Crystals

19 pages, 4516 KiB

Open AccessArticle

Molecular Recognition and Shape Studies of 3- and 4-Substituted Diarylamide Quasiracemates

by Ali K. Brandt, Derek J. Boyle, Jacob P. Butler, Abigail R. Gillingham, Scott E. Penner, Jacqueline M. Spaniol, Alaina K. Stockdill, Morgan M. Vanderwall, Almat Yeraly, Diana R. Schepens and Kraig A. Wheeler

Crystals 2021, 11(12), 1596; https://doi.org/10.3390/cryst11121596 - 20 Dec 2021

Cited by 2 | Viewed by 2879

Abstract

Families of quasiracemic materials constructed from 3- and 4-substituted chiral diarylamide molecular frameworks were prepared, where the imposed functional group differences systematically varied from H to CF₃–9 unique components for each isomeric framework. Cocrystallization from the melt via hot stage thermomicroscopy [...] Read more.

Families of quasiracemic materials constructed from 3- and 4-substituted chiral diarylamide molecular frameworks were prepared, where the imposed functional group differences systematically varied from H to CF₃–9 unique components for each isomeric framework. Cocrystallization from the melt via hot stage thermomicroscopy using all possible racemic and quasiracemic combinations probed the structural boundaries of quasiracemate formation. The crystal structures and lattice energies (differential scanning calorimetry and lattice energy calculations) for many of these systems showed that quasienantiomeric components organize with near inversion symmetry and lattice energetics closely resembling those found in the racemic counterparts. This study also compared the shape space of pairs of quasienantiomers using an in silico alignment-based method to approximate the differences in molecular shape and provide a diagnostic tool for quasiracemate prediction. Comparing these results to our recent report on related 2-substituted diarylamide quasiracemates shows that functional group position can have a marked effect on quasiracemic behavior and provide critical insight to a more complete shape space, essential for defining molecular recognition processes. Full article

(This article belongs to the Special Issue Feature Papers in Organic Crystalline Materials)

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12 pages, 5632 KiB

Open AccessArticle

Nanocrystalline Surface Layer of WO₃ for Enhanced Proton Transport during Fuel Cell Operation

by Xiang Song, Weiqing Guo, Yuhong Guo, Naveed Mushtaq, M. A. K. Yousaf Shah, Muhammad Sultan Irshad, Peter D. Lund and Muhammad Imran Asghar

Crystals 2021, 11(12), 1595; https://doi.org/10.3390/cryst11121595 - 20 Dec 2021

Cited by 9 | Viewed by 3055

Abstract

High ionic conductivity in low-cost semiconductor oxides is essential to develop electrochemical energy devices for practical applications. These materials exhibit fast protonic or oxygen-ion transport in oxide materials by structural doping, but their application to solid oxide fuel cells (SOFCs) has remained a [...] Read more.

High ionic conductivity in low-cost semiconductor oxides is essential to develop electrochemical energy devices for practical applications. These materials exhibit fast protonic or oxygen-ion transport in oxide materials by structural doping, but their application to solid oxide fuel cells (SOFCs) has remained a significant challenge. In this work, we have successfully synthesized nanostructured monoclinic WO₃ through three steps: co-precipitation, hydrothermal, and dry freezing methods. The resulting WO₃ exhibited good ionic conductivity of 6.12 × 10⁻² S cm⁻¹ and reached an excellent power density of 418 mW cm⁻² at 550 °C using as an electrolyte in SOFC. To achieve such a high ionic conductivity and fuel cell performance without any doping contents was surprising, as there should not be any possibility of oxygen vacancies through the bulk structure for the ionic transport. Therefore, laterally we found that the surface layer of WO₃ is reduced to oxygen-deficient when exposed to a reducing atmosphere and form WO_3−δ/WO₃ heterostructure, which reveals a unique ionic transport mechanism. Different microscopic and spectroscopic methods such as HR-TEM, SEM, EIS, Raman, UV-visible, XPS, and ESR spectroscopy were applied to investigate the structural, morphological, and electrochemical properties of WO₃ electrolyte. The structural stability of the WO₃ is explained by less dispersion between the valence and conduction bands of WO_3−δ/WO₃, which in turn could prevent current leakage in the fuel cell that is essential to reach high performance. This work provides some new insights for designing high-ion conducting electrolyte materials for energy storage and conversion devices. Full article

(This article belongs to the Special Issue Macromolecular Crystalline Materials (MCMs) for Clean Energy and Green Environment)

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14 pages, 4031 KiB

Open AccessArticle

Structural, Optical, Electrical and Antibacterial Properties of Fe-Doped CeO₂ Nanoparticles

by Shalendra Kumar, Suliman Yousef AlOmar, Kavita Kumari, Fadwa Albalawi, Rajesh Kumar, Faheem Ahmed, Naushad Ahmad, Sourabh Dwivedi and Parvez Ahmad Alvi

Crystals 2021, 11(12), 1594; https://doi.org/10.3390/cryst11121594 - 20 Dec 2021

Cited by 13 | Viewed by 3294

Abstract

This paper reports the structural, optical and antimicrobial study of Ce_1−xFe_xO_2−δ (

0 \leq

x

\leq 20

) nanoparticles (NPs) synthesized using a microwave-assisted hydrothermal method. The XRD pattern analysed using Rietveld refinement method clearly infers that all [...] Read more.

This paper reports the structural, optical and antimicrobial study of Ce_1−xFe_xO_2−δ (

0 \leq

x

\leq 20

) nanoparticles (NPs) synthesized using a microwave-assisted hydrothermal method. The XRD pattern analysed using Rietveld refinement method clearly infers that all the samples exhibit single phase nature and exclude the possibility of an impurity phase. The lattice parameters and unit cell volume were found to decrease with an increase in Fe-doping content in CeO₂ nanoparticles. The crystalline size determined using XRD pattern and TEM micrographs was found to decrease with Fe doping in CeO₂. Selective area electron diffraction (SAED) pattern also demonstrated the crystalline nature of the Fe-CeO₂ nanoparticles. Optical properties studied using UV–vis spectroscopy indicated that band gap decreased with an increase in Fe doping. The electrical properties have been investigated via dielectric constant, dielectric loss and AC conductivity. The dielectric constant was found to increase in the Fe-doped CeO₂ nanoparticles, while AC conductivity was found to be reduced, which shows good dielectric behaviour of the Fe-doped CeO₂ nanoparticles. The antibacterial activity of the synthesized NPs was achieved under ambient conditions with different bacteria, and the results showed that the properties were different for both bacteria. The antimicrobial activity reflects the possibility to develop Fe-doped CeO₂ NPs as antibacterial agents against extensive microorganisms to control and prevent the spread and persistence of bacterial infections. Full article

(This article belongs to the Section Inorganic Crystalline Materials)

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14 pages, 41124 KiB

Open AccessArticle

Bamboo Sawdust as a Partial Replacement of Cement for the Production of Sustainable Cementitious Materials

by Yunyun Tong, Abdel-Okash Seibou, Mengya Li, Abdelhak Kaci and Jinjian Ye

Crystals 2021, 11(12), 1593; https://doi.org/10.3390/cryst11121593 - 20 Dec 2021

Cited by 6 | Viewed by 4939

Abstract

This paper reports on the utilization of recycled moso bamboo sawdust (BS) as a substitute in a new bio-based cementitious material. In order to improve the incompatibility between biomass and cement matrix, the study firstly investigated the effect of pretreatment methods on the [...] Read more.

