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Crystals, Volume 10, Issue 6 (June 2020) – 129 articles

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Cover Story (view full-size image) The chiral complex cations in [Mn(en)3](NO3)2 and [Co(en)3](NO3)2 spontaneously resolve to form a [...] Read more.
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Open AccessArticle
Microstructures and Mechanical Properties of Nanocrystalline AZ31 Magnesium Alloy Powders with Submicron TiB2 Additions Prepared by Mechanical Milling
Crystals 2020, 10(6), 550; https://doi.org/10.3390/cryst10060550 - 26 Jun 2020
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Abstract
In this work, nanocrystalline AZ31 magnesium alloy powders, reinforced by submicron TiB2 particles, were prepared via mechanical milling. It was found that TiB2 particles stimulated the fracture and welding of AZ31/TiB2 powders, leading to the acceleration of the milling process. [...] Read more.
In this work, nanocrystalline AZ31 magnesium alloy powders, reinforced by submicron TiB2 particles, were prepared via mechanical milling. It was found that TiB2 particles stimulated the fracture and welding of AZ31/TiB2 powders, leading to the acceleration of the milling process. Meanwhile, the TiB2 particles were refined to submicron-scale size during the milling process, and their distribution was uniform in the Mg matrix. In addition, the matrix was significantly refined during the milling process, which was also accelerated by the TiB2 particles. The formation of grain boundary segregation layers also led to the weakened TiB2 peaks in the XRD patterns during the mechanical milling. The grain sizes of AZ31–2.5 wt % TiB2, AZ31–5 wt % TiB2 and AZ31–10 wt % TiB2 powders were refined to 53 nm, 37 nm and 23 nm, respectively, after milling for 110 h. Under the combined effect of the nanocrystalline matrix and the well-dispersed submicron TiB2 particles, the AZ31/TiB2 composites exhibited excellent micro-hardness. For the AZ31–10 wt % TiB2 composite, the micro-hardness was enhanced to 153 HV0.5. Full article
(This article belongs to the Special Issue Mechanical Behavior of Nanocrystalline Alloys)
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Open AccessArticle
Quantum-Sized Zinc Oxide Nanoparticles Synthesised within Mesoporous Silica (SBA-11) by Humid Thermal Decomposition of Zinc Acetate
Crystals 2020, 10(6), 549; https://doi.org/10.3390/cryst10060549 - 26 Jun 2020
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Abstract
A modified facile method is presented to synthesise quantum-sized zinc oxide nanoparticles within the pores of a mesoporous silica host (SBA-11). This method eliminates the 3 h alcohol reflux and the basic solution reaction steps of zinc acetate. The mesoporous structure and the [...] Read more.
A modified facile method is presented to synthesise quantum-sized zinc oxide nanoparticles within the pores of a mesoporous silica host (SBA-11). This method eliminates the 3 h alcohol reflux and the basic solution reaction steps of zinc acetate. The mesoporous structure and the ZnO nanoparticles were analysed by X-ray diffractometry, transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, nitrogen sorption analysis and UV–VIS spectroscopy. These tests confirm the synthesis of ~1 nm sized ZnO within the pores of SBA-11 and that the porous structure remained intact after ZnO synthesis. Full article
(This article belongs to the Special Issue Zinc Oxide Nanomaterials and Based Devices)
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Open AccessArticle
Unexpected Selective Gas Adsorption on a ‘Non-Porous’ Metal Organic Framework
Crystals 2020, 10(6), 548; https://doi.org/10.3390/cryst10060548 - 26 Jun 2020
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Abstract
A metal organic framework Cu(tpt)BF4·¾H2O was synthesized as a potential carbon capture material, with the aim being to exploit the Lewis base interaction of the incorporated ligand functionalities with acidic gas. The material displays high thermal stability but an [...] Read more.
A metal organic framework Cu(tpt)BF4·¾H2O was synthesized as a potential carbon capture material, with the aim being to exploit the Lewis base interaction of the incorporated ligand functionalities with acidic gas. The material displays high thermal stability but an exceptionally low surface area; however, this contrasts starkly with its ability to capture carbon dioxide, demonstrating significant activated diffusion within the framework. The full characterization of the material shows a robust structure, where the CO2 sorption is 120% greater than current industrial methods using liquid amine solutions; the thermal energy required for sorbent regeneration is reduced by 65%, indicating the true industrial potential of the synthesized material. Full article
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Open AccessArticle
Colossal Negative Magnetoresistance Effect in a La1.37Sr1.63Mn2O7 Single Crystal Grown by Laser-Diode-Heated Floating-Zone Technique
Crystals 2020, 10(6), 547; https://doi.org/10.3390/cryst10060547 - 26 Jun 2020
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Abstract
We have grown La 1.37 Sr 1.63 Mn 2 O 7 single crystals with a laser-diode-heated floating-zone furnace and studied the crystallinity, structure, and magnetoresistance (MR) effect by in-house X-ray Laue diffraction, X-ray powder diffraction, and resistance measurements. The La 1.37 Sr 1.63 [...] Read more.
We have grown La 1.37 Sr 1.63 Mn 2 O 7 single crystals with a laser-diode-heated floating-zone furnace and studied the crystallinity, structure, and magnetoresistance (MR) effect by in-house X-ray Laue diffraction, X-ray powder diffraction, and resistance measurements. The La 1.37 Sr 1.63 Mn 2 O 7 single crystal crystallizes into a tetragonal structure with space group I4/mmm at room temperature. At 0 T, the maximum resistance centers around ∼166.9 K. Below ∼35.8 K, it displays an insulating character with an increase in resistance upon cooling. An applied magnetic field of B = 7 T strongly suppresses the resistance indicative of a negative MR effect. The minimum MR value equals −91.23% at 7 T and 128.7 K. The magnetic-field-dependent resistance shows distinct features at 1.67, 140, and 322 K, from which we calculated the corresponding MR values. At 14 T and 140 K, the colossal negative MR value is down to −94.04(5)%. We schematically fit the MR values with different models for an ideal describing of the interesting features of the MR value versus B curves. Full article
(This article belongs to the Section Inorganic Crystalline Materials)
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Open AccessArticle
Dynamics of Radiation Damage in AlN Ceramics under High-Dose Irradiation, Typical for the Processes of Swelling and Hydrogenation
Crystals 2020, 10(6), 546; https://doi.org/10.3390/cryst10060546 - 26 Jun 2020
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Abstract
The use of nitride ceramics, in particular AlN, as structural materials for nuclear power is primarily limited by their resistance to swelling and hydrogenation processes due to the accumulation of poorly soluble helium and hydrogen ions in the structure of the surface layer. [...] Read more.
