Rietveld Structure Refinement Research Articles

The Synergic Effect of h-MoO3, α-MoO3, and β-MoO3 Phase Mixture as a Solid Catalyst to Obtain Methyl Oleate.

Extensive research in the last few decades has conclusively demonstrated the significant influence of experimental conditions, surfactants, and synthesis methods on semiconductors' properties in technological applications. Therefore, in this study, the synthesis of molybdenum oxide (MoO3) was reported by the addition of 2.5 (MoO3_2.5), 5 (MoO3_5), 7.5 (MoO3_7.5), and 10 mL (MoO3_10) of nitric acid, obtaining the respective concentrations of 0.6, 1.10, 1.6, and 0.6 mol L-1. In this study, all samples were synthesized by the hydrothermal method at 160 °C for 6 h. The materials obtained were structurally characterized by X-ray diffraction (XRD) and structural Rietveld refinement, Raman spectroscopy, and infrared spectroscopy (FTIR), confirming the presence of all crystallographic planes and bands associated with active modes for the pure hexagonal phase (h-MoO3) when the solution's concentration was 0.6 mol L-1 of nitric acid. For concentrations of 1.10, 1.60, and 2.10 mol L-1, the presence of crystallographic planes and active modes associated with the formation of mixtures of molybdenum oxide polymorphs was confirmed, in this case, the orthorhombic, monoclinic, and hexagonal phases. X-ray photoelectron spectroscopy reveals the occurrence of the states Mo4+, Mo5+, and Mo6+, which confirm the predominance of the acid Lewis sites, corroborating the analysis by adsorption of pyridine followed by characterization by infrared spectroscopy. The images collected by scanning electron microscopy confirmed the information presented in the structural characterization, where microcrystals with hexagonal morphology were obtained for the MoO3_2.5 sample. In contrast, the MoO3_5, MoO3_7.5, and MoO3_10 samples exhibited hexagonal and rod-shaped microcrystals, where the latter morphology is characteristic of the orthorhombic phase. The catalytic tests carried out in the conversion of oleic acid into methyl oleate, using the synthesized samples as a heterogeneous catalyst, resulted in conversion percentages of 52.5, 58.6, 69.1, and 97.2% applying the samples MoO3_2.5, MoO3_5, MoO3_7.5, and MoO3_10, respectively. The optimization of the catalytic tests with the MoO3_10 sample revealed that the conversion of oleic acid into methyl oleate is a thermodynamically favorable process, with a variation in the Gibbs free energy between -67.3 kJ mol-1 and 83.4 kJ mol-1 as also, the energy value of activation of 24.6 kJ mol-1, for the temperature range from 80 to 140 °C, that is, from 353.15 to 413.15 K, respectively. Meanwhile, the catalyst reuse tests resulted in percentages greater than 85%, even after the ninth catalytic cycle. Therefore, the expressive catalytic performance of the mixture of h-MoO3 and α-MoO3 (MoO3_10) phases is confirmed, associated with the synergistic effect, mainly due to the increase in the surface area and available Lewis sites of these phases.

Enhanced functionalities of isovalently substituted 0.67(Bi1-xLaxFe0.97Ga0.03O3)-0.33(BaTiO3) relaxor piezoceramics synthesized via air quenching

The isovalently substituted lead-free binary solid solution, 0.67(Bi1-xLaxFe0.97Ga0.03O3)-0.33(BaTiO3) (BF-BT) (x ≤ 0.07), has been synthesized by solid state ceramic method via air quenching sintering. FTIR and XRD along with Rietveld structure refinement confirmed a pure perovskite phase with a pseudocubic structure (space group Pm3‾m) for developed compositions. SEM revealed a dense microstructure with fine grain size (<1.5 μm) and minimal porosity. XPS analysis reveals predominantly Bi+3 and Fe+3 states, along with oxygen vacancies (VO··). Ferroelectric studies demonstrated a maximum remanent polarization (Pr) of 12.3 μC/cm2 and coercive field EC of 30.95 kV/cm for La3+ concentration of x = 0.03. Overall decrement in Pr can be attributed to dipolar defect-induced random fields reducing the activation barrier for domain nucleation. Leakage current measurement reveals improved resistivity (∼108 Ω cm) up to an applied field of 30 kV/cm. Dielectric measurements unveiled two frequency-dependent anomalies in temperature dependence above room temperature, indicative of diffuse phase transitions. The Vogel-Fulcher model depicted an increasing freezing temperature (from 465 K for x = 0.01–551 K for x = 0.07) and decreasing activation energy (from ∼0.61 eV to 0.07 eV) with increasing La3+ concentration. The estimated diffuseness parameter around ∼2 suggested relaxor behavior. Doping with La resulted in increased dielectric permittivity at 10 kHz (from 4100 to 24066), showcasing the efficacy of site engineering in augmenting the functional properties of BF-BT for high-temperature dielectric and transducer applications.