This paper reports on the utilization of recycled moso bamboo sawdust (BS) as a substitute in a new bio-based cementitious material. In order to improve the incompatibility between biomass and cement matrix, the study firstly investigated the effect of pretreatment methods on the BS. Cold water, hot water, and alkaline solution were used. The SEM images and mechanical results showed that alkali-treated BS presented a more favorable bonding interface in the cementitious matrix, while both compressive and flexural strength were higher than for the other two treatments. Hence, the alkaline treatment method was adopted for additional studies on the effect of BS content on the microstructural, physical, rheological, and mechanical properties of composite mortar. Cement was replaced by alkali-treated BS at 1%, 3%, 5%, and 7% by mass in the mortar mixture. An increased proportion of BS led to a delayed cement setting and a reduction in workability, but a lighter and more porous structure compared to the conventional mortar. Meanwhile, the mechanical performance of composite decreased with BS content, while the compressive and flexural strength ranged between 14.1 and 37.8 MPa and 2.4 and 4.5 MPa, respectively, but still met the minimum strength requirements of masonry construction. The cement matrix incorporated 3% and 5% BS can be classified as load-bearing lightweight concrete. This result confirms that recycled BS can be a sustainable component to produce a lightweight and structural bio-based cementitious material. Full article

(This article belongs to the Special Issue Advances in Sustainable Concrete System)

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17 pages, 2694 KiB

Open AccessReview

Thermodynamic Modeling and Mechanical Properties of Mg-Zn-{Y, Ce} Alloys: Review

by Mohammad Aljarrah, Jasim Alnahas and Mohammed Alhartomi

Crystals 2021, 11(12), 1592; https://doi.org/10.3390/cryst11121592 - 20 Dec 2021

Cited by 11 | Viewed by 5696

Abstract

Magnesium alloys are a strong candidate for various applications in automobile and aerospace industries due to their low density and specific strength. Micro-alloying magnesium with zinc, yttrium, and cerium enhances mechanical properties of magnesium through grain refinement and precipitation hardening. In this work, [...] Read more.

Magnesium alloys are a strong candidate for various applications in automobile and aerospace industries due to their low density and specific strength. Micro-alloying magnesium with zinc, yttrium, and cerium enhances mechanical properties of magnesium through grain refinement and precipitation hardening. In this work, a critical review of magnesium-based binary systems including Mg-Zn, Mg-Y, Mg-Ce, Zn-Y, and Zn-Ce is presented. Based on the CALPHAD approach and first-principles calculations, thermodynamic modeling of Mg-Zn-Y and Mg-Zn-Ce ternary phase diagrams have been summarized. The influence of micro-alloying (yttrium and cerium) on the mechanical properties of magnesium is discussed. A comparison between mechanical properties of magnesium commercial alloys and magnesium–zinc–{yttrium and cerium} have been summarized in tables. Full article

(This article belongs to the Special Issue Crystal Plasticity (Volume II))

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11 pages, 2998 KiB

Open AccessArticle

Iron Oxalate Humboldtine Crystallization by Fungus Aspergillus niger

by Marina S. Zelenskaya, Alina R. Izatulina, Olga V. Frank-Kamenetskaya and Dmitry Y. Vlasov

Crystals 2021, 11(12), 1591; https://doi.org/10.3390/cryst11121591 - 20 Dec 2021

Cited by 4 | Viewed by 3112

Abstract

Microfungi were able to alternate solid substrate in various environments and play a noticeable role in the formation of insoluble calcium oxalate crystals in subaerial biofilms on rock surfaces. The present work describes how iron oxalate dihydrate humboldtine is acquired under the influence [...] Read more.

Microfungi were able to alternate solid substrate in various environments and play a noticeable role in the formation of insoluble calcium oxalate crystals in subaerial biofilms on rock surfaces. The present work describes how iron oxalate dihydrate humboldtine is acquired under the influence of the acid-producing microscopic fungus Aspergillus niger on the surface of two iron- bearing mineral substrates in vitro. Pyrrhotite and siderite rocks, as well as the products of their alteration, were investigated using a complex of analytical methods, including powder X-ray diffraction, optical microscopy, scanning electron microscopy and EDX spectroscopy. The effect of the underlying rocks with different composition and solubility and different oxidation states of iron on Fe-oxalate crystallization and on the morphology of humboldtine crystals was shown. The mechanisms of humboldtine formation were discussed. The results obtained in vitro seem promising for using fungi in bioleaching iron and other metals from processed ores and for the development of environmentally friendly biotechnologies. Full article

(This article belongs to the Special Issue Women in Mineralogical Crystallography and Biomineralization)

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11 pages, 2771 KiB

Open AccessArticle

Enhanced Properties of Extended Wavelength InGaAs on Compositionally Undulating Step-Graded InAsP Buffers Grown by Molecular Beam Epitaxy

by Xuefei Li, Jianming Xu, Tieshi Wei, Wenxian Yang, Shan Jin, Yuanyuan Wu and Shulong Lu

Crystals 2021, 11(12), 1590; https://doi.org/10.3390/cryst11121590 - 20 Dec 2021

Cited by 7 | Viewed by 3352

Abstract

The extended wavelength InGaAs material (2.3 μm) was prepared by introducing compositionally undulating step-graded InAs_yP_1−y buffers with unequal layer thickness grown by solid-source molecular beam epitaxy (MBE). The properties of the extended wavelength InGaAs layer were investigated. The surface showed [...] Read more.

The extended wavelength InGaAs material (2.3 μm) was prepared by introducing compositionally undulating step-graded InAs_yP_1−y buffers with unequal layer thickness grown by solid-source molecular beam epitaxy (MBE). The properties of the extended wavelength InGaAs layer were investigated. The surface showed ordered crosshatch morphology and a low roughness of 1.38 nm. Full relaxation, steep interface and less than one threading dislocation in the InGaAs layer were demonstrated by taking advantage of the strain compensation mechanism. Room temperature photoluminescence (PL) exhibited remarkable intensity attributed to the lower density of deep non-radiative centers. The emission peak energy with varied temperatures was in good agreement with Varshni’s empirical equation, implying high crystal quality without inhomogeneity-induced localized states. Therefore, our work shows that compositionally undulating step-graded InAsP buffers with a thinner bottom modulation layer, grown by molecular beam epitaxy, is an effective approach to prepare InGaAs materials with wavelengths longer than 2.0 μm and to break the lattice limitation on the materials with even larger mismatch. Full article

(This article belongs to the Special Issue Advanced Materials and Devices for Photodetection)

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12 pages, 2897 KiB

Open AccessEditor’s ChoiceArticle

Synthesis, Crystal Structures, and Molecular Properties of Three Nitro-Substituted Chalcones

by Alam Yair Hidalgo, Manuel Velasco, Eduardo Sánchez-Lara, Abraham Gómez-Rivera, Miguel A. Vilchis-Reyes, Cuauhtémoc Alvarado, Maribel Herrera-Ruiz, Ricardo López-Rodríguez, Nancy Romero-Ceronio and Carlos E. Lobato-García

Crystals 2021, 11(12), 1589; https://doi.org/10.3390/cryst11121589 - 20 Dec 2021

Cited by 5 | Viewed by 4589

Abstract

Three functionalized chalcones containing combinations of nitro functional groups have been synthesized via Claisen-Schmidt condensation between 2-nitroacetophenone and nitrobenzaldehyde, and the crystal structures obtained ((E)-1,3-bis(2-nitrophenyl)prop-2-en-1-one, 1a, (E)-1-(2-nitrophenyl)-3-(3-nitrophenyl)prop-2-en-1-one, 1b and (E)-1-(2-nitrophenyl)-3-(4-nitrophenyl)prop-2-en-1-one, 1c), C₁₅H₁₀ [...] Read more.

