b>a</b>), 10:2 (<b>b</b>), 15:1 (<b>c</b>), 20:1 (<b>d</b>) and 25:1 (<b>e</b>).</p>
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<p>SEM cross-section images of the samples deposited at 15:1, 20:1 and 25:1 Ar:O<sub>2</sub> ratios. For sample names, please consult <a href="#crystals-14-00965-t001" class="html-table">Table 1</a>.</p>
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<p>SEM cross-section images of the samples deposited at 18 sccm Ar:0.9 sccm O<sub>2</sub> for various temperatures. The white horizontal bars denote 200 nm for each image.</p>
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<p>XRD patterns of the samples deposited at 18 sccm Ar:0.9 sccm O<sub>2</sub> for various temperatures. The thicker lines are drawn for the samples deposited between 200 and 400 °C, where the porous growth mode is observed.</p>
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<p>TEM images of the individual nanocrystals of the sample deposited at 300 °C. (<b>a</b>) Overview image with the frame showing the zoomed in area in (<b>c</b>). (<b>b</b>) Elemental mapping of the crystallites. (<b>c</b>) High-resolution image of the surface oxide on the Cu crystallite zoomed in from the yellow box in (<b>a</b>). Localized FFT profiles of the areas in white boxes show that the oxide is Cu<sub>4</sub>O<sub>3</sub> and the grain is Cu.</p>
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<p>Optical image of the nanostructured Cu samples on the <span class="html-italic">E. coli</span>-loaded agar: A—RT, B—50 °C, C—100 °C, E—150 °C, D—200 °C and F—300 °C.</p>
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<p>Proposed growth zones for the porous Cu as a function of substrate temperature.</p>
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33 pages, 9739 KiB  
Article
Numerical Modelling and Experimental Validation of Selective Laser Melting Processes Using a Custom Argon Chamber Setup for 316L Stainless Steel and Ti6AI4V
by Gasser Abdelal, Daniel Higgins, Chi-Wai Chan and Brian G. Falzon
Coatings 2024, 14(11), 1406; https://doi.org/10.3390/coatings14111406 - 5 Nov 2024
Viewed by 649
Abstract
Selective Laser Melting (SLM) is an advanced additive manufacturing technique that demands meticulous control over thermal dynamics to maintain the integrity and performance of manufactured parts. This study presents the development and validation of a thermal model designed to enhance the SLM process [...] Read more.
Selective Laser Melting (SLM) is an advanced additive manufacturing technique that demands meticulous control over thermal dynamics to maintain the integrity and performance of manufactured parts. This study presents the development and validation of a thermal model designed to enhance the SLM process for 316L stainless steel (316L SS) and titanium alloy Ti6Al4V. A specially constructed Argon Chamber Setup, equipped with a 200 W continuous-wave (CW) fibre laser system, was used to create an SLM-representative environment for 316L SS, enabling precise experimental validation of the model. This validation serves as a robust baseline, facilitating the model’s extension to more complex materials like Ti6Al4V, thereby supporting a cost-efficient and safe approach to initial testing. The rigorously validated thermal model offers a comprehensive link between experimental data and numerical simulations in SLM. It supports process optimisation by accurately predicting thermal behaviours, contributing significantly to additive manufacturing advancements. By fine-tuning processing parameters, this model enhances material characteristics, thereby providing practical insights applicable to industrial production and improving the consistency and quality of SLM-manufactured parts. Full article
(This article belongs to the Special Issue Laser Surface Engineering and Additive Manufacturing)
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<p>A 3D FE model schematic of geometry and mesh.</p>
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<p>A custom-designed gas chamber.</p>
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<p>Melt pool imaging at 30 W, 40 W, and 45 W [<a href="#B28-coatings-14-01406" class="html-bibr">28</a>]. (<b>a</b>) Melt pool image of the single-layer sample processed at 30 W, showing a thin and brittle structure with visible melt pool lines and some unmelted powder within the lines. (<b>b</b>) Melt pool image of the single-layer sample processed at 40 W, displaying a more robust structure with distinct melt pool lines and significantly fewer balling defects. However, balling is observed at the edges where the laser beam changes direction. (<b>c</b>) Melt pool image of the single-layer sample processed at 45 W, indicating increased balling defects, particularly at the edges, due to excessive melting and instability in the melt pool at higher powers.</p>
