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Ceramics, Volume 7, Issue 2 (June 2024) – 27 articles

Cover Story (view full-size image): Polymer-infiltrated ceramic network (PICN) composites were prepared using direct ink writing, with the primary goal of studying the relationship between manufacturing geometry and mechanical properties. The mechanical properties were investigated through compression testing and digital image correlation analysis. The results revealed that the compression strength of PICN pieces was significantly higher than that of ceramic scaffolds without polymer infiltration. View this paper
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19 pages, 18681 KiB  
Article
Influence of Nanoceramic-Plated Waste Carbon Fibers on Alkali-Activated Mortar Performance
by Matteo Sambucci, Yazeed A. Al-Noaimat, Seyed Mostafa Nouri, Mehdi Chougan, Seyed Hamidreza Ghaffar and Marco Valente
Ceramics 2024, 7(2), 821-839; https://doi.org/10.3390/ceramics7020054 - 19 Jun 2024
Viewed by 720
Abstract
Waste carbon fibers as reinforcing elements in construction materials have recently gained increasing interest from researchers, providing outstanding strength performance and a lower environmental footprint compared to virgin fibers. Combination with cement-free binders, namely alkali-activated materials, is becoming increasingly important for sustainable development [...] Read more.
Waste carbon fibers as reinforcing elements in construction materials have recently gained increasing interest from researchers, providing outstanding strength performance and a lower environmental footprint compared to virgin fibers. Combination with cement-free binders, namely alkali-activated materials, is becoming increasingly important for sustainable development in the construction industry. This paper presents results relating to the potential use of waste carbon fibers in alkali-activated mortars. The waste carbon fiber fraction utilized in this research is difficult to integrate as reinforcement in ceramic–cementitious matrices due to its agglomerated form and chemical inertness. For this reason, a nanoceramic coating pretreatment based on nanoclay has been implemented to attempt improvements in terms of deagglomeration, dispersibility, and compatibility with alkali-activated materials. After chemical–physical and microstructural analysis on the nanoclay-plated fibers (including X-ray diffraction, IR spectroscopy, contact angle measurements, and electron microscopy) mortars were produced with four different dosages of treated and untreated waste fibers (0.25 wt.%, 0.5 wt.%, 0.75 wt.%, and 1 wt.%). Mechanical tests and fractographic investigations were then performed. The nanoclay coating interacts compatibly with the waste carbon fibers and increases their degree of hydrophilicity to improve their deagglomeration and dispersion. Compared to the samples incorporating as-received fillers, the addition of nanoclay-coated fibers improved the strength behavior of the mortars, recording a maximum increase in flexural strength of 19% for a fiber content of 0.25 wt.%. This formulation is the only one providing an improvement in mechanical behavior compared to unreinforced mortar. Indeed, as the fibrous reinforcement content increases, the effect of the nanoclay is attenuated by mitigating the improvement in mechanical performance. Full article
(This article belongs to the Special Issue Research Progress in Ceramic Coatings)
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<p>Photograph of WCFs used in this study.</p>
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<p>Photograph of ANC used in this study.</p>
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<p>Preparation of WCF–ANC slurry for fiber treatment.</p>
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<p>Procedure for obtaining test samples of WCF treated with ANC: (<b>a</b>) placing WCF–ANC slurry on watch glass for drying, (<b>b</b>) oven-dried sample, and (<b>c</b>) sample extraction.</p>
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<p>XRD pattern of (<b>a</b>) as-received WCF, (<b>b</b>) ANC, and (<b>c</b>) WCF after treatment with ANC.</p>
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<p>FTIR analysis of ANC and WCF after treatment with ANC.</p>
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<p>WCA profile for (<b>a</b>) bare WCF and (<b>b</b>) WCF treated with ANC.</p>
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<p>SEM micrographs of WCF coated with ANC.</p>
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<p>EDS element analysis of WCF coated with ANC.</p>
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<p>Effect of WCF addition and ANC treatment of fiber on flexural strength of alkali-activated mortars.</p>
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<p>Effect of WCF addition and ANC treatment of fiber on compression strength of alkali activated mortars.</p>
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<p>Effect of ANC-treated WCF addition on the flexural behavior of AAM (present work) and cement-based [<a href="#B13-ceramics-07-00054" class="html-bibr">13</a>] mortars.</p>
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<p>SEM analysis of alkali-activated mortar with unconditioned WCF (<span class="html-italic">WCF0.5</span> sample): (<b>a</b>) fibrous agglomerate inside the matrix and (<b>b</b>) detail of the inner microstructure of the WCF cluster. Dotted circle highlights a fly ash particle trapped between the fibers.</p>
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<p>SEM interface analysis between the WCF–ANC and AAM matrix. The micrographs refer to the <span class="html-italic">WCF0.25-ANC</span> sample (optimal mix).</p>
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14 pages, 4561 KiB  
Article
Mullite 3D Printed Humidity Sensors
by Yurii Milovanov, Arianna Bertero, Bartolomeo Coppola, Paola Palmero and Jean-Marc Tulliani
Ceramics 2024, 7(2), 807-820; https://doi.org/10.3390/ceramics7020053 - 10 Jun 2024
Cited by 1 | Viewed by 983
Abstract
Mullite substrates with two different porosities were 3D printed, and tested as humidity sensors. To evaluate the effects of porosity on humidity sensitivity, the samples were sintered at 1400 °C (Sensor 1) and 1450 °C (Sensor 2). The sensors were tested in a [...] Read more.
Mullite substrates with two different porosities were 3D printed, and tested as humidity sensors. To evaluate the effects of porosity on humidity sensitivity, the samples were sintered at 1400 °C (Sensor 1) and 1450 °C (Sensor 2). The sensors were tested in a range from 0% to 85% relative humidity (RH) at room temperature. When exposed to water vapor at room temperature, the impedance value dropped down from 155 MΩ under dry air to 480 kΩ under 85 RH% for Sensor 1 and from 115 MΩ under dry air to 410 kΩ for Sensor 2. In addition, response time and recovery time were below 2 min, whatever the firing temperature, when RH changed from 0% to 74%. Finally, tests carried out involving ammonia, methane, carbon dioxide and nitrogenous oxide, as well as ethanol and acetone, showed no interference. Full article
(This article belongs to the Special Issue Innovative Manufacturing Processes of Silicate Materials)
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<p>Schematic diagram of thermal de-binding and sintering cycles.</p>
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<p>XRD patterns of the as-received mullite (m: mullite, c: cristobalite, A: aluminum oxide, a: corundum).</p>
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<p>Optical micrograph of the 3D printed mullite sensor with screen-printed interdigitated electrodes, sintered at 1400 °C for 60 min.</p>
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<p>FE-SEM micrographs of the 3D printed mullite sintered at 1400 °C (<b>a</b>,<b>c</b>) and 1450 °C (<b>b</b>,<b>d</b>) for 1 h.</p>
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<p>FE-SEM micrographs of the 3D printed mullite sintered at 1400 °C (<b>a</b>,<b>c</b>) and 1450 °C (<b>b</b>,<b>d</b>) for 1 h.</p>
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<p>Response as a function of relative humidity value for mullite Sensor 1, sintered at 1400 °C: (<b>a</b>) impedance variation and (<b>b</b>) phase variation.</p>
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<p>Response as a function of relative humidity values for mullite Sensor 2, sintered at 1450 °C: (<b>a</b>) impedance variation and (<b>b</b>) phase variation.</p>
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<p>Responses of Sensors 1 and 2 at different RH values (in the range 26–85% RH).</p>
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<p>Repeatability measurements of mullite Sensors 1 and 2 under 85% RH: (<b>a</b>) impedance variation and (<b>b</b>) phase variation.</p>
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<p>Calibration curves of mullite Sensor 1 and mullite Sensor 2 towards different RH values at room temperature.</p>
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11 pages, 3903 KiB  
Article
Fabrication of Dicarboxylic-Acid- and Silica-Substituted Octacalcium Phosphate Blocks with Stronger Mechanical Strength
by Yuki Sugiura, Yasuko Saito, Etsuko Yamada and Masanori Horie
Ceramics 2024, 7(2), 796-806; https://doi.org/10.3390/ceramics7020052 - 7 Jun 2024
Cited by 1 | Viewed by 981
Abstract
Octacalcium phosphate (OCP) is an attractive base material to combine into components developed for medical purposes, especially those used in bone replacement procedures, not only because of its excellent biocompatibility but also because of its ability to intercalate with multiple types of molecular [...] Read more.
Octacalcium phosphate (OCP) is an attractive base material to combine into components developed for medical purposes, especially those used in bone replacement procedures, not only because of its excellent biocompatibility but also because of its ability to intercalate with multiple types of molecular layers such as silica, dicarboxylic acid, and various cations. On the other hand, there are no examples of simultaneous substituting for several different compounds on OCPs. Therefore, in this study, the physical and mechanical strength (DTS: diametral tensile strength) of OCPs substituted with both silica and dicarboxylic acids (thiomalate: SH-malate) were evaluated. By optimizing the amount of SH-malate, we were able to prepare a block consisting of OCPs with both silica and SH-malate supported in the interlayer. The composition of the OCP-based compound comprising this block was Ca8Na1.07H6.33(PO4)4.44(SiO4)1.32(SH-malate)2.40·nH2O. Interestingly, the low mechanical strength, a drawback of silica-substituted OCP blocks, could be improved by dicarboxylic acid substituting. The dicarboxylic acid addition increased the mechanical strength of silica-substituted OCP blocks, and the acid successfully incorporated into the interlayer, even with the presence of silica. These results are expected to advance the creation of better silica-substituted OCPs and improved bone replacement materials. Full article
(This article belongs to the Special Issue Innovative Manufacturing Processes of Silicate Materials)
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Figure 1
<p>Photographs of the set blocks with different SH-malate amounts. (<b>a</b>) OCP-silica block as reference. (<b>b</b>) SH-malate: 0.00 g. (<b>c</b>) SH-malate: 0.15 g. (<b>d</b>) SH-malate: 0.30 g. (<b>e</b>) SH-malate: 0.45 g. (<b>f</b>) SH-malate: 0.60 g.</p>
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<p>XRD patterns of the set blocks. (<b>a</b>) Wide range. (<b>b</b>) Small angle. Green broken line: OCP-SH-malate <span class="html-italic">d</span>(100)’ peak. Red dotted line: OCP <span class="html-italic">d</span>(100) peak.</p>
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<p>FT-IR spectra of OCP-silica:SH-malate block with OCP–silica and OCP-SH-malate reference for facilitate comparison. (<b>a</b>) Wide range. (<b>b</b>) Hydrous. Blue band: silanol vibration. Red broken lines: -COOH vibration. Green dotted line: HPO<sub>4</sub> vibration [<a href="#B39-ceramics-07-00052" class="html-bibr">39</a>].</p>
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<p><sup>31</sup>P solid-state NMR spectra of OCP-silica:SH-malate block with conventional OCP, OCP-silica block, and OCP-silica powder for facilitate comparison. Broken lines corresponded each PO<sub>4</sub> state. Dark blue broken line: PO<sub>4</sub> of OCP-silica block state [<a href="#B35-ceramics-07-00052" class="html-bibr">35</a>,<a href="#B40-ceramics-07-00052" class="html-bibr">40</a>].</p>
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<p>DTS values of the set blocks with different SH-malate amounts. *: <span class="html-italic">p</span> &lt; 0.05.</p>
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<p>SEM micrographs of OCP-silica:SH-malate block and reference materials in 0.5 mm and 10 μm, respectively. (<b>a</b>,<b>b</b>) OCP-silica fabricated from MCPM-DCPD-Na<sub>2</sub>SiO<sub>3</sub> system. (<b>c</b>,<b>d</b>) OCP-silica fabricated from CaCO<sub>3</sub>-H<sub>3</sub>PO<sub>4</sub>-Na<sub>2</sub>SiO<sub>3</sub>. (<b>e</b>,<b>f</b>) OCP-silica:SH-malate block.</p>
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<p>Evaluation results of OCP-silica:succinate block fabrication. (<b>a</b>) Photographs of the set blocks with different succinate amounts. (<b>b</b>) Wide-range XRD patterns of the set blocks with different succinate amounts. (<b>c</b>) Small-angle XRD patterns of the set blocks with different succinate amounts. Green broken line: OCP-SH-malate <span class="html-italic">d</span>(100)’ peak. Red dotted line: OCP <span class="html-italic">d</span>(100) peak. (<b>d</b>) DTS values of the set blocks with different succinate amounts. *: <span class="html-italic">p</span> &lt; 0.05.</p>
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19 pages, 10793 KiB  
Article
CaCO3-Infused Carbon Fiber Aerogels: Synthesis and Characterization
by Cristina Mosoarca, Iosif Hulka, Pavel Șchiopu, Florina S. Rus and Radu Bănică
Ceramics 2024, 7(2), 777-795; https://doi.org/10.3390/ceramics7020051 - 6 Jun 2024
Viewed by 1233
Abstract
Carbon aerogels represent a distinctive category of high surface area materials derived from sol-gel chemistry. Functionalizing these aerogels has led to the development of composite aerogels with the potential for a wider range of applications. In this study, the technique of lyophilization was [...] Read more.
Carbon aerogels represent a distinctive category of high surface area materials derived from sol-gel chemistry. Functionalizing these aerogels has led to the development of composite aerogels with the potential for a wider range of applications. In this study, the technique of lyophilization was employed to fabricate aerogel composites consisting of inorganic salts and cellulosic fibers. Cellulose carbonization can occur through chemical dehydration by heat treatment in an inert atmosphere. X-ray diffraction analysis spectra and scanning electron microscopy images indicate that the formed polymeric composites contain partially carbonized cellulose fibers, amorphous carbon, and calcium carbonates. CaCO3 primarily forms through the reaction of CaCl2, which moistens cellulose or amorphous carbon fibers with CO2 in ammonia fumes. The water loss in 3D structures was analyzed using thermogravimetric analysis, Fourier Transform Infrared Spectroscopy, and ultraviolet-visible-near-infrared spectroscopy. Depending on the synthesis method, 3D structures can be created from partially or completely dehydrated cellulose fibers. The aerogels were examined for their ability to support the growth of bacterial biofilm and then adorned with metal silver and AgCl to produce bactericidal products. Due to their open pores and CaCO3 content, these aerogels can serve as durable and environmentally friendly thermal insulators with bactericidal properties, as well as a medium for absorbing acidic gases. Full article
(This article belongs to the Special Issue Advances in Ceramics, 2nd Edition)
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<p>Workflow representation of sample synthesis.</p>
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<p>(<b>a</b>) XRD spectrum for samples C1–C6; (<b>b</b>) XRD spectrum for C4A and C5A.</p>
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<p>EDX spectra and the atomic ratio of C:O and Ca:Cl corresponding to samples C1–C6.</p>
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<p>Photographic images of C4A and C5A samples before and after washing the Ag-decorated aerogel with distilled water.</p>
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<p>SEM micrographs for (<b>a</b>) C1, (<b>b</b>) C2, (<b>c</b>) C3, (<b>d</b>) C5, (<b>e</b>) C5, (<b>f</b>) C6, (<b>g</b>) C4A, (<b>h</b>) C5A samples.</p>
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<p>(<b>a</b>) TG/DTA and comparative DRS spectra (<b>b</b>) C1 and C4; (<b>c</b>) C2 and C5; (<b>d</b>) C3 and C6 samples.</p>
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<p>Detailed FT−IR spectra of the obtained C1–C6 aerogels.</p>
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<p>Live/Dead™ stained (<b>a</b>) C5B and (<b>b</b>) C5AB aerogels. Viable bacteria stained with SYTO 9 are represented by green fluorescence, while dead or compromised bacterial are depicted by orange fluorescence (Propidium Iodide); Concanavalin A-stained polysaccharides—green (ConA), matrix proteins—red (SYPROTM RUBY) for samples (<b>c</b>) C5B and (<b>d</b>) C5AB; SEM images of (<b>e</b>) C5B and (<b>f</b>) C5AB samples; (<b>g</b>) EDX spectra of C5B and C5AB samples.</p>
Full article ">Figure 8 Cont.