Revealing multiphase coexistence of R-O-T phases in BaTiO3-CaTiO3-BaSnO3 electroceramics for energy harvesting and storage response with piezo actuation

The (Ba1-xCax)(SnyTi1-y)O3 piezoelectric ceramics (where x=0.016, y=0.024; x=0.032, y=0.048; x=0.048, y=0.072; x=0.064, y=0.096; x=0.08, y=0.12) were designed by conventional solid state reaction method. The crystal structure for the composition of x=0.064 and y=0.096 (abbreviated as BCST-4) possesses the coexistence of non-centrosymmetric rhombohedral-orthorhombic-tetragonal (R-O-T) tri-lattice symmetries at room temperature, as demonstrated by the structural Rietveld refinement, Raman analysis, and temperature dependence of dielectric study. Because of the R-O-T multiphase coexistence, BCST-4 possesses a superior electromechanical and piezoelectric property viz. kp ∼ 0.45, strain ∼ 0.100 %, d33* ∼ 649 pm/V, and an improved d33 ∼ 452 pC/N, which is comparable to commercially available soft PZT ceramics (d33 ⁓ 370 pC/N). For BCST-4 ceramics, an exceptional electrostriction coefficient Q33 ∼ 0.0434 m4/C2 value was attained. The intrinsic piezo-actuation DC strain was observed to be 130 microstrain (με) and 188 με with ε33 and ε31 modes respectively. The BCST-4 ceramic exhibits a maximum output power of 1.03 mW, a power density of 13.5 µW/mm3, a maximum output current of 88 µA, and an open circuit voltage Vpp of 28 V which successfully glowed ‘SPPU’ panel having 40 red commercial light-emitting diodes (LEDs). The energy storage study reveals that BCST-4 ceramics exhibit a maximum energy storage density (Wrec) of 165.87 mJ/cm3 with efficiency (ƞ) 68.00 %. Therefore, the improvement in electrostriction coefficient, piezoelectric charge coefficient, and energy storage response indicates that BCST-4 ceramic has the potential for actuator, energy harvesting, and energy storage applications.

Investigations on ancient bronze drums from Majiang, Guangxi, P. R. China

Six different types of Majiang bronze drums from Hechi City, Guangxi, China were collected from the Guangxi Museum to characterize the original scheme of polychromy and materials used for the drums. The composition of all the samples were determined by using scanning electron microscopy with energy-dispersive X-ray spectroscopy. All the bronze drums contain mainly Cu, Sn, Pb, and As. Qualitative analysis of the structure by X-ray powder diffraction indicates that each of the six bronze drums contains four or five phases, namely (Cu, As), Pb, Cu3Sn, and Cu10Sn3 or Cu, Pb, As0.2Cu1.8, Cu3Sn, and Cu10Sn3. The Rietveld structural refinement is performed first time for the quantitative analysis of ancient bronze drums and inorganic cultural relics. This paper reports the result.