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<p>Melt pool imaging at 30 W, 40 W, and 45 W [<a href="#B28-coatings-14-01406" class="html-bibr">28</a>]. (<b>a</b>) Melt pool image of the single-layer sample processed at 30 W, showing a thin and brittle structure with visible melt pool lines and some unmelted powder within the lines. (<b>b</b>) Melt pool image of the single-layer sample processed at 40 W, displaying a more robust structure with distinct melt pool lines and significantly fewer balling defects. However, balling is observed at the edges where the laser beam changes direction. (<b>c</b>) Melt pool image of the single-layer sample processed at 45 W, indicating increased balling defects, particularly at the edges, due to excessive melting and instability in the melt pool at higher powers.</p>
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<p>Sample at 45 W/90 @ 55 W [<a href="#B28-coatings-14-01406" class="html-bibr">28</a>].</p>
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<p>Sample at 40 W/90 @ 60 W [<a href="#B28-coatings-14-01406" class="html-bibr">28</a>].</p>
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<p>316L SS experimental measurements [<a href="#B28-coatings-14-01406" class="html-bibr">28</a>].</p>
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<p>Comparison of experimentally measured and simulated melt pool widths for 316L SS at various laser power settings. The melt pool width was determined using high-resolution optical microscopy and image analysis of cross-sectional samples [<a href="#B28-coatings-14-01406" class="html-bibr">28</a>].</p>
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<p>Temperature contour and melt pool dimensions when laser power = 100 W, scanning speed = 1000 mm/s [<a href="#B28-coatings-14-01406" class="html-bibr">28</a>].</p>
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<p>Ti6AI4V thermal history when laser power = 100 W, scanning speed = 1000 mm/s. Liquidus and solidus lines have been marked [<a href="#B28-coatings-14-01406" class="html-bibr">28</a>].</p>
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<p>Temperature distribution for different laser powers (100 W, 150 W, and 200 W) showing (<b>a</b>) temperature versus time and (<b>b</b>) temperature versus distance along the scanning direction at t = 1t = 1t = 1 ms [<a href="#B28-coatings-14-01406" class="html-bibr">28</a>].</p>
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<p>Temperature distribution for different laser powers (100 W, 150 W, and 200 W) showing (<b>a</b>) temperature versus time and (<b>b</b>) temperature versus distance along the scanning direction at t = 1t = 1t = 1 ms [<a href="#B28-coatings-14-01406" class="html-bibr">28</a>].</p>
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<p>Temperature distribution at t = 1 ms for different laser speeds. (<b>a</b>) Temperature versus time, showing how different scanning speeds affect the duration above the melting point. (<b>b</b>) Temperature versus distance along the scanning direction, illustrating the spatial temperature gradients for different scanning speeds [<a href="#B28-coatings-14-01406" class="html-bibr">28</a>].</p>
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<p>Temperature distribution at t = 1 ms for different laser speeds. (<b>a</b>) Temperature versus time, showing how different scanning speeds affect the duration above the melting point. (<b>b</b>) Temperature versus distance along the scanning direction, illustrating the spatial temperature gradients for different scanning speeds [<a href="#B28-coatings-14-01406" class="html-bibr">28</a>].</p>
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<p>Calculated melt pool dimensions with varying powers.</p>
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<p>Calculated melt pool dimensions with varying scanning velocities.</p>
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10 pages, 5685 KiB  
Article
Improvement and Characterisation of the ArCLight Large-Area Dielectric Light Detector for Liquid-Argon Time Projection Chambers
by Jonas Bürgi, Livio Calivers, Richard Diurba, Fabian Frieden, Anja Gauch, Laura Francesca Iacob, Igor Kreslo, Jan Kunzmann, Saba Parsa and Michele Weber
Instruments 2024, 8(4), 48; https://doi.org/10.3390/instruments8040048 - 4 Nov 2024
Viewed by 486
Abstract
The detection of scintillation light in noble-liquid detectors is necessary for identifying neutrino interaction candidates from beam, astrophysical, or solar sources. Large monolithic detectors typically have highly efficient light sensors, like photomultipliers, mounted outside their electric field. This option is not available for [...] Read more.