<p>Live/Dead™ stained (<b>a</b>) C5B and (<b>b</b>) C5AB aerogels. Viable bacteria stained with SYTO 9 are represented by green fluorescence, while dead or compromised bacterial are depicted by orange fluorescence (Propidium Iodide); Concanavalin A-stained polysaccharides—green (ConA), matrix proteins—red (SYPROTM RUBY) for samples (<b>c</b>) C5B and (<b>d</b>) C5AB; SEM images of (<b>e</b>) C5B and (<b>f</b>) C5AB samples; (<b>g</b>) EDX spectra of C5B and C5AB samples.</p>
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<p>SEM micrograph of the C4A sample.</p>
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<p>(<b>a</b>) SEM micrograph of the C5A sample at high magnification; (<b>b</b>) SEM micrograph of the C5A sample at lower magnification.</p>
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<p>(<b>a</b>) SEM micrograph of the C5A sample at high magnification; (<b>b</b>) SEM micrograph of the C5A sample at lower magnification.</p>
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<p>SEM images and EDX spectra of particles collected from liquid culture medium of C5AB sample.</p>
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18 pages, 6817 KiB  
Article
Investigation of Variability of Flaw Strength Distributions on Brittle SiC Ceramic
by Jacques Lamon
Ceramics 2024, 7(2), 759-776; https://doi.org/10.3390/ceramics7020050 - 4 Jun 2024
Viewed by 669
Abstract
The present paper investigates flaw strength distributions established using various flexural tests on batches of SiC bar test specimens, namely four-point bending as well as three-point bending tests with different span lengths. Flaw strength is provided by the elemental stress operating on the [...] Read more.
The present paper investigates flaw strength distributions established using various flexural tests on batches of SiC bar test specimens, namely four-point bending as well as three-point bending tests with different span lengths. Flaw strength is provided by the elemental stress operating on the critical flaw at the fracture of a test specimen. Fracture-inducing flaws and their locations are identified using fractography. A single population of pores was found to dominate the fracture. The construction of diagrams of p-quantile vs. elemental strengths was aimed at assessing the Gaussian nature of flaw strengths. Then, empirical cumulative distributions of strengths were constructed using the normal distribution function. The Weibull distributions of strengths are then compared to the normal reference distributions. The parameters of the Weibull cumulative probability distributions are estimated using maximum likelihood and moment methods. The cumulative distributions of flexural strengths for the different bending tests are predicted from the flaw strength density function using the elemental strength model, and from the cumulative distribution of flexural strength using the Weibull function. Flaw strength distributions that include the weaker flaws that are potentially present in larger test pieces are extrapolated using the p-quantile diagrams. Implications are discussed regarding the pertinence of an intrinsically representative flaw strength distribution, considering failure predictions. Finally, the influence of the characteristics of fracture-inducing flaw populations expressed in terms of flaw strength interval, size, dispersion, heterogeneity, and reproducibility with volume change is examined. Full article
(This article belongs to the Special Issue Advances in Ceramics, 2nd Edition)
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Figure 1
<p>Pores in the fracture surface of a silicon carbide specimen. The scale bar indicates 10 μm.</p>
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<p>p-quantile diagrams obtained for the sets of strength data obtained on the bending tests. The solid lines indicate the regression lines.</p>
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<p>Comparison of Weibull (referred to as W) and normal (referred to as N) cumulative distribution functions for the elemental strengths.</p>
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<p>Comparison of the Weibull (PDW) and Gauss (PDn) probability density functions.</p>
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<p>Size effects: predictions of the flexural strengths using the multiaxial elemental strength model equation for the flaw strength parameters derived from the 4pt bending tests. Comparison with the experimental flexural strength distributions.</p>
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<p>Size effects: predictions of the flexural strengths using the Weibull model equation for the statistical parameters derived from the 4pt bending tests. Comparison with the experimental flexural strength distributions.</p>
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<p>Size effects: predictions of the flaw strengths using the Weibull model for the flaw strength parameters derived from 4pt bending tests. Comparison with the experimental flaw strength distributions.</p>
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<p>Merged and extrapolated p-quantile–flaw strength diagrams. Comparison with those obtained from the 3-point and 4-point bending tests.</p>
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<p>Normal CDFs derived from the merged and extrapolated p-quantile–flaw strength diagrams.</p>
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<p>Gaussian PDFs derived from the merged and extrapolated p-quantile–flaw strength diagrams.</p>
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<p>Influence of the number of flaw strength data <span class="html-italic">n</span> on the extreme values <span class="html-italic">z<sub>pmax</sub></span> (=−<span class="html-italic">z<sub>pmin</sub></span>).</p>
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<p>Variation in the coefficient of variation (Equation (18)) with m. Comparison with functions 1/m, 1.2/m, and 1.3/m.</p>
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<p>Influence on <span class="html-italic">n</span> on standard deviation when the flaw strength interval and <span class="html-italic">μ</span> are constant.</p>
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<p>Influence of <span class="html-italic">n</span> on <span class="html-italic">m</span> when the strength interval and the mean strength are kept constant.</p>
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16 pages, 3660 KiB  
Article
Improving the Transparency of a MgAl2O4 Spinel Damaged by Sandblasting through a SiO2-ZrO2 Coating
by Akram Zegadi, Abdelwahhab Ayadi, Ikram Khellaf, Mohamed Hamidouche, Gilbert Fantozzi, Alicia Durán and Yolanda Castro
Ceramics 2024, 7(2), 743-758; https://doi.org/10.3390/ceramics7020049 - 28 May 2024
Viewed by 804
Abstract
Transparent materials in contact with harmful environments such as sandstorms are exposed to surface damage. Transparent MgAl2O4 spinel used as protective window, lens or laser exit port, among others, is one of the materials affected by natural aggressions. The impact [...] Read more.
Transparent materials in contact with harmful environments such as sandstorms are exposed to surface damage. Transparent MgAl2O4 spinel used as protective window, lens or laser exit port, among others, is one of the materials affected by natural aggressions. The impact of sand particles can cause significant defects on the exposed surface, thus affecting its optical and mechanical behavior. The aim of this work is to improve the surface state of a spinel damaged surface by the deposition of a thin layer of SiO2-ZrO2. For this purpose, spinel samples obtained from different commercial powders sintered by Spark Plasma Sintering were sandblasted and further coated with a SiO2-ZrO2 thin layer. The coating was successfully synthesized by the sol/gel method, deposited on the sandblasted samples and then treated at 900 °C, reaching a final thickness of 250 nm. The results indicated that sandblasting significantly affects the surface of the spinel samples as well as the optical transmission, confirmed by UV-visible spectroscopy and profilometry tests. However, the deposition of a SiO2-ZrO2 coating modifies the UV-visible response. Thus, the optical transmission of the S25CRX12 sample presents the best transmission values of 81%, followed by the S25CRX14 sample then the S30CR sample at 550 nm wavelength. An important difference was observed between sandblasted samples and coated samples at low and high wavelengths. At low wavelengths (around 200 nm), sandblasting tends to improve significantly the transmission of spinel samples, which exhibit a low transmission in the pristine state. This phenomenon can be attributed to the healing of small superficial defects responsible for the degradation of transmission such as pores or flaws. When the initial transmission at 200 nm is high, the sandblasting worsens the transmission. Sandblasting reduces slightly the transmission values for long wavelengths due to the formation of large superficial defects like chipping by creation and propagation of lateral cracks. The coating of the sandblasted samples exhibits some healing of defects induced by sandblasting. The deposition of the SiO2-ZrO2 layer induces a clear increase in the optical transmission values, sometimes exceeding the initial values of the transmission in the pristine state. Full article
(This article belongs to the Special Issue Transparent Ceramics—a Theme Issue in Honor of Dr. Adrian Goldstein)
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Graphical abstract
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<p>SEM images of samples (<b>a</b>) S25CRX12, (<b>b</b>) S25CRX14 and (<b>c</b>) S30CR sintered at 1310 °C.</p>
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<p>Micrograph of used sand particles from the desert region of Ouargla.</p>
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<p>Particle size distribution of the used sand.</p>
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<p>Infrared spectrum of the SiO<sub>2</sub>-ZrO<sub>2</sub> solution.</p>
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<p>Evolution of optical transmission before and after sandblasting, then after coating of S25CRX12 spinel samples sintered at 1290, 1310 and 1330 °C.</p>
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<p>Evolution of optical transmission before and after sandblasting then after coating of S25CRX14 spinel samples sintered at 1290, 1310 and 1330 °C.</p>
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<p>Evolution of optical transmission before and after sandblasting then after coating of S30CR spinel samples sintered at 1290, 1310 and 1330 °C.</p>
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<p>Surface roughness after sandblasting and after coating for samples; left: uncoated, right: coated. (<b>a</b>) S25CRX14 sintered at 1310 °C, (<b>b</b>) S30CR sintered at 1310 °C.</p>
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<p>Best optical transmission values obtained after coating.</p>
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8 pages, 3462 KiB  
Communication
Microwave-Assisted Hydrothermal Synthesis of Hydroxyapatite Flakes as Substrates for Titanium Dioxide Film Deposition
by Néstor Méndez-Lozano, Eduardo E. Pérez-Ramírez and Miguel de la Luz-Asunción
Ceramics 2024, 7(2), 735-742; https://doi.org/10.3390/ceramics7020048 - 28 May 2024
Viewed by 675
Abstract
This article describes the synthesis of hydroxyapatite (HAp) flakes through a microwave-assisted hydrothermal method. These flakes suggest possible applications as a substrate for depositing titanium dioxide (TiO2) films using chemical vapor deposition with metal–organic precursors (MOCVD). The results reveal the formation [...] Read more.
This article describes the synthesis of hydroxyapatite (HAp) flakes through a microwave-assisted hydrothermal method. These flakes suggest possible applications as a substrate for depositing titanium dioxide (TiO2) films using chemical vapor deposition with metal–organic precursors (MOCVD). The results reveal the formation of crystalline hydroxyapatite characterized by a uniform morphology. Additionally, we demonstrated the successful deposition of TiO2 coatings on the hydroxyapatite flakes, resulting in a distinctive faceted prism morphology. Our findings affirm the effective synthesis of the HAp/TiO2 composite material. To further explore the material’s practical applications, we recommend assessing the photocatalytic activity of these composite membranes in future research. Full article
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Figure 1
<p>Schematic diagram to obtain TiO<sub>2</sub> coatings on hydroxyapatite flakes.</p>
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<p>(<b>a</b>) XRD diffraction pattern of HAp flake; (<b>b</b>) XRD diffraction pattern of TiO<sub>2</sub>-coated flake; (<b>c</b>) SEM micrograph of HAp; (<b>d</b>) SEM micrograph of TiO<sub>2</sub>.</p>
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<p>(<b>a</b>) SEM micrograph of HAp flakes at 5000×; (<b>b</b>) SEM micrograph of HAp flakes at 2000×; (<b>c</b>) SEM micrograph of TiO<sub>2</sub> at 5000×; (<b>d</b>) SEM micrograph at TiO<sub>2</sub> to 2000×.</p>
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<p>EDS spectra of TiO<sub>2</sub> coating: (<b>a</b>) micrograph at ×500; (<b>b</b>) micrograph at ×5000.</p>
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<p>EDS spectra of HAp flakes.</p>
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23 pages, 5735 KiB  
Review
Lead-Free NaNbO3-Based Ceramics for Electrostatic Energy Storage Capacitors
by Sairatun Nesa Soheli, Zhilun Lu, Dongyang Sun and Islam Shyha
Ceramics 2024, 7(2), 712-734; https://doi.org/10.3390/ceramics7020047 - 23 May 2024
Viewed by 1674
Abstract
The burgeoning significance of antiferroelectric (AFE) materials, particularly as viable candidates for electrostatic energy storage capacitors in power electronics, has sparked substantial interest. Among these, lead-free sodium niobate (NaNbO3) AFE materials are emerging as eco-friendly and [...] Read more.
