Powder Diffraction Research Articles

The impact of alcohol and ammonium fluoride on pressure-induced amorphization of cubic structure I clathrate hydrates.

We have investigated pressure-induced amorphization (PIA) of an alcohol clathrate hydrate (CH) of cubic structure type I (sI) in the presence of NH4F utilizing dilatometry and x-ray powder diffraction. PIA occurs at 0.98GPa at 77K, which is at a much lower pressure than for other CHs of the same structure type. The amorphized CH also shows remarkable resistance against crystallization upon decompression. While amorphized sI CHs could not be recovered previously at all, this is possible in the present case. By contrast to other CHs, the recovery of the amorphized CHs to ambient pressure does not even require a high-pressure annealing step, where recovery without any loss of amorphicity is possible at 120K and below. Furthermore, PIA is accessible upon compression at unusually high temperatures of up to 140K, where it reaches the highest degree of amorphicity. Molecular dynamics simulations confirm that polar alcoholic guests, as opposed to non-polar guests, induce cage deformation at lower pressure. The substitution of NH4F into the host-lattice stabilizes the collapsed state more than the crystalline state, thereby enhancing the collapse kinetics and lowering the pressure of collapse.

Seeing the Unseen: The Structural Influence of the Lone Pair Electrons in PbWO4.

Pair distribution function (PDF) analysis of the scheelite-type material PbWO4 reveals previously unidentified short-range structural distortions in the PbO8 polyhedra and WO4 tetrahedra not observed in the similarly structured CaWO4. These local distortions are a result of the structural influence of the Pb2+ 6s2 lone pair electrons. These are not evident from the Rietveld analysis of synchrotron X-ray or neutron powder diffraction data, nor do they strongly influence the X-ray PDF (XPDF). This illustrates the importance of neutron PDF (NPDF) in the study of such materials. First-principles density function theory (DFT) calculations show that the Pb2+ 6s2 electrons are hybridized with the O2- 2p electrons near the Fermi level. The presence of local-scale distortions has previously been neglected in studies of structure-functionality relationships in PbWO4 and other scheelite-structured photocatalytic materials, including BiVO4, and this observation opens new avenues for their optimization.

Synthesis and Properties of the Ba2PrWO6 Double Perovskite.

We report details on the synthesis and properties of barium praseodymium tungstate, Ba2PrWO6, a double perovskite that has not been synthesized before. Room-temperature (RT) powder X-ray diffraction identified the most probable space group (SG) as monoclinic I2/m, but it was only slightly distorted from the cubic structure. X-ray photoelectron spectroscopy confirmed that the initial (postsynthesis) material contained praseodymium in both 3+ and 4+ charge states. The former (Pr3+) disappeared after exposure to UV light at RT. Photoluminescence studies of Pr3+ revealed that Ba2PrWO6 is an insulator with a band gap exceeding 4.93 eV. Pressure-dependent Raman spectroscopy excluded the possibility of a phase transition up to 20 GPa; however, measurements between 8 and 873 K signified that there might be a change toward the lower symmetry SG below 200 K. Electron paramagnetic resonance spectra revealed the presence of interstitial oxygen which acts as a deep electron trap.

Microhardness, Surface Roughness, and Wear Resistance Enhancement of Reinforced Conventional Glass Ionomer Cement Using Fluorinated Graphene Oxide Nanosheets.

Conventional glass ionomer cements (GICs) have been considered the most prevalent restorative material however; the reduced mechanical qualities and decreased wear resistance have been the main challenges facing their wide clinical application. This study was designed to assess the mechanical properties of fluorinated graphene (FG) oxide-modified conventional GIC. Composites of FG/GIC samples were prepared using (Medifil from PROMEDICA, Germany, shade A3) at different concentrations (0wt%) control group and (1wt%, 2wt% and 3wt% FG) groups using cylindrical molds (3mm × 6mm). FG was prepared using hydrothermal technique and characterized using XPERT-PRO Powder Diffractometer system for X-ray diffraction analysis and JEOL JEM-2100 high resolution transmission electron microscope. Vickers' hardness and wear resistance of GI samples were measured. Mechanical abrasion was performed via three-body tooth brushing wear test using ROBOTA chewing simulator coupled with a thermocycling protocol (Model ACH-09075DC-T, AD-Tech Technology Co., Ltd., Leinfelden-Echterdingen, Germany). Comparisons between groups with respect to normally distributed numeric variables were performed using one-way analysis of variance test followed by posthoc test. While paired t-test was utilized for comparing data within the same group. The surface roughness values of GICs (1wt% FG) and (2wt% FG) composites were significantly lower than those of the control and 3wt%FG groups. Vickers' hardness numbers were significantly higher in FG/GICs composites than in the control group (p≤0.05). GIC/FG combinations have sufficient strength to resist the occlusion stresses with improved hardness as compared with conventional GIC. GIC/FG appeared to be a promising restorative material.

