Microstructural and Optical Properties of MgAl2O4 Spinel: Effects of Mechanical Activation, Y2O3 and Graphene Additions

Magnesium aluminate and other alumina-based spinels attract attention due to their high hardness, high mechanical strength, and low dielectric constant. MgAl2O4 was produced by a solid-state reaction between MgO and α-Al2O3 powders. Mechanical activation for 30 min in a planetary ball mill was used to increase the reactivity of powders. Yttrium oxide and graphene were added to prevent abnormal grain growth during sintering. Samples were sintered by hot pressing under vacuum at 1450 °C. Phase composition and microstructure of sintered specimens were characterized by X-ray powder diffraction and scanning electron microscopy. Rietveld analysis revealed 100% pure spinel phase in all sintered specimens, and a decrease in crystallite size with the addition of yttria or graphene. Density measurements indicated that the mechanically activated specimen reached 99.6% relative density. Furthermore, the highest solar absorbance and highest spectral selectivity as a function of temperature were detected for the mechanically activated specimen with graphene addition. Mechanical activation is an efficient method to improve densification of MgAl2O4 prepared from mixed oxide powders, while additives improve microstructure and optical properties.

Effect of Al2TiO5 Content and Sintering Temperature on the Microstructure and Residual Stress of Al2O3–Al2TiO5 Ceramic Composites

A series of Al2O3–Al2TiO5 ceramic composites with different Al2TiO5 contents (10 and 40 vol.%) fabricated at different sintering temperatures (1450 and 1550 °C) was studied in the present work. The microstructure, crystallite structure, and through-thickness residual stress of these composites were investigated by scanning electron microscopy, X-ray diffraction, time-of-flight neutron diffraction, and Rietveld analysis. Lattice parameter variations and individual peak shifts were analyzed to calculate the mean phase stresses in the Al2O3 matrix and Al2TiO5 particulates as well as the peak-specific residual stresses for different hkl reflections of each phase. The results showed that the microstructure of the composites was affected by the Al2TiO5 content and sintering temperature. Moreover, as the Al2TiO5 grain size increased, microcracking occurred, resulting in decreased flexure strength. The sintering temperatures at 1450 and 1550 °C ensured the complete formation of Al2TiO5 during the reaction sintering and the subsequent cooling of Al2O3–Al2TiO5 composites. Some decomposition of AT occurred at the sintering temperature of 1550 °C. The mean phase residual stresses in Al2TiO5 particulates are tensile, and those in the Al2O3 matrix are compressive, with virtually flat through-thickness residual stress profiles in bulk samples. Owing to the thermal expansion anisotropy in the individual phase, the sign and magnitude of peak-specific residual stress values highly depend on individual hkl reflection. Both mean phase and peak-specific residual stresses were found to be dependent on the Al2TiO5 content and sintering temperature of Al2O3–Al2TiO5 composites, since the different developed microstructures can produce stress-relief microcracks. The present work is beneficial for developing Al2O3–Al2TiO5 composites with controlled microstructure and residual stress, which are crucial for achieving the desired thermal and mechanical properties.

Exploring the structural, optical and photoluminescent properties of (1-x)NiCo2O4/xPbS nanocomposites for optoelectronic applications

(1-x)NiCo2O4/xPbS (0≤x≤0.2) nanocomposite samples were synthesized using the hydrothermal and thermolysis procedures. The different phases developed in the obtained nanocomposite samples were accurately determined using the x-ray diffraction technique equipped with a line-detector. The percentage of the formed phases (NiCo2O4 (NCO), PbS, PbSO4), structural and microstructure parameters were determined using Rietveld quantitative phase analysis. The transmission electron microscope (TEM) images and Rietveld analysis reveal almost isotropic particle size in the nano range with a very narrow size distribution. The obtained phase percentages of PbS and PbSO4 are smaller than nominated values (x) suggesting dissolving of some Pb and S ions in NCO which then confirmed by the analysis of Fourier-transform infrared (FTIR) spectra of nanocomposite samples. The absorption spectra are modified upon doping NCO with PbS. The optical band gaps of the nanocomposites increase as the amount of PbS is increased. The effect of alloying on extinction coefficient, refractive index, dielectric constant, optical conductivity, the intensity, and emitted color from the photoluminescence of the nanocomposite samples are also studied. The refractive index values of NCO and NCO-PbS nanocomposite samples exhibit normal dispersions. The photoluminescent measurements reveal that NCO-PbS nanocomposites could emit a violet color. The improvement in the values of the non-linear optical (NLO) parameters of pristine NCO at high frequencies or the nanocomposite samples at low frequencies, nominated them to be used in NLO photonic applications.