The burgeoning significance of antiferroelectric (AFE) materials, particularly as viable candidates for electrostatic energy storage capacitors in power electronics, has sparked substantial interest. Among these, lead-free sodium niobate (NaNbO3) AFE materials are emerging as eco-friendly and promising alternatives to lead-based materials, which pose risks to human health and the environment, attributed to their superior recoverable energy density and dielectric breakdown strength. This review offers an insightful overview of the fundamental principles underlying antiferroelectricity and the applications of AFE materials. It underscores the recent advancements in lead-free NaNbO3-based materials, focusing on their crystal structures, phase transitions, and innovative strategies devised to tailor their electrostatic energy storage performance. Finally, this review delineates the prevailing challenges and envisages future directions in the realm of NaNbO3-based electrostatic energy storage capacitors, with the goal of fostering further advancements in this pivotal field. Full article
(This article belongs to the Special Issue Advances in Electronic Ceramics)
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Graphical abstract

Graphical abstract
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<p>Ragone plot of various energy storage devices with characteristic times represented by straight dashed lines.</p>
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<p>Publications on lead-free AFE materials for electrostatic energy storage (2015–2024).</p>
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<p>Schematic illustrations showing the polarisation versus electric field (<math display="inline"><semantics> <mrow> <mi mathvariant="normal">P</mi> <mo>−</mo> <mi mathvariant="normal">E</mi> </mrow> </semantics></math>) curve: (<b>a</b>) linear dielectrics, (<b>b</b>) FEs, (<b>c</b>) relaxor ferroelectrics (RFEs), and (<b>d</b>) AFEs with the recoverable energy density (<math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">J</mi> </mrow> <mrow> <mi mathvariant="normal">r</mi> <mi mathvariant="normal">e</mi> <mi mathvariant="normal">c</mi> </mrow> </msub> </mrow> </semantics></math>) and the dissipated energy density (<math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">J</mi> </mrow> <mrow> <mi mathvariant="normal">l</mi> <mi mathvariant="normal">o</mi> <mi mathvariant="normal">s</mi> <mi mathvariant="normal">s</mi> </mrow> </msub> </mrow> </semantics></math>) indicated in blue and orange areas, respectively.</p>
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<p>Crystal structures of <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">a</mi> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">b</mi> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>3</mn> </mrow> </msub> </mrow> </semantics></math>, with Na⁺ in gold, Nb⁵⁺ in green, and O<sup>2</sup>⁻ in white: (<b>a</b>) the antipolar P phase and (<b>b</b>) the polar Q phase [<a href="#B69-ceramics-07-00047" class="html-bibr">69</a>].</p>
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<p>Temperature-dependent phase transitions in <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">a</mi> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">b</mi> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>3</mn> </mrow> </msub> </mrow> </semantics></math>.</p>
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<p><math display="inline"><semantics> <mrow> <mi mathvariant="normal">P</mi> <mo>−</mo> <mi mathvariant="normal">E</mi> </mrow> </semantics></math> loops of <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">a</mi> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">b</mi> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>3</mn> </mrow> </msub> </mrow> </semantics></math> bulk ceramics, as reported by (<b>a</b>) Luo et al. [<a href="#B86-ceramics-07-00047" class="html-bibr">86</a>] and (<b>b</b>) Chao et al. [<a href="#B87-ceramics-07-00047" class="html-bibr">87</a>].</p>
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<p><math display="inline"><semantics> <mrow> <mi mathvariant="normal">P</mi> <mo>−</mo> <mi mathvariant="normal">E</mi> </mrow> </semantics></math> loops of (<b>a</b>) <math display="inline"><semantics> <mrow> <mn>0.9</mn> <msub> <mrow> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">a</mi> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">b</mi> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>3</mn> </mrow> </msub> <mo>−</mo> <msub> <mrow> <mn>0.06</mn> <mi mathvariant="normal">B</mi> <mi mathvariant="normal">a</mi> <mi mathvariant="normal">Z</mi> <mi mathvariant="normal">r</mi> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>3</mn> </mrow> </msub> <mo>−</mo> <msub> <mrow> <mn>0.04</mn> <mi mathvariant="normal">C</mi> <mi mathvariant="normal">a</mi> <mi mathvariant="normal">Z</mi> <mi mathvariant="normal">r</mi> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>3</mn> </mrow> </msub> </mrow> </semantics></math> [<a href="#B98-ceramics-07-00047" class="html-bibr">98</a>], (<b>b</b>) <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">a</mi> </mrow> <mrow> <mn>0.7</mn> </mrow> </msub> <msub> <mrow> <mi mathvariant="normal">A</mi> <mi mathvariant="normal">g</mi> </mrow> <mrow> <mn>0.3</mn> </mrow> </msub> <msub> <mrow> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">b</mi> </mrow> <mrow> <mn>0.7</mn> </mrow> </msub> <msub> <mrow> <mi mathvariant="normal">T</mi> <mi mathvariant="normal">a</mi> </mrow> <mrow> <mn>0.3</mn> </mrow> </msub> <msub> <mrow> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>3</mn> </mrow> </msub> </mrow> </semantics></math> [<a href="#B99-ceramics-07-00047" class="html-bibr">99</a>].</p>
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<p>The second electric field cycle at 1 <math display="inline"><semantics> <mrow> <mi mathvariant="normal">H</mi> <mi mathvariant="normal">z</mi> </mrow> </semantics></math> produced <math display="inline"><semantics> <mrow> <mi mathvariant="normal">P</mi> <mo>−</mo> <mi mathvariant="normal">E</mi> </mrow> </semantics></math> loops for (<b>a</b>) <math display="inline"><semantics> <mrow> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">N</mi> </mrow> </semantics></math>, (<b>b</b>) <math display="inline"><semantics> <mrow> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">N</mi> <mn>5</mn> <mi mathvariant="normal">S</mi> <mi mathvariant="normal">S</mi> </mrow> </semantics></math>, (<b>c</b>) <math display="inline"><semantics> <mrow> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">N</mi> <mn>5</mn> <mi mathvariant="normal">S</mi> <mi mathvariant="normal">S</mi> <mo>_</mo> <mn>0.1</mn> <mi mathvariant="normal">M</mi> <mi mathvariant="normal">n</mi> </mrow> </semantics></math> and <math display="inline"><semantics> <mrow> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">N</mi> <mn>5</mn> <mi mathvariant="normal">S</mi> <mi mathvariant="normal">S</mi> <mo>_</mo> <mn>1.0</mn> <mi mathvariant="normal">M</mi> <mi mathvariant="normal">n</mi> </mrow> </semantics></math>, (<b>d</b>) <math display="inline"><semantics> <mrow> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">N</mi> <mn>7</mn> <mi mathvariant="normal">S</mi> <mi mathvariant="normal">S</mi> <mo>_</mo> <mn>1.0</mn> <mi mathvariant="normal">M</mi> <mi mathvariant="normal">n</mi> </mrow> </semantics></math>, and (<b>e</b>) <math display="inline"><semantics> <mrow> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">N</mi> <mn>9</mn> <mi mathvariant="normal">S</mi> <mi mathvariant="normal">S</mi> <mo>_</mo> <mn>1.0</mn> <mi mathvariant="normal">M</mi> <mi mathvariant="normal">n</mi> </mrow> </semantics></math>; (<b>f</b>) recoverable energy storage density and efficiency; (<b>g</b>) tanδ as a function of frequency; and (<b>h</b>) Nyquist plot of the <math display="inline"><semantics> <mrow> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">N</mi> <mo>,</mo> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">N</mi> <mn>5</mn> <mi mathvariant="normal">S</mi> <mi mathvariant="normal">S</mi> <mo>,</mo> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">N</mi> <mn>5</mn> <msub> <mrow> <mi mathvariant="normal">S</mi> <mi mathvariant="normal">S</mi> </mrow> <mrow> <mn>0.1</mn> <mi mathvariant="normal">M</mi> <mi mathvariant="normal">n</mi> </mrow> </msub> <mo>,</mo> </mrow> </semantics></math> and <math display="inline"><semantics> <mrow> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">N</mi> <mn>5</mn> <mi mathvariant="normal">S</mi> <mi mathvariant="normal">S</mi> <mo>_</mo> <mn>1.0</mn> <mi mathvariant="normal">M</mi> <mi mathvariant="normal">n</mi> </mrow> </semantics></math> samples [<a href="#B100-ceramics-07-00047" class="html-bibr">100</a>].</p>
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<p>Schematic diagrams illustrating the enhancement of <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">J</mi> </mrow> <mrow> <mi mathvariant="normal">r</mi> <mi mathvariant="normal">e</mi> <mi mathvariant="normal">c</mi> </mrow> </msub> </mrow> </semantics></math> by adding <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">B</mi> <mi mathvariant="normal">i</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> <msub> <mrow> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>3</mn> </mrow> </msub> </mrow> </semantics></math> to <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">a</mi> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">b</mi> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>3</mn> </mrow> </msub> </mrow> </semantics></math>: (<b>a</b>) pure <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">a</mi> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">b</mi> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>3</mn> </mrow> </msub> </mrow> </semantics></math> ceramics exhibit low <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">J</mi> </mrow> <mrow> <mi mathvariant="normal">r</mi> <mi mathvariant="normal">e</mi> <mi mathvariant="normal">c</mi> </mrow> </msub> </mrow> </semantics></math> due to high <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">P</mi> </mrow> <mrow> <mi mathvariant="normal">r</mi> </mrow> </msub> </mrow> </semantics></math> and small <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">E</mi> </mrow> <mrow> <mi mathvariant="normal">m</mi> <mi mathvariant="normal">a</mi> <mi mathvariant="normal">x</mi> </mrow> </msub> </mrow> </semantics></math>; (<b>b</b>) <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">a</mi> </mrow> <mrow> <mn>1</mn> <mo>−</mo> <mn>3</mn> <mi mathvariant="normal">x</mi> </mrow> </msub> <msub> <mrow> <mi mathvariant="normal">B</mi> <mi mathvariant="normal">i</mi> </mrow> <mrow> <mi mathvariant="normal">x</mi> </mrow> </msub> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">b</mi> <msub> <mrow> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>3</mn> </mrow> </msub> </mrow> </semantics></math> ceramics exhibit high <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">J</mi> </mrow> <mrow> <mi mathvariant="normal">r</mi> <mi mathvariant="normal">e</mi> <mi mathvariant="normal">c</mi> </mrow> </msub> </mrow> </semantics></math> due to low <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">P</mi> </mrow> <mrow> <mi mathvariant="normal">r</mi> </mrow> </msub> </mrow> </semantics></math> and large <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">E</mi> </mrow> <mrow> <mi mathvariant="normal">m</mi> <mi mathvariant="normal">a</mi> <mi mathvariant="normal">x</mi> </mrow> </msub> </mrow> </semantics></math> [<a href="#B107-ceramics-07-00047" class="html-bibr">107</a>].</p>
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<p>(<b>a</b>) The relationship between recoverable energy density and electric field at <math display="inline"><semantics> <mrow> <mn>250</mn> <mo> </mo> <mi mathvariant="normal">k</mi> <mi mathvariant="normal">V</mi> <mo>/</mo> <mi mathvariant="normal">c</mi> <mi mathvariant="normal">m</mi> </mrow> </semantics></math> as a function of temperature is illustrated by the <math display="inline"><semantics> <mrow> <mi mathvariant="normal">P</mi> <mo>−</mo> <mi mathvariant="normal">E</mi> </mrow> </semantics></math> loops obtained within an operating temperature range of <math display="inline"><semantics> <mrow> <mo>−</mo> <mn>90</mn> <mo> </mo> <mo>°</mo> <mi mathvariant="normal">C</mi> </mrow> </semantics></math> to <math display="inline"><semantics> <mrow> <mn>150</mn> <mo> </mo> <mo>°</mo> <mi mathvariant="normal">C</mi> </mrow> </semantics></math>. (<b>b</b>) The dependence of recoverable energy density and <math display="inline"><semantics> <mrow> <mi mathvariant="sans-serif">η</mi> </mrow> </semantics></math> on an electric field strength of <math display="inline"><semantics> <mrow> <mn>250</mn> <mo> </mo> <mi mathvariant="normal">k</mi> <mi mathvariant="normal">V</mi> <mo>/</mo> <mi mathvariant="normal">c</mi> <mi mathvariant="normal">m</mi> </mrow> </semantics></math> is demonstrated through <math display="inline"><semantics> <mrow> <mi mathvariant="normal">P</mi> <mo>−</mo> <mi mathvariant="normal">E</mi> </mrow> </semantics></math> loops from measurements conducted over several cycles, up to <math display="inline"><semantics> <mrow> <msup> <mrow> <mn>10</mn> </mrow> <mrow> <mn>5</mn> </mrow> </msup> </mrow> </semantics></math>, at this field strength [<a href="#B108-ceramics-07-00047" class="html-bibr">108</a>].</p>
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<p>(<b>a</b>–<b>e</b>) SEM images of <math display="inline"><semantics> <mrow> <mn>0.955</mn> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">a</mi> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">b</mi> <msub> <mrow> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>3</mn> </mrow> </msub> <mo>−</mo> <msub> <mrow> <mn>0.045</mn> <mi mathvariant="normal">L</mi> <mi mathvariant="normal">a</mi> <mo>(</mo> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">b</mi> </mrow> <mrow> <mn>0.33</mn> </mrow> </msub> <msub> <mrow> <mi mathvariant="normal">M</mi> <mi mathvariant="normal">g</mi> </mrow> <mrow> <mn>0.67</mn> </mrow> </msub> <mo>)</mo> <msub> <mrow> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>3</mn> </mrow> </msub> </mrow> </semantics></math> with varying additions of <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">M</mi> <mi mathvariant="normal">n</mi> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> </mrow> </semantics></math>: (<b>a</b>) 0 wt% <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">M</mi> <mi mathvariant="normal">n</mi> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> </mrow> </semantics></math>, (<b>b</b>) 0.5 wt% <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">M</mi> <mi mathvariant="normal">n</mi> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> </mrow> </semantics></math>, (<b>c</b>) 1.0 wt% <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">M</mi> <mi mathvariant="normal">n</mi> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> </mrow> </semantics></math>, (<b>d</b>) 1.5 wt% <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">M</mi> <mi mathvariant="normal">n</mi> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> </mrow> </semantics></math>, (<b>e</b>) 2.0 wt% <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">M</mi> <mi mathvariant="normal">n</mi> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> </mrow> </semantics></math> [<a href="#B134-ceramics-07-00047" class="html-bibr">134</a>].</p>
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<p>(<b>a</b>) Comparison between <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">E</mi> </mrow> <mrow> <mi mathvariant="normal">t</mi> <mi mathvariant="normal">e</mi> <mi mathvariant="normal">s</mi> <mi mathvariant="normal">t</mi> <mo>−</mo> <mi mathvariant="normal">m</mi> <mi mathvariant="normal">a</mi> <mi mathvariant="normal">x</mi> </mrow> </msub> </mrow> </semantics></math>, <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">J</mi> </mrow> <mrow> <mi mathvariant="normal">r</mi> <mi mathvariant="normal">e</mi> <mi mathvariant="normal">c</mi> </mrow> </msub> </mrow> </semantics></math> and <math display="inline"><semantics> <mrow> <mi mathvariant="sans-serif">η</mi> </mrow> </semantics></math> of NN–BNT, (<b>b</b>) NN–BNT–15BMH ceramic, (<b>c</b>) NN–BNT–15BMH MLCCs [<a href="#B124-ceramics-07-00047" class="html-bibr">124</a>].</p>
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<p>(<b>a</b>) Temperature-dependent measurements of dielectric permittivity at various frequencies for AFE samples of <math display="inline"><semantics> <mrow> <msub> <mrow> <mo>(</mo> <mn>1</mn> <mo>−</mo> <mi mathvariant="normal">x</mi> <mo>)</mo> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">a</mi> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">b</mi> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>3</mn> </mrow> </msub> <mo>−</mo> <mi mathvariant="normal">x</mi> <mo>(</mo> <msub> <mrow> <mi mathvariant="normal">B</mi> <mi mathvariant="normal">i</mi> </mrow> <mrow> <mn>0.8</mn> </mrow> </msub> <msub> <mrow> <mi mathvariant="normal">S</mi> <mi mathvariant="normal">r</mi> </mrow> <mrow> <mn>0.2</mn> </mrow> </msub> <mo>)</mo> <mo>(</mo> <msub> <mrow> <mi mathvariant="normal">F</mi> <mi mathvariant="normal">e</mi> </mrow> <mrow> <mn>0.9</mn> </mrow> </msub> <msub> <mrow> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">b</mi> </mrow> <mrow> <mn>0.1</mn> </mrow> </msub> <mo>)</mo> <msub> <mrow> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>3</mn> </mrow> </msub> </mrow> </semantics></math> [<a href="#B125-ceramics-07-00047" class="html-bibr">125</a>]; (<b>b</b>) <math display="inline"><semantics> <mrow> <mi mathvariant="normal">P</mi> <mo>−</mo> <mi mathvariant="normal">E</mi> </mrow> </semantics></math> loops for <math display="inline"><semantics> <mrow> <msub> <mrow> <mo>(</mo> <mn>1</mn> <mo>−</mo> <mi mathvariant="normal">x</mi> <mo>)</mo> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">a</mi> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">b</mi> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>3</mn> </mrow> </msub> <mo>−</mo> <mi mathvariant="normal">x</mi> <mo>(</mo> <msub> <mrow> <mi mathvariant="normal">B</mi> <mi mathvariant="normal">i</mi> </mrow> <mrow> <mn>0.8</mn> </mrow> </msub> <msub> <mrow> <mi mathvariant="normal">S</mi> <mi mathvariant="normal">r</mi> </mrow> <mrow> <mn>0.2</mn> </mrow> </msub> <mo>)</mo> <mo>(</mo> <msub> <mrow> <mi mathvariant="normal">F</mi> <mi mathvariant="normal">e</mi> </mrow> <mrow> <mn>0.9</mn> </mrow> </msub> <msub> <mrow> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">b</mi> </mrow> <mrow> <mn>0.1</mn> </mrow> </msub> <mo>)</mo> <msub> <mrow> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>3</mn> </mrow> </msub> </mrow> </semantics></math> ceramics under 30 kV/mm at room temperature [<a href="#B125-ceramics-07-00047" class="html-bibr">125</a>].</p>
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<p>(<b>a</b>) Temperature-dependent dielectric permittivity; (<b>b</b>) domain morphology of the HRTEM images; (<b>c</b>) PDF analysis of relaxor states of the <math display="inline"><semantics> <mrow> <mi mathvariant="normal">N</mi> <mi mathvariant="normal">N</mi> <mn>9</mn> <mi mathvariant="normal">S</mi> <mi mathvariant="normal">S</mi> <mo>_</mo> <mn>1.0</mn> <mi mathvariant="normal">M</mi> <mi mathvariant="normal">n</mi> </mrow> </semantics></math> samples [<a href="#B100-ceramics-07-00047" class="html-bibr">100</a>].</p>
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14 pages, 4588 KiB  
Article
Origin of Temperature Coefficient of Resonance Frequency in Rutile Ti1−xZrxO2 Microwave Ceramics
by Izaz Khan, Aneela Khan, Raz Muhammad, Minmin Mao, Dandan Han, Kaixin Song, Wen Lei and Dawei Wang
Ceramics 2024, 7(2), 698-711; https://doi.org/10.3390/ceramics7020046 - 23 May 2024
Viewed by 911
Abstract
In this study, we report the effect of Zr4+ doping on the optical energy gap and microwave dielectric properties of rutile TiO2. Rietveld analysis explicitly confirmed that Zr4+ occupies the octahedral site, forming a single-phase tetragonal structure below the [...] Read more.