Al-Si Order and Chemical Composition Model across Scapolite Solid Solutions with Evidence from Rietveld Structure Refinements

Scapolite forms solid solutions between the end members marialite, Na4[Al3Si9O24]Cl = Me0, and meionite, Ca4[Al6Si6O24]CO3 = Me100. Al-Si order and chemical composition models are proposed for the scapolite solid solutions. These models predict the chemical composition, Al-Si order, and average &lt;T–O&gt; distances between Me0–Me100. These models are based on the observed order of clusters and on two solid solutions that meet at Me75 coupled with predicted chemical compositions and &lt;T–O&gt; distances. The [Na4·Cl]3+ and [NaCa3·CO3]5+ clusters are ordered between Me0–Me75, whereas the clusters [NaCa3·CO3]5+ and [Ca4·CO3]6+ are disordered from Me75–Me100. To confirm the structural model, the crystal structure of 27 scapolite samples between Me6–Me93 has been obtained using synchrotron high-resolution powder X-ray diffraction (HRPXRD) data and Rietveld structure refinements. The structure was refined in space group P42/n for all the samples. The &lt;T–O&gt; distances indicate that the T1 (=Si), T2 (=Al), and T3 (=Si) sites are completely ordered at Me37.5, where the 1:1 ratio of [Na4·Cl]3+:[NaCa3·CO3]5+ clusters are ordered and gives rise to antiphase domain boundaries (APBs) based on Cl-CO3 order instead of Al-Si order. The presence of APBs based on Cl-CO3 order and cluster order indicate that neither space group P42/n nor I4/m are correct for the structure of scapolite, but the lower symmetry space group P42/n is a good approximation for modeling the average structure of scapolite. The complete Al-Si order at Me37.5 changes in a regular and predictable manner toward the end members: Me0, Me75, and Me100. The observed unit cell and several structural parameters show a discontinuity at Me75, where the series is divided into two. There is no structural evidence to support any phase transition in the scapolite series. The T1 site contains only Si from Me0–Me37.5; from Me37.5–Me100, Al atoms enter the T1 site and the &lt;T1–O&gt; distance increases linearly to Me100.

The effects of aluminate compounds on the free Ba generation and electron emission performance of dispenser cathode

Free barium (Ba) is critical to the formation of the active layer on the surface of dispenser cathode, which is contributed to the electron emission properties of the cathode. The Ba in the active layer of the dispenser cathode is generated by the chemical reaction between aluminate compounds and tungsten (W) under vacuum and high temperature. Nowadays, the effect of aluminate compounds on the generation of free Ba is not clear. In this work, aluminate impregnants called 411, 532 and 612 impregnants were prepared by coprecipitation method. The structure of the dominate compounds in 411, 532 and 612 impregnants were determined with density functional theory (DFT) calculation and Rietveld structure refinement. It was found that the dominate compounds of 411, 532 and 612 impregnants are Ba3.5Ca0.5Al2O7, Ba5CaAl4O12 and Ba3CaAl2O7, respectively. Then, the temperature dependence of the thermodynamic properties, such as Debye temperature, entropy, heat capacity and enthalpy, of the aluminate compounds were calculated. Based on the thermodynamic properties, the potential chemical reaction between aluminate compounds and W are energetically determined by deviation Gibbs energy. The effects of different aluminate compounds on the free Ba generation were evaluated with the equilibrium Ba(g) amounts that generated by the chemical reactions between aluminate compounds and W. It is shown that the equilibrium Ba(g) amounts generated by Ba3.5Ca0.5Al2O7 is higher than that by Ba5CaAl4O12 and Ba3CaAl2O7, implying the superiority of electron emission performance of Ba3.5Ca0.5Al2O7. The electron emission densities of the dispenser cathodes that impregnated with the 411, 612 and 532 impregnants are 5.06, 4.31 and 4.05 A/cm2, respectively. It is revealed that the Ba3.5Ca0.5Al2O7 has superiority in generating free Ba, which agreed well with thermodynamic simulation results.

Novel kosnarite-based M0.5Zr2(AsO4)x(PO4)3-x (M – Sr, Ba and Cd) ceramics for radwaste incorporation

Mineral-like single-phase NZP materials of variable composition M0.5Zr2(AsO4)x(PO4)3−x (M − Sr, Ba, Cd) are of interest as matrices for isolation of high-level Sr, Ba and Cd wastes generated during reprocessing of irradiated nuclear fuel. Such polycrystalline phases were synthesized by sol-gel method with subsequent heat treatment and investigated by X-ray diffraction, IR spectroscopy and electron-probe microanalysis. Rietveld structure refinement showed that the framework is formed by ZrO6 octahedra and mixed AsO4/PO4 tetrahedra connected by vertices; Sr, Ba or Cd cations are located in extra-framework positions. Arsenate-phosphates can be classified as medium thermal expansion materials due to their average coefficient of linear thermal expansion of 2.8∙10−6 °C−1. Chemical durability test indicates that the leaching rate of Sr2+ ions from the NZP structure type solid solution is of the order of 10−5 g cm−2d−1.