Structural and Spectroscopic Effects of Li+ Substitution for Na+ in LixNa1-xCaGd0.5Ho0.05Yb0.45(MoO4)3 Scheelite-Type Upconversion Phosphors

A set of new triple molybdates, LixNa1-xCaGd0.5(MoO4)3:Ho3+0.05/Yb3+0.45, was successfully manufactured by the microwave-accompanied sol–gel-based process (MAS). Yellow molybdate phosphors LixNa1-xCaGd0.5(MoO4)3:Ho3+0.05/Yb3+0.45 with variation of the LixNa1-x (x = 0, 0.05, 0.1, 0.2, 0.3) ratio under constant doping amounts of Ho3+ = 0.05 and Yb3+ = 0.45 were obtained, and the effect of Li+ on their spectroscopic features was investigated. The crystal structures of LixNa1-xCaGd0.5(MoO4)3:Ho3+0.05/Yb3+0.45 (x = 0, 0.05, 0.1, 0.2, 0.3) at room temperature were determined in space group I41/a by Rietveld analysis. Pure NaCaGd0.5Ho0.05Yb0.45(MoO4)3 has a scheelite-type structure with cell parameters a = 5.2077 (2) and c = 11.3657 (5) Å, V = 308.24 (3) Å3, Z = 4. In Li-doped samples, big cation sites are occupied by a mixture of (Li,Na,Gd,Ho,Yb) ions, and this provides a linear cell volume decrease with increasing Li doping level. The evaluated upconversion (UC) behavior and Raman spectroscopic results of the phosphors are discussed in detail. Under excitation at 980 nm, the phosphors provide yellow color emission based on the 5S2/5F4 → 5I8 green emission and the 5F5 → 5I8 red emission. The incorporated Li+ ions gave rise to local symmetry distortion (LSD) around the cations in the substituted crystalline structure by the Ho3+ and Yb3+ ions, and they further affected the UC transition probabilities in triple molybdates LixNa1-xCaGd0.5(MoO4)3:Ho3+0.05/Yb3+0.45. The complex UC intensity dependence on the Li content is explained by the specificity of unit cell distortion in a disordered large ion system within the scheelite crystal structure. The Raman spectra of LixNa1-xCaGd0.5(MoO4)3 doped with Ho3+ and Yb3+ ions were totally superimposed with the luminescence signal of Ho3+ ions in the range of Mo–O stretching vibrations, and increasing the Li+ content resulted in a change in the Ho3+ multiplet intensity. The individual chromaticity points (ICP) for the LiNaCaGd(MoO4)3:Ho3+,Yb3+ phosphors correspond to the equal-energy point in the standard CIE (Commission Internationale de L’Eclairage) coordinates.

Phase Analysis of Bio-Based Derived Tricalcium Disilicate From 2CaO:1SiO2 By X-ray Diffraction

In this paper, tricalcium disilicate was formed from dicalcium silicate compound powder, synthesised via a mechanochemical technique using a stoichiometric 2CaO:1SiO2. Compound CaO and SiO2 were derived from the bio-waste of eggshell and rice husk at the calcination temperature of 900°C and 800°C, respectively. The dicalcium disilicate powder was sintered for 2 hours at different temperatures ranging from 1150°C to 1350°C. Using X-ray diffraction with Rietveld analysis, it was found that the amount of tricalcium disilicate with monoclinic (beta) crystal structure increases on sintering temperature at the expense of dicalcium silicate. The complete formation of single-phase tricalcium disilicate began at a sintering temperature of 1300°C. The effect of sintering temperatures on the crystallisation and phase transition of dicalcium silicate is reported. The size of crystallites depends on the sintering temperature. The finding of this study rebound to the benefit of society by reducing the risk-off pollution cause by accessive redundant bio-waste eggshell and rice husk and also reduced the amount of CaO and SiO2 used in the fabrication of Ca3Si2O7.

Strategic synthon approach in obtaining cocrystals and cocrystal polymorphs of a high-Z′ system deferiprone – an anti-thalassemia drug

Compounds with more than one molecule in the crystallographic asymmetric unit (Z′ > 1) display a noticeably stronger propensity to form cocrystals. Deferiprone is an anti-thalassemia drug known to exhibit polymorphic behaviour. Previously, three polymorphs were reported out of which one of them exhibited Z′ > 1. In the present manuscript, a fourth polymorph of deferiprone was identified and it also possessed Z′ > 1. All the four polymorphs showed similar hydrogen bonding features and differed in crystal packing. The ability of deferiprone to crystallize as Z′ > 1 prompted us to investigate the hydrogen bonding and synthon variation upon cocrystallization of deferiprone with hydroxyl-group-containing coformers such as catechol, hydroquinone, phloroglucinol, resorcinol and pyrogallol. Crystallization attempts along with PXRD analysis aided in obtaining 11 new cocrystal structures which involve different stoichiometric cocrystals and some polymorphs. Synthon analysis, crystal packing as well as thermal behaviour were assessed and compared. The presence of multiple phases in each cocrystal system in its respective bulk powders was identified and quantified using PXRD and Rietveld analysis. Homosynthons were observed in three co-crystal systems, while a heterosynthon was observed in five systems. The combination of both homo- and heterosynthon was observed in three cocrystal systems. The phase transformation events were observed in most of the systems. In nine co-crystal systems, the melting points were observed intermediate between those of the API and the coformers.