Ni Single Atom Decorated Porous Hollow Carbon Nanosphere-Based Electrodes for High Performance Symmetric Solid-State Supercapacitors.

Ni single atom containing hollow carbon nanospheres with nitrogen doping has been synthesized by carbonization of Ni(NO3)2/phloroglucinol-formaldehyde polymer/silica composite. The samples have been characterized by powder X-ray diffraction, nitrogen adsorption/desorption, electron microscopic, Raman and X-ray photoelectron spectroscopic studies. The microstructure and surface area vary with the amount of Ni(NO3)2 employed in the syntheses and the carbonization environment. An optimized amount of nickel and argon as the carbonization gas afford Ni-1.0@N@HCN-Ar which possesses overall superior features. The uniformly dispersed Ni single atoms within the hollow porous carbon framework fully utilize all the electroactive sites thereby improving the supercapacitive performance. The specific capacitance of Ni-1.0@N@HCN-Ar reaches 777 F∙g-1 at 1 A∙g-1 with a Coulombic efficiency of 98.4% and excellent recyclability. The energy and power density of Ni-1.0@N@HCN-Ar are found to be high; at 1 A∙g-1 its energy density is 155.4 Wh∙kg-1 with a power density of 600.3 W∙kg-1. At a high current density of 10 A∙g-1 the material shows a high energy density of 118.4 Wh∙kg-1 with excellent power density of 6003.4 W∙kg-1. A symmetric solid-state supercapacitor assembled with this material, Ni-1.0@N@HCN-Ar//Ni-1.0@N@HCN-Ar using H2SO4/PVA gel electrolyte shows a superior energy density value of 30 Wh∙kg-1 at a power density of 1200 W∙kg-1.

Kinetic evaluation of the uranyl peroxide synthetic route on morphology

Abstract An important challenge in utilizing particle morphology in nuclear forensic or fuel fabrication applications is understanding why differences in morphologies are observed following varying processing conditions. This is often due to competition and interplay between thermodynamic and kinetic influences. To that end, some of the kinetic influences in the uranyl peroxide precipitation reaction were evaluated and compared to thermodynamic influences studied previously. Metastudtite (UO2O2·2H2O) was synthesized from solutions of uranyl nitrate or chloride, and the reaction time was varied from 100 s to 230 min enabling an evaluation of kinetic and thermodynamic influences. The metastudtite was then calcined to U3O8, and all materials were analyzed by powder X-ray diffraction (p-XRD) and scanning electron microscopy (SEM). Analysis by p-XRD confirmed the sample purity of metastudtite and U3O8. SEM images were analyzed using the Morphological Analysis for Materials (MAMA) software to measure the size and shape of the nanoparticles for a statistical comparison between materials. Metastudtite produced at shorter reaction times exhibited a kinetically controlled shape by forming smaller and rounder particles than metastudtite produced at longer reaction times. Metastudtite produced at the longer reaction times exhibited differences between the uranyl nitrate and uranyl chloride routes with the nitrate exhibiting a more angular and faceted morphology than the chloride. Overall, the control of the supersaturation ratio (S) played a significant role in determining the morphology of the metastudtite. Morphological differences between the U3O8 confirmed the role of nanoparticle agglomeration in forming larger sintered particles. The results help demonstrate the importance of understanding particle formation mechanisms in the long-term development of morphology in nuclear forensics or in developing advanced fuels with specific characteristics.

Terahertz Spectroscopy Unambiguously Determines the Orientation of Guest Water Molecules in a Structurally Elusive Metal-Organic Framework.