The use of nitride ceramics, in particular AlN, as structural materials for nuclear power is primarily limited by their resistance to swelling and hydrogenation processes due to the accumulation of poorly soluble helium and hydrogen ions in the structure of the surface layer. In this regard, research in this area is of great importance not only from a fundamental point of view, but also practical, since any new data on radiation resistance can make a great contribution to the development of the theory of resistance to radiation influences of structural materials of a new generation. This work is devoted to a systematic study and comparative analysis of the dynamics of radiation damage during high-dose irradiation with protons and helium ions in nitride ceramics, which have great potential for use as structural materials for GenIV reactors. The choice of irradiation doses of 1 × 1017–5 × 1017 ion/cm2 is due to the possibility of modeling the processes of radiation damage characteristic of displacements of 10–50 dpa. During the study, the dependences of the change in the dielectric and conductive characteristics of nitride ceramics depending on the radiation dose, as well as on the type of ions, were established. The kinetics of degradation and accelerated aging was determined depending on the type of exposure. The mechanical and strength properties of ceramics were determined. Full article
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Open AccessArticle
Determination of Mechanical Characteristics for Fiber-Reinforced Concrete with Straight and Hooked Fibers
Crystals 2020, 10(6), 545; https://doi.org/10.3390/cryst10060545 - 25 Jun 2020
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Abstract
Fiber-reinforced concrete has a wide application in practice, and many fields of research are devoted to it. In most cases, this is a specific problem, i.e., the determination of the mechanical properties or the test method. However, wider knowledge of the effect of [...] Read more.
Fiber-reinforced concrete has a wide application in practice, and many fields of research are devoted to it. In most cases, this is a specific problem, i.e., the determination of the mechanical properties or the test method. However, wider knowledge of the effect of fiber in concrete is unavailable or insufficient for selected test series that cannot be compared. This article deals with the processing of a comprehensive test study and the impact of two types of fibers on the quantitative and qualitative parameters of concrete. Testing was performed for fiber dosages of 0, 40, 75, and 110 kg/m3. The fibers were hooked and straight. The influence of the fibers on the mechanical properties in fiber-reinforced concrete was analyzed by functional dependence. The selected mechanical properties were compressive strength, splitting tensile strength, bending tensile strength, and fracture energy. The results also include the resulting load–displacement diagrams and summary recommendations for the structural use and design of fiber-reinforced concrete structures. The shear resistance of reinforced concrete beams with hooked fibers was also verified by tests. Full article
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Open AccessArticle
Inhibition of Poly(ethylenediaminetetraacetic acid-diethanolamine) on Deposition of Calcium Sulfate Crystal in Simulated Industrial Water
Crystals 2020, 10(6), 544; https://doi.org/10.3390/cryst10060544 - 25 Jun 2020
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Abstract
Calcium sulfate scale is a typical deposit on the equipment pieces or pipes of an industrial water system. Scale inhibitors could obviously reduce the precipitation of calcium sulfate crystal. The development and research of late-model environmentally friendly polymer inhibitors are often urgent problems [...] Read more.
Calcium sulfate scale is a typical deposit on the equipment pieces or pipes of an industrial water system. Scale inhibitors could obviously reduce the precipitation of calcium sulfate crystal. The development and research of late-model environmentally friendly polymer inhibitors are often urgent problems to be addressed. A water-soluble poly(ethylenediaminetetraacetic acid-diethanolamine) (PEDTA-DEA) was successfully synthesized by thermal polycondensation of ethylenediaminetetraacetic acid (EDTA) with diethanolamine (DEA). The polymer product was characterized by Fourier infrared spectrum (FTIR) and the molecular weight was measured by gel chromatography, which confirms the polymerization of the two monomers. The inhibition effect of the polymer against calcium sulfate deposition was studied by static scale inhibition tests. When the Ca2+ concentration is 3000 mg/L, and the dosage of the polymer inhibitor is 10 mg/L, the inhibition effect exceeds 90%. The results show that PEDTA-DEA can inhibit the precipitation of calcium sulfate and reduce the deposition of calcium sulfate scale. The precipitate of calcium sulfate collected from the static scale inhibition test solution was analyzed by FTIR, scanning electron microscope (SEM) and X-ray diffraction (XRD). The results revealed that the addition of the polymer significantly changes the calcium sulfate crystal’s growth shape. Therefore, PEDTA-DEA is a potential calcium sulfate precipitation inhibitor for the industrial water system. Full article
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Open AccessArticle
Influence of the Aggregate Surface Conditions on the Strength of Quick-Converting Track Concrete
Crystals 2020, 10(6), 543; https://doi.org/10.3390/cryst10060543 - 24 Jun 2020
Viewed by 229
Abstract
This experimental study investigates the effects of the aggregate surface conditions on the compressive strength of quick-converting track concrete (QTC). The compressive strength of QTC and interfacial fracture toughness (IFT) were investigated by changing the amount of fine abrasion dust particles (FADPs) on [...] Read more.