Three functionalized chalcones containing combinations of nitro functional groups have been synthesized via Claisen-Schmidt condensation between 2-nitroacetophenone and nitrobenzaldehyde, and the crystal structures obtained ((E)-1,3-bis(2-nitrophenyl)prop-2-en-1-one, 1a, (E)-1-(2-nitrophenyl)-3-(3-nitrophenyl)prop-2-en-1-one, 1b and (E)-1-(2-nitrophenyl)-3-(4-nitrophenyl)prop-2-en-1-one, 1c), C₁₅H₁₀N₂O_5, are reported. Compounds 1a and 1c crystallized in the triclinic centrosymmetric space group P

\bar{1}

, whereas compound 1b crystallized in the orthorhombic space group Pbca. The X-ray analysis reveals that structures 1a and 1b exhibits s-trans conformation, whereas structure 1c exists in s-cis conformation, concerning the olefinic double bonds. In addition, the results show that the position of the nitro substituent attached to the aromatic B-ring has a direct effect on the molecular coplanarity of these compounds. The Hirshfeld surface analysis suggests that the non-covalent π-π stacking interactions are the most important contributors for the crystal packing of 1a and 1b. In 1c, the crystal packing is mainly stabilized by weak intermolecular C―H···O interactions due to the planar nature of the molecule. Full article

(This article belongs to the Section Organic Crystalline Materials)

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8 pages, 1544 KiB

Open AccessArticle

Surface-Passivated CsPbBr₃ for Developing Efficient and Stable Perovskite Photovoltaics

by Hyeon Ju Tak, Ji Hyeon Lee, Seunghwan Bae and Jea Woong Jo

Crystals 2021, 11(12), 1588; https://doi.org/10.3390/cryst11121588 - 20 Dec 2021

Cited by 7 | Viewed by 3347

Abstract

All-inorganic perovskites consisting of only inorganic elements have been recently considered as highly stable semiconductors for photoactive layer of optoelectronics applications. However, the formation of high-quality thin film and trap-reduced interface has still remains an important task, which should be solved for improving [...] Read more.

All-inorganic perovskites consisting of only inorganic elements have been recently considered as highly stable semiconductors for photoactive layer of optoelectronics applications. However, the formation of high-quality thin film and trap-reduced interface has still remains an important task, which should be solved for improving the performances of all-inorganic perovskite-based photovoltaics. Here, we adopted facile method that could reduce charge-carrier recombination by depositing a passivation agent on the top surface of the CsPbBr₃ all-inorganic perovskite layer. We also found that the CsPbBr₃ perovskite photovoltaic prepared from surface treatment method using n-octylammonium bromide provides an improved stability in ambient environment and 1-sun illuminating condition. Therefore, the perovskite photovoltaics fabricated from our approach offered an improved power conversion efficiency of 5.44% over that of the control device without surface treatment (4.12%). Full article

(This article belongs to the Special Issue Advance in Application of Perovskite Materials in Optoelectronic Devices)

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13 pages, 3550 KiB

Open AccessEditor’s ChoiceArticle

Partially Yttria-Stabilized Zirconia Crystals Co-Doped with Neodymium, Cerium, Terbium, Erbium or Ytterbium Oxides

by Mikhail A. Borik, Alexey V. Kulebyakin, Elena E. Lomonova, Filipp O. Milovich, Valentina A. Myzina, Polina A. Ryabochkina, Natalia Y. Tabachkova, Natalia V. Sidorova and Artem S. Chislov

Crystals 2021, 11(12), 1587; https://doi.org/10.3390/cryst11121587 - 20 Dec 2021

Cited by 3 | Viewed by 3208

Abstract

In this work, we studied the phase composition, local structure and mechanical characteristics of ZrO₂ crystals partially stabilized with Y₂O₃ and co-doped with Nd₂O₃, CeO₂, Er₂O₃, Tb₂O [...] Read more.

In this work, we studied the phase composition, local structure and mechanical characteristics of ZrO₂ crystals partially stabilized with Y₂O₃ and co-doped with Nd₂O₃, CeO₂, Er₂O₃, Tb₂O₃ and Yb₂O₃. Crystals were grown by directional melt crystallization in a cold container. The phase composition and structure of crystals were studied by X-ray diffractometry and transmission electron microscopy. The study of the features of the incorporation of rare-earth cations with different ionic radii into the transformable (t) and nontransformable (t’) tetragonal phases was carried out by the method of selective laser spectroscopy and time-resolved spectroscopy. Mechanical characteristics such as microhardness and fracture toughness were studied by the indentation method. It is shown that the phase composition and structure of crystals at the same total concentration of doping oxides depends on the degree of substitution of Y³⁺ cations by rare-earth cations. Rare earth ions of the beginning of the lanthanide series predominantly occupy positions in the nontransformable tetragonal phase of crystals based on zirconium dioxide. Ions of the end of a series of lanthanides do not show selectivity when entering the transformable (t) phase and nontransformable (t’) phase. The study of the mechanical characteristics of the crystals showed that the values of fracture toughness increase with an increase in the ionic radius of the rare earth element of the co-doped oxide, while the values of the microhardness of the crystals slightly decrease. Full article

(This article belongs to the Special Issue Advances in Zr-Based Alloys)

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15 pages, 1966 KiB

Open AccessArticle

Effect of Sodium Hydroxide, Liquid Sodium Silicate, Calcium Hydroxide, and Slag on the Mechanical Properties and Mineral Crystal Structure Evolution of Polymer Materials

by Guodong Huang, Yaqian Li, Yuting Zhang, Jielei Zhu, Dawei Li and Bo Wang

Crystals 2021, 11(12), 1586; https://doi.org/10.3390/cryst11121586 - 20 Dec 2021

Cited by 11 | Viewed by 3365

Abstract

To study the key factors that affect the mechanical properties of polymer materials and explore the relationship between mineral crystal formation and strength development, fly ash (FA) polymer samples were prepared using sodium hydroxide, slag, liquid sodium silicate, and hydrated lime as activators. [...] Read more.