Porous materials, particularly metal-organic frameworks (MOFs), hold great promise for advanced applications. MIL-53(Al) is an exceptionally well-studied MOF that exhibits a phase transition upon guest capture─in this case, water─resulting in a dramatic change in the pore volume. Despite extensive studies, the structure of the water-loaded narrow-pore phase, MIL-53(Al)-np, remains controversial, particularly with respect to the positions of the adsorbed water molecules. We use terahertz spectroscopy, coupled with powder X-ray diffraction and density functional theory simulations, to unambiguously resolve this controversy. We show that the low-frequency (<100 cm-1) vibrational spectrum depends on weak long-range forces that are extremely sensitive to the orientation of the adsorbed water molecules. This enables definitively determining the correct structure of MIL-53(Al)-np while highlighting the extreme sensitivity of terahertz spectroscopy to bulk structure, suggesting its potential as a robust complement to X-ray diffraction for precise characterization of host-guest complexes.

Sweeteners Show a Plasticizing Effect on PVP K30—A Solution for the Hot-Melt Extrusion of Fixed-Dose Amorphous Curcumin-Hesperetin Solid Dispersions

The co-administration of curcumin and hesperetin might be beneficial in terms of neuroprotective activity; therefore, in this study, we attempted to develop a fixed-dose formulation comprising these two compounds in an amorphous state. The aim of obtaining an amorphous state was to overcome the limitations of the low solubility of the active compounds. First, we assessed the possibility of using popular sweeteners (erythritol, xylitol, and sorbitol) as plasticizers to reduce the glass transition temperature of PVP K30 to prepare the polymer–excipient blends, which allowed the preparation of amorphous solid dispersions via hot-melt extrusion at a temperature below the original glass transition of PVP K30. Erythritol proved to be the superior plasticizer. Then, we focused on the development of fixed-dose amorphous solid dispersions of curcumin and hesperetin. Powder X-ray diffraction and thermal analysis confirmed the amorphous character of dispersions, whereas infrared spectroscopy helped to assess the presence of intermolecular interactions. The amorphous state of the produced dispersions was maintained for 6 months, as shown in a stability study. Pharmaceutical parameters such as dissolution rate, solubility, and in vitro permeability through artificial membranes were evaluated. The best improvement in these features was noted for the dispersion, which contained 15% of the total content of the active compounds with erythritol used as the plasticizer.

An Investigation of the Impact of Precipitation Temperature and Filter Cake Thickness on the Physical Stability of Amorphous Solids: A Case Study

The purpose of this study was to resolve the issue of physical instability in amorphous solid drugs, which can result in unwanted crystallization, affecting solubility and dissolution rates. The focus was on precipitating physically stable amorphous forms of the nilotinib free base, an anticancer drug, by monitoring preparation conditions such as precipitation temperature and filter cake thickness. A comprehensive set of characterization techniques, including powder X-ray diffraction (PXRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and focused beam reflectance measurement (FBRM), were used. These were supplemented by advanced data analysis methods that incorporated pair distribution function (PDF), reduced crystallization temperature (Rc), and principal component analysis (PCA) to evaluate the physical stability of the amorphous samples. Results emphasized that optimal physical stability was achieved when amorphous solids were prepared at a precipitation temperature of 10 °C and a filter cake thickness of 4 cm. Moreover, the integration of PDF analysis with Rc values was confirmed as an innovative approach for assessing physical stability, thus offering enhanced efficiency and accuracy over conventional accelerated stability testing methods.

Allylthiourea‐mediated self‐healing hydrogels based on poly(vinyl alcohol): Enhanced cell viability/biocompatibility and sustained drug release

AbstractHydrogel‐based materials represent promising candidates for drug delivery. In our research, we synthesized a series of hydrogels—PVATU‐1 (2:1), PVATU‐2 (1:1), and PVATU‐3 (0.5:1)—by adjusting the poly(vinyl alcohol) (PVA) ratio while maintaining a constant ratio of allylthiourea (ATU) monomer and glutaraldehyde cross‐linker, aiming to understand their impacts on gelation. These PVATU hydrogels displayed impressive swelling in neutral conditions and exhibited visible self‐healing capabilities. Notably, PVATU‐1 shows superior mechanical strength among the variants. Surface analysis using AFM and SEM unveiled porous structures within the hydrogels, while thermal stability tests indicated their resilience up to 200°C. DSC analysis revealed minimal variation in glass transition temperatures (Tg), affirming stability. A distinct endothermic peak around 250–350°C across all hydrogels confirmed their semi‐crystalline nature, corroborated by powder XRD. Noteworthy, PVATU‐1 demonstrated optimal loading and releasing efficiency for levofloxacin, with 74.5% loading and 82.8% releasing efficiency within 18 h. Biocompatibility assessments on HeLa cells affirmed the nontoxicity of PVATU hydrogel treatments.