In this study, we report the effect of Zr4+ doping on the optical energy gap and microwave dielectric properties of rutile TiO2. Rietveld analysis explicitly confirmed that Zr4+ occupies the octahedral site, forming a single-phase tetragonal structure below the solubility limit (x < 0.10). Notably, at x = 0.025, a significant enhancement in Q × fo was observed. This enhancement was attributed to the reduction in dielectric loss, associated with a decrease in oxygen vacancies and a lower concentration of Ti3+ paramagnetic centers. This conclusion was supported by Raman and electron paramagnetic resonance spectroscopy, respectively. The origin of high τf in rutile Ti1−xZrxO2 is explained on the basis of the octahedral distortion/tetragonality ratio, covalency, and bond strength. Full article
(This article belongs to the Special Issue Advances in Electronic Ceramics)
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Figure 1

Figure 1
<p>(<b>a</b>) XRD patterns of rutile Ti<sub>1−<span class="html-italic">x</span></sub>Zr<span class="html-italic"><sub>x</sub></span>O<sub>2</sub> (<span class="html-italic">x</span> = 0−0.1), and (<b>b</b>) fitted XRD patterns for <span class="html-italic">x</span> = 0.025.</p>
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<p>Raman spectra of rutile Ti<sub>1−<span class="html-italic">x</span></sub>Zr<span class="html-italic"><sub>x</sub></span>O<sub>2</sub> (<span class="html-italic">x</span> = 0–0.1).</p>
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<p>The room-temperature EPR spectra of rutile Ti<sub>1−<span class="html-italic">x</span></sub>Zr<span class="html-italic"><sub>x</sub></span>O<sub>2</sub> (<span class="html-italic">x</span> = 0–0.1).</p>
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<p>SEM micrographs of thermally etched and polished Ti<sub>1−<span class="html-italic">x</span></sub>Zr<span class="html-italic"><sub>x</sub></span>O<sub>2</sub> at (<b>a</b>) <span class="html-italic">x</span> = 0, (<b>b</b>) <span class="html-italic">x</span> = 0.025, (<b>c</b>) <span class="html-italic">x</span> = 0.05, (<b>d</b>) <span class="html-italic">x</span> = 0.075, (<b>e</b>) <span class="html-italic">x</span> = 0.1; (<b>f</b>) grain size distribution as a function of the Zr concentration; (<b>g</b>) elemental distribution and EDX mapping of (<b>h</b>) Ti, (<b>i</b>) O, and (<b>j</b>) Zr for a sample with <span class="html-italic">x</span> = 0.025.</p>
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<p>EDX mapping of (<b>a</b>) Ti<sub>1−<span class="html-italic">x</span></sub>Zr<span class="html-italic"><sub>x</sub></span>O<sub>2</sub> (<span class="html-italic">x</span> = 0.1), (<b>b</b>) Ti, (<b>c</b>) O, and (<b>d</b>) Zr.</p>
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<p>(<b>a</b>) Reflection spectra and (<b>b</b>) Tauc plots of Ti<sub>1−<span class="html-italic">x</span></sub>Zr<span class="html-italic"><sub>x</sub></span>O<sub>2</sub> (<span class="html-italic">x</span> = 0–0.1).</p>
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<p>(<b>a</b>) Relationship between the c/a ratio and τ<sub>f</sub> value and/or ε<sub>r</sub> and (<b>b</b>) the variation in τ<sub>f</sub> with the unit cell volume of Ti<sub>1−<span class="html-italic">x</span></sub>Zr<span class="html-italic"><sub>x</sub></span>O<sub>2</sub> (<span class="html-italic">x</span> = 0–0.1).</p>
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9 pages, 1139 KiB  
Article
Effect of Acid Surface Treatments on the Shear Bond Strength of Metal Bracket to Zirconia Ceramics
by Punchanit Wongrachit, Bancha Samruajbenjakun, Boonlert Kukiattrakoon, Tanapat Jearanai, Supontep Teerakanok and Pannapat Chanmanee
Ceramics 2024, 7(2), 689-697; https://doi.org/10.3390/ceramics7020045 - 14 May 2024
Viewed by 952
Abstract
The surface treatment of zirconia prior to bonding remains controversial and unclear. This study aimed to compare the shear bond strength (SBS) of metal brackets to zirconia under surface treatments with either 4% HF or 37% PA in both immediate loading (IML) and [...] Read more.
The surface treatment of zirconia prior to bonding remains controversial and unclear. This study aimed to compare the shear bond strength (SBS) of metal brackets to zirconia under surface treatments with either 4% HF or 37% PA in both immediate loading (IML) and artificial aging by thermocycling (TMC). Methods: Eighty-four zirconia were randomly assigned to six groups based on the surface treatment and artificial aging by TMC: (1) No surface treatment (NT); (2) NT + TMC; (3) HF (4% HF for 2 min); (4) HF + TMC; (5) PA (37% PA for 2 min); and (6) PA + TMC. After bracket bonding, only the TMC groups were thermocycled for 5000 cycles. The SBS and adhesive remnant index (ARI) of all groups were analyzed (p < 0.01). Results: TMC significantly lowered the SBS more than the IML in all acid surface treatment groups (p < 0.01). The ARI score after TMC was significantly higher than the IML in all acid surface treatment groups (p < 0.001). No significant differences in the SBS values or ARI scores were observed among the surface treatments (p > 0.01). Conclusions: Two-minute simple etching methods, using either 4% HF or 37% PA, showed an insufficient SBS of metal orthodontic brackets to zirconia after TMC. Full article
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<p>Flow chart of the sample allocation into six groups based on surface treatment methods and treatment conditions. ARI—adhesive remnant index; SBS—shear bond strength; SEM—scanning electron microscopy; TMC—thermocycling.</p>
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<p>Bracket bonding procedure. (<b>A</b>) The bonding area was defined by a custom-made waterproof sticker. (<b>B</b>) The bracket was placed onto the zirconia surface. (<b>C</b>) After light-curing, the sticker was peeled off.</p>
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<p>(<b>A</b>,<b>B</b>) Shear bond strength test with the universal testing machine.</p>
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<p>Adhesive remnant index (ARI) score 1–5 at 40× magnification under a 3D profilometer. (<b>A</b>) Score 1: All of the resin remained on the zirconia and showed a bracket base impression. (<b>B</b>) Score 2: Equal to or more than 90% of the resin remained on the zirconia. (<b>C</b>) Score 3: Between 10% and 90% of the resin remained on the zirconia. (<b>D</b>) Score 4: Less than 10% of the resin remained on the zirconia. (<b>E</b>) Score 5: No resin remained on the zirconia surface. This figure used samples from this study to illustrate the amounts of adhesive remnant after bracket removal. The scoring followed the index reported in a study by Bishara et al. [<a href="#B28-ceramics-07-00045" class="html-bibr">28</a>].</p>
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<p>Zirconia surface topography under scanning electron microscopy at (<b>1</b>) 500×; (<b>2</b>) 1000×; (<b>3</b>) 2000×; and (<b>4</b>) 4000× magnification. (<b>A</b>) Specimen had no surface treatment (NT). (<b>B</b>) Specimen was etched with 4% hydrofluoric etchant (HF). (<b>C</b>) Specimen was etched with 37% phosphoric etchant (PA).</p>
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9 pages, 3570 KiB  
Article
Nanosized Tungsten Powder Synthesized Using the Nitridation–Decomposition Method
by Qing-Yin He, Ben-Li Zhao and Shi-Kuan Sun
Ceramics 2024, 7(2), 680-688; https://doi.org/10.3390/ceramics7020044 - 11 May 2024
Viewed by 962
Abstract
A facile, one-step nitridation–decomposition method was developed for the synthesis of nanosized tungsten powder with a high surface area. This approach involved the nitridation of WO3 in NH3 to form mesoporous tungsten nitride (W2N), followed by in situ decomposition [...] Read more.
A facile, one-step nitridation–decomposition method was developed for the synthesis of nanosized tungsten powder with a high surface area. This approach involved the nitridation of WO3 in NH3 to form mesoporous tungsten nitride (W2N), followed by in situ decomposition of W2N to directly yield single-phase W particles. The phase and morphology evolution during the synthesis were systematically investigated and compared with the carbothermal reduction of WO3. It was revealed that powdered tungsten product with single-phase particles was obtained after nitridation at 800 °C combined with in situ decomposition at 1000 °C, displaying an average particle size of 15 nm and a large specific surface area of 6.52 m2/g. Furthermore, the proposed method avoided the limitations associated with intermediate phase formation and coarsening observed in carbothermal reduction, which resulted in the growth of W particles up to ~4.4 μm in size. This work demonstrates the potential of the nitridation–decomposition approach for the scalable and efficient synthesis of high-quality, fine-grained tungsten powder. Full article
(This article belongs to the Special Issue Advances in Electronic Ceramics)
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<p>XRD patterns (<b>a</b>), TEM (<b>b</b>), and SEM observations (<b>c</b>,<b>d</b>) of the W product after carbothermal reduction of WO<sub>3</sub> at 1300 °C for 3 h under vacuum.</p>
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<p>XRD patterns of the intermediate product after nitridation of WO<sub>3</sub> at 800 °C for 3 h (<b>a</b>) and in situ nitridation–decomposition at 900 °C for 2 h (<b>b</b>) and 6 h (<b>c</b>) and at 1000 °C for 2 h (<b>d</b>) and 6 h (<b>e</b>) in flowing Ar.</p>
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<p>TEM observation of W<sub>2</sub>N powders after being heat-treated at 800 °C under low (<b>a</b>) and high magnification (<b>b</b>).</p>
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<p>TEM images of W powder after in situ decomposition at 1000 °C in Ar atmosphere showing (<b>a</b>) elongated particle, (<b>b</b>) agglomeration.</p>
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<p>Schematic of the mechanism showing morphological changes of WO<sub>3</sub> during the nitridation process.</p>
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28 pages, 7118 KiB  
Review
Ceramic Matrix Composites: Classifications, Manufacturing, Properties, and Applications
by Shriya Shrivastava, Dipen Kumar Rajak, Tilak Joshi, Dwesh K. Singh and D. P. Mondal
Ceramics 2024, 7(2), 652-679; https://doi.org/10.3390/ceramics7020043 - 10 May 2024
Cited by 1 | Viewed by 4256
Abstract
Ceramic matrix composites (CMCs) are a significant advancement in materials science and engineering because they combine the remarkable characteristics of ceramics with the strength and toughness of fibers. With their unique properties, which offer better performance and endurance in severe settings, these advanced [...] Read more.