To study the key factors that affect the mechanical properties of polymer materials and explore the relationship between mineral crystal formation and strength development, fly ash (FA) polymer samples were prepared using sodium hydroxide, slag, liquid sodium silicate, and hydrated lime as activators. A change in the compressive strength was observed, and X-ray diffraction measurements were carried out to confirm the change. The effects of different types and amounts of activators on the formation and transformation of mineral crystals in FA polymer samples as well as on the development of compressive strength were studied. Moreover, the relationship between the formation and transformation of mineral crystals and the development of compressive strength was established. The results show that the strongly alkaline excitation environment established by sodium hydroxide is the prerequisite for crystal formation and development of compressive strength. Under this strongly alkaline excitation environment, slag, hydrated lime, and liquid sodium silicate can increase the amounts of calcium and silicon, which promote the formation and development of hydrated calcium silicate and hydrated calcium silicoaluminate in polymers and significantly improve the compressive strength. Full article

(This article belongs to the Special Issue Advances in Green Building Materials and Structural Performances)

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15 pages, 5158 KiB

Open AccessArticle

Effect of Nitrate/Bromide on the Hydration Process of Cement Paste Mixed with Alkali Free Liquid Accelerator at Low Temperature

by Yongdong Xu and Tingshu He

Crystals 2021, 11(12), 1585; https://doi.org/10.3390/cryst11121585 - 19 Dec 2021

Cited by 8 | Viewed by 2736

Abstract

The effects of different inorganic salt accelerators (CaBr₂, NaBr, Ca(NO₃)₂, NaNO₃) and an alkali-free liquid accelerator were researched at a low temperature of 10 °C. The results showed the effects of 1.5% NaBr and 1.5% [...] Read more.

The effects of different inorganic salt accelerators (CaBr₂, NaBr, Ca(NO₃)₂, NaNO₃) and an alkali-free liquid accelerator were researched at a low temperature of 10 °C. The results showed the effects of 1.5% NaBr and 1.5% NaNO₃ inorganic accelerator were pronounced. The 1-d compressive strengths of the mortar with these two inorganic salts were increased by 185.8% and 184.2%, respectively, and the final setting times were shortened from 7.74 to 6.08 min and 6.12 min, respectively. The hydration temperatures at 10 °C were measured, and the promotion effects of the inorganic accelerators were calculated: the relationship between the hydration degree was α_{AS + NN} > α_{AS + NB} > α_{AS + CB} > α_{AS + CN} > α_AS. In addition, the reaction of C₃A with NaBr and NaNO₃ was used to analyze the products in an ettringite phase, i.e., Ca₄Al₂O₆Br₂10·H₂O, 3CaOAl₂O₃Ca(NO₃)₂X·H₂O. The formation of these phases was detected in the hydration products of the cement paste hydration for 12 h, 24 h, and 28 d. Combined with the mass loss of the ettringite phase at 90–120 °C, determined using TG/DTG, the synergetic acceleration mechanism of the inorganic accelerators was comprehensively inferred. Full article

(This article belongs to the Special Issue Advances in Cement-Based Composites and Novel Construction Products)

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20 pages, 3252 KiB

Open AccessArticle

Accelerated Weathering and Carbonation (Mild to Intensified) of Natural Canadian Silicates (Kimberlite and Wollastonite) for CO₂ Sequestration

by Ye Eun Chai, Salma Chalouati, Hugo Fantucci and Rafael M. Santos

Crystals 2021, 11(12), 1584; https://doi.org/10.3390/cryst11121584 - 19 Dec 2021

Cited by 8 | Viewed by 3686

Abstract

Canada’s mineral reserves can play a very important role in curbing climate change if natural alkaline minerals are used for the process of mineral carbonation. In this work, the potential of using two Canadian natural silicates for accelerated carbonation is experimentally assessed: kimberlite [...] Read more.

Canada’s mineral reserves can play a very important role in curbing climate change if natural alkaline minerals are used for the process of mineral carbonation. In this work, the potential of using two Canadian natural silicates for accelerated carbonation is experimentally assessed: kimberlite mine tailing (Mg_0.846Al_0.165Fe_0.147Ca_0.067SiO_3.381) from the Northwest Territories, and mined wollastonite ore (Ca_0.609Mg_0.132Al_0.091Fe_0.024SiO_2.914) from Ontario. The aim of this work was to evaluate the weathering reactivity and CO₂ uptake capacity via carbonation of these two comminuted rocks, both of which are made up of a mixture of alkaline minerals, under process conditions that spanned from milder to intensified. Research questions addressed include: does kimberlite contain a sufficient amount of reactive minerals to act as an effective carbon sink; is dehydroxylation necessary to activate kimberlite, and to what extent does it do this; do secondary phases of wollastonite hinder its reactivity; and can either of these minerals be carbonated without pH buffering, or only weathered? Incubator, slurry, and pressurized slurry methods of accelerated weathering and carbonation were used, and the effect of the process parameters (temperature, solid-to-liquid ration, reaction time, CO₂ level, pH buffer) on the CO₂ uptake and crystalline carbonates formation is tested. The reacted samples were analyzed by pH test, loss-on-ignition test, calcimeter test, and X-ray diffraction analysis. Results showed that wollastonite ore (rich in fast-weathering CaSiO₃) is more suitable for accelerated carbonation than kimberlite tailing (containing slow-weathering hydrated magnesium silicates and aluminosilicates) when only its capability to rapidly form solid carbonates is considered. Incubator and pressurized buffered slurry methods proved to be most effective as under these conditions the precipitation of carbonates was more favorable, while the unbuffered slurry reaction conditions were more akin to accelerated weathering rather than accelerated carbonation. Full article

(This article belongs to the Special Issue Mineral Processes for Climate Change Mitigation)

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10 pages, 5736 KiB

Open AccessArticle

Ultrathin and Optically Transparent Microwave Absorber Based on Flexible Silver Nanowire Film

by Yanfei Dong, Dingwang Yu, Guochao Li, Yulin Cao, Youde Ruan and Mingtuan Lin

Crystals 2021, 11(12), 1583; https://doi.org/10.3390/cryst11121583 - 19 Dec 2021

Cited by 5 | Viewed by 2518

Abstract

The design of an optically transparent and flexible metamaterial absorber was presented and fabricated. For this purpose, we use two different patterned silver nanowire films separated by the space layer, forming a transparent sandwiched structure with an ultrathin thickness. By analyzing the equivalent [...] Read more.

The design of an optically transparent and flexible metamaterial absorber was presented and fabricated. For this purpose, we use two different patterned silver nanowire films separated by the space layer, forming a transparent sandwiched structure with an ultrathin thickness. By analyzing the equivalent circuit model and distribution of electric field and current, the absorption physical mechanism has been theoretically investigated. The results show that the structure can achieve above 0.8 absorptions from 6 GHz to 18 GHz, and at the same time, this absorber also can obtain wide-angle property. The optical transmittance of the fabricated absorber exceeds 82% in the visible band. The results demonstrate that transparency and flexibility are the additional benefits that make the proposed absorber suitable for various potential applications. Full article

(This article belongs to the Special Issue Crystalline Patterns as Bases for Design of Engineering Structures, Mechanisms and Metamaterials)

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17 pages, 5325 KiB

Open AccessArticle

Facile Synthesis Sandwich-Structured Ge/NrGO Nanocomposite as Anodes for High-Performance Lithium-Ion Batteries

by Thanapat Autthawong, Theeraporn Promanan, Bralee Chayasombat, Ai-Shui Yu, Kohei Uosaki, Atsushi Yamaguchi, Hiroki Kurata, Torranin Chairuangsri and Thapanee Sarakonsri

Crystals 2021, 11(12), 1582; https://doi.org/10.3390/cryst11121582 - 19 Dec 2021

Cited by 5 | Viewed by 2762

Abstract

This work aimed to design a facile preparation of sandwich-liked Ge nanoparticles/nitrogen-doped reduced graphene oxide (Ge/NrGO) nanocomposites used as anode in lithium-ion batteries through the chemical solution route. The advanced electron microscopy, STEM-HAADF and STEM-EDS mapping, evidenced that the individual Ge particles with [...] Read more.