Ni-Co Complex Ionic Synergistically Modifying Octahedron Lattice of Cordierite Ceramics for the Application of 5G Microwave-Millimeter-wave Antennas.

In this work, phase-pure Mg1.8(Ni1-xCox)0.2Al4Si5O18 (0 ≤ x ≤ 1) ceramics were synthesized by a high-temperature solid-state method. On the basis of Rietveld refinement data of X-ray powder diffraction and Phillips-Vechten-Levine theory, the atomic ionicity, lattice energy, and bond energy of the compound were calculated to explore their influence on the microwave dielectric properties of ceramics. The Mg1.8Ni0.1Co0.1Al4Si5O18 (x = 0.5) ceramic exhibited the best microwave dielectric properties: εr = 4.44, Qf = 73 539 GHz@13 GHz, and τf = -23.9 ppm/°C. (Ni1-xCox)2+ complex ionic doping, compared with only Ni2+ or Co2+, is beneficial for improving the symmetry of [Si4Al2O18] hexagonal rings and reducing distortion. Subsequently, 8 wt % TiO2 was added to Mg1.8Ni0.1Co0.1Al4Si5O18, resulting in a near-zero τf and high Qf values for the composite ceramic, with εr = 5.22, Qf = 58 449 GHz@13 GHz, and τf = -2.06 ppm/°C. Finally, a 5G millimeter-wave antenna with a central operating frequency of 25.52 GHz was designed and fabricated using the Mg1.8Ni0.1Co0.1Al4Si5O18-8 wt % TiO2 ceramics. Operating in the 24.7-26.0 GHz range, it demonstrated favorable radiation characteristics with a simulated efficiency of 85.2% and a gain of 4.58 dBi. The antenna's performance confirms the high potential of the cordierite composite for application in 5G communication systems.

{SeO2(OH)} Bridging Lanthanide-Containing Antimono-Seleno-Tungstates.

A series of new trigonal pyramidal {SeO2(OH)} bridging lanthanide-containing antimono-seleno-tungstates [H2N(CH3)2]8Na8Cs4H9[Ln2SeW4O11(OH)(H2O)4(SbW9O33)(SeW9O33)(Se1/2Sb1/2W9O33)]2·32H2O [Ln = Tb (1), Dy (2), Ho (3), Er (4)] have been prepared by the synthetic strategy of simultaneously using the antimonotungstate precursor and simple material in an acidic aqueous solution and structurally characterized by single-crystal X-ray diffraction, powder X-ray diffraction, IR spectrometry, and thermogravimetric analysis. Their molecular structures contain an unprecedented hexameric polyoxoanion [Ln2SeW4O11(OH)(H2O)4(SbW9O33)(SeW9O33)(Se1/2Sb1/2W9O33)]229- constituted by two equivalent trimeric subunits Ln2W4O9(H2O)4(SbW9O33)(SeW9O33)(Se1/2Sb1/2W9O33) bridged via two μ2-{SeO2(OH)} linkers. Furthermore, the catalytic oxidation of various aromatic sulfides and sulfur mustard simulant 2-chloroethyl ethyl sulfide (CEES) by compound 3 as the heterogeneous catalyst has been investigated, exhibiting high conversion and selectivity as well as good stability and recyclability.