The detection of scintillation light in noble-liquid detectors is necessary for identifying neutrino interaction candidates from beam, astrophysical, or solar sources. Large monolithic detectors typically have highly efficient light sensors, like photomultipliers, mounted outside their electric field. This option is not available for modular detectors that wish to maximize their active volume. The ArgonCube light readout system detectors (ArCLights) are large-area thin-wavelength-shifting (WLS) panels that can operate in highly proximate modular detectors and within the electric field. The WLS plastic forming the bulk structure of the ArCLight has Tetraphenyl Butadiene (TPB) and sheets of dichroic mirror layered across its surface. It is coupled to a set of six silicon photomultipliers (SiPMs). This publication compares TPB coating techniques for large surface areas and describes quality control methods for large-scale production. Full article
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<p>Diagram of an ArCLight with an example of a VUV photon travelling through the TPB and shifting to blue (peak at 430 <math display="inline"><semantics> <mi mathvariant="normal">n</mi> </semantics></math><math display="inline"><semantics> <mi mathvariant="normal">m</mi> </semantics></math>) to then pass into the dichroic mirror. The photon shifts to green (peak at 490 <math display="inline"><semantics> <mi mathvariant="normal">n</mi> </semantics></math><math display="inline"><semantics> <mi mathvariant="normal">m</mi> </semantics></math>) inside the WLS plastic. The green photons travelling in the plastic are eventually detected by the SiPM.</p>
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<p>Microscopic images of the TPB layer achieved with airbrush (<b>left</b>) and evaporation deposition (<b>right</b>). Both images are magnified by a factor of 500.</p>
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<p>Image of the ArCLight TPB coating chamber. In the vacuum chamber, the TPB support plate is attached to the heating table. The aluminium plate holder, on which the cooling plate rests, hangs above it.</p>
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<p>A TPB evaporation cycle overview, illustrating the chamber pressure (blue), the temperatures of the dichroic mirror (green) and the turning on and off of the heating table (red). The first blue peak represents the moment the chamber is opened to place the dichroic mirror inside. The pumping process lowers the pressure before the heating table is activated. Once the heater is turned on, water and TPB evaporate, leading to increased pressure within the chamber. The temperature of the foil increases as the heating table operates.</p>
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<p>A bare WLS plate EJ280 with prepared threads for SiPM mounting (<b>left</b>). ArCLight after attachment of the TPB-coated foil and edge mirrors (<b>right</b>).</p>
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<p>Example of the two different crystals observed on the coated ArCLight. The magnification of both images is the same.</p>
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<p>The black box used to scan ArCLights. The movable LED that produces light during scanning is shown on the top.</p>
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<p>Conceptual sketch of the scanning procedure of an ArCLight.</p>
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<p>The detected number of p.e.s in a high-resolution scan by each of the six SiPM channels for the LED at a distance of 20 <math display="inline"><semantics> <mi mathvariant="normal">m</mi> </semantics></math><math display="inline"><semantics> <mi mathvariant="normal">m</mi> </semantics></math>, with the SiPMs positioned on the x-axis. The colour scale represents the detected number of photoelectrons (p.e.s). The absolute signal strength is arbitrary and depends on the LED light emission power, which is kept constant for the different scans.</p>
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<p>Example scan of an ArCLight with corrected light yields using monitoring SiPMs. The scan measures the total photoelectrons of 27 × 29 positions.</p>
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<p>For each ArCLight, the means of the collected p.e.s for every position are added up to a total amount of p.e.s collected per scan. The different performances of the ArCLight are shown based on the total p.e.s measured per scan. The error bars are estimated based on the largest difference observed between scans of the same ArCLight.</p>
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16 pages, 12424 KiB  
Article
Studying the Constitutive Model of Damage for a Stainless Steel Argon–Oxygen Decarburization Slag Mixture
by Liuyun Huang, Zhuxin Lan, Guogao Wei, Yuliang Chen and Tun Li
Appl. Sci. 2024, 14(21), 10006; https://doi.org/10.3390/app142110006 - 1 Nov 2024
Viewed by 512
Abstract
The purpose of this study was to fully explore the mechanical properties of five different doses of an Argon–Oxygen Decarburization slag mixture in an unconfined compressive strength test. The peak stress, elastic modulus, and stress–strain curve of the mixture were studied for 90 [...] Read more.
The purpose of this study was to fully explore the mechanical properties of five different doses of an Argon–Oxygen Decarburization slag mixture in an unconfined compressive strength test. The peak stress, elastic modulus, and stress–strain curve of the mixture were studied for 90 days. Based on the experimental data and according to the theory of damage mechanics, the concept of damage threshold (t) was introduced to construct a damage constitutive model. Referring to the damage threshold of concrete, that of the mixture was determined to be 0.7 times higher than the peak strain, and the correlation coefficient between the established model and the test curve was above 0.85. These results indicate that the addition of AOD slag and fly ash can cause hydration reactions, increase the quantity of hydration products, and enhance the peak stress and elastic modulus of the mixture. The maximum increases were 94.9% and 43.1%, respectively. Parameters a and b reflect the peak stress and brittleness of the mixture, respectively. The incorporation of Argon–Oxygen Decarburization slag can make the mixture less brittle and improve its properties. The incorporation of Argon–Oxygen Decarburization slag can protect the mixture from damage. The maximum decrease is 40.2%. Full article