This work aimed to design a facile preparation of sandwich-liked Ge nanoparticles/nitrogen-doped reduced graphene oxide (Ge/NrGO) nanocomposites used as anode in lithium-ion batteries through the chemical solution route. The advanced electron microscopy, STEM-HAADF and STEM-EDS mapping, evidenced that the individual Ge particles with sizes ranging from 5 to 20 nm were distributed and wrapped as sandwiches within the multi-layered NrGO sheets, which were mainly composed of the pyridinic-N form (4.8%wt.). The battery performances of the 20Ge/NrGO nanocomposite anode exhibit a high reversible capacity (700 mAh g⁻¹) and retained its outstanding stability during long-term cycling. The internal resistance (28.0 Ω) was also decreased after cycling, according to EIS measurement. The sandwiched structure of Ge-based nanocomposite with the interconnected NrGO layers discussed in this article possessed the high-performance LIBs with great potential application in energy storage technologies. Full article

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9 pages, 2899 KiB

Open AccessArticle

Numerical Simulation of a Novel Method for PVT Growth of SiC by Adding a Graphite Block

by Hao Luo, Xuefeng Han, Yuanchao Huang, Deren Yang and Xiaodong Pi

Crystals 2021, 11(12), 1581; https://doi.org/10.3390/cryst11121581 - 18 Dec 2021

Cited by 16 | Viewed by 5106

Abstract

SiC crystal is an excellent substrate material for high power electronic devices and high-frequency electronic devices. Being cost-effective and defect-free are the two biggest challenges at present. For the physical vapor transport (PVT) growth of a SiC single crystal, SiC powder is used [...] Read more.

SiC crystal is an excellent substrate material for high power electronic devices and high-frequency electronic devices. Being cost-effective and defect-free are the two biggest challenges at present. For the physical vapor transport (PVT) growth of a SiC single crystal, SiC powder is used as the source material, which determines the cost and the quality of the crystal. In this paper, we propose a new design in which graphite blocks are substituted for the non-sublimated SiC powder. Temperature distribution in the SiC powder, the evolution of the SiC powder, and the vapor transport are investigated by using finite element calculations. With the addition of graphite blocks, the utilization and sublimation rate of SiC powder is higher. In addition, the reverse vapor transport above the SiC powder is eliminated. This design provides a new idea to reduce the cost of SiC crystals in industrialization. Full article

(This article belongs to the Special Issue Wide Bandgap Semiconductor Materials and Devices)

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10 pages, 3022 KiB

Open AccessEditor’s ChoiceArticle

Optically Tunable and Thermally Erasable Terahertz Intensity Modulators Using Dye-Doped Liquid Crystal Cells with Metasurfaces

by Yi-Hong Shih, Harry Miyosi Silalahi, Ting-I Tsai, Yi-Chen Chen, Jou-Yu Su, Chia-Rong Lee and Chia-Yi Huang

Crystals 2021, 11(12), 1580; https://doi.org/10.3390/cryst11121580 - 18 Dec 2021

Cited by 7 | Viewed by 2679

Abstract

A terahertz metasurface that is imbedded into a dye-doped liquid crystal (DDLC) cell is fabricated in this work. After the metasurface-imbedded DDLC cell is irradiated with a linearly polarized pump beam, the irradiated cell is measured with a terahertz spectrometer. The irradiation of [...] Read more.

A terahertz metasurface that is imbedded into a dye-doped liquid crystal (DDLC) cell is fabricated in this work. After the metasurface-imbedded DDLC cell is irradiated with a linearly polarized pump beam, the irradiated cell is measured with a terahertz spectrometer. The irradiation of the pump beam causes the adsorption of the dye on one of the substrates of the cell, scattering incident terahertz waves and decreasing the transmittances of the terahertz metasurface at all the frequencies of its resonance spectrum. In addition, these transmittances decrease with an increase in the irradiation times of the pump beam. The adsorbed dye molecules are erased from the substrate after the cell is heated by a hot plate. The cell has similar spectra before the irradiation of the pump beam and after the heating of the hot plate. The aforementioned results reveal that the metasurface-imbedded DDLC cell is an optically tunable and thermally erasable terahertz intensity modulator. Therefore, this cell has the potential in developing intensity attenuators for terahertz imaging, frequency isolators for terahertz telecommunication, and spatial light modulators for terahertz information encryption and decryption. Full article

(This article belongs to the Special Issue Liquid Crystals-Based Metamaterials)

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14 pages, 29402 KiB

Open AccessArticle

Case Study of High-Throughput Drug Screening and Remote Data Collection for SARS-CoV-2 Main Protease by Using Serial Femtosecond X-ray Crystallography

by Omur Guven, Mehmet Gul, Esra Ayan, J Austin Johnson, Baris Cakilkaya, Gozde Usta, Fatma Betul Ertem, Nurettin Tokay, Busra Yuksel, Oktay Gocenler, Cengizhan Buyukdag, Sabine Botha, Gihan Ketawala, Zhen Su, Brandon Hayes, Frederic Poitevin, Alexander Batyuk, Chun Hong Yoon, Christopher Kupitz, Serdar Durdagi, Raymond G. Sierra and Hasan DeMirci Show full author list Hide full author list

Crystals 2021, 11(12), 1579; https://doi.org/10.3390/cryst11121579 - 17 Dec 2021

Cited by 6 | Viewed by 4451

Abstract

Since early 2020, COVID-19 has grown to affect the lives of billions globally. A worldwide investigation has been ongoing for characterizing the virus and also for finding an effective drug and developing vaccines. As time has been of the essence, a crucial part [...] Read more.

Since early 2020, COVID-19 has grown to affect the lives of billions globally. A worldwide investigation has been ongoing for characterizing the virus and also for finding an effective drug and developing vaccines. As time has been of the essence, a crucial part of this research has been drug repurposing; therefore, confirmation of in silico drug screening studies have been carried out for this purpose. Here we demonstrated the possibility of screening a variety of drugs efficiently by leveraging a high data collection rate of 120 images/second with the new low-noise, high dynamic range ePix10k2M Pixel Array Detector installed at the Macromolecular Femtosecond Crystallography (MFX) instrument at the Linac Coherent Light Source (LCLS). The X-ray Free-Electron Laser (XFEL) is used for remote high-throughput data collection for drug repurposing of the main protease (Mpro) of SARS-CoV-2 at ambient temperature with mitigated X-ray radiation damage. We obtained multiple structures soaked with nine drug candidate molecules in two crystal forms. Although our drug binding attempts failed, we successfully established a high-throughput Serial Femtosecond X-ray crystallographic (SFX) data collection protocol. Full article

(This article belongs to the Special Issue Novel Structural Studies of Coronavirus Proteins)

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12 pages, 3164 KiB

Open AccessArticle

Sensing Glucose Concentration Using Symmetric Metasurfaces under Oblique Incident Terahertz Waves

by Ibraheem Al-Naib

Crystals 2021, 11(12), 1578; https://doi.org/10.3390/cryst11121578 - 17 Dec 2021

Cited by 15 | Viewed by 2895

Abstract

In this article, a planar metamaterial sensor designed at terahertz (THz) frequencies is utilized to sense glucose concentration levels that cover hypoglycemia, normal, and hyperglycemia conditions that vary from 54 to 342 mg/dL. The sensor was developed using a symmetric complementary split rectangular [...] Read more.