Understanding the Solid-State Structure of Riboflavin through a Multitechnique Approach.

Crystalline riboflavin (vitamin B2) performs an important biological role as an optically functional material in the tapetum lucidum of certain animals, notably lemurs and cats. The tapetum lucidum is a reflecting layer behind the retina, which serves to enhance photon capture and vision in low-light settings. Motivated by the aim of rationalizing its biological role, and given that the structure of biogenic solid-state riboflavin remains unknown, we have used a range of experimental and computational techniques to determine the solid-state structure of synthetic riboflavin. Our multitechnique approach included microcrystal XRD, powder XRD, three-dimensional electron diffraction (3D-ED), high-resolution solid-state 13C NMR spectroscopy, and dispersion-augmented density functional theory (DFT-D) calculations. Although an independent report of the crystal structure of riboflavin was published recently, our structural investigations reported herein provide a different interpretation of the intermolecular hydrogen-bonding arrangement in this material, supported by all the experimental and computational approaches utilized in our study. We also discuss, more generally, potential pitfalls that may arise in applying DFT-D geometry optimization as a bridging step between structure solution and Rietveld refinement in the structure determination of hydrogen-bonded materials from powder XRD data. Finally, we report experimental and computational values for the refractive index of riboflavin, with implications for its optical function.

Cation doping for enhanced layer spacing and electrochemical performance in Li-rich Mn-based lithium-ion cathode materials

Lithium-rich manganese-based cathode materials offer promising research avenues owing to their high capacity. This study delved into the impact of cation doping on Li1.2Ni0.13Co0.13Mn0.54O2(LNCMO). A range of layered Li1.2BXNi0.13Co0.13Mn0.54O2 (LNCMOxB, B = Ca, Na, Al) cathode materials were produced utilizing calcium, sodium, and aluminum chloride as dopants. Combining these elements with the lithium-rich materials improves the capacity retention of the positive electrode and mitigates voltage decay. X-ray diffraction analysis, Rietveld structural refinement, SEM, and XPS verified the inclusion of Ca, Na, and Al in the synthesized samples. Electrochemical analysis revealed that the LNCMO-0.01Na sample, possessing the largest dopant radius, exhibited favorable cyclic stability at 0.2C. Conversely, the LNCMO-0.01Al sample, featuring the smallest doped cation radius, demonstrated superior rate performance. Specifically, after 30 cycles at varying rates, the capacity reached 170 mAh·g−1 at 0.2C. The LNCMO-0.007Ca sample exhibited the highest residual capacity, maintaining 151.4 mAh·g−1 after 100 cycles at 0.2C. Doping Li sites in Li1.2Ni0.13Co0.13Mn0.54O2 materials with appropriately sized divalent cations significantly enhances their overall electrochemical performance. This enhancement is attributed to ion doping within the Li and TM layers, expediting the diffusion kinetics of Li ions, and augmenting ion and electronic conductivity. Investigating the doping modification of lithium-rich manganese-based oxide microspheres is instrumental in advancing positive electrode materials for lithium-ion batteries, aiming for increased specific capacity and more stable material structures.

Yellowish light emitting Dy3+ doped single phase – BaNb2O6 phosphors for solid state lighting applications

BaNb2O6:Dy3+ phosphors that emit cool light has been synthesized via traditional solid-state reaction technique. Developed samples show orthorhombic structure with space group C2221 according to X-Ray Diffraction (XRD) and Rietveld structural refinement. Observations made using a scanning electron microscope (SEM) show densely packed particles with irregular shapes in the micrometre range. Optical bandgap was also determined using Diffuse Reflectance Spectroscopy (DRS). When excited at 389 nm, the as-prepared phosphors show blue (481 nm) and yellow (577 nm) emissions, which correspond to the 4F9/2 → 6HJ (J = 15/2, 13/2) transitions of Dy3+ ions. A thorough investigation has been done on the energy transfer process between Dy3+ ions. The optimized phosphor's computed chromaticity coordinates for the Commission Internationale de L'Eclairage (CIE) are x = 0.392 and y = 0.414. The values of CIE chromaticity coordinates and correlated colour temperature (CCT) of 3995 K endorse near cool light emission from the phosphor. Thermal stability and temperature dependent photoluminescence spectroscopy were studied for optimized phosphor which revealed that the phosphor can be a potential material for lighting applications at higher temperature. The study also reveals that BaNb2O6:Dy3+ phosphor could be a promising candidate for near ultra-violet (NUV) excited, yellowish LED applications.