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<p>XRD pattern of AOD.</p>
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<p>Grain size frequency and cumulative grain size distribution curves. (<b>a</b>) AOD. (<b>b</b>) Fly ash.</p>
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<p>The shapes of the specimens during the compression process. (<b>a</b>) Initial loading stage. (<b>b</b>) Crack germination stage. (<b>c</b>) Crack propagation stage. (<b>d</b>) After destruction.</p>
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<p>Stress–strain curve of AOD slag.</p>
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<p>Relationship between peak stress and dosage.</p>
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<p>Relationship between elastic modulus and dosage.</p>
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<p>XRD patterns of hydration products in mixtures at 90 days.</p>
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<p>SEM micro-morphology of AOD slag with different dosages. (<b>a</b>,<b>b</b>) A-0; (<b>c</b>,<b>d</b>) A-3; and (<b>e</b>,<b>f</b>) A-12.</p>
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<p>SEM micro-morphology of AOD slag with different dosages. (<b>a</b>,<b>b</b>) A-0; (<b>c</b>,<b>d</b>) A-3; and (<b>e</b>,<b>f</b>) A-12.</p>
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<p>Comparison of test and model curves under different damage thresholds. (<b>a</b>) A-0; (<b>b</b>) A-3; (<b>c</b>) A-6; (<b>d</b>) A-9; and (<b>e</b>) A-12.</p>
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<p>Effect of parameters on damage constitutive model curves. (<b>a</b>) <span class="html-italic">a</span>; (<b>b</b>) <span class="html-italic">b</span>.</p>
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<p>Relationship between parameters and substitution rate. (<b>a</b>) <span class="html-italic">a</span>; (<b>b</b>) <span class="html-italic">b</span>.</p>
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<p>Test and model curves. (<b>a</b>) A-0; (<b>b</b>) A-3; (<b>c</b>) A-6; (<b>d</b>) A-9; and (<b>e</b>) A-12.</p>
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<p>Mixture damage variables. (<b>a</b>) Mixture damage variable curve; (<b>b</b>) damage growth rate.</p>
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21 pages, 3075 KiB  
Article
Façade Retrofit Strategies for Energy Efficiency Improvement Considering the Hot Climatic Conditions of Saudi Arabia
by Wesam Rababa and Omar S. Asfour
Appl. Sci. 2024, 14(21), 10003; https://doi.org/10.3390/app142110003 - 1 Nov 2024
Viewed by 787
Abstract
Saudi Arabia faces significant challenges in managing the rising energy consumption in buildings driven largely by its hot climatic conditions. As a result, retrofitting building facades to enhance energy efficiency has become a critical strategy. This study assesses the effectiveness of various façade [...] Read more.
Saudi Arabia faces significant challenges in managing the rising energy consumption in buildings driven largely by its hot climatic conditions. As a result, retrofitting building facades to enhance energy efficiency has become a critical strategy. This study assesses the effectiveness of various façade retrofit strategies in reducing cooling electricity consumption using a real-time case study in Dhahran, Saudi Arabia. The strategies explored include external wall upgrades, window replacements, and installation of shading devices. Each strategy was evaluated individually, considering the reduction in heat gains, cooling load, and payback period as key performance indicators. To further maximize energy efficiency, these strategies were also analyzed in combination using the genetic algorithm optimization method, yielding 224 possible facade configurations. The optimal solution included the use of an External Thermal Insulation Composite System (ETCIS) in walls, louvers in windows, and low-emissivity coating with Argon gas-filled glazing, achieving a cooling energy reduction of approximately 16% and a payback period of 14.8 years. This study provides several recommendations for improving the efficiency of retrofitting building façades in hot climatic conditions. Full article
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<p>Methodology framework.</p>
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<p>(<b>a</b>): Ground floor plan of the examined case study, (<b>b</b>,<b>c</b>): External view of the examined case study in the field and in DesignBuilder.</p>
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<p>The water-cooled chiller system in the examined case study.</p>
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<p>Heat gains (<b>left</b>) and cooling electricity consumption (<b>right</b>) of the base case.</p>
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<p>Thermography of the base case façade (<b>left</b>) and window (<b>right</b>).</p>
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<p>Percentage of the annual reduction in wall heat gains in the different external wall retrofit strategies (wall heat gains in the base case were 56,650 kWh).</p>
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<p>Percentage of the annual reduction in glazing heat gains in the different window retrofit strategies (glazing heat gains in the base case were 30,118 kWh).</p>
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<p>Percentage of the annual reduction in glazing heat gains in the different shading devices retrofit strategies (glazing heat gains in the base case were 30,118 kWh).</p>
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<p>Optimization analysis results, where red points represent the optimal scenarios.</p>
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16 pages, 2682 KiB  
Article
Argon Ion Implantation as a Method of Modifying the Surface Properties of Wood–Plastic Composites
by Izabela Betlej, Marek Barlak, Karolina Lipska, Piotr Borysiuk and Piotr Boruszewski
Materials 2024, 17(21), 5347; https://doi.org/10.3390/ma17215347 - 31 Oct 2024
Viewed by 543
Abstract
Wood–plastic composites (WPCs) combine the properties of plastics and lignocellulosic fillers. A particular limitation in their use is usually a hydrophobic, poorly wettable surface. The surface properties of materials can be modified using ion implantation. The research involved using composites based on polyethylene [...] Read more.