In this article, a planar metamaterial sensor designed at terahertz (THz) frequencies is utilized to sense glucose concentration levels that cover hypoglycemia, normal, and hyperglycemia conditions that vary from 54 to 342 mg/dL. The sensor was developed using a symmetric complementary split rectangular resonator at an oblique incidence angle. The resonance frequency shift was used as a measure of the changes in the glucose level of the samples. The increase in the glucose concentration level exhibited clear and noticeable redshifts in the resonance frequency. For instance, a 67.5 GHz redshift has been observed for a concentration level of 54 mg/dL and increased up to 122 GHz for the 342 mg/dL concentration level. Moreover, a high sensitivity level of 75,700 nm/RIU was observed for this design. In the future, the proposed THz sensors may have potential applications in diagnosing hypocalcemia and hyperglycemia cases. Full article

(This article belongs to the Special Issue Advances in Metamaterials)

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10 pages, 3528 KiB

Open AccessEditor’s ChoiceArticle

Acoustic Tunneling Study for Hexachiral Phononic Crystals Based on Dirac-Cone Dispersion Properties

by Luyun Chen, Yong Liu and Hui Kong

Crystals 2021, 11(12), 1577; https://doi.org/10.3390/cryst11121577 - 17 Dec 2021

Cited by 2 | Viewed by 2701

Abstract

Acoustic tunneling is an essential property for phononic crystals in a Dirac-cone state. By analyzing the linear dispersion relations for the accidental degeneracy of Bloch eigenstates, the influence of geometric parameters on opening the Dirac-cone state and the directional band gaps’ widths are [...] Read more.

Acoustic tunneling is an essential property for phononic crystals in a Dirac-cone state. By analyzing the linear dispersion relations for the accidental degeneracy of Bloch eigenstates, the influence of geometric parameters on opening the Dirac-cone state and the directional band gaps’ widths are investigated. For two-dimensional hexachiral phononic crystals, for example, the four-fold accidental degenerate Dirac point emerges at the center of the irreducible Brillouin zone (IBZ). The Dirac cone properties and the band structure inversion problem are discussed. Finally, to verify acoustic transmission properties near the double-Dirac-cone frequency region, the numerical calculation of the finite-width phononic crystal structure is carried out, and the acoustic transmission tunneling effect is proved. The results enrich and expand the manipulating method in the topological insulator problem for hexachiral phononic crystals. Full article

(This article belongs to the Section Liquid Crystals)

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14 pages, 5696 KiB

Open AccessArticle

Surface Acoustic Wave-Based Flexible Piezocomposite Strain Sensor

by Rishikesh Srinivasaraghavan Govindarajan, Eduardo Rojas-Nastrucci and Daewon Kim

Crystals 2021, 11(12), 1576; https://doi.org/10.3390/cryst11121576 - 17 Dec 2021

Cited by 18 | Viewed by 3804

Abstract

A surface acoustic wave (SAW), device composed of polymer and ceramic fillers, exhibiting high piezoelectricity and flexibility, has a wide range of sensing applications in the aerospace field. The demand for flexible SAW sensors has been gradually increasing due to their small size, [...] Read more.

A surface acoustic wave (SAW), device composed of polymer and ceramic fillers, exhibiting high piezoelectricity and flexibility, has a wide range of sensing applications in the aerospace field. The demand for flexible SAW sensors has been gradually increasing due to their small size, wireless capability, low fabrication cost, and fast response time. This paper discusses the structural, thermal, and electrical properties of the developed sensor, based on different micro- and nano-fillers, such as lead zirconate titanate (PZT), calcium copper titanate (CCTO), and carbon nanotubes (CNTs), along with polyvinylidene fluoride (PVDF) as a polymer matrix. The piezocomposite substrate of the SAW sensor is fabricated using a hot press, while interdigital transducers (IDTs) are deposited through 3D printing. The piezoelectric properties are also enhanced using a non-contact corona poling technique under a high electric field to align the dipoles. Results show that the developed passive strain sensor can measure mechanical strains by examining the frequency shifts of the detected wave signals. Full article

(This article belongs to the Special Issue Piezoelectric Sensors Application)

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11 pages, 2960 KiB

Open AccessArticle

Low Temperature and High-Pressure Study of Bending L-Leucinium Hydrogen Maleate Crystals

by Kseniya D. Skakunova and Denis A. Rychkov

Crystals 2021, 11(12), 1575; https://doi.org/10.3390/cryst11121575 - 16 Dec 2021

Cited by 5 | Viewed by 2757 | Correction

Abstract

The polymorphism of molecular crystals is a well-known phenomenon, resulting in modifications of physicochemical properties of solid phases. Low temperatures and high pressures are widely used to find phase transitions and quench new solid forms. In this study, L-Leucinium hydrogen maleate (LLHM), the [...] Read more.

The polymorphism of molecular crystals is a well-known phenomenon, resulting in modifications of physicochemical properties of solid phases. Low temperatures and high pressures are widely used to find phase transitions and quench new solid forms. In this study, L-Leucinium hydrogen maleate (LLHM), the first molecular crystal that preserves its anomalous plasticity at cryogenic temperatures, is studied at extreme conditions using Raman spectroscopy and optical microscopy. LLHM was cooled down to 11 K without any phase transition, while high pressure impact leads to perceptible changes in crystal structure in the interval of 0.0–1.35 GPa using pentane-isopentane media. Surprisingly, pressure transmitting media (PTM) play a significant role in the behavior of the LLHM system at extreme conditions—we did not find any phase change up to 3.05 GPa using paraffin as PTM. A phase transition of LLHM to amorphous form or solid–solid phase transition(s) that results in crystal fracture is reported at high pressures. LLHM stability at low temperatures suggests an alluring idea to prove LLHM preserves plasticity below 77 K. Full article

(This article belongs to the Special Issue Applications of Crystal Plasticity in Forming Technologies)

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13 pages, 3968 KiB

Open AccessArticle

Theoretical Investigations of a BN Polymorph with sp² + sp³ Hybridizations

by Xinhai Yu, Riguge Su, Bei He and Binchang Ma

Crystals 2021, 11(12), 1574; https://doi.org/10.3390/cryst11121574 - 16 Dec 2021

Cited by 6 | Viewed by 2373

Abstract

The crystal structure, mechanical anisotropy, elastic properties and electronic characteristics, as well as the stability, of P4/m BN are predicted by means of density functional theory. In this work, BN in the P4/m phase demonstrates mechanical and dynamical stability. [...] Read more.