Ceramic matrix composites (CMCs) are a significant advancement in materials science and engineering because they combine the remarkable characteristics of ceramics with the strength and toughness of fibers. With their unique properties, which offer better performance and endurance in severe settings, these advanced composites have attracted significant attention in various industries. At the same time, lightweight ceramic matrix composites (LCMCs) provide an appealing alternative for a wide range of industries that require materials with excellent qualities such as high-temperature stability, low density, corrosion resistance, and excellent mechanical performance. CMC uses will expand as production techniques and material research improve, revolutionizing aerospace, automotive, and other industries. The effectiveness of CMCs primarily relies on the composition of their constituent elements and the methods employed in their manufacturing. Therefore, it is crucial to explore the functional properties of various global ceramic matrix reinforcements, their classifications, and the manufacturing techniques used in CMC fabrication. This study aims to overview a diverse range of CMCs reinforced with primary fibers, including their classifications, manufacturing techniques, functional properties, significant applications, and global market size. Full article
(This article belongs to the Special Issue Advances in Ceramics, 2nd Edition)
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<p>Classification of composites (based on matrix).</p>
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<p>Classification of CMCs based on the nature of the matrix.</p>
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<p>O-CMC material categories.</p>
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<p>Non-oxide CMC material categories.</p>
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<p>Synthesis of CMC using PIP.</p>
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<p>Synthesis of CMC using CVI.</p>
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<p>Synthesis of CMCs using direct melt oxidation.</p>
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<p>Synthesis of CMCs using LSI.</p>
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<p>Flowchart of synthesis of CMCs using sol–gel infiltration.</p>
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<p>Flowchart of synthesis of CMCs using slurry infiltration.</p>
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<p>EPD cell process.</p>
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<p>Illustration of SPS process.</p>
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<p>Directed energy deposition process.</p>
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<p>Additive manufacturing of CMC using a laser-embedded system [<a href="#B72-ceramics-07-00043" class="html-bibr">72</a>].</p>
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<p>Stress–strain behavior of CMCs, compared with monolithic ceramics [<a href="#B76-ceramics-07-00043" class="html-bibr">76</a>].</p>
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<p>Comparing the bending strength of composites to the tensile strength of reinforcement fibers involves exploring three densification cycles, utilizing the matrix polymer wacker silres H62 C, and subjecting the material to calcination at a temperature of 750 °C [<a href="#B78-ceramics-07-00043" class="html-bibr">78</a>].</p>
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<p>Application of CMCs in various fields [<a href="#B107-ceramics-07-00043" class="html-bibr">107</a>,<a href="#B108-ceramics-07-00043" class="html-bibr">108</a>,<a href="#B109-ceramics-07-00043" class="html-bibr">109</a>,<a href="#B110-ceramics-07-00043" class="html-bibr">110</a>,<a href="#B111-ceramics-07-00043" class="html-bibr">111</a>,<a href="#B112-ceramics-07-00043" class="html-bibr">112</a>,<a href="#B113-ceramics-07-00043" class="html-bibr">113</a>,<a href="#B114-ceramics-07-00043" class="html-bibr">114</a>,<a href="#B115-ceramics-07-00043" class="html-bibr">115</a>].</p>
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<p>Application of CMCs in various fields [<a href="#B125-ceramics-07-00043" class="html-bibr">125</a>,<a href="#B126-ceramics-07-00043" class="html-bibr">126</a>,<a href="#B127-ceramics-07-00043" class="html-bibr">127</a>,<a href="#B128-ceramics-07-00043" class="html-bibr">128</a>,<a href="#B129-ceramics-07-00043" class="html-bibr">129</a>,<a href="#B130-ceramics-07-00043" class="html-bibr">130</a>,<a href="#B131-ceramics-07-00043" class="html-bibr">131</a>].</p>
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<p>The global market of CMCs will increase from 2021–2030.</p>
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13 pages, 3419 KiB  
Article
Utilization of Waste Marble and Bi2O3-NPs as a Sustainable Replacement for Lead Materials for Radiation Shielding Applications
by Khalid Alsafi, Mohamed A. El-Nahal, Wafa M. Al-Saleh, Haifa M. Almutairi, Esraa H. Abdel-Gawad and Mohamed Elsafi
Ceramics 2024, 7(2), 639-651; https://doi.org/10.3390/ceramics7020042 - 7 May 2024
Cited by 1 | Viewed by 1013
Abstract
In an attempt to reutilize marble waste, a new approach is presented in the current study to promote its use in the field of shielding against ionizing radiation. In this study, we aimed to develop a novel and sustainable/eco-friendly lead-free radiation shielding material [...] Read more.
In an attempt to reutilize marble waste, a new approach is presented in the current study to promote its use in the field of shielding against ionizing radiation. In this study, we aimed to develop a novel and sustainable/eco-friendly lead-free radiation shielding material by improving artificial marble (AM) produced from marble waste combined with polyester by reinforcing it with bismuth oxide (Bi2O3) nanoparticles. Six samples of AM samples doped with different concentrations (0%, 5%, 10%, 15%, 20%, and 25%) of Bi2O3 nanoparticles were prepared. The linear attenuation coefficient (LAC) values were measured experimentally through the narrow beam method at different energies (0.0595 MeV, 0.6617 MeV, 1.1730 MeV, and 1.330 MeV) for all samples with various concentrations of Bi2O3. Radiological shielding parameters such as half value layer (HVL), tenth-value layer (TVL), and radiation shielding efficiency (RSE) were estimated and compared for all the different samples. The results prove that increasing the concentration of Bi2O3 leads to the enhancement of the radiation shielding properties of the AM as a shielding material. It was observed that as the energy increases, the efficiency of the samples falls. High energy dependence was found when calculating the HVL and TVL values of the samples, which increased with increases in the energy of the incident photons. A comparison between the sample with the most efficient gamma radiation attenuation capability (AM-25%), concrete, and lead was conducted, and a discussion regarding their radiation shielding properties is presented herein. The results show that the AM-25% sample is superior to the ordinary concrete over all the studied energy ranges, as evidenced by its significantly lower HVLs. On the contrary, lead is superior to the AM-25% sample over all the studied energy ranges owing to its unbeatable density as a shielding material. Overall, this new type of artificial marble has the potential to be used as a radiation shielding material at low- to medium-gamma energy regions, specifically in medical imaging and radiation therapy. Full article
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<p>SEM image of Bi<sub>2</sub>O<sub>3</sub> nanoparticles.</p>
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<p>The experimental setup for measuring the attenuation coefficient.</p>
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<p>The experimental and theoretical <math display="inline"><semantics> <mrow> <mi>L</mi> <mi>A</mi> <mi>C</mi> <mi>s</mi> </mrow> </semantics></math> of the pure artificial sample and the relative deviations.</p>
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<p>The <math display="inline"><semantics> <mrow> <mi>L</mi> <mi>A</mi> <mi>C</mi> <mi>s</mi> </mrow> </semantics></math> of the designed artificial marble samples.</p>
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<p>The <math display="inline"><semantics> <mrow> <mi>H</mi> <mi>V</mi> <mi>L</mi> </mrow> </semantics></math>s of the designed artificial marble samples.</p>
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<p>The <math display="inline"><semantics> <mrow> <mi>T</mi> <mi>V</mi> <mi>L</mi> </mrow> </semantics></math>s of the designed artificial marble samples.</p>
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<p>The <math display="inline"><semantics> <mrow> <mi>R</mi> <mi>P</mi> <mi>E</mi> </mrow> </semantics></math> values of the designed artificial marble samples.</p>
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<p>The <math display="inline"><semantics> <mrow> <mi>H</mi> <mi>V</mi> <mi>L</mi> <mi>s</mi> </mrow> </semantics></math> of ordinary concrete, AM-<math display="inline"><semantics> <mrow> <mn>25</mn> <mo>%</mo> </mrow> </semantics></math>, and lead.</p>
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14 pages, 1744 KiB  
Article
Effect of Processing Routes on Physical and Mechanical Properties of Advanced Cermet System
by Vikas Verma, Margarita García-Hernández, Jorge Humberto Luna-Domínguez, Edgardo Jonathan Suárez-Domínguez, Samuel Monteiro Júnior and Ronaldo Câmara Cozza
Ceramics 2024, 7(2), 625-638; https://doi.org/10.3390/ceramics7020041 - 2 May 2024
Cited by 1 | Viewed by 1356
Abstract
The present research focuses on the effects of different processing routes on the physical and mechanical properties of nano Ti(CN)-based cermets with metallic binders. Tungsten carbide (WC) is added as a secondary carbide and Ni-Co is added as a metallic binder to nano [...] Read more.
The present research focuses on the effects of different processing routes on the physical and mechanical properties of nano Ti(CN)-based cermets with metallic binders. Tungsten carbide (WC) is added as a secondary carbide and Ni-Co is added as a metallic binder to nano Ti(CN)-based cermet processed via conventional and spark plasma sintering (SPS). A systematic comparison of the composition and sintering conditions for different cermets’ systems was carried out to design novel composition and sintering conditions. Nano TiCN powder was prepared by 30 h of ball milling. The highest density of >98.5% was achieved for the SPS-processed cermets sintered at 1200 °C and 1250 °C for 3 min at 60 MPa of pressure in comparison to the conventionally sintered cermets at 1400 °C for 1 h with a two-stage compaction process—uniaxially at 150 MPa and isostatically at 300 MPa of pressure. Comparative X-ray diffraction (XRD) analysis of the milled powders at different time intervals was performed to understand the characteristics of the as-received and milled powders. Peak broadening was observed after 5 h of ball milling, and it increased to 30 hr. Also, peak broadening and a refined carbide size was observed in the XRD and scanning electron microscope (SEM) micrographs of the SPS-processed cermet. Transmission electron microscope (TEM) analysis of the milled powder showed that its internal structure had a regular periodic arrangement of planes. SEM base scattered electron (BSE) images of all the cermets primarily showed three major microstructural phases of the core–rim–binder with black, grey, and white contrast, respectively. With the present sintering conditions, a high hardness of ~16 GPa and a fracture toughness of ~9 MPa m1/2 were obtained for SPS-processed cermets sintered at higher temperatures. Full article
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<p>XRD analysis showing peaks of as-received and ball-milled Ti(CN) powder.</p>
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<p>SEM (<b>a</b>); EDS (<b>b</b>), with TEM images of 30 h ball-milled Ti(CN) powder (<b>c</b>,<b>d</b>).</p>
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<p>XRD patterns of sintered TiCN-based cermets: (<b>a</b>) SPS-processed at 1250 °C; (<b>b</b>) SPS-processed at 1200 °C; (<b>c</b>) conventionally sintered at 1400 °C.</p>
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<p>SEM (BSE) (<b>a</b>) and EDS (<b>b</b>–<b>d</b>) of core–rim–binder phases of conventionally processed Ti(CN)-based cermet at 1400 °C for 3 min.</p>
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<p>Micrograph of SPS cermet processed at 1200 °C (<b>a</b>) and 1250 °C (<b>b</b>).</p>
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<p>Micrograph of EDS of SPS-processed cermet (<b>a</b>) with the core (<b>b</b>), rim (<b>c</b>), and binder (<b>d</b>) regions with their respective chemical compositions.</p>
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18 pages, 4897 KiB  
Article
Enhancing Transparency in Non-Cubic Calcium Phosphate Ceramics: Effect of Starting Powder, LiF Doping, and Spark Plasma Sintering Parameters
by Kacper Albin Prokop, Sandrine Cottrino, Vincent Garnier, Gilbert Fantozzi, Yannick Guyot, Georges Boulon and Małgorzata Guzik
Ceramics 2024, 7(2), 607-624; https://doi.org/10.3390/ceramics7020040 - 30 Apr 2024
Viewed by 1159
Abstract
Our objective is to achieve a new good-quality and mechanically durable high-transparency material that, when activated by rare earth ions, can be used as laser sources, scintillators, or phosphors. The best functional transparent ceramics are formed from high-symmetry systems, mainly cubic. Considering hexagonal [...] Read more.
Our objective is to achieve a new good-quality and mechanically durable high-transparency material that, when activated by rare earth ions, can be used as laser sources, scintillators, or phosphors. The best functional transparent ceramics are formed from high-symmetry systems, mainly cubic. Considering hexagonal hydroxyapatite, which shows anisotropy, the particle size of the initial powder is extremely important and should be of the order of several tens of nanometers. In this work, transparent micro-crystalline ceramics of non-cubic Ca10(PO4)6(OH)2 calcium phosphate were fabricated via Spark Plasma Sintering (SPS) from two types of nanopowders i.e., commercially available (COM. HA) and laboratory-made (LAB. HA) via the hydrothermal (HT) protocol. Our study centered on examining how the quality of sintered bodies is affected by the following parameters: the addition of LiF sintering agent, the temperature during the SPS process, and the quality of the starting nanopowders. The phase purity, microstructure, and optical transmittance of the ceramics were investigated to determine suitable sintering conditions. The best optical ceramics were obtained from LAB. HA nanopowder with the addition of 0.25 wt.% of LiF sintered at 1000 °C and 1050 °C. Full article
(This article belongs to the Special Issue Transparent Ceramics—a Theme Issue in Honor of Dr. Adrian Goldstein)
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<p>Powder XRD patterns of COM. HA and LAB. HA nano-crystalline calcium phosphates together with simulated PDF #01-086-1203 of hexagonal hydroxyapatite.</p>
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<p>TEM image of COM. HA and LAB. HA nano-crystalline calcium phosphates.</p>
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<p>TEM images and particle size distribution of COM. HA (<b>a</b>) and LAB. HA (<b>b</b>).</p>
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<p>Photographs and total transmission spectra of translucent ceramics obtained by SPS at 1050 °C from COM. HA powder with different LiF contents. Transmittance normalized to ceramics’ thickness = 1 mm.</p>
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<p>SEM micrographs of surfaces of ceramics obtained by SPS at 1050 °C from COM. HA nanopowder with different LiF contents.</p>
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<p>Photographs and total transmission spectra of ceramics obtained by SPS at different temperatures from COM. HA nanopowder with 0.25% LiF. Transmittance normalized to ceramics’ thickness = 1 mm.</p>
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<p>SEM micrographs of surfaces of ceramics obtained by SPS at different temperatures from COM.HA nanopowder with 0.25% LiF.</p>
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<p>Photographs and total transmission spectra of ceramics obtained by SPS from COM. HA and LAB. HA nanopowders with and without the addition of LiF and sintered at 1000 °C or 1050 °C. Transmittance normalized to ceramic thickness = 1 mm.</p>
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<p>SEM micrographs of surfaces of ceramics obtained by SPS from COM. HA and LAB. HA nanopowders with and without the addition of LiF and sintered at 1000 °C or 1050 °C.</p>
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11 pages, 2900 KiB  
Communication
Experimental Design of the Adhesion between a PEI/Glass Fiber Composite and the AA1100 Aluminum Alloy with Oxide Coating Produced via Plasma Electrolytic Oxidation (PEO)
by Rafael Resende Lucas, Luis Felipe Barbosa Marques, Luis Rogerio de Oliveira Hein, Edson Cocchieri Botelho and Rogério Pinto Mota
Ceramics 2024, 7(2), 596-606; https://doi.org/10.3390/ceramics7020039 - 29 Apr 2024
Cited by 3 | Viewed by 1060
Abstract
In this study, the AA1100 aluminum alloy underwent the plasma electrolytic oxidation (PEO) process to enhance its adhesion to a thermoplastic composite of polyetherimide (PEI) reinforced with glass fiber, following ASTM D1002:10 standards. A 23 factorial design was employed, varying three parameters [...] Read more.