Similarities and differences in the ordering at short and long ranges in a NaNbO3 based Pb-free smart system: A key to functional properties

Abstract In this study, we have investigated the crystal structure of the solid solution of antiferroelectric NaNbO3(NN)&amp;#xD; with ferroelectric Ba0.9Ca0.1TiO3(BCT), i.e. (1-x)NN- xBCT for 0 ≤ x ≤ 1.0 using High-resolution powder X-ray diffraction (HR-XRD) data, dielectric measurements in conjunction with Raman spectroscopic studies. The&amp;#xD; investigation of long-range structural phase transitions as a function of composition(x) using X-ray diffraction is&amp;#xD; complemented by short-range structural insights from Raman spectroscopy. The incorporation of BCT disrupts&amp;#xD; the delicate antiferroelectric ordering of NN and stabilises various ferroelectric phases with increasing BCT&amp;#xD; content(x). At x=0.10, the simultaneous presence of two ferroelectric phases viz., Pmc21 and Amm2, results in&amp;#xD; a threefold rise in remanent polarization compared to off-boundary compositions. The composition with higher&amp;#xD; BCT content (i.e., x ≥ 0.50) has shown the anomalous existence of two long-range cubic structures, both of&amp;#xD; which are characterised by Pm-3m space group. In spite of having a two-phase long-range centrosymmetric&amp;#xD; structure, we have observed a slim Polarization vs. Electric field(P-E) hysteresis loop for 0.50 ≤ x ≤ 0.80.&amp;#xD; This contrapositive behaviour(i.e., hysteresis loop in a centrosymmetric structure) has been attributed to the&amp;#xD; correlations among local static polar distortions of rhombohedral type ascertained using Raman spectroscopy.&amp;#xD; The coexistence of two ferroelectric phases at room temperature(for x=0.10) and a slim hysteresis loop (for&amp;#xD; 0.50 ≤ x ≤ 0.80) make these compositions potential ingredients for applications in ferroelectric memory and&amp;#xD; energy storage devices.

Synthesis and Physical Properties of the Misfit Layered Compound (EuS)1.13(NbSe2)2.

A new misfit layered compound with the stoichiometry (EuS)1+δ(NbSe2)2 (δ ≈ 0.13) has been successfully synthesized. High-resolution transmission electron microscopy and powder X-ray diffraction confirm the misfit structure with (EuS)-(EuS) spacing of 18.30(1) Å. Magnetization, electrical resistivity, heat capacity, and thermal transport measurements show that the material is a heavily doped semiconductor or poor metal with a low thermal conductivity of ∼1 W/m K and an antiferromagnetic ordering transition at TN = 4.7 K. In contrast to the parent materials, the misfit is neither ferromagnetic nor superconducting down to T = 0.4 K. We find evidence of a field-driven transition to a ferromagnetic state due to reorientation of ferromagnetic EuS layers at μoH = 0.5 T at T = 2 K.

Intramolecular Charge Transfer and Stimuli-Responsive Emission in Cholesterol-Appended Phenothiazine-Cyanostyryl-Based Donor-Acceptor Systems.

Organic fluorescent molecules have received considerable attention owing to their various optoelectronic applications. Herein, we report the design and synthesis of two cholesterol-functionalized cyanostyrene-phenothiazine-based D-π-A systems that are emissive in both the solution and solid states. The newly synthesized cholesterol-appended phenothiazine-cyanostyrene diads PTCS-1 and PTCS-2 vary in the N-alkylation of phenothiazine, respectively, with─octyl and─hexyl chains. Both molecules are highly fluorescent and show reasonably good quantum yields in nonpolar solvents because of twisted intramolecular charge transfer (TICT). The molecules exhibit aggregation-induced emission in the solid state. Due to the presence of flexible alkyl chains in the phenothiazine and cholesterol moieties, PTCS-1 and PTCS-2 show mechanochromic luminescence switching in response to external shear stress and emission recovery under methanol vapor. Powder X-ray diffraction studies prove that the emission switching on the applied stimuli in both PTCS-1 and PTCS-2 is attributed to the reversible transformation between the crystalline and amorphous states. Time-dependent density functional theory (TD-DFT) studies are carried out to gain insight into the ICT interactions. TD-DFT analysis at the TD-M06-2X/def2-TZVP level further revealed that in both molecules, the lowest unoccupied molecular orbital (LUMO) + 2, LUMO, highest occupied molecular orbital (HOMO), and HOMO - 1 orbitals are responsible for the charge transfer interactions. These ICT interactions are identified as π-π* type interactions.