Wood–plastic composites (WPCs) combine the properties of plastics and lignocellulosic fillers. A particular limitation in their use is usually a hydrophobic, poorly wettable surface. The surface properties of materials can be modified using ion implantation. The research involved using composites based on polyethylene (PE) filled with sawdust or bark (40%, 50%, and 60%). Their surfaces were modified by argon ion implantation in three fluencies (1 × 1015, 1 × 1016, and 1 × 1017 cm−2) at an accelerating voltage of 60 kV. Changes in the wettability, surface energy, and surface colour of the WPCs were analysed. It was shown that argon ion implantation affects the distinct colour change in the WPC surface. The nature of the colour changes depends on the filler used. Implantation also affects the colour balance between the individual variants. Implantation of the WPC surface with argon ions resulted in a decrease in the wetting angle. In most of the variants tested, the most significant effect on the wetting angle changes was the ion fluence of 1 × 1017 cm−2. Implantation of the WPC surface also increased the surface free energy of the composites. The highest surface free energy values were also recorded for the argon ion fluence of 1 × 1017 cm−2. Full article
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<p>General view of the implanter of gaseous ion (<b>a</b>) and the implanted samples on XY table (<b>b</b>).</p>
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<p>Modelled depth profiles for two kinds of polyethylene and three kinds of wood–plastic composites.</p>
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<p>Naked-eye observation results of the surface of the virgin and the implanted samples.</p>
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<p>Changes in the wetting angle values of HDPE- and bark-based WPC composite surfaces depending on the argon ion implantation dose.</p>
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<p>Changes in the wetting angle of the polyethylene surface depending on the argon ion implantation dose.</p>
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<p>Changes in the wetting angle values of HDPE- and sawdust-based WPC composite surfaces depending on the argon ion implantation dose.</p>
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21 pages, 2610 KiB  
Article
Thermal Decomposition and Kinetic Analysis of Amazonian Woods: A Comparative Study of Goupia glabra and Manilkara huberi
by Mark Dany Veloso Junior, Fidel Guerrero, Felipe Moura Araújo da Silva, Glenda Quaresma Ramos, Robert Saraiva Matos, Ștefan Țălu, Dung Nguyen Trong and Henrique Duarte da Fonseca Filho
Fire 2024, 7(11), 390; https://doi.org/10.3390/fire7110390 - 29 Oct 2024
Viewed by 570
Abstract
This study presents a detailed analysis of the thermal degradation and kinetic behavior of two Amazonian wood species, Goupia glabra (cupiúba) and Manilkara huberi (maçaranduba), using thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), Fourier-transform infrared spectroscopy (FTIR-ATR), and direct infusion mass spectrometry (DIMS). [...] Read more.
This study presents a detailed analysis of the thermal degradation and kinetic behavior of two Amazonian wood species, Goupia glabra (cupiúba) and Manilkara huberi (maçaranduba), using thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), Fourier-transform infrared spectroscopy (FTIR-ATR), and direct infusion mass spectrometry (DIMS). Wood samples were subjected to controlled heating rates of 20, 40, and 60 °C/min from 25 to 800 °C under an argon atmosphere. TGA revealed moisture evaporation below 120 °C, with hemicellulose degradation occurring between 220 and 315 °C, cellulose decomposition between 315 and 400 °C, and lignin breakdown over a broader range from 180 to 900 °C. The highest rate of mass loss occurred at 363.99 °C for G. glabra and 360.27 °C for M. huberi at a heating rate of 20 °C/min, with shifts to higher temperatures at faster heating rates. Activation energies were calculated using Arrhenius and Kissinger models, yielding values between 53.46–61.45 kJ/mol for G. glabra and 58.18–62.77 kJ/mol for M. huberi, confirming their stable thermal profiles. DSC analysis identified a significant endothermic peak related to moisture evaporation below 100 °C, followed by two exothermic peaks. For G. glabra, the first exothermic peak appeared at 331.45 °C and the second at 466.08 °C, while for M. huberi, these occurred at 366.41 °C and 466.08 °C, indicating the decomposition of hemicellulose, cellulose, and lignin. Enthalpy values for G. glabra were 12,633.37 mJ and 18,652.66 mJ for the first and second peaks, respectively, while M. huberi showed lower enthalpies of 9648.04 mJ and 14,417.68 mJ, suggesting a higher energy release in G. glabra. FTIR-ATR analysis highlighted the presence of key functional groups in both species, with strong absorption bands in the 3330–3500 cm−1 region corresponding to O-H stretching vibrations, indicative of hydroxyl groups in cellulose and hemicellulose. The 1500–1600 cm−1 region, representing aromatic C=C vibrations, confirmed the presence of lignin. Quantitatively, these results suggest a high content of cellulose and lignin in both species. DIMS analysis further identified polyphenolic compounds and triterpenoids in M. huberi, with major ions at m/z 289 and 409, while G. glabra showed steroidal and polyphenolic compounds with a base peak at m/z 395. These findings indicate the significant presence of bioactive compounds, contributing to the wood’s resistance to microbial degradation. This comprehensive thermal and chemical characterization suggests that both species have potential industrial applications in environments requiring high thermal stability. Full article