In this study, the AA1100 aluminum alloy underwent the plasma electrolytic oxidation (PEO) process to enhance its adhesion to a thermoplastic composite of polyetherimide (PEI) reinforced with glass fiber, following ASTM D1002:10 standards. A 23 factorial design was employed, varying three parameters in the oxidation process: immersion time, applied electric potential, and electrolyte concentration (Na2B4O7). The joining of aluminum and thermoplastic composite samples was achieved through oxy-fuel welding (OFW), using oxygen and acetylene gases. For the characterization of the joined samples, a universal tensile testing machine was utilized with a displacement speed of 1.5 mm/min. The analysis of the oxide coating involved scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and Fourier transform infrared spectroscopy (FT-IR). Through variance analysis, it was determined that the statistical model encompasses approximately 80% of the variability in the adhesion process between materials. An improvement of up to 104% in adhesion between the materials was observed with the process, indicating an effective bond due to the presence of the thermoplastic matrix in the treated aluminum sample. This improvement is attributed to the morphology of the oxide coating, resembling corals, with micro-pores and recesses that facilitated mechanical anchoring. Full article
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<p>Graph of voltage and current in the system over time.</p>
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<p>Welding equipment, A—gas cylinders oxygen and acetylene, B—movable arm and torch, C—Aluminum and thermoplastic composite being welded.</p>
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<p>Radar chart with some PEO process parameters that affect oxide coating characteristics.</p>
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<p>Scanning electron microscopy image of the AA1100 aluminum alloy treated using the PEO process, from process 6.</p>
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<p>ATR FT-IR spectra of aluminum sample in the 3 states.</p>
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17 pages, 8091 KiB  
Article
Hot Corrosion Behavior of Plasma-Sprayed Gd2Zr2O7/YSZ Functionally Graded Thermal Barrier Coatings
by Rajasekaramoorthy Manogaran, Karthikeyan Alagu, Anderson Arul, Anandh Jesuraj, Dinesh Kumar Devarajan, Govindhasamy Murugadoss and Kamalan Kirubaharan Amirtharaj Mosas
Ceramics 2024, 7(2), 579-595; https://doi.org/10.3390/ceramics7020038 - 29 Apr 2024
Cited by 1 | Viewed by 1168
Abstract
The development of advanced thermal barrier coating (TBC) materials with better hot corrosion resistance, phase stability, and residual stresses is an emerging research area in the aerospace industry. In the present study, four kinds of TBCs, namely, single-layer yttria-stabilized zirconia (YSZ), single-layer gadolinium [...] Read more.
The development of advanced thermal barrier coating (TBC) materials with better hot corrosion resistance, phase stability, and residual stresses is an emerging research area in the aerospace industry. In the present study, four kinds of TBCs, namely, single-layer yttria-stabilized zirconia (YSZ), single-layer gadolinium zirconate (GZ), bilayer gadolinium zirconate/yttria-stabilized zirconia (YSZ/GZ), and a multilayer functionally graded coating (FGC) of YSZ and GZ, were deposited on NiCrAlY bond-coated nickel-based superalloy (Inconel 718) substrates using the atmospheric plasma spray technique. The hot corrosion behavior of the coatings was tested by applying a mixture of Na2SO4 and V2O5 onto the surface of TBC, followed by isothermal heat treatment at 1273 K for 50 h. The characterization of the corroded samples was performed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) to identify physical and chemical changes in the coatings. GIXRD was used to analyze the residual stresses of the coatings. Residual stress in the FGC coating was found to be −15.2 ± 10.6 MPa. The wear resistance of TBCs is studied using a linear reciprocating tribometer, and the results indicate that gadolinium zirconate-based TBCs showed better performance when deposited in bilayer and multilayered functionally graded TBC systems. The wear rate of as-coated FGC coatings was determined to be 2.90 × 10−4 mm3/Nm, which is lower than the conventional YSZ coating. Full article
(This article belongs to the Special Issue Research Progress in Ceramic Coatings)
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<p>Schematic representation of TBCs: (<b>a</b>) YSZ, (<b>b</b>) GZ, (<b>c</b>) YSZ/GZ bilayer, and (<b>d</b>) FGC of YSZ/GZ.</p>
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<p>High magnification FE-SEM images of (<b>a</b>) NiCrAlY bond coat powder, (<b>b</b>) YSZ and, (<b>c</b>) GZ.</p>
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<p>Corrosive salt paste was applied to samples on (<b>a</b>) YSZ, (<b>b</b>) GZ, (<b>c</b>) YSZ/GZ bilayer, and (<b>d</b>) FGC TBCs. Images after hot corrosion tests of (<b>e</b>) YSZ (<b>f</b>) GZ (<b>g</b>) YSZ/GZ, (<b>h</b>) delaminated top layer of YSZ/GZ, and (<b>i</b>) FGC.</p>
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<p>XRD pattern of (<b>a</b>) as-coated YSZ and (<b>b</b>) YSZ after the hot corrosion test and (<b>c</b>) as-coated GZ and (<b>d</b>) GZ after the hot corrosion test.</p>
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<p>XRD pattern of the (<b>a</b>) as-coated YSZ/GZ bilayer and (<b>b</b>) YSZ/GZ bilayer after the hot corrosion test and (<b>c</b>) as-coated FGC and (<b>d</b>) FGC after the hot corrosion test.</p>
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<p>High-magnification HR-SEM images of as-coated TBCs (<b>a</b>) YSZ, (<b>b</b>) GZ, (<b>c</b>) YSZ/GZ, and (<b>d</b>) FGC and high-magnification HR SEM images of hot corrosion-tested samples (<b>e</b>) YSZ, (<b>f</b>) GZ, (<b>g</b>) the YSZ/GZ bilayer, and (<b>h</b>) FGC.</p>
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<p>SEM micrographs and EDS spectra of TBCs after the hot corrosion test: (<b>a</b>) SEM micrograph of YSZ and (<b>b</b>) EDS spectrum of YSZ. (<b>c</b>) SEM micrograph of GZ, (<b>d</b>) EDS spectrum of GZ, (<b>e</b>) SEM micrograph of the YSZ/GZ bilayer, (<b>f</b>) EDS spectrum of the YSZ/GZ bilayer, (<b>g</b>) SEM micrograph of FGC TBC, and (<b>h</b>) EDS spectrum of FGC TBC.</p>
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<p>Residual stress measurement plots: (<b>a</b>) YSZ XRD pattern, (<b>b</b>) GZ XRD pattern, (<b>c</b>) YSZ d vs. sin<sup>2</sup>ψ plot, and (<b>d</b>) GZ d vs. sin<sup>2</sup>ψ plot.</p>
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<p>Residual stress measurement plots: (<b>a</b>) DL XRD pattern, (<b>b</b>) FGC XRD pattern, (<b>c</b>) YSZ/GZ bilayer, d vs. sin<sup>2</sup>ψ plot, and (<b>d</b>) FGC d vs. sin<sup>2</sup>ψ plot.</p>
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<p>Coefficient of friction vs. sliding distance of coatings (<b>a</b>) as-coated TBC, (<b>b)</b> heat-treated TBC, and (<b>c</b>) wear at high temperature (673 K) and depth vs. scan length wear profile of (<b>d</b>) as-coated TBC, (<b>e</b>) heat-treated TBC, and (<b>f</b>) wear profile at high temperature.</p>
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17 pages, 7052 KiB  
Article
Ultra-Broadband Plasmon Resonance in Gold Nanoparticles Precipitated in ZnO-Al2O3-SiO2 Glass
by Georgiy Shakhgildyan, Leon Avakyan, Grigory Atroshchenko, Maxim Vetchinnikov, Alexandra Zolikova, Elena Ignat’eva, Mariam Ziyatdinova, Elena Subcheva, Lusegen Bugaev and Vladimir Sigaev
Ceramics 2024, 7(2), 562-578; https://doi.org/10.3390/ceramics7020037 - 25 Apr 2024
Viewed by 1256
Abstract
Optical materials with a tunable localized surface plasmon resonance (LSPR) are of great interest for applications in photonics and optoelectronics. In the present study, we explored the potential of generating an LSPR band with an ultra-broad range of over 1000 nm in gold [...] Read more.
Optical materials with a tunable localized surface plasmon resonance (LSPR) are of great interest for applications in photonics and optoelectronics. In the present study, we explored the potential of generating an LSPR band with an ultra-broad range of over 1000 nm in gold nanoparticles (NPs), precipitated through a thermal treatment in ZnO-Al2O3-SiO2 glass. Using optical absorption spectroscopy, we demonstrated that the LSPR band’s position and shape can be finely controlled by varying the thermal treatment route. Comprehensive methods including Raman spectroscopy, X-ray diffraction, and high-resolution transmission electron microscopy were used to study the glass structure, while computational approaches were used for the theoretical description of the absorption spectra. The obtained results allowed us to suggest a scenario responsible for an abnormal LSPR band broadening that includes a possible interparticle plasmonic coupling effect taking place during the liquid–liquid phase separation of the heat-treated glass. The formation of gold NPs with an ultra-broad LSPR band in glasses holds promise for sensitizing rare earth ion luminescence for new photonics devices. Full article
(This article belongs to the Special Issue Innovative Manufacturing Processes of Silicate Materials)
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<p>Absorption spectra of the raw glass and glasses heat-treated in the 800–850 °C range for 5 h. Insets show visual appearance of glasses treated at 800 and 850 °C in transmitted and reflected light (left and right panel, respectively). Each glass sample size is ≈1 cm × 1 cm.</p>
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<p>Absorption spectra of the raw glass and glasses heat-treated in the 750–820 °C range for 20 h. Insets show the visual appearance of glasses treated at 800 and 815 °C in transmitted and reflected light (left and right panel, respectively). Each glass sample size is ≈1 cm × 1 cm.</p>
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<p>XRD patterns of glasses heat-treated for 5 h (<b>a</b>) and 20 h (<b>b</b>); Raman spectra of raw glass and glasses heat-treated for 5 h (<b>c</b>) and 20 h (<b>d</b>). Heat treatment temperatures are indicated.</p>
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<p>TEM and HRTEM images of glass samples heat-treated for 5 h at 815 °C (<b>a</b>) and 850 °C (<b>b</b>). Insets show enlarged images and Fourier-filtered images of the marked zones with corresponding numbers.</p>
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<p>Particle size distribution (<b>a</b>–<b>c</b>) and interparticle distance (<b>d</b>–<b>f</b>) obtained from the TEM images of the glass samples treated for 5 h at 800, 815, and 850 °C (from left to right).</p>
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<p>TEM and HRTEM images of glass samples heat-treated for 20 h at 800 °C. Insets show enlarged images and Fourier-filtered images of the marked zones with corresponding numbers.</p>
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<p>TEM and HRTEM images of glass samples heat-treated for 20 h at 810 °C. Insets show enlarged images and Fourier-filtered images of the marked zones with corresponding numbers.</p>
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<p>TEM and HRTEM images of glass samples heat-treated for 20 h at 815 °C. Insets show enlarged images and Fourier-filtered images of the marked zones with corresponding numbers.</p>
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<p>Particle size distribution (<b>a</b>–<b>c</b>) and interparticle distance (<b>d</b>–<b>f</b>) obtained from the TEM images of the glass samples treated for 20 h at 800, 810, and 815 °C (from left to right).</p>
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<p>The comparison of the experimental absorption spectrum of the sample 780-20 (blue dots) with the calculated spectra for different models of single gold NPs: top panel—50 nm spherical particle (red dashes) and 10 nm spherical particle (solid red), both in the in matrix with n<sub>D</sub> = 1.6; middle panel—50 nm spherical particle (purple dashed) and 10 nm spherical particle (solid purple), both in the in matrix with n<sub>D</sub> = 2.0; bottom panel—60 nm oblate spheroid particle and 10 nm oblate spheroid particle, both in the in matrix with n<sub>D</sub> = 1.6. The smaller 10 nm particles cannot explain the experimental data, while big particles (50–60 nm) are able to describe the experiment but are not presented in the sample.</p>
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<p>Evolution with heat treatment temperature at 20 h for the following parameters: LSPR band peak position (squares), particle size (triangles), and interparticle distance (circles).</p>
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<p>(<b>a</b>) The absorption efficiencies calculated for isolated gold nanoparticle and agglomerates containing 19, 43, or 87 nanoparticles. (<b>b</b>) The absorption (left y axis) and scattering (right y axis) efficiencies calculated for an agglomerate of 87 nanoparticles (solid curves) and isolated nanoparticles (short dashes).</p>
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15 pages, 2645 KiB  
Article
Study of the Surface-Layer Softening Effects in xLi2ZrO3–(1−x)Li4SiO4 Ceramics under Irradiation with He2+ Ions
by Dmitriy I. Shlimas, Daryn B. Borgekov, Kayrat K. Kadyrzhanov, Artem L. Kozlovskiy and Maxim V. Zdorovets
Ceramics 2024, 7(2), 547-561; https://doi.org/10.3390/ceramics7020036 - 16 Apr 2024
Viewed by 1130
Abstract
The study investigates alterations in the mechanical and thermophysical properties of ceramics composed of xLi2ZrO3–(1−x)Li4SiO4 as radiation damage accumulates, mainly linked to helium agglomeration in the surface layer. This research is motivated by the potential to [...] Read more.
The study investigates alterations in the mechanical and thermophysical properties of ceramics composed of xLi2ZrO3–(1−x)Li4SiO4 as radiation damage accumulates, mainly linked to helium agglomeration in the surface layer. This research is motivated by the potential to develop lithium-containing ceramics characterized by exceptional strength properties and a resistance to the accumulation of radiation damage and ensuing deformation distortions in the near-surface layer. The study of the radiation damage accumulation processes in the near-surface layer was conducted through intense irradiation of ceramics using He2+ ions at a temperature of 700 °C, simulating conditions closely resembling operation conditions. Following this, a correlation between the accumulation of structural modifications (value of atomic displacements) and variations in strength and thermophysical characteristics was established. During the research, it was observed that two-component ceramics exhibit significantly greater resistance to external influences and damage accumulation related to radiation exposure compared to their single-component counterparts. Furthermore, the composition that provides the highest resistance to softening in two-component ceramics is an equal ratio of the components of 0.5Li2ZrO3–0.5Li4SiO4 ceramics. Full article
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<p>(<b>a</b>) The results of calculated data for simulation of the distribution of the value of atomic displacements along the trajectory of ion motion in the near-surface layer depending on the irradiation fluence. (<b>b</b>) The dependence of the variation in the value of atomic displacements at the maximum with a change in irradiation fluence (the dependence is presented on a logarithmic scale).</p>
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<p>SEM images of the morphological features of synthesized ceramics depending on the variation of components: (<b>a</b>) Li<sub>2</sub>ZrO<sub>3</sub>; (<b>b</b>) 0.75Li<sub>2</sub>ZrO<sub>3</sub>–0.25Li<sub>4</sub>SiO<sub>4</sub>; (<b>c</b>) 0.5Li<sub>2</sub>ZrO<sub>3</sub>–0.5Li<sub>4</sub>SiO<sub>4</sub>; (<b>d</b>) 0.25Li<sub>2</sub>ZrO<sub>3</sub>–0.75Li<sub>4</sub>SiO<sub>4</sub>; and (<b>e</b>) Li<sub>4</sub>SiO<sub>4</sub>.</p>
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<p>The measurement results of the strength characteristics of Li<sub>2</sub>ZrO<sub>3</sub>–Li<sub>4</sub>SiO<sub>4</sub> ceramics (hardness, maximum pressure that the ceramic can withstand during a single compression, and stress intensity factor) depending on the variation in the ratio of the components.</p>
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<p>The results of a comparative analysis of the factors of change in strength characteristics depending on the concentration in the composition of Li<sub>4</sub>SiO<sub>4</sub> ceramics (the comparison was carried out with respect to the original Li<sub>2</sub>ZrO<sub>3</sub> sample, which did not contain Li<sub>4</sub>SiO<sub>4</sub> in its composition).</p>
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<p>(<b>a</b>) The data on alterations in the thermal conductivity coefficient depending on changes in the ratio of components in ceramics. (<b>b</b>) The data on alterations in the coefficient of volumetric thermal expansion depending on the ratio of components in ceramics after 150 h of thermal exposure.</p>
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<p>The results of alterations in the strength characteristics of the studied Li<sub>2</sub>ZrO<sub>3</sub>–Li<sub>4</sub>SiO<sub>4</sub> ceramics depending on the value of accumulated atomic displacements in the damaged surface layer: (<b>a</b>) changes in hardness; (<b>b</b>) change in resistance to single compression (change in maximum pressure); and (<b>c</b>) change in stress intensity factor in the damaged layer under mechanical action.</p>
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<p>The assessment results of changes in the ceramics’ resistance to degradation of strength characteristics during irradiation and accumulation of structural damage (the value of atomic displacements): (<b>a</b>) change in the softening value; (<b>b</b>) change in resistance to mechanical stress during a single compression; and (<b>c</b>) change in crack resistance (resistance to cracking under external mechanical influences).</p>
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<p>The assessment results of changes in the thermophysical parameters of xLi<sub>2</sub>ZrO<sub>3</sub>–(1−x)Li<sub>4</sub>SiO<sub>4</sub> ceramics exposed to irradiation: (<b>a</b>) results of changes in the thermal conductivity coefficient and (<b>b</b>) the results of changes in the value of reduction in thermal conductivity.</p>
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17 pages, 6794 KiB  
Article
Effect of Thermal Cycling or Simulated Gastric Acid on the Surface Characteristics of Dental Ceramic Materials
by Panagiotis Pandoleon, Katia Sarafidou, Georgia K. Pouroutzidou, Anna Theocharidou, George A. Zachariadis and Eleana Kontonasaki
Ceramics 2024, 7(2), 530-546; https://doi.org/10.3390/ceramics7020035 - 15 Apr 2024
Viewed by 1296
Abstract
(1) Background: The presence of various dental ceramic materials with different chemical compositions complicates clinicians’ decision making, especially in cases with a highly acidic environment appearing in patients suffering from gastroesophageal reflux disease or other eating disorders. Thermal alterations in the oral cavity [...] Read more.