The crystal structure, mechanical anisotropy, elastic properties and electronic characteristics, as well as the stability, of P4/m BN are predicted by means of density functional theory. In this work, BN in the P4/m phase demonstrates mechanical and dynamical stability. Compared with the values of bulk B, E and G in the P4/m phase, the B of BN in the P4/m phase is greater than that of dz4 BN, while the G and E of P4/m BN are greater than those of Pnc2 BN and dz4 BN. The ratio of the bulk-to-shear modulus for P4/m BN is less than 1.75 and dz4 BN, dz2 BN and lzlz2 BN, indicating that P4/m BN is more brittle than dz4 BN, dz2 BN and lzlz2 BN. P4/m BN exhibits stronger mechanical anisotropy in G and E than Pbca BN, P4₂/mnm BN and Pm-3m BN but much weaker mechanical anisotropy than P4/mbm BN, B₇N₇, B₁₁N₁₁ and B₁₅N₁₅. In addition, P4/m BN is a quasi-direct bandgap semiconductor, and the difference between the direct and the indirect bandgap is 0.008 eV. In order to obtain further characteristics of P4/m BN for future synthetic verification, the X-ray diffraction (XRD) patterns for P4/m BN are also calculated. Given its properties, P4/m BN is a good candidate for photoelectric devices. Full article

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14 pages, 6664 KiB

Open AccessArticle

Joining 3YSZ Electrolyte to AISI 441 Interconnect Using the Ag Particle Interlayer: Enhanced Mechanical and Aging Properties

by Xiaoqing Si, Xiaoyang Wang, Chun Li, Tong Lin, Junlei Qi and Jian Cao

Crystals 2021, 11(12), 1573; https://doi.org/10.3390/cryst11121573 - 16 Dec 2021

Cited by 7 | Viewed by 2603

Abstract

Reactive air brazing has been widely used in fabricating solid oxide fuel/electrolysis cell (SOFC/SOEC) stacks. However, the conventional Ag–CuO braze can lead to (I) over oxidation at the steel interconnect interface caused by its adverse reactions with the CuO and (II) many voids [...] Read more.

Reactive air brazing has been widely used in fabricating solid oxide fuel/electrolysis cell (SOFC/SOEC) stacks. However, the conventional Ag–CuO braze can lead to (I) over oxidation at the steel interconnect interface caused by its adverse reactions with the CuO and (II) many voids caused by the hydrogen-induced decomposition of CuO. The present work demonstrates that the Ag particle interlayer can be used to join yttria-stabilized zirconia (YSZ) electrolytes to AISI 441 interconnect in air instead of Ag–CuO braze. Reliable joining between YSZ and AISI 441 can be realized at 920 °C. A dense and thin oxide layer (~2 μm) is formed at the AISI 441 interface. Additionally, an interatomic joining at the YSZ/Ag interface was observed by TEM. Obtained joints displayed a shear strength of ~86.1 MPa, 161% higher than that of the joints brazed by Ag–CuO braze (~33 MPa). After aging in reducing and oxidizing atmospheres (800 °C/300 h), joints remained tight and dense, indicating a better aging performance. This technique eliminates the CuO-induced issues, which may extend lifetimes for SOFC/SOEC stacks and other ceramic/metal joining applications. Full article

(This article belongs to the Special Issue Preparation, Microstructure Evolution and Mechanical Study of the Brazed Joints)

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12 pages, 3276 KiB

Open AccessArticle

Effect of Nutrient Solution Composition on Bio-Cemented Sand

by Shihua Liang, Xueli Xiao, Zhanlin Li and Deluan Feng

Crystals 2021, 11(12), 1572; https://doi.org/10.3390/cryst11121572 - 16 Dec 2021

Cited by 4 | Viewed by 2438

Abstract

Microbial-induced carbonate precipitation is an environmentally friendly foundation treatment technology that effectively improves soil engineering performance. The various nutrient components of liquid curing compounds significantly influence the curing effect. On the basis of penetration, dry density, water absorption, and unconfined compressive strength tests, [...] Read more.

Microbial-induced carbonate precipitation is an environmentally friendly foundation treatment technology that effectively improves soil engineering performance. The various nutrient components of liquid curing compounds significantly influence the curing effect. On the basis of penetration, dry density, water absorption, and unconfined compressive strength tests, this study showed the effect of nutrient solution composition, including urea, calcium chloride, sodium bicarbonate, ammonium chloride, and nutrient broth, on the physicomechanical properties of bio-cemented sand. The morphological differences of calcium carbonate precipitates under nutrient solution composition were compared through scanning electron microscopy (SEM). Results showed that the curing effect of compound nutrient solution was improved compared with the basic nutrient solution (urea and calcium chloride). Among the individual components added, ammonium chloride had the most remarkable effect, followed by sodium bicarbonate and nutrient broth. Among the paired components added, sodium bicarbonate + ammonium chloride had the most significant effect, followed by sodium bicarbonate + nutrient broth and ammonium chloride + nutrient broth. The strength of bio-cemented sand cured with compound nutrient solution containing five components could reach 3.43 MPa, which was 1.92 times higher than the strength of the basic nutrient solution. As shown by the SEM image, the calcium carbonate precipitation in the solidified sand was distributed in the clearance of sand particles, effectively bonding the sand particles. The calcium carbonate obtained by the composition of the compound nutrient solution precipitated the sand particles, and some of the sand particles were wrapped. Moreover, the amount of precipitation was evidently greater than that of the basic nutrient solution. Compared with the basic nutrient solution, the compound nutrient solution effectively reduced the apparent porosity and average pore size of the sand. Thus, the curing effect of the compound nutrient solution was better than that of the basic nutrient solution. Full article

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11 pages, 1785 KiB

Open AccessArticle

Potassium Sulfate: A New Candidate to Explore Non-Photochemical Laser-Induced Nucleation Mechanisms

by Mélody Briard, Clément Brandel, Sandrine Morin-Grognet, Gérard Coquerel and Valérie Dupray

Crystals 2021, 11(12), 1571; https://doi.org/10.3390/cryst11121571 - 16 Dec 2021

Cited by 4 | Viewed by 2310

Abstract

In this paper, we report a study on the nucleation behavior of potassium sulfate (K₂SO₄) from aqueous solutions under the influence of unfocused nanosecond laser pulses. The objective is to contribute to the general understanding of the Non-Photochemical Laser-Induced [...] Read more.

In this paper, we report a study on the nucleation behavior of potassium sulfate (K₂SO₄) from aqueous solutions under the influence of unfocused nanosecond laser pulses. The objective is to contribute to the general understanding of the Non-Photochemical Laser-Induced Nucleation (NPLIN) mechanism. First, the influence of several parameters such as supersaturation as well as laser parameters (pulse energy, number of pulses, and laser polarization) on induction time, probability of nucleation and mean number of crystals in comparison with spontaneous nucleation was investigated. Then, we examined the influence of gas composition (i.e., degassing and gas bubbling (CO₂ and N₂)) of the supersaturated solutions on the NPLIN kinetics, showing no correlation between gas content (or nature) on the crystallization behavior. Our study questions the role of impurities within the solution regarding the mechanism of laser-induced nucleation. Full article

(This article belongs to the Section Inorganic Crystalline Materials)

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8 pages, 2000 KiB

Open AccessArticle

A 3D Lead Iodide Hybrid Based on a 2D Perovskite Subnetwork

by Maroua Ben Haj Salah, Justine Tessier, Nicolas Mercier, Magali Allain, Antonin Leblanc, Xiaoyang Che, Claudine Katan and Mikael Kepenekian

Crystals 2021, 11(12), 1570; https://doi.org/10.3390/cryst11121570 - 16 Dec 2021

Cited by 2 | Viewed by 2754

Abstract

Lead halide perovskites have emerged as promising materials for various optoelectronic applications. For photovoltaics, the reference compound is the 3D perovskite (MA)PbI₃ (MA⁺ = methylammonium). However, this material suffers from instabilities towards humidity or light. This makes the search of new [...] Read more.