(This article belongs to the Special Issue Biomass-Burning)
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<p>Photos of wood chips and powders after using a Willye Super-type knife mill, referring to (<b>a</b>) <span class="html-italic">Goupia glabra</span> Aubl. and (<b>b</b>) <span class="html-italic">Manilkara huberi</span> (Ducke) Standl.</p>
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<p>Two 100× optical microscope images of the transversal direction of the samples: (<b>a</b>) <span class="html-italic">Goupia glabra</span> and (<b>b</b>) <span class="html-italic">Manilkara huberi</span>.</p>
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<p>FTIR spectra from <span class="html-italic">Goupia glabra</span> Aubl. and <span class="html-italic">Manilkara huberi</span> (Ducke) Standl. woods.</p>
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<p>Positive (<b>above</b>) and negative (<b>below</b>) ion mass spectra of the methanol extract of maçaranduba wood.</p>
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<p>MS/MS spectrum of the ion at <span class="html-italic">m</span>/<span class="html-italic">z</span> 289 present in methanol extract of maçaranduba wood.</p>
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<p>Positive (<b>above</b>) and negative (<b>below</b>) ion mass spectra of the methanol extract of <span class="html-italic">Goupia glabra</span> (cupiúba) wood.</p>
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<p>MS/MS spectrum of the ion at <span class="html-italic">m</span>/<span class="html-italic">z</span> 639 present in methanol extract of cupiúba wood.</p>
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<p>(<b>a</b>) TGA and (<b>b</b>) DTG curves of <span class="html-italic">Goupia glabra</span> using different heating rates in an argon atmosphere.</p>
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<p>(<b>a</b>) TGA and (<b>b</b>) DTG curves of <span class="html-italic">Manilkara huberi</span> using different heating rates in an argon atmosphere.</p>
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<p>DSC curves of cupiúba (<span class="html-italic">Goupia glabra</span>) and maçaranduba (<span class="html-italic">Manilkara huberi</span>) a heating rate of 20 °C/min at argon atmosphere.</p>
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<p>Comparative analysis of temperature-dependent properties for <span class="html-italic">Goupia glabra</span> and <span class="html-italic">Manilkara huberi</span>, showing distinct slopes.</p>
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18 pages, 9114 KiB  
Article
Two-Dimensional X-Ray Diffraction (2D-XRD) and Micro-Computed Tomography (Micro-CT) Characterization of Additively Manufactured 316L Stainless Steel
by Puskar Pathak, Goran Majkic, Timmons Erickson, Tian Chen and Venkat Selvamanickam
Metals 2024, 14(11), 1232; https://doi.org/10.3390/met14111232 - 29 Oct 2024
Viewed by 589
Abstract
In-depth quality assessment of 3D-printed parts is vital in determining their overall characteristics. This study focuses on the use of 2D X-Ray diffraction (2D-XRD) and X-Ray micro-computed tomography (micro-CT) techniques to evaluate the crystallography and internal defects of 316L SS parts fabricated by [...] Read more.
In-depth quality assessment of 3D-printed parts is vital in determining their overall characteristics. This study focuses on the use of 2D X-Ray diffraction (2D-XRD) and X-Ray micro-computed tomography (micro-CT) techniques to evaluate the crystallography and internal defects of 316L SS parts fabricated by the powder-based direct energy deposition (DED) technique. The test samples were printed in a controlled argon environment with variable laser power and print speeds, using a customized deposition pattern to achieve a high-density print (>99%). Multiple features, including hardness, elastic modulus, porosity, crystallographic orientation, and grain morphology and size were evaluated as a function of print parameters. Micro-CT was used for in-depth internal defect analysis, revealing lack-of-fusion and gas-induced (keyhole) pores and no observable micro-cracks or inclusions in most of the printed body. Some porosity was found mostly concentrated in the initial layers of print and decreased along the build direction. 2D-XRD was used for phase analysis and grain size determination. The phase analysis revealed single phase γ-austenitic FCC phase without any detectable presence of the δ-ferrite phase. A close correlation was found between Electron Backscatter Diffraction (EBSD) and 2D-XRD results on the average size distribution and the crystallographic orientation of grains in the sample. This work demonstrates the fast and reliable as-printed crystallography analysis using 2D-XRD compared to the EBSD technique, with potential for in-line integration. Full article
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<p>(<b>a</b>) SEM image of 316L SS powder with numbered locations of EDS analysis. (<b>b</b>) 316L SS particle size distribution.</p>
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<p>A schematic of the customized deposition pattern used in this study.</p>
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<p>(<b>a</b>) SEM micrograph of the S8 printed sample; (<b>b</b>) micrograph of the center area in (<b>a</b>) at higher magnification with locations of EDS analysis.</p>
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<p>EBSD orientation maps of S2 sample (<b>a</b>), S4 sample (<b>c</b>), and S8 sample (<b>e</b>) along the build direction and (<b>b</b>,<b>d</b>,<b>f</b>) corresponding to {100}, {110}, and {111} FCC-iron pole figures, respectively.</p>