Enhancing the Analysis of Eu3+ Photoluminescence in Coordination Compounds in the Solid State by Determining their Refractive Index

AbstractThis study is focused on determining the refractive index as a crucial parameter for evaluating the intrinsic quantum yield and the ligand sensitisation efficiency in solid‐state trivalent lanthanide coordination compounds. For this, eight trivalent europium complexes with phenyl‐terpyridine ([EuX3(ptpy)(L)], X=Cl− or NO3−, ptpy=4′‐phenyl‐2,2′ : 6′,2′′‐terpyridine, L=H2O or other molecules) were examined. Their refractive indices were determined using the Becke lines test by immersing transparent material in a series of media with known refractive indices. Using the set of media presented here, determining crystalline materials′ refractive indices from 1.41 to 1.73 with a step of 0.01 is possible. Assessment of the refractive indices of the complexes mentioned above allowed a comprehensive analysis of their photophysical properties in the solid state. Moreover, this method can be extrapolated for other solid‐state materials, offering valuable insights in the broader field of photophysics. In addition to photoluminescence investigations, the compounds presented were characterised by single‐crystal X‐ray diffraction (SCXRD), powder X‐ray diffraction (PXRD), Hirschfeld surface area analysis, UV‐Vis reflectance spectroscopy, hydrolysis sensitivity analysis, and simultaneous thermogravimetry and differential thermal analysis coupled with mass‐spectrometry (STA‐MS).

Integrating K+ into Eu and Tb doped GdCa4O(BO3)3: A dual study on photoluminescence and structure

In this study, we investigate the structural and photoluminescence (PL) properties of rare-earth-doped GdCa4O(BO3)3 (GdCOB) phosphors, specifically focusing on the spectral behaviour induced by doping with Eu³⁺ and Tb³⁺ ions. The powder X-ray diffraction (XRD) spectra confirm the formation of a monoclinic phase. The XRD data were also refined by a Rietveld refinement method. The existence of B, O, Ca, Gd, Tb, Eu and K elements was verified by EDS spectra. We introduce a detailed examination of the charge compensation process using Kröger-Vink notation to clarify the mechanisms essential for tailoring the optical properties of the phosphors. The PL excitation spectrum of GdCOB:Eu3+, monitored at 611 nm, reveals sharp excitation peaks at 319, 361, 380, and 392 nm, corresponding to 7F0→5H3, 7F0→5D4, 7F0→7F0, and 7F0→5L6 transitions, respectively. The PL spectrum under excitation of 392 nm exhibits that phosphors doped with Eu3+ a significant red emission at 611 nm, which is attributed to the 5D₀→7F₂ transition. This emission intensity is particularly enhanced at non-centrosymmetric sites of the Eu³⁺ ions. Similarly, the PL excitation spectrum of GdCOB:Tb3+, monitored at 552 nm, displays distinct excitation peaks at 316, 341, 353, and 379 nm, which correspond to the transitions 7F₆→5D₀, 7 F₆→5L₇, 7F₆→5D₂, and 7F₆→5D₃, respectively. Tb³⁺-doped phosphors display a bright green emission, with a dominant peak at 552 nm, resulting from the 5D₄→7F₅ transition. Additionally, the introduction of K⁺ ions as co-dopants results in modifications to the local environments of Eu³⁺ and Tb³⁺ ions. These changes allow for fine-tuning of the emission peaks, significantly enhancing the luminescent output of the phosphors. Optimal doping concentrations of 5 mol% for Eu³⁺ and 1 mol% for Tb³⁺ enhance luminescent intensity and prevent concentration quenching. This phenomenon, often resulting in reduced PL intensity at higher dopant levels, is primarily due to dipole-dipole interactions, consistent with Dexter's theory of energy transfer. Strategic modulation of doping concentrations, coupled with a deep understanding of energy transfer mechanisms are critical for the development of advanced luminescent materials Our analysis of the Commission de l′Eclairage (CIE) chromaticity coordinates reveals enhanced energy transfer dynamics in rare-earth-doped borates, facilitating the tuning of luminescent properties. These results not only deepen our understanding of the fundamental physics governing such phosphors but also open pathways for the development of optoelectronic applications requiring consistent color output, such as LED technologies and solid-state lighting.