Electrical and optical properties of environmental friendly Li(1‐x)Smx/3NbO3 ceramics for high‐temperature energy storage applications

AbstractThis research article delves into the synthesis and characterization of Li(1‐x)Sm(x/3)NbO3 ceramic, employing a high‐energy ball milling process. The investigation explores the incorporation of Sm3+ at the Li+1 site across a range of compositions (x = 0, 0.01, 0.02, 0.03, 0.04, 0.05). Structural analysis, using x‐ray diffraction (XRD) and Rietveld structural refinement, establishes that within the investigated composition range, no significant changes in the crystal structure are evident. The x‐ray photoelectron spectroscopy revealed the presence of oxygen vacancies as well as the stable oxidation state of different elements like O2−, Nb5+, Sm3+, and Li1+. At sintering temperature 1050°C, the average grain sizes vary approximately from 1.5 to 3.8 μm for different compositions with regular grain morphology. The UV‐Vis analysis reveals a noteworthy reduction in the band gap to 3.09 eV for the x = 0.01 composition. Photoluminescence studies exhibit distinct green, orange, and red bands, with the highest intensity observed for x = 0.01, showcasing promising optical properties. The dielectric permittivity of Sm‐substituted compositions surpasses the response of pure LiNbO3, demonstrating an increasing trend with temperature in the frequency range 100 Hz‐1 MHz intriguingly, no Curie temperature is observed up to 500°C for any composition. The polarization vs electric field hysteresis loop response highlights better polarization characteristics at the room temperature and maximum polarization is 0.66 μC/cm2 for the composition x = 0.05. The energy storage response of the developed compositions is investigated, which reveals a maximum efficiency of 46.64% for x = 0.04 in Li(1‐x)Sm(x/3)NbO3. The tunable optical properties, enhanced dielectric response, and notable energy efficiency of these high TC ceramics suggest their utility across diverse applications. These findings not only contribute to the understanding of functional ceramic materials but also pave the way for their optimized utilization in advanced technological applications, particularly in energy storage devices under nonambient conditions at high temperatures.

Nanostructured Niobium and Titanium Carbonitrides as Electrocatalyst Supports.

Nanostructured niobium-titanium carbonitrides, (Nb,Ti)C1-xNx, with the cubic-rock salt structure are prepared without the use of reactive gases via thermal treatment (700-1200 °C) under nitrogen of mixtures of guanidine carbonate and ammonium niobate (V) oxalate hydrate, with addition of ammonium titanyl oxalate monohydrate as a titanium source. The bulk structure and chemical composition of the materials are characterized using powder X-ray diffraction (XRD) and powder neutron diffraction, elemental homogeneity is studied using energy dispersive spectroscopy (EDS) mapping using transmission electron microscopy (TEM), and surface chemical analysis is examined using X-ray photoelectron spectroscopy (XPS). Nanoscale crystallites of between 10 and 50 nm are observed by TEM, where EDS reveals the homogeneity of metal distribution for the mixed-metal materials. Titanium carbonitrides are found to be air sensitive, reacting with air under ambient conditions, while titanium-niobium carbonitrides are found to degrade in aqueous sulfuric acid. The niobium carbonitrides, however, show some stability toward acidic solutions. Materials are produced with composition NbC1-xNx with x between 0.35 and 0.45, and more carbon-rich materials (x ≈ 0.35) are found as the synthesis temperature is increased, as proven by Rietveld refinement of crystal structure against powder neutron diffraction data. Despite phase purity seen by diffraction and negligible bulk carbon content, XPS shows a complex surface chemistry for the NbC1-xNx materials, with evidence for Nb2O5-like oxide species in a carbon-rich environment. The NbC1-xNx prepared at 900 °C has a surface area around 50 m2 g-1, making it suitable as a catalyst support. Loading with iridium provides a material active for the oxygen evolution reaction in 0.1 M sulfuric acid, with minimal leaching of either Nb or Ir after 1000 cycles.