(1) Background: The presence of various dental ceramic materials with different chemical compositions complicates clinicians’ decision making, especially in cases with a highly acidic environment appearing in patients suffering from gastroesophageal reflux disease or other eating disorders. Thermal alterations in the oral cavity can also affect surface structure and roughness, resulting in variations in both degradation mechanisms and/or bacteria adhesion. The aim of the present in vitro study was to evaluate the effect of thermal cycling and exposure to simulated gastric acid on the surface roughness of different ceramics; (2) Methods: Five groups of different ceramics were utilized, and twenty specimens were fabricated for each group. Specimens were either thermocycled for 10,000 cycles in distilled water or immersed in simulated gastric acid for 91 h. The evaluation of surface roughness was performed with optical profilometry, while scanning electron microscopy, X-ray diffraction analysis and inductively coupled plasma atomic emission spectroscopy were also performed; (4) Conclusions: Based on the combination of the surface roughness profile and structural integrity, zirconia specimens presented the smallest changes after immersion in simulated gastric acid followed by lithium disilicate materials. Zirconia-reinforced lithium silicate ceramic presented the most notable changes in microstructure and roughness after both treatments. Full article
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<p>SEM micrographs of Enamic (<b>A</b>–<b>C</b>), Suprinity (<b>D</b>–<b>F</b>) and Katana (<b>G</b>–<b>I</b>). Below each micrograph, a respective EDS spectrum is presented, received from backscattered micrographs.</p>
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<p>SEM micrographs of e*max (<b>A</b>–<b>C</b>) and Lisi Press (<b>D</b>–<b>F</b>). Below each micrograph, a respective EDS spectrum is presented, received from backscattered micrographs.</p>
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<p>XRD patterns of specimens from the Enamic (E), Suprinity (S) and Katana (K) groups before treatment (E1, S1 and K1), after TC (E11, S11 and K11) and after SGA (E1-HCl, S1-HCl and K1-HCl).</p>
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<p>XRD patterns of specimens from the e*max (I) and Lisi press (L) group before treatment (I1 and L1), after TC (I11 and L11) and after SGA (I1-HCl and L1-HCl).</p>
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<p>Results of cell metabolic activity/viability after direct metabolic-based tests (MTT assay). OD values were normalized compared to the control (cells without any material).</p>
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14 pages, 6859 KiB  
Article
Effect of B2O3 and Basic Oxides on Network Structure and Chemical Stability of Borosilicate Glass
by Ming Lian, Tian Wang and Chong Wei
Ceramics 2024, 7(2), 516-529; https://doi.org/10.3390/ceramics7020034 - 15 Apr 2024
Cited by 1 | Viewed by 1256
Abstract
Glass properties play crucial roles in ensuring the safety and reliability of electronic packaging. However, challenges, such as thermal expansion and resistance to acid corrosion, pose long-term service difficulties. This study investigated the impact of the microstructure on acid resistance by adjusting the [...] Read more.
Glass properties play crucial roles in ensuring the safety and reliability of electronic packaging. However, challenges, such as thermal expansion and resistance to acid corrosion, pose long-term service difficulties. This study investigated the impact of the microstructure on acid resistance by adjusting the glass composition. A glass material with excellent acid resistance was obtained by achieving a similar coefficient of thermal expansion to tantalum; it exhibited a weight loss rate of less than 0.03% when submerged in 38% sulfuric acid at 85 °C for 200 h. Theoretically, this glass can be used to seal wet Ta electrolytic capacitors. Differential scanning calorimetry (DSC) was used to analyze the glass transition temperature and thermal stability of borosilicate glasses. X-ray diffractometry (XRD), scanning electron microscopy (SEM), and Raman spectroscopy were used to study the microstructure of the amorphous phase of the borosilicate glass, which revealed a close relationship between the degree of network phase separation in the borosilicate glass and the degree of polymerization (isomorphic polyhedron value, IP) of the glass matrix. The IP value decreased from 3.82 to 1.98 with an increasing degree of phase separation. Boron transitions from [BO4] to [BO3] within the glass network structure with increasing boron oxide content, which diminishes the availability of free oxygen provided by alkaline oxide, resulting in a lower acid resistance. Notably, the glass exhibited optimal acid resistance at boron trioxide and mixed alkaline oxide contents of 15% and 6%, respectively. Raman experiments revealed how the distributions of various bridging oxygen atoms (Qn) affect the structural phase separation of the glass network. Additionally, Raman spectroscopy revealed the depolymerization of Q4 into Q3, thereby promoting high-temperature phase separation and highlighting the unique advantages of Raman spectroscopy for phase recognition. Full article
(This article belongs to the Special Issue Advances in Ceramics, 2nd Edition)
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<p>XRD pattern of base glass.</p>
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<p>Glass transition temperature (<b>a</b>) and thermal expansion coefficient (<b>b</b>) of base glass.</p>
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<p>Micromorphologies of samples under light microscope after 4% HF solution etching for 60 s ((<b>A<sub>1</sub></b>–<b>A<sub>6</sub></b>) in order).</p>
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<p>SEM and EDS of borosilicate glass after 60 s by 4% HF etching solution (green area represents B element EDS).</p>
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<p>EDS of glass dendritic phase separation.</p>
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<p>Raman spectrum of base glass after peak fitting.</p>
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<p>The Raman spectra of the stretching vibration (700 cm<sup>−1</sup>–1200 cm<sup>−1</sup>) of borosilicate glass (A<sub>1</sub>–A<sub>6</sub>).</p>
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<p>Basic glass expansion coefficient curve and acid resistance weight loss rate curve.</p>
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<p>Network structure mechanism diagram of B<sub>2</sub>O<sub>3</sub>-reinforced borosilicate base glass.</p>
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<p>Raman spectrum at stretching vibration (700 cm<sup>−1</sup>–1200 cm<sup>−1</sup>) of A<sub>2</sub> base glass after peak separation and fitting.</p>
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<p>Percentage of Q<sub>n</sub> (n = 1,2,3,4) in bending vibration (<b>a</b>) and stretching vibration (<b>b</b>) of sample A<sub>1</sub>–A<sub>6</sub>.</p>
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12 pages, 2760 KiB  
Article
Experiments Using Different Types of Waste to Manufacture Ceramic Materials: Examples on a Laboratory Scale
by Manuel M. Jordán Vidal
Ceramics 2024, 7(2), 504-515; https://doi.org/10.3390/ceramics7020033 - 4 Apr 2024
Viewed by 1573
Abstract
Reusing waste as raw materials to produce other materials can entail a decrease in production costs and in the abusive use of natural resources. Furthermore, it can even improve the properties of the end product or material. In this sense, a review of [...] Read more.
Reusing waste as raw materials to produce other materials can entail a decrease in production costs and in the abusive use of natural resources. Furthermore, it can even improve the properties of the end product or material. In this sense, a review of the most relevant literature published in recent decades shows that numerous solutions have been proposed or implemented, such as its use to produce construction materials, catalysts, pigments, pozzolana, refractory materials, glass-ceramic products, etc. Our research group has verified the viability of using different types of waste as secondary raw materials to obtain several types of ceramic, glassy and glassceramic materials, as well as frits. This article highlights several types of industrial waste that have both non-toxic (Li, Ca and Mn) and highly toxic (Cr VI) differentiating elements that can be used in sintering and vitrification industrial processes to immobilise them or render them inert. We studied the compositions and characterised the various materials obtained, conducting toxicity and leaching tests on waste/materials designed with high amounts of chromium. A suggestion for future lines of research has been proposed. Full article
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<p>Deposited material, found on a beach, showing the general appearance of the samples taken during the sampling process and which can be classified into two types according to its visual features: (<b>a</b>,<b>b</b>) glassy-crystalline material and (<b>c</b>) glassy material with conchoidal fractures and a glassy shine [<a href="#B16-ceramics-07-00033" class="html-bibr">16</a>].</p>
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<p>Appearance of a thin sheet of the glass obtained by melting the material rich in manganese oxide at 1450 °C, observed through a binocular loupe (<b>a</b>) and showing its amber colour when thinned (<b>b</b>); and (<b>c</b>) the optical absorption spectrum, which shows a 95% transmission for wavelengths greater than 700 nm.</p>
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<p>Variation in the water absorption of the tiles obtained as a function of the residue content added in the formulation of the original paste [<a href="#B1-ceramics-07-00033" class="html-bibr">1</a>].</p>
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<p>XRD of the samples of the material rich in manganese oxide: (<b>a</b>) glassier sample (G: gehlenite, Sil: replaced aluminium silicate); (<b>b</b>) XRD diffractogram of the glass-ceramic sample (G: gehlenite; Sil: replaced aluminium silicate; and SMn: manganese sulphide).</p>
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<p>DTA/TG traces from the vitreous and vitro-crystalline sample [<a href="#B6-ceramics-07-00033" class="html-bibr">6</a>].</p>
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<p>Thermal behaviour (DTA) for G1, G2 and G3 glass samples.</p>
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13 pages, 1960 KiB  
Article
The Origin of the Low-Temperature Minimum of Electrical Resistivity in Strontium Ferromolybdate Ceramics
by Gunnar Suchaneck, Evgenii Artiukh and Gerald Gerlach
Ceramics 2024, 7(2), 491-503; https://doi.org/10.3390/ceramics7020032 - 1 Apr 2024
Viewed by 1310
Abstract
In this work, we analyze the electrical behavior of strontium ferromolybdate below room temperature. We demonstrate that in SFMO ceramics, SFMO thin films deposited by pulsed laser deposition including (100) and (111) textured thin films, as well as in nonstoichiometric SFMO ceramics, an [...] Read more.
In this work, we analyze the electrical behavior of strontium ferromolybdate below room temperature. We demonstrate that in SFMO ceramics, SFMO thin films deposited by pulsed laser deposition including (100) and (111) textured thin films, as well as in nonstoichiometric SFMO ceramics, an intergrain tunneling mechanism of charge carrier conduction leads to a decrease in resistivity with increasing temperature in the low-temperature region. This intergrain tunneling can be attributed to fluctuation-induced tunneling. On the other hand, bulk metallic resistivity of the grains, which increases with temperature, becomes dominant at higher temperatures and magnetic fluxes. The interplay of these conduction mechanisms leads to a resistivity minimum, i.e., a resistivity upturn below the temperature of minimum resistivity. Several mechanisms have been discussed in the literature to describe the low-temperature upturn in resistivity. Based on available literature data, we propose a revised model describing the appearance of a low-temperature resistivity minimum in SFMO ceramics by an interplay of fluctuation-induced tunneling and metallic conductivity. Additionally, we obtained that in the region of metallic conductivity at higher temperatures and magnetic fluxes, the pre-factor Rm of the temperature-dependent term of metallic conductivity written as a power law decreases exponentially with the temperature exponent m of this power law. Here, the value of m is determined by the charge scattering mechanism. Full article
(This article belongs to the Special Issue Advances in Electronic Ceramics)
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<p>Fit of resistivity data of polycrystalline SFMO ceramics fabricated by the solid-state reaction technique [<a href="#B29-ceramics-07-00032" class="html-bibr">29</a>] to Equation (14).</p>
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<p>Fit of resistivity data (<b>a</b>) from [<a href="#B71-ceramics-07-00032" class="html-bibr">71</a>] and (<b>b</b>) from [<a href="#B73-ceramics-07-00032" class="html-bibr">73</a>] of ordered SFMO thin films deposited by pulsed laser deposition to Equation (14).</p>
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<p>Fit of resistivity data from [<a href="#B74-ceramics-07-00032" class="html-bibr">74</a>] of nonstoichiometric Sr<sub>2</sub>Fe<span class="html-italic"><sub>x</sub></span>Mo<sub>2-<span class="html-italic">x</span></sub>O<sub>6</sub> ceramics prepared by solid-state reaction and sintered for 12 h at 1280 °C in a stream of 5% H<sub>2</sub>/Ar to Equation (14).</p>
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<p>Correlation between pre-factor <span class="html-italic">R<sub>m</sub></span> and exponent <span class="html-italic">m</span> in Equation (8). 1—[<a href="#B29-ceramics-07-00032" class="html-bibr">29</a>], 2—[<a href="#B71-ceramics-07-00032" class="html-bibr">71</a>], 3—[<a href="#B74-ceramics-07-00032" class="html-bibr">74</a>], 4—[<a href="#B77-ceramics-07-00032" class="html-bibr">77</a>], 5—[<a href="#B78-ceramics-07-00032" class="html-bibr">78</a>], 6—[<a href="#B79-ceramics-07-00032" class="html-bibr">79</a>].</p>
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14 pages, 4204 KiB  
Article
Sonochemical Synthesis of Indium Nitride Nanoparticles and Photocatalytic Composites with Titania
by Aikaterina Paraskevopoulou, Pavlos Pandis, Christos Argirusis and Georgia Sourkouni
Ceramics 2024, 7(2), 478-490; https://doi.org/10.3390/ceramics7020031 - 27 Mar 2024
Cited by 1 | Viewed by 1418
Abstract
Indium nitride is an excellent semiconductor that belongs to the group of III nitride materials. Due to its unique properties, it is applied to various optoelectronic applications. However, its low thermal stability makes it difficult to synthesize. The present study introduces the synthesis [...] Read more.