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<p>Rocking curve 12-frame stitched 2D-XRD patterns of 2θ vs. χ (<b>a</b>,<b>b</b>) S2 top and bottom sections; (<b>c</b>,<b>d</b>) S4 top and bottom sections; (<b>e</b>,<b>f</b>) S8 top and bottom sections, respectively.</p>
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<p>Pole figure of {111} peak. (<b>a</b>,<b>b</b>) S2 top and bottom sections; (<b>c</b>,<b>d</b>) S4 top and bottom sections; (<b>e</b>,<b>f</b>) S8 top and bottom sections, respectively.</p>
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<p>(<b>Left</b>) X-Ray micro-CT-reconstructed 3D images showing the distribution of the pores along the build height of all S2, S4, and S8 samples. (<b>Right</b>) a magnified higher resolution region of interest (ROI) scan at the top, middle, and bottom sections of the S8 sample, revealing the morphology and distribution of porosity.</p>
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<p>Porosity variations in S2, S4, and S8 samples along the build height.</p>
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<p>(<b>a</b>) Micro-hardness variation along the build distance of samples. (<b>b</b>) Samples’ average indentation hardness (HV) and indentation elastic modulus (E*) plot.</p>
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19 pages, 10777 KiB  
Article
Electrochemical Impedance Spectroscopy Study of Ceria- and Zirconia-Based Solid Electrolytes for Application Purposes in Fuel Cells and Gas Sensors
by Małgorzata Dziubaniuk, Robert Piech and Beata Paczosa-Bator
Materials 2024, 17(21), 5224; https://doi.org/10.3390/ma17215224 - 26 Oct 2024
Viewed by 591
Abstract
In this study, the structural and electrochemical properties of commercial powders of the nominal compositions Ce0.8Gd0.2O1.9, Sc0.1Ce0.01Zr0.89O1.95, and Sc0.09Yb0.01Zr0.9O1.95 were investigated. The [...] Read more.
In this study, the structural and electrochemical properties of commercial powders of the nominal compositions Ce0.8Gd0.2O1.9, Sc0.1Ce0.01Zr0.89O1.95, and Sc0.09Yb0.01Zr0.9O1.95 were investigated. The materials are prospective candidates to be used in electrochemical devices, i.e., gas sensors and fuel cells. Based on a comparison of the EIS spectra in different atmospheres (synthetic air, 3000 ppm NH3 in argon, 10% H2 in argon), the reactions on the three-phase boundaries were proposed, as well as the conduction mechanisms of the electrolytes were described. The Ce0.8Gd0.2O1.9 material is a mixed ionic–electronic conductor, which makes it suitable for anode material in fuel cells. Moreover, it exhibits an apparent and reversible response for ammonia, indicating the possibility of usage as an NH3 gas-sensing element. In zirconia-based materials, electrical conduction is realized by oxygen ion carriers. Among them, the most promising from an applicative point of view seems to be Sc0.09Yb0.01Zr0.9O1.95, showing a high, reversible reaction with hydrogen. Full article
(This article belongs to the Section Smart Materials)
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<p>The comparison of green bodies (bottom row) with sintered specimens (upper row) in order: GDC, ScCeSZ, and ScYbSZ.</p>
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<p>Experimental set for EIS measurements.</p>
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<p>The specimen holder for EIS measurements.</p>
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<p>The XRD patterns with labeled peaks characteristic for cubic phase recorded for sintered samples (a) GDC, (b) ScCeSZ, (c) ScYbSZ.</p>
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<p>Surface morphology of sintered samples presented on SEM images at different magnifications for (<b>1a</b>,<b>1b</b>) GDC, (<b>2a</b>,<b>2b</b>) ScCeSZ, and (<b>3a</b>,<b>3b</b>) ScYbSZ.</p>
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<p>Evolution of EIS spectrum of GDC in H<sub>2</sub>-containing atmosphere with rising temperature; red line obtained using presented equivalent circuits for parameters values collated in tables at temperatures (<b>a</b>) 200 °C, (<b>b</b>) 500 °C, and (<b>c</b>) 550 °C.</p>
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<p>Changes in electrical properties caused by exposition on ammonia- and hydrogen-containing atmospheres presented as Nyquist spectra from EIS at 450 °C for (<b>1</b>) GDC, (<b>2</b>) ScCeSZ, and (<b>3</b>) ScYbSZ; column (<b>b</b>) contains magnified high-frequency bottom-right corner region of spectra from (<b>a</b>) column.</p>
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<p>Summary of electrochemical response and reversibility of the probes for exposition on ammonia- and hydrogen-containing atmospheres presented in Arrhenius plots with calculated energy of activation values for (<b>1</b>) GDC, (<b>2</b>) ScCeSZ, and (<b>3</b>) ScYbSZ.</p>
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22 pages, 6802 KiB  
Article
Effect of Deposition Temperature on Zn Interstitials and Oxygen Vacancies in RF-Sputtered ZnO Thin Films and Thin Film-Transistors
by Sasikala Muthusamy, Sudhakar Bharatan, Sinthamani Sivaprakasam and Ranjithkumar Mohanam
Materials 2024, 17(21), 5153; https://doi.org/10.3390/ma17215153 - 23 Oct 2024
Viewed by 572
Abstract
ZnO thin films were deposited using RF sputtering by varying the argon:oxygen gas flow rates and substrate temperatures. Structural, optical and electrical characterization of ZnO thin films were systematically carried out using X-Ray diffraction (XRD), scanning electron microscopy (SEM), UV–visible spectroscopy, X-Ray photoelectron [...] Read more.