This experimental study investigates the effects of the aggregate surface conditions on the compressive strength of quick-converting track concrete (QTC). The compressive strength of QTC and interfacial fracture toughness (IFT) were investigated by changing the amount of fine abrasion dust particles (FADPs) on the aggregate surface from 0.00 to 0.15 wt% and the aggregate water saturation from 0 to 100%. The effects of aggregate water saturation on the compressive strength of the QTC and IFT were notably different, corresponding to the amount of FADPs. As the aggregate water saturation increased from 0 to 100%, in the case of 0.00 wt% FADPs, the IFT decreased from 0.91 to 0.58 MPa∙mm1/2, and thus, the compressive strength of the QTC decreased from 34.8 to 31.4 MPa because the aggregate water saturation increased the water/cement ratio at the interface and, consequently, the interfacial porosity. However, as the aggregate water saturation increased from 0 to 100%, in the case of 0.15 wt% FADPs, the compressive strength increased from 24.6 to 28.1 MPa, while the IFT increased from 0.41 to 0.88 MPa∙mm1/2 because the water/cement ratio at the interface was reduced as a result of the absorption by the FADPs on the surface of the aggregates and the cleaning effects of the aggregate surface. Full article
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Open AccessArticle
The Steps from Batchwise to Continuous Crystallization for a Fine Chemical: A Case Study
Crystals 2020, 10(6), 542; https://doi.org/10.3390/cryst10060542 - 24 Jun 2020
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Abstract
Many processes to produce fine chemicals and precursors of pharmaceuticals are still operated in batchwise mode. However, recently, more producers have taken a change to continuous operation mode into consideration, performing studies and trials on such a change, while some have even already [...] Read more.
Many processes to produce fine chemicals and precursors of pharmaceuticals are still operated in batchwise mode. However, recently, more producers have taken a change to continuous operation mode into consideration, performing studies and trials on such a change, while some have even already exchanged their production mode from batchwise to continuous operation. In this paper, the stepwise development from an initial idea to industrial implementation via laboratory testing and confirmation is revealed through the example of an organic fine chemical from the perspective of a crystallization plant manufacturer. We begin with the definition of the objectives of the project and a brief explanation of the advantages of continuous operation and the associated product properties. The results of the laboratory tests, confirming the assumptions made upfront, are reported and discussed. Finally, the implementation of an industrial plant using a draft tube baffled (DTB) crystallizer and the final product properties are shown. Product properties such as crystal size distribution, crystal shape, related storage stability and flowability have successfully been improved. Full article
(This article belongs to the Special Issue Advances in Industrial Crystallization)
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Open AccessArticle
Optical Kossel Lines and Fluorescence in Photonic Liquid Crystals
Crystals 2020, 10(6), 541; https://doi.org/10.3390/cryst10060541 - 24 Jun 2020
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Abstract
We propose a general analytical way to describe the fluorescence peculiarities in photonic liquid crystals (revealing themselves as an optical analog of the X-ray Kossel lines in conventional crystals) based at the localized optical edge modes existing in perfect photonic liquid crystal layers. [...] Read more.
We propose a general analytical way to describe the fluorescence peculiarities in photonic liquid crystals (revealing themselves as an optical analog of the X-ray Kossel lines in conventional crystals) based at the localized optical edge modes existing in perfect photonic liquid crystal layers. The proposed approach allows us to predict theoretically the properties of optical Kossel lines in photonic liquid crystal (fluorescence polarization, spectral and angular fluorescence distribution, influence of the light absorption in liquid crystal, and, in particular, existing the optical Borrmann effect if the absorption in liquid crystal is locally anisotropic). Comparison of the theoretical results and the known experimental data shows that the theory reproduces sufficiently well the observation results on the fluorescence in photonic liquid crystals. For confirming a direct connection of the optical Kossel lines to the localized optical edge modes in perfect photonic liquid crystal, we propose the application of time-delayed techniques in studying the optical Kossel lines. Full article
(This article belongs to the Special Issue Localized Optical Modes in Liquid Crystals)
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Open AccessArticle
Material Properties of Zr–Cu–Ni–Al Thin Films as Diffusion Barrier Layer
Crystals 2020, 10(6), 540; https://doi.org/10.3390/cryst10060540 - 24 Jun 2020
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Abstract
Due to the rapid increase in current density encountered in new chips, the phenomena of thermomigration and electromigration in the solder bump become a serious reliability issue. Currently, Ni or TiN, as a barrier layer, is widely academically studied and industrially accepted to [...] Read more.
Due to the rapid increase in current density encountered in new chips, the phenomena of thermomigration and electromigration in the solder bump become a serious reliability issue. Currently, Ni or TiN, as a barrier layer, is widely academically studied and industrially accepted to inhibit rapid copper diffusion in interconnect structures. Unfortunately, these barrier layers are polycrystalline and provide inadequate protection because grain boundaries may presumably serve as fast diffusion paths for copper and could react to form Cu–Sn intermetallic compounds (IMCs). Amorphous metallic films, however, have the potential to be the most effective barrier layer for Cu metallization due to the absence of grain boundaries and immiscibility with copper. In this article, the diffusion properties, the strength of the interface between polycrystalline and amorphous ZrCuNiAl thin film, and the effects of quenching rate on the internal microstructures of amorphous metal films were individually investigated by molecular dynamics (MD) simulation. Moreover, experimental data of the diffusion process for three different cases, i.e., without barrier layer, with an Ni barrier layer, and with a Zr53Cu30Ni9Al8 thin film metallic glass (TFMG) barrier layer, were individually depicted. The simulation results show that, for ZrCuNiAl alloy, more than 99% of the amorphous phase at a quenching rate between 0.25 K/ps and 25 K/ps can be obtained, indicating that this alloy has superior glass-forming ability. The simulation of diffusion behavior indicated that a higher amorphous ratio resulted in better barrier performance. Moreover, a very small and uniformly distributed strain appears in the ZrCuNiAl layer in the simulation of the interfacial tension test; however, almost all the voids are initiated and propagated in the Cu layer. These phenomena indicate that the strength of the ZrCuNiAl/Cu interface and ZrCuNiAl layer is greater than polycrystalline Cu. Experimental results show that the Zr53Cu30Ni9Al8 TFMG layer exhibits a superior barrier effect. Almost no IMCs appear in this TFMG barrier layer even after aging at 125 °C for 500 h. Full article
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Open AccessArticle
Thick β-SiC CVD-Coated SiC Die System for Dry Cold Forging of Metals
Crystals 2020, 10(6), 539; https://doi.org/10.3390/cryst10060539 - 24 Jun 2020
Viewed by 221
Abstract
A thick β-SiC CVD (chemical vapor deposition)-coated SiC device was developed as a new punch and die system for dry, cold forging of pure titanium and austenitic stainless-steel works. This β-SiC coating thickness was 4 mm, enough to make mechanical machining of a [...] Read more.