Structural analysis and Rietveld refinement of YCr1-xFexO3 (x=0, 0.5) perovskite samples calcined at two different temperatures

In the present work, we have synthesized polycrystalline YCr1-xFexO3 (x = 0, 0.5) perovskite samples using the traditional high-temperature solid-state reaction route (HT-SSRR) at two different temperatures for calcination (1000 °C as well as 1150 °C). The main objective of our investigation is to observe how these calcination temperatures impact the structural properties of the polycrystalline YCr1-xFexO3 (x = 0, 0.5) perovskite samples and reveal the comparative difference based on structural analysis and Rietveld refinement. The powder XRD analysis confirmed the presence of secondary phases, including Y2O3, Cr2O3, and Fe2O3, in the synthesized samples at both calcination temperatures. Notably, a higher calcination temperature (1150 °C) led to a reduction in the secondary phases and an increase in the crystalline size as determined by the Debye-Scherrer method (DSM). The FullProf software suite was used for performing a Rietveld refinement of the powder X-ray diffraction (PXRD) data. These findings suggest the crucial role of calcination temperature in tailoring the phase purity and crystallinity of YCr1-xFexO3 (x = 0, 0.5) perovskites.

Effect of cobalt and aluminum doping on the structural and magnetic properties of zinc oxide nanoparticles

A systematic study of the substitution effect of Co and Al on ZnO nanoparticles was carried out by x-ray diffraction (XRD) and transmission electron microscopy and using a superconducting quantum interference device magnetometer to study their structural, morphological, and magnetic properties. Zn1−xMxO (M = Co, Al) at different doping concentrations was prepared using a hydrothermal technique. The XRD results with structural Rietveld refinement reveal that the major phase of all samples had a hexagonal wurtzite crystal structure with a P63mc space group. Hysteresis loops with no magnetic saturation at high fields were analyzed at 2 K in all samples. Zero magnetic remanence and zero coercivity were also examined. The results demonstrated that the magnetic ground state at 2 K in all samples was magnetism with the coexistence of antiferromagnetic, ferromagnetic, and superparamagnetic phases. This behavior persisted at 100 and 300 K in the Al-doped sample, while Co-doped ones exhibited a paramagnetic state only. The role of non-magnetic doping, which leads to the appearance of magnetism in ZnO nanoparticles persisting at high temperatures, is discussed herein.

Synthesis and Crystal Structures of Two Crystalline Silicic Acids: Hydrated H-Apophyllite, H16Si16O40 • 8–10 H2O and H-Carletonite, H32Si64O144

Hydrated H-Apophyllite (HH-Apo) and H-carletonite (H-Car) were synthesized at 0 °C by leaching an apophyllite and a carletonite single crystal in a large surplus of 1.2 molar hydrochloric acid. The XRD powder patterns of HH-Apo and H-Car were indexed with space group symmetries of P4/ncc and I4/mcm and lattice parameters of a = 8.4872(2) Å, c = 16.8684(8) Å and a = 13.8972(3) Å, c = 20.4677(21) Å, respectively. The crystal structures were solved based on model building of the structures of the precursors and a physico-chemical characterization. Rietveld structure refinements confirmed the structure models. HH-Apo and H-Car are among the very few crystalline silicic acids whose structures have been determined and confirmed based on a structure refinement. The structure of HH-Apo contains thin silicate monolayers that can be regarded as constructed by rings of interconnected [SiO3OH] tetrahedra which form a puckered silicate layer. A sheet of water molecules is intercalated between the silicate layers. There are no direct hydrogen bonds between the silanol groups, but there are hydrogen bonds of different strengths between the terminal O atoms of the silicate layers and the intercalated water molecules. The 1H MAS NMR spectrum presents a strong signal at 4.9 ppm related to the aforementioned bonds and interactions between the water molecules, as well as a small signal at 22.5 ppm corresponding to an extremely strong hydrogen bond with d(O...O) ≈ 2.2 Å. The structure of H-Car is free of structural water and consists exclusively of microporous silicate double-layers with 4-connected [SiO4] and 3-connected [SiO3OH] tetrahedra in a ratio of 1:1 and a thickness of 9.2 Å. Neighboring layers are connected to each other by medium–strong hydrogen bonds with O...O distances of 2.56 Å. The structure of HH-Apo decays within several hours while H-Car is stable. A topotactic condensation reaction applied to H-Car forms an irregularly condensed silicate which still contains the layers in a distorted form as building blocks.