Enhanced Magnetic and Dielectric Properties of YFeO3 Ceramics via Formation of Solid‐Solution with Sr2Bi4Ti5O18 and ZnSnO3 Oxides

In the present investigation, magnetic and dielectric properties of solid‐solution formed between the YFeO3 with the similar crystal structure of other oxide materials are focused on. Orthorhombic crystal structure of YFeO3 (YFO), Sr2Bi4Ti5O18 (SBT), and ZnSnO3 (ZS) nanomaterials are considered to prepare the solid solutions at 1150 °C/3 h. YFO and solid solutions exhibit the orthorhombic crystal structure, which is conformed through Rietveld refinement using X‐Ray powder diffraction pattern. The decreased average grain size is observed for the solid solution (3.0 μm for YFO and ZS and 2.6 μm for YFO and SBT) when compared to YFO (3.4 μm) through scanning electron microscopy. Oxidation state of each atom/ion/element present in the YFO and solid solutions are conformed through X‐Ray photoelectron spectroscopy studies. The solid solution formed between the YFO and SBT exhibits high magnetization value (2.92 emu g−1) and high coercive filed (67.5 Oe) when compared to solid solution formed between the YFO and ZS (magnetization value = 2.48 emu g−1, and coercive filed = 46.4 Oe) and YFO (magnetization value = 1.91 emu g−1, and coercive filed = 61.8 Oe). High dielectric permittivity (εr), low dielectric loss (tan δ), and low conductivity are observed for the solid solution formed between the YFO and SBT, when compared to other materials in this study.

Reverse Separation of Carbon Dioxide and Acetylene in Two Isostructural Copper Pyridine‐Carboxylate Frameworks

Separating acetylene from carbon dioxide is important but highly challenging due to their similar molecular shapes and physical properties. Adsorptive separation of carbon dioxide from acetylene can directly produce pure acetylene but is hardly realized because of relatively polarizable acetylene binds more strongly. Here, we reverse the CO2 and C2H2 separation by adjusting the pore structures in two isoreticular ultramicroporous metal−organic frameworks (MOFs). Under ambient conditions, copper isonicotinate (Cu(ina)2), with relatively large pore channels shows C2H2‐selective adsorption with a C2H2/CO2 selectivity of 3.4, whereas its smaller‐pore analogue, copper quinoline‐5‐carboxylate (Cu(Qc)2) shows an inverse CO2/C2H2 selectivity of 5.6. Cu(Qc)2 shows compact pore space that well matches the optimal orientation of CO2 but is not compatible for C2H2. Neutron powder diffraction experiments confirmed that CO2 molecules adopt preferential orientation along the pore channels during adsorption binding, whereas C2H2 molecules bind in an opposite fashion with distorted configurations due to their opposite quadrupole moments. Dynamic breakthrough experiments have validated the separation performance of Cu(Qc)2 for CO2/C2H2 separation.

Thermogravimetry as a research tool for the development of an ammonium sulphate roasting process for selective metal extraction from minerals

AbstractThe ammonium sulphate roasting process involves reacting mineral-bearing materials with ammonium sulphate via a solid–solid roasting process and subjecting the resulting roast residue to aqueous leaching. This process enables the simultaneous, non-selective co-extraction of strategic metals from the starting materials. However, effective separation of the extracted metals is often mandatory to produce quality products of high purity. In this study, the combined application of thermogravimetric analysis, X-ray powder diffraction and inductively coupled plasma optical emission spectrometry confirmed the non-selectivity of the process when applied to a South African diamond mine residue residue roasted with ammonium sulphate in a 1:2 mass ratio (m/m) at 450 °C for 2 h, with magnesium, iron and aluminium being co-extracted into water-soluble metal sulphates. Thermogravimetry was then applied to develop a multi-step, multi-temperature selective roasting process using mixtures of pure commercial metal sulphate salts. The first step of the modified process successfully separated iron and aluminium sulphates from magnesium-sulphates in the roast residues by thermally decomposing soluble iron and aluminium sulphates into insoluble oxides via calcination at 750 °C for 2 h. This temperature was lower than the one at which magnesium sulphates convert into magnesium oxide. In the second and final step, iron and aluminium were recovered from the oxide minerals via solid–solid re-roasting with ammonium sulphate at 450 °C for 1 h, causing the oxides to revert back to their water-soluble sulphate forms. The effectiveness of the modified process was subsequently verified using a diamond mine residue, showing that the soluble iron and aluminium contents in the magnesium-bearing leachate could be reduced by over 90%.