A thick β-SiC CVD (chemical vapor deposition)-coated SiC device was developed as a new punch and die system for dry, cold forging of pure titanium and austenitic stainless-steel works. This β-SiC coating thickness was 4 mm, enough to make mechanical machining of a cavity into β-SiC coating core die. These β-SiC-coated punch and core dies were fixed into the cassette die for dry, cold forging experiments. The stainless steel and titanium wires with diameters of 1.0 mm were employed as the work material. Different from the conventional metallic and ceramic die systems suffering from work material transfer, this system sustained the galling-free cold, dry forging behavior up to a higher reduction of thickness than 30%. The power to stroke the relationship was in situ monitored to describe this forging behavior up to the specified reduction of the wires together with observations on the geometric change from a circular wire to a pentagonal prism bar. Precise scanning electron microscopy-electron-dispersive X-ray spectroscopy (SEM-EDX) analyses were performed to describe the material compatibility on the contact interface between β-SiC coating and elastoplastically deforming works. Full article
(This article belongs to the Special Issue Development and Investigation of SiC and SiC-based devices)
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Open AccessArticle
Properties of Fourier Syntheses and New Syntheses
Crystals 2020, 10(6), 538; https://doi.org/10.3390/cryst10060538 - 24 Jun 2020
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Abstract
In this study, the properties of observed, difference, and hybrid syntheses (hybrid indicates a combination of observed and difference syntheses) are investigated from two points of view. The first has a statistical nature and aims to estimate the amplitudes of peaks corresponding to [...] Read more.
In this study, the properties of observed, difference, and hybrid syntheses (hybrid indicates a combination of observed and difference syntheses) are investigated from two points of view. The first has a statistical nature and aims to estimate the amplitudes of peaks corresponding to the model atoms, belonging or not belonging to the target structure; the amplitudes of peaks related to the target atoms, missed or shared with the model; and finally, the quality of the background. The latter point deals with the practical features of Fourier syntheses, the special role of weighted syntheses, and their usefulness in practical applications. It is shown how the properties of the various syntheses may vary according to the available structural model and, in particular, how weighted hybrid syntheses may act like an observed and difference or a full hybrid synthesis. The theoretical results obtained in this paper suggest new Fourier syntheses using novel Fourier coefficients: their main features are first discussed from a mathematical point of view. Extended experimental applications show that they meet the basic mission of the Fourier syntheses, enhancing peaks corresponding to the missed target atoms, depleting peaks corresponding to the model atoms not belonging to the target, and significantly reducing the background. A comparison with the results obtained via the most popular modern Fourier syntheses is made, suggesting a role for the new syntheses in modern procedures for phase extension and refinement. The most promising new Fourier synthesis has been implemented in the current version of SIR2014. Full article
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Open AccessArticle
Effect of Modification on Microstructure and Properties of AZ91 Magnesium Alloy
Crystals 2020, 10(6), 536; https://doi.org/10.3390/cryst10060536 - 24 Jun 2020
Viewed by 330
Abstract
Refinement of α-Mg solid solution grains has a significant influence on the improvement of mechanical properties of cast magnesium alloys. In the article, the effects of three modifiers on microstructure and properties of AZ91 magnesium alloy casted to a sand mould were described. [...] Read more.
Refinement of α-Mg solid solution grains has a significant influence on the improvement of mechanical properties of cast magnesium alloys. In the article, the effects of three modifiers on microstructure and properties of AZ91 magnesium alloy casted to a sand mould were described. Overheating, hexachloroethane and wax-CaF2-carbon powder were applied. The research procedure comprised microstructure analysis by means of light microscopy, scanning electron microscopy and quantitative analysis with AnalySIS Pro® software and mechanical properties’ investigation. The microstructure of AZ91 alloy in the as-cast condition consists of α-Mg solid solution with precipitates of Mg17Al12, Mg2Si and Al8Mn5 phases. It was reported that all applied modifiers cause refinement of α-Mg solid solution grains and a decrease of the volume fraction of α-Mg+Mg17Al12 compound discontinuous precipitates. The best results were obtained in the case of wax-CaF2-carbon powder. Full article
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Open AccessEditorial
Non-Covalent Interactions in Coordination and Organometallic Chemistry
Crystals 2020, 10(6), 537; https://doi.org/10.3390/cryst10060537 - 23 Jun 2020
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Abstract
The problem of non-covalent interactions in coordination and organometallic compounds is a hot topic in modern chemistry, material science, crystal engineering and related fields of knowledge. Researchers in various fields of chemistry and other disciplines (physics, crystallography, computer science, etc.) are welcome to [...] Read more.
The problem of non-covalent interactions in coordination and organometallic compounds is a hot topic in modern chemistry, material science, crystal engineering and related fields of knowledge. Researchers in various fields of chemistry and other disciplines (physics, crystallography, computer science, etc.) are welcome to submit their works on this topic for our Special Issue “Non-Covalent Interactions in Coordination and Organometallic Chemistry”. The aim of this Special Issue is to highlight and overview modern trends and draw the attention of the scientific community to various types of non-covalent interactions in coordination and organometallic compounds. In this editorial, I would like to briefly highlight the main successes of our research group in the field of the fundamental study of non-covalent interactions in coordination and organometallic compounds over the past 5 years. Full article
Open AccessArticle
A Complex Assemblage of Crystal Habits of Pyrite in the Volcanic Hot Springs from Kamchatka, Russia: Implications for the Mineral Signature of Life on Mars
Crystals 2020, 10(6), 535; https://doi.org/10.3390/cryst10060535 - 23 Jun 2020
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Abstract
In this study, the crystal habits of pyrite in the volcanic hot springs from Kamchatka, Russia were surveyed using scanning electron microscopy. Pyrite crystals occur either as single euhedral crystals or aggregates with a wide range of crystal sizes and morphological features. Single [...] Read more.