Synthesis of Niobium-Alumina Composite Aggregates and Their Application in Coarse-Grained Refractory Ceramic-Metal Castables

Niobium-alumina aggregate fractions with particle sizes up to 3150 µm were produced by crushing pre-synthesised fine-grained composites. Phase separation with niobium enrichment in the aggregate class 45–500 µm was revealed by XRD/Rietveld analysis. To reduce the amount of carbon-based impurities, no organic additives were used for the castable mixtures, which resulted in water demands of approximately 27 vol.% for the fine- and coarse-grained castables. As a consequence, open porosities of 18% and 30% were determined for the fine- and coarse-grained composites, respectively. Due to increased porosity, the modulus of rupture at room temperature decreased from 52 MPa for the fine-grained composite to 11 MPa for the coarse-grained one. However, even the compressive yield strength decreased from 49 MPa to 18 MPa at 1300 °C for the fine-grained to the coarse-grained composite, the latter showed still plasticity with a strain up to 5%. The electrical conductivity of fine-grained composite samples was in the range between 40 and 60 MMS/cm, which is fifteen magnitudes above the values of pure corundum.

Improved mechanical strength, proton conductivity and power density in an ‘all-protonic’ ceramic fuel cell at intermediate temperature

Protonic ceramic fuel cells (PCFCs) have become the most efficient, clean and cost-effective electrochemical energy conversion devices in recent years. While significant progress has been made in developing proton conducting electrolyte materials, mechanical strength and durability still need to be improved for efficient applications. We report that adding 5 mol% Zn to the Y-doped barium cerate-zirconate perovskite electrolyte material can significantly improve the sintering properties, mechanical strength, durability and performance. Using same proton conducting material in anodes, electrolytes and cathodes to make a strong structural backbone shows clear advantages in mechanical strength over other arrangements with different materials. Rietveld analysis of the X-ray and neutron diffraction data of BaCe0.7Zr0.1Y0.15Zn0.05O3−δ (BCZYZn05) revealed a pure orthorhombic structure belonging to the Pbnm space group. Structural and electrochemical analyses indicate highly dense and high proton conductivity at intermediate temperature (400–700 °C). The anode-supported single cell, NiO-BCZYZn05|BCZYZn05|BSCF-BCZYZn05, demonstrates a peak power density of 872 mW cm−2 at 700 °C which is one of the highest power density in an all-protonic solid oxide fuel cell. This observation represents an important step towards commercially viable SOFC technology.

Crystal Chemistry, Rietveld Analysis, Structural and Electrical Properties of Cobalt-Erbium Nano-Ferrites

Synthesis of Cobalt-Erbium nano-ferrites with formulation CoErxFe2-xO4 (x = 0, 0.005, 0.010, 0.015, 0.020, 0.025, and 0.030) using technique of citrate-gel auto-combustion was done. Characterization of prepared powders was done by using XRD, EDAX, FESEM, AFM and FTIR Spectroscopy, DC resistivity properties respectively. XRD Rietveld Analysis, SEM, TEM and EDAX analysis were taken up in studying spectral, structural, magnetic and electrical properties. XRD pattern of CEF nano particles confirm single phase cubic spinal structure. The structural variables given by lattice constant (a), lattice volume (v), average crystallite size (D) and X-ray density(dx), Bulk density (d), porosity (p), percentage of pore space (P%), surface area (s), strain (ε), dislocation density (δ), along with ionic radii, bond length and hoping length were calculated. SEM and TEM results reveal homogeneous nature of particles accompanied by clusters having no impurity pickup. TEM analysis gives information about particle size of nanocrystalline ferrite while EDAX analysis confirm elemental composition. Emergence of two arch shaped frequency bands (ν1 and ν2) that represent vibrations at tetrahedral site (A) and octahedral site(B) was indicated by spectra of FTIR. The samples electrical resistivity (DC) was measured between 30°C -600°C with Two probe method. XRD Rietveld analysis confirm crystallite size lying between 20.84 nm–14.40 nm while SEM analysis indicate formation of agglomerates and TEM analysis indicate particle size ranging between 24 nm–16 nm. DC Electrical measurements indicate continuous decrease in resistivity with increasing temperature while increasing doping decreases curie temperature. The Magnetic parameters such as Saturation magnetization (Ms), Remanent magnetization (Mr), Coercivity (Hc) and Squareness ratio (R = Mr/Ms), Magnetic moment (nB) were altered by doping of Er+3 content in the increasing order (x = 0.00 to 0.030). The increasing erbium content decreases magnetization thus converting the sample into soft magnetic material. Observations indicated strong dependence of magnetic properties on Erbium substitution and coercivity varies in accordance with anisotropy constant. Due to the presence of magnetic dipole Erbium substituted cobalt ferrites can be used in electromagnetic applications. The present study investigates the effect of different compositions of Er3+ replaced for Fe on structural properties and electrical resistivity of cobalt ferrites.