Indium nitride is an excellent semiconductor that belongs to the group of III nitride materials. Due to its unique properties, it is applied to various optoelectronic applications. However, its low thermal stability makes it difficult to synthesize. The present study introduces the synthesis of indium nitride nanoparticles, using ultrasound power (sonochemistry). The sonochemical method provides a low-cost and rapid technique for nanomaterial synthesis. InN nanoparticles were produced in only 3 h through the sonochemical reaction of InCl3 and LiN3. Xylene was used as a reaction solvent. X-ray powder diffraction (XRD) as well as high-resolution transmission electron microscopy (HRTEM) were adopted for the characterization of the obtained powder. According to our results, ultrasound contributed to the synthesis of InN nanocrystals in a cubic and a hexagonal phase. The obtained InN nanoparticles were further used to decorate titanium dioxide (TiO2) by means of ultrasound. The contribution of InN nanoparticles on the processes of photocatalysis was investigated through the degradation of methylene blue (MB), a typical organic substance acting in place of an environment pollutant. According to the obtained results, InN nanoparticles improved the photocatalytic activity of TiO2 by 41.8% compared with commercial micrometric titania. Full article
(This article belongs to the Special Issue Advances in Ceramics, 2nd Edition)
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<p>(<b>a</b>) XRD pattern of InN nanoparticles produced by the sonochemical method. (<b>b</b>) Typical XRD pattern of InN nanoparticles according to Bai et al. [<a href="#B14-ceramics-07-00031" class="html-bibr">14</a>].</p>
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<p>HRTEM images of InN nanoparticles: (<b>a</b>) 2 nm scale bar; (<b>b</b>) 50 nm scale bar; (<b>c</b>) 20 nm scale bar.</p>
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<p>XRD pattern of KRONOS<sup>®</sup> TiO<sub>2</sub> [<a href="#B59-ceramics-07-00031" class="html-bibr">59</a>] decorated with InN nanoparticles.</p>
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<p>HRTEM images showing the decoration of TiO<sub>2</sub> with InN nanoparticles: (<b>a</b>) low magnification; (<b>b</b>) (101) TiO<sub>2</sub>; (<b>c</b>) (102) InN.</p>
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<p>Absorbance spectrum of MB using TiO<sub>2</sub> Kronos 1077 as a photocatalyst.</p>
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<p>Absorbance spectra of MB using TiO<sub>2</sub> decorated with InN nanoparticles, proving its activity as a photocatalyst.</p>
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<p>Development of the decolouration over time using different materials in this study.</p>
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12 pages, 3362 KiB  
Article
Zero-Temperature Coefficient of Resonant Frequency in [(Mg0.6Zn0.4)0.95Co0.05]1.02TiO3.02-Ca0.6(La0.9Y0.1)0.2667TiO3 Ultra-Low-Loss Composite Dielectrics
by Yuan-Bin Chen and Jie Peng
Ceramics 2024, 7(2), 466-477; https://doi.org/10.3390/ceramics7020030 - 26 Mar 2024
Viewed by 1189
Abstract
Investigating the microwave dielectric properties of ceramics prepared through the conventional solid-state route, such as x[(Mg0.6Zn0.4)0.95Co0.05]1.02TiO3.02-(1−x)Ca0.6(La0.9Y0.1)0.2667TiO3, reveals notable characteristics. [(Mg0.6 [...] Read more.
Investigating the microwave dielectric properties of ceramics prepared through the conventional solid-state route, such as x[(Mg0.6Zn0.4)0.95Co0.05]1.02TiO3.02-(1−x)Ca0.6(La0.9Y0.1)0.2667TiO3, reveals notable characteristics. [(Mg0.6Zn0.4)0.95Co0.05]1.02TiO3.02 shows a permittivity (εr) of approximately 20, a high quality factor (Q × f) ranging between 250,000 and 560,000 GHz, and a temperature coefficient of resonant frequency (τf) of approximately −65 ppm/°C. To enhance the temperature stability, Ca0.6(La0.9Y0.1)0.2667TiO3 featuring a τf value of +374 ppm/°C was incorporated into the [(Mg0.6Zn0.4)0.95Co0.05]1.02TiO3.02 composition. τf demonstrated an increase with rising Ca0.6(La0.9Y0.1)0.2667TiO3 content, reaching zero at x = 0.95. A ceramic composition of 0.95[(Mg0.6Zn0.4)0.95Co0.05]1.02TiO3.02-0.05Ca0.6(La0.9Y0.1)0.2667TiO3, incorporating 3wt.% BaCu(B2O5) as sintering aids, exhibited outstanding microwave dielectric properties: εr~22.5, Q × f~195,000 (at 9 GHz), and τf~0.1ppm/°C, with a sintering temperature at 950 °C. This material is proposed as a prospective candidate for 6G band components and GPS antennas. Full article
(This article belongs to the Special Issue Advances in Electronic Ceramics)
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<p>X-ray diffraction patterns of 0.95MZCT-0.05CLYT ceramics doped with 3wt.% BCB and sintered at various temperatures for 4 h: (<b>a</b>) 900 °C, (<b>b</b>) 925 °C, (<b>c</b>) 950 °C, (<b>d</b>) 975 °C, and (<b>e</b>) 1000 °C (♣: MZCT; ★: CLYT).</p>
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<p>SEM micrographs of 0.95MZCT-0.05CLYT ceramics doped with 3wt.% BCB and sintered at (<b>a</b>) 900, (<b>b</b>) 925, (<b>c</b>) 950, (<b>d</b>) 975, and (<b>e</b>) 1000 °C.</p>
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<p>SEM micrographs of 0.95MZCT-0.05CLYT ceramics doped with 3wt.% BCB and sintered at (<b>a</b>) 900, (<b>b</b>) 925, (<b>c</b>) 950, (<b>d</b>) 975, and (<b>e</b>) 1000 °C.</p>
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<p>The marks of SEM for the 0.95MZCT-0.05CLYT ceramics doped with 3wt.% BCB and sintered at 950 °C.</p>
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<p>(<b>a</b>) Bulk density, (<b>b</b>) relative density, and (<b>c</b>) porosity of xMZCT-(1-x)CLYT ceramics with 3wt.% BCB as a function of the sintering temperature.</p>
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<p>(<b>a</b>) Bulk density, (<b>b</b>) relative density, and (<b>c</b>) porosity of xMZCT-(1-x)CLYT ceramics with 3wt.% BCB as a function of the sintering temperature.</p>
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<p>Permittivity curves of xMZCT-(1−x)CLYT ceramics doped with 3wt.% BCB at different sintering temperatures for 4 h.</p>
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<p>Q × f values of xMZCT-(1−x)CLYT ceramics doped with 3wt.% BCB as a function of the sintering temperature.</p>
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<p>τ<sub>f</sub> values of the xMZCT-(1−x)CLYT ceramic system with 3 wt.% BCB sintered at different temperatures for 4 h.</p>
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14 pages, 4272 KiB  
Article
Negative Temperature Coefficient Properties of Natural Clinoptilolite
by Loredana Schiavo, Lucrezia Aversa, Roberto Verucchi, Rachele Castaldo, Gennaro Gentile and Gianfranco Carotenuto
Ceramics 2024, 7(2), 452-465; https://doi.org/10.3390/ceramics7020029 - 23 Mar 2024
Viewed by 1611
Abstract
Negative temperature coefficient (NTC) materials are usually based on ceramic semiconductors, and electrons are involved in their transport mechanism. A new type of NTC material, adequate for alternating current (AC) applications, is represented by zeolites. Indeed, zeolites are single charge carrier ionic conductors [...] Read more.
Negative temperature coefficient (NTC) materials are usually based on ceramic semiconductors, and electrons are involved in their transport mechanism. A new type of NTC material, adequate for alternating current (AC) applications, is represented by zeolites. Indeed, zeolites are single charge carrier ionic conductors with a temperature-dependent electrical conductivity. In particular, electrical transport in zeolites is due to the monovalent charge-balancing cations, like K+, capable of hopping between negatively charged sites in the aluminosilicate framework. Owing to the highly non-linear electrical behavior of the traditional electronic NTC materials, the possibility to have alternative types of materials, showing linearity in their electrical behavior, is very desirable. Among different zeolites, natural clinoptilolite has been selected for investigating NTC behavior since it is characterized by high zeolite content, a convenient Si/Al atomic ratio, good mechanical strength due to its compact microstructure, and low toxicity. Clinoptilolite has shown a rapid and quite reversible impedance change under heating, characterized by a linear dependence on temperature. X-ray diffraction (XRD) has been used to identify the natural zeolite, to establish all types of crystalline phases present in the mineral, and to investigate the thermal stability of these phases up to 150 °C. X-ray photoelectron spectroscopy (XPS) analysis was used for the chemical characterization of this natural clinoptilolite sample, providing important information on the cationic content and framework composition. In addition, since electrical transport takes place in the zeolite free-volume, a Brunauer–Emmett–Teller (BET) analysis of the mineral has also been performed. Full article
(This article belongs to the Special Issue Advances in Ceramics, 2nd Edition)
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<p>Schematic representation of the channels structure in clinoptilolite crystals.</p>
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<p>Square-shaped clinoptilolite monoliths (<b>a</b>) and electrodes painted on the specimen (<b>b</b>).</p>
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<p>Schematic representation of the electric circuit used for tests.</p>
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<p>XRD patterns of clinoptilolite sample before (black line) and after (red line) a thermal treatment (t.t.) of 5 h at 150 °C.</p>
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<p>SEM micrographs of the etched clinoptilolite mineral surface at different magnifications (<b>a</b>,<b>b</b>).</p>
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<p>XPS long-range (<b>a</b>) and Fe2p (<b>b</b>) (pass energy 50 eV) spectra of natural clinoptilolite powder.</p>
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<p>Surface atomic percentages of clinoptilolite-K, Ca, after thermal treatments in UHV.</p>
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<p>Nitrogen adsorption/desorption isotherm (<b>a</b>) and NLDFT pore size distribution (<b>b</b>) of clinoptilolite.</p>
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<p>Temporal evolution of effective current intensity with the turning on/off of the heat source (<b>a</b>) and NTC material behavior under repeated thermal pulses (<b>b</b>). Linearity of the temporal current intensity behavior is shown in the inset.</p>
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<p>Temporal evolution of Z with the turning on/off of the heat source, (<b>a</b>) and NTC material impedance behavior under repeated thermal pulses (<b>b</b>).</p>
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<p>I<sub>eff</sub>-T curve (<b>a</b>) and related impedance curve (<b>b</b>).</p>
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16 pages, 9753 KiB  
Article
Polymer-Infiltrated Ceramic Network Produced by Direct Ink Writing: The Effects of Manufacturing Design on Mechanical Properties
by Junhui Zhang, Paula Pou, Ludmila Hodásová, Mona Yarahmadi, Sergio Elizalde, Jose-Maria Cabrera, Luis Llanes, Elaine Armelin and Gemma Fargas
Ceramics 2024, 7(2), 436-451; https://doi.org/10.3390/ceramics7020028 - 22 Mar 2024
Cited by 1 | Viewed by 1504
Abstract
Polymer-infiltrated ceramic network (PICN) materials have gained considerable attention as tooth-restorative materials due to their mechanical compatibility with human teeth, especially with computer-aided design and computer-aided manufacturing (CAD/CAM) technologies. However, the designed geometry affects the mechanical properties of PICN materials. This study aims [...] Read more.
Polymer-infiltrated ceramic network (PICN) materials have gained considerable attention as tooth-restorative materials due to their mechanical compatibility with human teeth, especially with computer-aided design and computer-aided manufacturing (CAD/CAM) technologies. However, the designed geometry affects the mechanical properties of PICN materials. This study aims to study the relationship between manufacturing geometry and mechanical properties. In doing so, zirconia-based PICN materials with different geometries were fabricated using a direct ink-writing process, followed by copolymer infiltration. Comprehensive analyses of the microstructure and structural properties of zirconia scaffolds, as well as PICN materials, were performed. The mechanical properties were assessed through compression testing and digital image correlation analysis. The results revealed that the compression strength of PICN pieces was significantly higher than the respective zirconia scaffolds without polymer infiltration. In addition, two geometries (C-grid 0 and C-grid 45) have the highest mechanical performance. Full article
(This article belongs to the Special Issue Advances in Ceramics, 2nd Edition)
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<p>Schematic diagram of direct ink writing of scaffolds and preparation of PICNs.</p>
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<p>Three-dimensional models of samples shaped by DIW with different manufacturing designs.</p>
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<p>(<b>a</b>) SEM micrograph of 3Y-ZrO<sub>2</sub> powder; (<b>b</b>) Particle size distribution histogram from the SEM image; (<b>c</b>) SEM micrograph of sintered zirconia sample; (<b>d</b>) Grain size distribution obtained from image (<b>c</b>).</p>
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<p>XRD spectra of zirconia powder and 3D–printed zirconia scaffold. t: tetragonal ZrO<sub>2</sub>, m: monoclinic ZrO<sub>2</sub> phases.</p>
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<p>Top view of the sintered zirconia samples with different manufacturing designs: (<b>a</b>) C-rectilinear, (<b>b</b>) C-grid 0°, (<b>c</b>) C-grid 45°, (<b>d</b>) C-concentric, (<b>e</b>) CY-A. Chords, and (<b>f</b>) H-triangles p.</p>
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<p>The pore size of the sintered zirconia scaffolds with different manufacturing designs: (<b>a</b>) C-rectilinear, (<b>b</b>) C-grid 0°, (<b>c</b>) C-grid 45°, (<b>d</b>) C-concentric, (<b>e</b>) CY-A.chords, and (<b>f</b>) H-triangles p.</p>
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<p>Tomographic analysis of sintered zirconia samples with different manufacturing designs: (<b>a1</b>,<b>a2</b>) C-rectilinear, (<b>b1</b>,<b>b2</b>) C-grid 0°, (<b>c1</b>,<b>c2</b>) C-concentric, (<b>d1</b>,<b>d2</b>) CY-A.chords, and (<b>e1</b>,<b>e2</b>) H-triangles p.</p>
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<p>Photograph of 3D-printed PICN with different manufacturing designs: (<b>a</b>) C-grid 45, (<b>b</b>) C-concentric, and (<b>c</b>) H-triangles p. The pores represent the Bis-GMA/TEGDMA copolymer coating and filling materials.</p>
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<p>Stress–strain curves for PICN specimens with different geometry.</p>
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<p>Strain distribution under 2% strain for PICN specimens with different printing designs obtained from DIC: (<b>a</b>) C-rectilinear, (<b>b</b>) CY-A.chords, and (<b>c</b>) H-triangles p.</p>
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<p>Optical images of fractured PICN samples with different geometries.</p>
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