ZnO thin films were deposited using RF sputtering by varying the argon:oxygen gas flow rates and substrate temperatures. Structural, optical and electrical characterization of ZnO thin films were systematically carried out using X-Ray diffraction (XRD), scanning electron microscopy (SEM), UV–visible spectroscopy, X-Ray photoelectron spectroscopy (XPS) and Hall measurements. Film deposited at room temperature and annealed at 300 °C exhibited low O2 incorporation with localized defects and a high percentage of Zn interstitials. A large crystalline size and fewer grain boundaries resulted in a high Hall mobility of 46.09 cm2/V-s Deposition at higher substrate temperatures resulted in improvement in O2 incorporation through the annihilation of localized defects and decrease in oxygen vacancies and Zn interstitials. Urbach tails within the bandgap were identified using the absorption spectrum and compared with the % defects from XPS. Bottom-gate thin-film transistors were subsequently fabricated on a SiO2/p-Si substrate using the combination of RF sputtering, wet etching and photolithography. Variation in the substrate temperature showed performance enhancement in terms of the leakage current, threshold voltage, sub-threshold swing and ION/IOFF ratio. Thin-film transistor (TFT) devices deposited at 300 °C resulted in an O2-rich surface through chemisorption, which led to a reduction in the leakage current of up to 10−12 A and a 10-fold reduction in the sub-threshold swing (SS) from 30 V to 2.8 V. Further TFT optimization was carried out by reducing the ZnO thickness to 50 nm, which resulted in a field-effect mobility of 1.1 cm2/V-s and ION/IOFF ratio of 105. Full article
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<p>Schematic structure of ZnO TFT.</p>
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<p>GIXRD spectra of ZnO thin-film Samples A, B and C with different Ar:O<sub>2</sub> flow rates.</p>
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<p>GIXRD spectra of samples with different substrate temperatures.</p>
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<p>SEM image of ZnO thin-film Samples (<b>a</b>) A, (<b>b</b>) B, (<b>c</b>) C (Red arrows represents small voids between the crystallites), (<b>d</b>) D and (<b>e</b>) E.</p>
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<p>Tauc plot of Samples C, D and E.</p>
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<p>ln α vs. energy bandgap (E<sub>g</sub>).</p>
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<p>Core-level spectrum of Zn 2P peak.</p>
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<p>(<b>a</b>) XPS spectrum of O 1s peak—Sample C. (<b>b</b>) XPS spectrum of O 1s peak—Sample D. (<b>c</b>) XPS spectrum of O 1s peak—Sample E, with the following color representations: Red—Original XPS data, Green—O Vacancies component and Burgundy—O 1s peak component.</p>
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<p>(<b>a</b>) Zn LMM Auger peak—Sample C. (<b>b</b>) Zn LMM Auger peak—Sample D. (<b>c</b>) Zn LMM Auger peak—Sample E, with the following color representations: Red—Original XPS data, Green—Zn interstitials component and Burgundy—Zn-O component.</p>
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<p>Plot of Zn interstitials, O<sub>2</sub> vacancy and mobility of ZnO thin films.</p>
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<p>(<b>a</b>) Drain characteristics of TFT Device C1. (<b>b</b>) Drain characteristics of TFT Device D1. (<b>c</b>) Drain characteristics of TFT Device E1.</p>
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<p>(<b>a</b>) Drain characteristics of TFT Device C1. (<b>b</b>) Drain characteristics of TFT Device D1. (<b>c</b>) Drain characteristics of TFT Device E1.</p>
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<p>(<b>a</b>) Transfer characteristics of TFT Device C1. (<b>b</b>) Transfer characteristics of TFT Device D1. (<b>c</b>) Transfer characteristics of TFT Device E1.</p>
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<p>(<b>a</b>) Transfer characteristics of TFT Device C1. (<b>b</b>) Transfer characteristics of TFT Device D1. (<b>c</b>) Transfer characteristics of TFT Device E1.</p>
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<p>Transfer characteristics of ZnO TFT with variation in channel layer thickness.</p>
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