In this study, the crystal habits of pyrite in the volcanic hot springs from Kamchatka, Russia were surveyed using scanning electron microscopy. Pyrite crystals occur either as single euhedral crystals or aggregates with a wide range of crystal sizes and morphological features. Single euhedral crystals, with their sizes ranging from ~200 nm to ~40 µm, exhibit combinations of cubic {100}, octahedral {111}, and pyritohedral {210} and {310} forms. Heterogeneous geochemical microenvironments and the bacterial activities in the long-lived hot springs have mediated the development and good preservation of the complex pyrite crystal habits: irregular, spherulitic, cubic, or octahedral crystals congregating with clay minerals, and nanocrystals attaching to the surface of larger pyrite crystals and other minerals. Spherulitic pyrite crystals are commonly covered by organic matter-rich thin films. The coexistence of various sizes and morphological features of those pyrite crystals indicates the results of secular interactions between the continuous supply of energy and nutritional elements by the hot springs and the microbial communities. We suggest that, instead of a single mineral with unique crystal habits, the continuous deposition of the same mineral with a complex set of crystal habits results from the ever-changing physicochemical conditions with contributions from microbial mediation. Full article
(This article belongs to the Special Issue Mineralogical Crystallography)
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Open AccessArticle
Growth and Magnetism of MnxGe1−x Heteroepitaxial Quantum Dots Grown on Si Wafer by Molecular Beam Epitaxy
Crystals 2020, 10(6), 534; https://doi.org/10.3390/cryst10060534 - 23 Jun 2020
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Abstract
Self-assembled MnGe quantum dots (QDs) were grown on Si (001) substrates using molecular beam epitaxy with different growth temperatures and Ge deposition thicknesses to explore the interaction among Mn doping, Ge deposition, the formation of intermetallics, and the ferromagnetism of QDs. With the [...] Read more.
Self-assembled MnGe quantum dots (QDs) were grown on Si (001) substrates using molecular beam epitaxy with different growth temperatures and Ge deposition thicknesses to explore the interaction among Mn doping, Ge deposition, the formation of intermetallics, and the ferromagnetism of QDs. With the introduction of Mn atoms, the QDs become large and the density significantly decreases due to the improvement in the surface migration ability of Ge atoms. The growth temperature is one of the most important factors deciding whether intermetallic phases form between Mn and Ge. We found that Mn atoms can segregate from the Ge matrix when the growth temperature exceeds 550 °C, and the strongest ferromagnetism of QDs occurs at a growth temperature of 450 °C. As the Ge deposition thickness increases, the morphology of QDs changes and the ferromagnetic properties decrease gradually. The results clearly indicate the morphological evolution of MnGe QDs and the formation conditions of intermetallics between Mn and Ge, such as Mn5Ge3 and Mn11Ge8. Full article
(This article belongs to the Special Issue Intermetallic)
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Open AccessArticle
Gold Nanoisland Agglomeration upon the Substrate Assisted Chemical Etching Based on Thermal Annealing Process
Crystals 2020, 10(6), 533; https://doi.org/10.3390/cryst10060533 - 23 Jun 2020
Viewed by 259
Abstract
In this study, we proposed the self-organization process and its localized surface plasmon resonance property (LSPR) to study the effect of chemically treated quartz glass substrates for gold nanoisland array formation. Firstly, we etched a quartz glass substrate using a sputter etching machine. [...] Read more.
In this study, we proposed the self-organization process and its localized surface plasmon resonance property (LSPR) to study the effect of chemically treated quartz glass substrates for gold nanoisland array formation. Firstly, we etched a quartz glass substrate using a sputter etching machine. Secondly, n-butanol was treated on the surface of the substrate. Then, we deposited a gold thin film on the substrate with assisted chemical etching. Finally, the self-organization method examined the thermal annealing of gold nanoisland arrays on a substrate. The results showed that the gold nanoisland that was aggregated on an etched quartz glass substrate was large and sparse, while the gold nanoisland aggregated on a chemically treated substrate was small and dense. Further, it was revealed that a substrate’s surface energy reduced chemical treating and increased the gold nanoisland contact angle on the substrate via the thermal annealing process. It was also confirmed that chemical treatment was useful to control the morphology of gold nanoisland arrays on a substrate, particularly when related to tuning their optical property. Full article
(This article belongs to the Special Issue Optical and Microstructural Characterization of Thin Layers)
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Open AccessArticle
Finite Element Simulation of Multilayer Electron Beam Melting for the Improvement of Build Quality
Crystals 2020, 10(6), 532; https://doi.org/10.3390/cryst10060532 - 23 Jun 2020
Viewed by 250
Abstract
Macroscale modeling plays an essential role in simulating additive manufacturing (AM) processes. However, models at such scales often pay computational time in output accuracy. Therefore, they cannot forecast local quality issues like lack of fusion or surface roughness. For these reasons, this kind [...] Read more.
Macroscale modeling plays an essential role in simulating additive manufacturing (AM) processes. However, models at such scales often pay computational time in output accuracy. Therefore, they cannot forecast local quality issues like lack of fusion or surface roughness. For these reasons, this kind of model is never used for process optimization, as it is supposed to work with optimized parameters. In this work, a more accurate but still simple three-dimensional (3D) model is developed to estimate potential faulty process conditions that may cause quality issues or even process failure during the electron beam melting (EBM) process. The model is multilayer, and modeling strategies are developed to have fast and accurate responses. A material state variable allows for the molten material to be represented. That information is used to analyze process quality issues in terms of a lack of fusion and lateral surface roughness. A quiet element approach is implemented to limit the number of elements during the calculation, as well as to simulate the material addition layer by layer. The new material is activated according to a predefined temperature that considers the heat-affected zone. Heat transfer analysis accuracy is comparatively demonstrated with a more accurate literature model. Then, a multilayer simulation validates the model capability in predicting the roughness of a manufactured Ti6Al4V sample. The model capability in predicting a lack of fusion is verified under a critical process condition. Full article
(This article belongs to the Special Issue Additive Manufacturing (AM) of Metallic Alloys)
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Open AccessArticle
Efficient Design Method for Plasmonic Filter for Tuning Spectral Selectivity
Crystals 2020, 10(6), 531; https://doi.org/10.3390/cryst10060531 - 23 Jun 2020
Viewed by 249
Abstract
Nano-structure-based color technologies have been reported as alternatives for conventional pigment- or dye-based color filters due to their simple design methods and durable characteristics. Since structure-based optical resonances accompany multiple resonance modes, spectral selectivity could be degraded. In this work, a simple and [...] Read more.