Synthesis and Characterization of Vanadium Doped Hexagonal Rubidium Tungsten Bronze

Attempts have been made to synthesize vanadium doped rubidium hexagonal tungsten bronzes with the nominal composition RbxVyW1-yO3 (x = 0.30, 0.25, and 0.0 ≤ y ≤ x). The samples were synthesized using the solid state synthesis method in a silica glass tube under vacuum at (10-2 Torr) 700°C. The X-ray diffraction measurements reveal that a pure hexagonal tungsten bronze (HTB) phase can be formed with a 60% replacement of W5+ by V5+. The systematic incorporation of vanadium into the HTB lattice, as well as the reduction of V/W-O bond lengths in the xy plane and the lengthening of these bonds in the crystallographic c direction, are also revealed by Rietveld structure refinement of XRD data. The XRD results are supported by FTIR absorption spectra of the oxidized phases. Furthermore, an absorption signature develops as a function of y and exhibits a considerable increase in intensity with the eventual replacement of W5+ by V5+, showing a large decrease in the metallic like contribution and revealing the compounds' nonmetallic nature. Elemental analysis indicates good agreement with nominal values, demonstrating that vanadium was systematically incorporated into the RbxVyW1-yO3 system. Dhaka Univ. J. Sci. 72(1): 77-84, 2024 (January)

Enhanced dielectrics, ferroelectric and optical properties of lithium niobate for high temperature applications using potassium oxide (K2O) additive

Dielectrics, Ferroelectric and Optical properties of Lithium Niobate has been examined using Potassium Oxide (K2O) as an additive on the samples prepared by solid state reaction method using high energy ball milling. The crystal structure analysis by Rietveld structure refinement confirms that the LiNbO3 (LN) with K2O additive also exhibit the rhombohedral structure with R3c space group. The SEM characterization of the microstructure reveals that the samples sintered at a temperature of 1050 °C, have regular and uniform grain morphology and better density. The average grain size decreases for the K2O added compositions in the beginning and increases later for higher concentration of additive. Thermal study with TGA suggests that as the activation energy is decreases, the polarization is enhanced and the LN composition with 2.72 wt% K2O additive shows the best thermal stability. The frequency and temperature dependent dielectric properties were investigated in a wide range of frequency and a substantial enhancement in the dielectric constant of LN is obtained by K2O addition. A useful enhancement in permittivity is obtained with increase of temperature. The band gap values for direct and indirect band gaps for the various compositions are also determined. The least direct band gap is discovered to be 2.36 eV for the composition with 2.72 wt% K2O additive. The composition-dependent photoluminescence (PL) emission studies reveal that the emission spectra for both the pure LiNbO3 and K2O added LiNbO3 compositions lies in the UV–visible region. All the investigated compositions exhibit distinct green, yellow, and red emission peaks. The LN with 2.72 wt% K2O additive shows the best dielectric, thermal stability and polarization response with maximum polarization Ps ∼1.16 μC/cm2. The present investigations suggest that properties of LN can be significantly improved by using K2O additive for sustainable, low cost, environmental friendly energy storage material for high temperature applications.

High-pressure study of a 3d-4f heterometallic CuEu-organic skeleton.