Lead halide perovskites have emerged as promising materials for various optoelectronic applications. For photovoltaics, the reference compound is the 3D perovskite (MA)PbI₃ (MA⁺ = methylammonium). However, this material suffers from instabilities towards humidity or light. This makes the search of new stable 3D lead halide materials very relevant. A strategy is the use of intermediate size cations instead of MA, which are not suitable to form the 3D ABX₃ perovskites or 2D perovskites. Here, we report on a novel 3D metal halide hybrid material based on the intermediate size cation hydroxypropylammonium (HPA⁺), (HPA)₆(MA)Pb₅I₁₇. We will see that extending the carbon chain length from two CH₂ units (in the hydroxylethylammonium cation, HEA+) to three (HPA⁺) precludes the formation of a perovskite network as found in the lead and iodide deficient perovskite (HEA,MA)_1+xPb_xI_3−x. In (HPA)₆(MA)Pb₅I₁₇ the 3D lead halide network results from a 2D perovskite subnetworks linked by a PbI₆ octahedra sharing its faces. DFT calculations confirm the direct band gap and reveal the peculiar band structure of this 3D network. On one hand the valence band has a 1D nature involving the p orbitals of the halide. On the other, the conduction band possesses a clear 2D character involving hybridization between the p orbitals of the metal and the halide. Full article

(This article belongs to the Section Hybrid and Composite Crystalline Materials)

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10 pages, 3782 KiB

Open AccessArticle

Effect of Continuous Annealing Temperature on the Microstructure, Mechanical Properties and Texture of Annealed Drawn and Ironed Plate

by Zhiying Mo, Xiaohong Chu, Pengfei Gao, Dengcui Yang, Heng Cui, Yuan Fang, Haixu Li, Xiandong Yin and Zhengzhi Zhao

Crystals 2021, 11(12), 1569; https://doi.org/10.3390/cryst11121569 - 16 Dec 2021

Cited by 6 | Viewed by 3120

Abstract

To improve the production process and produce high-quality annealed drawn and ironed (DI) plate, continuous annealing experiments were carried out at 620 °C, 640 °C, 680 °C, and 720 °C, and the effect of continuous annealing temperature on the microstructure, mechanical characteristics, and [...] Read more.

To improve the production process and produce high-quality annealed drawn and ironed (DI) plate, continuous annealing experiments were carried out at 620 °C, 640 °C, 680 °C, and 720 °C, and the effect of continuous annealing temperature on the microstructure, mechanical characteristics, and texture of annealed DI plate were clarified. The microstructure was tested with a scanning electron microscope (SEM); the mechanical properties and weighted average of the plastic strain ratio (

\bar{r}

) were measured using a tension test; and the texture characterizations were tested by X-ray powder diffractometer (XRD) and electron backscatter diffraction (EBSD). The results reveal that, with the increase of the annealing temperature, the average grain size grew from 5.14 μm to 6.56 μm, the yield strength and tensile strength decreased, and the elongation increased. The rolling textures drastically reduced after annealing. When annealed at a lower temperature of 620 °C, the texture content of {111} <110> was the highest. When the annealing temperature increased to 640 °C, 680 °C and 720 °C, the texture content of {111} <112> was higher than that of {111} <110>. The mechanical properties of the DI plate that was annealed at 640 °C are the best, with a higher

\bar{r}

value and a lower planar anisotropy value. Full article

(This article belongs to the Special Issue Microstructure Characterization and Design of Alloys)

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12 pages, 3408 KiB

Open AccessArticle

Physics-Based Predictive Model of Lack-of-Fusion Porosity in Laser Powder Bed Fusion Considering Cap Area

by Wenjia Wang and Steven Y. Liang

Crystals 2021, 11(12), 1568; https://doi.org/10.3390/cryst11121568 - 16 Dec 2021

Cited by 5 | Viewed by 2677

Abstract

This work proposed a computationally efficient analytical modeling strategy to calculate the product porosity in laser powder bed fusion (LPBF) induced by a lack-of-fusion defect, with the consideration of cap area in solidified molten pools, influence of powder bed characteristics on material properties, [...] Read more.

This work proposed a computationally efficient analytical modeling strategy to calculate the product porosity in laser powder bed fusion (LPBF) induced by a lack-of-fusion defect, with the consideration of cap area in solidified molten pools, influence of powder bed characteristics on material properties, and un-melted powders in the lack-of-fusion portion. The powder packing pattern and powder bed void fraction were estimated by an advancing front method and the technique of image analysis. The effects of powder bed characteristics on the material properties were considered by analytical models with solid properties and powder bed void fraction as inputs. A physics-based thermal model was utilized to calculate the temperature distribution and molten pool size. The molten pool cross section in transvers direction was assumed to be dual half-elliptical. Based on this assumption and molten pool size, the geometry of the molten pool cross section with cap area was determined. The overlapping pattern of molten pools in adjacent scan tracks and layers was then obtained with given hatch space and layer thickness. The lack-of-fusion area fraction was obtained through image analysis of the overlapping pattern. The lack-of-fusion porosity was the multiplication of the lack-of-fusion area fraction and powder bed void fraction. The predictions of porosity under different process conditions were compared with experimental results of 316L stainless steel and showed a better predictive accuracy than the predictions that did not consider cap area. The proposed analytical modeling method has no numerical calculations, which ensures its low computational cost. Thus, the proposed model can be a convenient tool for the fast computation of lack-of-fusion-induced porosity and can help the quality control in LPBF. Full article

(This article belongs to the Topic Structure and Properties Modification in Additive Manufacturing)

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15 pages, 5193 KiB

Open AccessArticle

Dosimeter Based on YAG: Ce Phosphor via Sol-Gel Method for Online X-ray Radiation Monitoring

by Yuheng Yan, Changfeng Zhang, Luchuan Zheng, Taiqi Wang, Mao Li, Feiyang Xie, Qiang Guo and Gangding Peng

Crystals 2021, 11(12), 1567; https://doi.org/10.3390/cryst11121567 - 16 Dec 2021

Cited by 8 | Viewed by 2591

Abstract

This paper focuses on the preparation of cerium-doped yttrium aluminum garnet (YAG: Ce) powder with several concentration gradients via the sol-gel method by detecting its structural characteristics via X-ray diffraction (XRD) patterns and scanning electron microscope (SEM) to verify the generation of a [...] Read more.

This paper focuses on the preparation of cerium-doped yttrium aluminum garnet (YAG: Ce) powder with several concentration gradients via the sol-gel method by detecting its structural characteristics via X-ray diffraction (XRD) patterns and scanning electron microscope (SEM) to verify the generation of a complete crystal phase and evenly distributed nanopowder. On this basis, the luminescence characteristics of Ce³⁺ are explored, the mechanism and model are discussed based on the spectra, and the ideal doping concentration was obtained by comparing the luminescence intensity along with the fluorescence quenching theory and fluorescence decay spectra of samples with different doping concentrations. Several radiation dosimeters based on YAG: Ce phosphors were made; the online radiation monitoring function was realized under the exposure of a standard X-ray source; the repeatability, accuracy, and sensitivity of the system were verified by experiments; and the factors affecting dosimeter response are discussed. This paper verifies the possibility of adhibiting YAG: Ce fluorescent powder for online X-ray monitoring, and lays the foundation for further research. Full article

(This article belongs to the Special Issue Single-Crystalline Composition Materials)

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