Nano-structure-based color technologies have been reported as alternatives for conventional pigment- or dye-based color filters due to their simple design methods and durable characteristics. Since structure-based optical resonances accompany multiple resonance modes, spectral selectivity could be degraded. In this work, a simple and effective design of a plasmonic color filter that combines the plasmonic filter with one-dimensional photonic crystals. The introduced photonic crystal provides a photonic band gap, and it helps in suppressing the undesirable transmission peaks of the plasmonic color filter that originates from higher order resonance modes. Finally, the proposed design achieves high color purity. In addition, the simplicity of the design makes it both suitable for large-area fabrication and cost effective. This work is expected to provide a practical alternative to traditional color filters. Full article
(This article belongs to the Special Issue Plasmonic Nanostructures)
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Open AccessCommunication
Generalized Methodology for Inserting Metal Heteroatoms into the Layered Zeolite Precursor RUB-36 by Interlayer Expansion
Crystals 2020, 10(6), 530; https://doi.org/10.3390/cryst10060530 - 21 Jun 2020
Viewed by 266
Abstract
The incorporation of metal heteroatoms into zeolites is an effective modification strategy for enhancing their catalytic performance. Herein, for the first time we report a generalized methodology for inserting metal heteroatoms (such as Sn, Fe, Zn, and Co) into the layered zeolite precursor [...] Read more.
The incorporation of metal heteroatoms into zeolites is an effective modification strategy for enhancing their catalytic performance. Herein, for the first time we report a generalized methodology for inserting metal heteroatoms (such as Sn, Fe, Zn, and Co) into the layered zeolite precursor RUB-36 via interlayer expansion by using the corresponding metal acetylacetate salt. Through this generalized methodology, Sn-JHP-1, Fe-JHP-1, Zn-JHP-1 and Co-JHP-1 zeolites could be successfully prepared by the reaction of RUB-36 and corresponding metal acetylacetate salt at 180 °C for 24 h in the presence of HCl solution. As a typical example, Sn-JHP-1 and calcined Sn-JHP-1 (Sn-JHP-2) zeolite is well characterized by the X-ray diffraction (XRD), diffuse reflectance ultraviolet-visible (UV-Vis), inductively coupled plasma (ICP), N2 sorption, temperature-programmed-desorption of ammonia (NH3-TPD) and X-ray photoelectron spectroscopy (XPS) techniques, which confirm the expansion of adjacent interlayers and thus the incorporation of isolated Sn sites within the zeolite structure. Notably, the obtained Sn-JHP-2 zeolite sample shows enhanced catalytic performance in the conversion of glucose to levulinic acid (LA) reaction. Full article
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Open AccessArticle
Characterization of Bioactive Glass Synthesized by Sol-Gel Process in Hot Water
Crystals 2020, 10(6), 529; https://doi.org/10.3390/cryst10060529 - 21 Jun 2020
Viewed by 311
Abstract
Bioactive glass 70SiO2-30CaO (mol.%) was successfully synthesized by modified sol–gel in hot water without using an acid catalyst. TG-DSC analysis showed that the amorphous glass could be synthesized by sintering the sample at 700 °C for three hours. The N2 [...] Read more.
Bioactive glass 70SiO2-30CaO (mol.%) was successfully synthesized by modified sol–gel in hot water without using an acid catalyst. TG-DSC analysis showed that the amorphous glass could be synthesized by sintering the sample at 700 °C for three hours. The N2 adsorption/desorption and TEM investigations highlighted that the synthetic glass had a mesoporous structure, consisting of spherical particles with sizes in the range of 11–20 nm. The specific surface area, pore volume, and average pore diameter of synthetic glass were 150.13 m2/g, 0.37 cm3/g, and 11.84 nm, respectively. Moreover, synthetic bioactive glass presented interesting bioactivity and good biocompatibility after in vitro experiments in simulated body fluid (SBF) and in cellular medium. Full article
(This article belongs to the Special Issue Sol-Gel Method Applied to Crystalline Materials)
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Open AccessArticle
Synthesis, Crystal Structures and Catalytic Activities of Two Copper Coordination Compounds Bearing an N,N’-Dibenzylethylenediamine Ligand
Crystals 2020, 10(6), 528; https://doi.org/10.3390/cryst10060528 - 21 Jun 2020
Viewed by 357
Abstract
Two copper coordination compounds bearing an N,N’-dibenzylethylenediamine ligand, namely [Cu3L(CH3COO)6]n (1) and [(CuCl4)∙(C6H5CH2NH2CH2)2] (2) (L = N,N’-dibenzylethylenediamine) were [...] Read more.