We prepared a 3d-4f heterobimetallic CuEu-organic framework NBU-8 with a density of 1921 kg m-3 belonging to the family of dense packing materials (dense metal-organic frameworks or MOFs). This MOF material was prepared from 4-(pyrimidin-5-yl)benzoic acid (HPBA) with a bifunctional ligand site as a tripodal ligand and Cu2+ and Eu3+ as the metal centres; the molecular formula is Cu3Eu2(PBA)6(NO3)6·H2O. This material is a very promising dimethylformamide (DMF) molecular chemical sensor. Systematic high-pressure studies of NBU-8 were carried out by powder X-ray diffraction, high-pressure X-ray diffraction and molecular dynamics simulation. The high-pressure experiment shows that the (006) diffraction peak of the crystal structure moves toward a low angle with increasing pressure, accompanied by the phenomenon that the d-spacing increases, and as the pressure increases, the (10-2) diffraction peak moves to a higher angle, the amplitude of the d-spacing is significantly reduced and finally merges with the (006) diffraction peak into one peak. The amplitude of the d-spacing is significantly reduced, indicating that NBU-8 compresses and deforms along the a-axis direction when subjected to uniform pressure. This is caused by tilting of the ligands to become more vertical along the c direction, leading to its expansion. This allows greater contraction along the a direction. We also carried out a Rietveld structure refinement and a Birch-Murnaghan solid-state equation fitting for the high-pressure experimental results. We calculated the bulk modulus of the material to be 45.68 GPa, which is consistent with the calculated results. The framework is among the most rigid MOFs reported to date, exceeding that of Cu-BTC. Molecular dynamics simulations estimated that the mechanical energy absorbed by the system when pressurized to 5.128 GPa was 249.261 kcal mol-1. The present work will provide fresh ideas for the study of mechanical energy in other materials.

Ambient pressure synthesis and structure and magnetic properties of a new A- and B-site ordered multinary quadruple perovskite.

Quadruple perovskites with high magnetic transition temperatures are an interesting class of compounds but are synthesized typically under high pressure. Ambient pressure synthesis of new multinary quadruple perovskites having a high global instability index (GII) and transition temperature can be interesting for future exploration of high-TC oxides. A new A- and B-site ordered multinary quadruple perovskite, LaCu3Fe2RuSbO12, is synthesized by conventional solid-state reactions at ambient pressure. Rietveld structure refinement revealed that the compound crystallizes in the Pn3̄ space group with a lattice parameter of 7.4556(4) Å. The compound showed complete 1 : 3 ordering of La and Cu at the A-site and 1 : 1 rock-salt ordering of Fe with Ru/Sb at the B-site. The compound is also probed with scanning and transmission electron microscopy and XPS to investigate the chemical composition, microstructure, lattice and oxidation states of the elements. Magnetic studies revealed antiferromagnetic (AFM) correlations with magnetic ordering transitions at ∼170 and 40 K. Furthermore, the M-H hysteretic behavior at 100 and 5 K indicated ferrimagnetism due to short-range AFM interactions among Fe3+(3d5) and Ru4+(4d4) spins involving Cu2+(↑)-Fe3+(↓)-Ru4+(↑) triads. The specific heat data reaffirmed the magnetic signatures while electrical transport showed semiconducting behavior with variable range hopping. The details of synthesis and structural and compositional studies along with the magnetic and electrical transport properties of LaCu3Fe2RuSbO12 are reported in this paper.

Enhancement of magnetism by tailoring synthesis conditions in electron-doped superconducting nanoparticles.

A study on the effects of sample synthesis conditions on the particle size, structure, and magnetic properties of electron-doped cuprate superconductors of Eu1.85Ce0.15CuO4+α-δ (ECCO) nanoparticles has been carried out using transmission electron microscopy (TEM), X-ray diffraction (XRD) and the superconducting quantum interference device magnetometer (SQUID). The ECCO nanoparticles were prepared through the sol-gel method with various sintering and annealing temperatures. From TEM characterization, the average particle sizes are 87 nm and 103 nm for the sintering temperatures of 700 °C and 900 °C, respectively. The XRD results with structural Rietveld refinement reveal that the lattice constants and bond distance Cu-O change considerably compared to the bulk case. Reducing the particle and crystallite size to below 200 nm causes strong suppression in the superconducting state. From SQUID measurements it is found that none of the samples show superconducting behavior. An upturn in magnetic susceptibility below 10 K is observed in the sample when the crystallite size is in the range of 69 nm to 88 nm, indicating the existence of magnetism. The lower the sintering temperature of the sample synthesis, the higher the effective magnetic moment and Curie temperature. It suggests that the magnetic correlation is more developed in the smaller samples.