Two copper coordination compounds bearing an N,N’-dibenzylethylenediamine ligand, namely [Cu3L(CH3COO)6]n (1) and [(CuCl4)∙(C6H5CH2NH2CH2)2] (2) (L = N,N’-dibenzylethylenediamine) were synthesized by the ethanol refluxing method. Powder X-ray diffraction (PXRD), infrared spectra (IR), elemental analyses, and single crystal X-ray diffraction were used to characterize and verify their structures. Structural analyses showed that the asymmetric unit of compound (1), composed of two Cu(II) cations, three acetate anions, and half of the ligand, was bridged by one acetate to obtain an infinite 1D chain structure. The analyses further showed that the asymmetric unit of compound (2), composed of two crystallographically independent [C6H5CH2NH2CH2]+ units, four chloride anions, and one central Cu(II) cation is connected into an infinite 2D network structure by the hydrogen bonding interactions. The copper compounds were used to catalyze the decomposition of H2O2, and the results showed that both of the compounds exhibited excellent catalytic activities under optimized conditions. Full article
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Open AccessArticle
Liquid Phase Separation in Ag-Co-Cr-Fe-Mn-Ni, Co Cr-Cu-Fe-Mn-Ni and Co-Cr-Cu-Fe-Mn-Ni-B High Entropy Alloys for Biomedical Application
Crystals 2020, 10(6), 527; https://doi.org/10.3390/cryst10060527 - 20 Jun 2020
Viewed by 377
Abstract
The liquid phase separation (LPS) behavior in Co-Cr-based high-entropy alloys (HEAs) is an important target for the development of Co-Cr-based HEAs for metallic biomaterials (BioHEAs). The solidification microstructure in Ag-Co-Cr-Fe-Mn-Ni-Ag, Co-Cr-Cu-Fe-Mn-Ni-Cu, and Co-Cr-Cu-Fe-Mn-Ni-B HEAs, which were designed as the combination of the equiatomic [...] Read more.
The liquid phase separation (LPS) behavior in Co-Cr-based high-entropy alloys (HEAs) is an important target for the development of Co-Cr-based HEAs for metallic biomaterials (BioHEAs). The solidification microstructure in Ag-Co-Cr-Fe-Mn-Ni-Ag, Co-Cr-Cu-Fe-Mn-Ni-Cu, and Co-Cr-Cu-Fe-Mn-Ni-B HEAs, which were designed as the combination of the equiatomic CoCrFeMnNi with Ag, Cu, and the interstitial element of B, was investigated as the fundamental research of LPS in Co-Cr-based HEAs. Ingots of equiatomic AgCoCrFeMnNi, equiatomic CoCrCuFeMnNi, non-equiatomic CoCrCuxFeMnNi (x = 2, 3), and CoCrCuxFeMnNiB0.2 (x = 1, 2, 3) with a small amount of B were fabricated using the arc-melting process. A macroscopic phase-separated structure was observed in the ingots of the equiatomic AgCoCrFeMnNi and CoCrCuxFeMnNiB0.2 (x = 2, 3) HEAs. The addition of a small amount of B enhanced the LPS tendency in the Co-Cr-Fe-Mn-Ni-Cu HEAs. The LPS behavior was discussed through the heat of mixing and computer coupling of phase diagrams and thermochemistry (CALPHAD). Full article
(This article belongs to the Special Issue Development of High Entropy Alloys)
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Open AccessArticle
Analysis of the Phase Stability of LiMO2 Layered Oxides (M = Co, Mn, Ni)
Crystals 2020, 10(6), 526; https://doi.org/10.3390/cryst10060526 - 20 Jun 2020
Viewed by 352
Abstract
Transition-metal (TM) layered oxides have been attracting enormous interests in recent decades because of their excellent functional properties as positive electrode materials in lithium-ion batteries. In particular LiCoO2 (LCO), LiNiO2 (LNO) and LiMnO2 (LMO) are the structural prototypes of a [...] Read more.
Transition-metal (TM) layered oxides have been attracting enormous interests in recent decades because of their excellent functional properties as positive electrode materials in lithium-ion batteries. In particular LiCoO2 (LCO), LiNiO2 (LNO) and LiMnO2 (LMO) are the structural prototypes of a large family of complex compounds with similar layered structures incorporating mixtures of transition metals. Here, we present a comparative study on the phase stability of LCO, LMO and LNO by means of first-principles calculations, considering three different lattices for all oxides, i.e., rhombohedral (hR12), monoclinic (mC8) and orthorhombic (oP8). We provide a detailed analysis—at the same level of theory—on geometry, electronic and magnetic structures for all the three systems in their competitive structural arrangements. In particular, we report the thermodynamics of formation for all ground state and metastable phases of the three compounds for the first time. The final Gibbs Energy of Formation values at 298 K from elements are: LCO(hR12) −672 ± 8 kJ mol−1; LCO(mC8) −655 ± 8 kJ mol−1; LCO(oP8) −607 ± 8 kJ mol−1; LNO(hR12) −548 ± 8 kJ mol−1; LNO(mC8) −557 ± 8 kJ mol−1; LNO(oP8) −548 ± 8 kJ mol−1; LMO(hR12) −765 ± 10 kJ mol−1; LMO(mC8) −779 ± 10 kJ mol−1; LMO(oP8) −780 ± 10 kJ mol−1. These values are of fundamental importance for the implementation of reliable multi-phase thermodynamic modelling of complex multi-TM layered oxide systems and for the understanding of thermodynamically driven structural phase degradations in real applications such as lithium-ion batteries. Full article
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Open AccessArticle
Piezoelectric Resonators Excited by Lateral Electric Fields Based on a LiTaO3 Single Crystal
Crystals 2020, 10(6), 525; https://doi.org/10.3390/cryst10060525 - 18 Jun 2020
Viewed by 272
Abstract
In the present study, piezoelectric resonators under lateral field excitation (LFE) based on a LiTaO3 single crystal are modeled and analyzed. An electrically forced vibration study is employed to acquire the motional capacitance curve and vibration mode shapes. A finite element approach [...] Read more.
In the present study, piezoelectric resonators under lateral field excitation (LFE) based on a LiTaO3 single crystal are modeled and analyzed. An electrically forced vibration study is employed to acquire the motional capacitance curve and vibration mode shapes. A finite element approach is utilized to investigate the influences of some basic parameters, such as the electrode/plate mass ratio, electrode gap, and electrode width on resonance characteristics. In addition, the design criteria for the gap and width of the electrode of the LiTaO3 LFE resonators are obtained by analyzing the effects of those parameters on vibration strain distributions. The obtained results are essential for designing LFE piezoelectric resonators by using a LiTaO3 single crystal. Full article
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Open AccessReview
In Situ Monitoring Systems of The SLM Process: On the Need to Develop Machine Learning Models for Data Processing
Crystals 2020, 10(6), 524; https://doi.org/10.3390/cryst10060524 - 18 Jun 2020
Viewed by 236
Abstract
In recent years, technological advancements have led to the industrialization of the laser powder bed fusion process. Despite all of the advancements, quality assurance, reliability, and lack of repeatability of the laser powder bed fusion process still hinder risk-averse industries from adopting it [...] Read more.
In recent years, technological advancements have led to the industrialization of the laser powder bed fusion process. Despite all of the advancements, quality assurance, reliability, and lack of repeatability of the laser powder bed fusion process still hinder risk-averse industries from adopting it wholeheartedly. The process-induced defects or drifts can have a detrimental effect on the quality of the final part, which could lead to catastrophic failure of the finished part. It led to the development of in situ monitoring systems to effectively monitor the process signatures during printing. Nevertheless, post-processing of the in situ data and defect detection in an automated fashion are major challenges. Nowadays, many studies have been focused on incorporating machine learning approaches to solve this problem and develop a feedback control loop system to monitor the process in real-time. In our study, we review the types of process defects that can be monitored via process signatures captured by in situ sensing devices and recent advancements in the field of data analytics for easy and automated defect detection. We also discuss the working principles of the most common in situ sensing sensors to have a better understanding of the process. Commercially available in situ monitoring devices on laser powder bed fusion systems are also reviewed. This review is inspired by the work of Grasso and Colosimo, which presented an overall review of powder bed fusion technology. Full article
(This article belongs to the Special Issue Additive Manufacturing (AM) of Metallic Alloys)
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Open AccessArticle
Imprinting the Polytype Structure of Silicon Carbide by Rapid Thermal Processing
Crystals 2020, 10(6), 523; https://doi.org/10.3390/cryst10060523 - 18 Jun 2020
Viewed by 235
Abstract
Silicon carbide is a material with a multistable crystallographic structure, i.e., a polytypic material. Different polytypes exhibit different band gaps and electronic properties with nearly identical basal plane lattice constants, making them interesting for heterostructures without concentration gradients. The controlled formation of this [...] Read more.
Silicon carbide is a material with a multistable crystallographic structure, i.e., a polytypic material. Different polytypes exhibit different band gaps and electronic properties with nearly identical basal plane lattice constants, making them interesting for heterostructures without concentration gradients. The controlled formation of this heterostructure is still a challenge. The ability to adjust a defined temperature–time profile using rapid thermal processing was used to imprint the polytype transitions by controlling the nucleation and structural evolution during the temperature ramp-up and the steady state. The influence of the linear heating-up rate velocity during ramp-up and steady-state temperature on the crystal structure of amorphized ion-implanted silicon carbide layers was studied and used to form heteropolytype structures. Integrating the structural selection properties of the non-isothermal annealing stage of the ion-implanted layers into an epitaxial growth process allows the imprinting of polytype patterns in epitaxial layers due to the structural replication of the polytype pattern during epitaxial growth. The developed methodology paves the way for structural selection and vertical and lateral polytype patterning. In rapid thermal chemical vapor deposition, the adjustment of the process parameters or the buffer layer allowed the nucleation and growth of wurtzite silicon carbide. Full article
(This article belongs to the Special Issue Development and Investigation of SiC and SiC-based devices)
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Open AccessArticle
Crystallization of GeO2–Al2O3–Bi2O3 Glass
Crystals 2020, 10(6), 522; https://doi.org/10.3390/cryst10060522 - 18 Jun 2020
Viewed by 296
Abstract
In the presented work, two kinds of germanium oxide glass with different compositions, namely GeO2 and GeO2–Al2O3–Bi2O3, were investigated. After controlled crystallization of a glassy sample, the emission in the NIR-range was [...] Read more.
In the presented work, two kinds of germanium oxide glass with different compositions, namely GeO2 and GeO2–Al2O3–Bi2O3, were investigated. After controlled crystallization of a glassy sample, the emission in the NIR-range was determined (1165 nm with excitation at 470 nm). To better understanding the kinetics of the glass crystallization, the activation energy was also determined by applying the Kissinger method. The obtained results show that in the case of GeO2–Al2O3–Bi2O3, activation energy value was 400 and 477 kJ/mol, which means that such values are significantly larger than for pure GeO2 (254 kJ/mol). The investigations also show that two phases crystallized in the complex glass matrix: the mullite-like phase and germanium oxide. Full article
(This article belongs to the Special Issue Transparent Glass Ceramics)
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Open AccessArticle
Effect of Bi Substitution on Structural and AC Magnetic Susceptibility Properties of Nd1−xBixMnO3
Crystals 2020, 10(6), 521; https://doi.org/10.3390/cryst10060521 - 17 Jun 2020
Viewed by 317
Abstract
This study synthesizes the neodymium-based manganites with Bi doping, Nd1−xBixMnO3 (x = 0, 0.25 and 0.50) using the solid-state reaction route. The crystal structural, morphological and magnetic properties were determined using X-ray diffraction (XRD), fourier transform infrared spectroscopy [...] Read more.
This study synthesizes the neodymium-based manganites with Bi doping, Nd1−xBixMnO3 (x = 0, 0.25 and 0.50) using the solid-state reaction route. The crystal structural, morphological and magnetic properties were determined using X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FESEM) and AC magnetic susceptibility. The Rietveld refinement confirmed that the compounds were in the single-phase orthorhombic structure of the NdMnO3 with Pbnm space group and lattice parameter b increased with doping from 5.5571 (x = 0) to 5.6787 (x = 0.5). FTIR spectra showed that absorption bands were located within the range of 550–600 cm−1, which corresponded to the Mn–O stretching vibration. FESEM exhibited homogenous compound. The AC magnetic susceptibility measurement studies showed a strong antiferromagnetic (AFM) to paramagnetic (PM) transition existed at 76 K, 77 K and 67 K for samples (x = 0, 0.25 and 0.50), respectively. Full article
(This article belongs to the Special Issue Intermetallic Compound)
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