Deposition of Gadolinia-Doped Zirconia Layers Using Metalorganic Compounds at Low Temperatures

This paper shows the results of an investigation on the synthesis of non-porous and nanocrystalline ZrO₂-Gd₂O₃ layers by metalorganic chemical vapor deposition (MOCVD) with the use of Zr(tmhd)₄ (tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionato)zirconium(IV)) and Gd(tmhd)₃ (tris(2,2,6,6-tetramethyl-3,5-heptanedionato)gadolinium(III)). Argon and air were used as carrier gases. The molar content of Gd(tmhd)₃ in the gas reaction mixture was as follows: 10% and 20%. The layers were synthesized on tubular substrates made of quartz glass at the temperatures of 550–700 °C. Synthesis conditions were established using the Gr_x/Re_x² expression (Gr is the Grashof number; Re is the Reynolds number; x is the distance from the gas inflow point). The value of this criterion was below 0.01. ZrO₂-Gd₂O₃ layers synthesized at 600–700 °C were crystalline. When the molar content of Gd(tmhd)₃ in the gas reaction mixture was 10 mol.%, a relationship between the chemical composition of the gas reaction mixture and that of the deposited layer could be observed. The synthesized layers underwent scanning electron microscopy, as well as X-ray analysis. The transparency of coated and uncoated glass was tested using UV–Vis spectroscopy. Their chemical composition was examined with the use of an EDS analyzer.     

Al2O3/ZrO2 Materials as an Environmentally Friendly Solution for Linear Infrastructure Applications

The present work deals with the evaluation of the effect of ZrO₂ on the structure and selected properties of shapes obtained using the centrifugal slip casting method. The samples were made of alumina and zirconia. The applied technology made it possible to produce tubes with a high density reaching 99–100% after sintering. Very good bonding was obtained at the Al₂O₃/ZrO₂ interphase boundaries with no discernible delamination or cracks, which was confirmed by STEM observations. In the case of Al₂O₃/ZrO₂ composites containing 5 vol.% and 10 vol.% ZrO₂, the presence of equiaxial ZrO₂ grains with an average size of 0.25 µm was observed, which are distributed along the grain boundaries of Al₂O₃. At the same time, the composites exhibited a very high hardness of 22–23 GPa. Moreover, the environmental influences accompanying the sintering process were quantified. The impacts were determined using the life cycle analysis method, in the phase related to the extraction and processing of raw materials and the process of producing Al₂O₃/ZrO₂ composites. The results obtained show that the production of 1 kg of sintered composite results in greenhouse gas emissions of 2.24–2.9 kg CO₂ eq. which is comparable to the amount of emissions accompanying the production of 1 kg of Polyvinyl Chloride (PVC), Polypropylene (PP), or hot-rolled steel products.     

High-Temperature Chemical Stability of Cr(III) Oxide Refractories in the Presence of Calcium Aluminate Cement

Al₂O₃-CaO-Cr₂O₃ castables are used in various furnaces due to excellent corrosion resistance and sufficient early strength, but toxic Cr(VI) generation during service remains a concern. Here, we investigated the relative reactivity of analogous Cr(III) phases such as Cr₂O₃, (Al_1−xCr_x)₂O₃ and in situ Cr(III) solid solution with the calcium aluminate cement under an oxidizing atmosphere at various temperatures. The aim is to comprehend the relative Cr(VI) generation in the low-cement castables (Al₂O₃-CaO-Cr₂O₃-O₂ system) and achieve an environment-friendly application. The solid-state reactions and Cr(VI) formation were investigated using powder XRD, SEM, and leaching tests. Compared to Cr₂O₃, the stability of (Al_1−xCr_x)₂O₃ against CAC was much higher, which improved gradually with the concentration of Al₂O₃ in (Al_1−xCr_x)₂O₃. The substitution of Cr₂O₃ with (Al_1−xCr_x)₂O₃ in the Al₂O₃-CaO-Cr₂O₃ castables could completely inhibit the formation of Cr(VI) compound CaCrO₄ at 500–1100 °C and could drastically suppress Ca₄Al₆CrO₁₆ generation at 900 to 1300 °C. The Cr(VI) reduction amounting up to 98.1% could be achieved by replacing Cr₂O₃ with (Al_1−xCr_x)₂O₃ solid solution. However, in situ stabilized Cr(III) phases as a mixture of (Al_1−xCr_x)₂O₃ and Ca(Al_12−xCr_x)O₁₉ solid solution hardly reveal any reoxidation. Moreover, the CA₆ was much more stable than CA and CA₂, and it did not participate in any chemical reaction with (Al_1−xCr_x)₂O₃ solid solution.     

The Effect of Temperature and Sputtered Particles on the Wettability of Al/Al2O3

Two kinds of Al₂O₃ ceramic samples with and without Al film deposited were designed respectively. The influences of temperature and high kinetic energy sputtering particles on the wettability and interface strength of Al/Al₂O₃ were studied by comparing the wetting behavior of molten aluminum on two samples. The results show that molten aluminum does not wet the Al₂O₃ sample without Al film deposited at 700 °C, the contact angle is 165°, and the interfacial shear strength is 28 MPa. With the increase of temperature, the contact angle decreases continuously, and the interface shear strength gradually increases. The fracture of the brazed joint is transferred from the interface to the brazing seam. In comparison, the sample deposited with Al film is wetted by molten aluminum at 700 °C, and the contact angle is only 12°. The interface shear strength is about 120 MPa and is less affected by temperature. The shear fracture of the joint occurs in the brazed seam of Al metal. Therefore, the high energy generated by either the temperature increase or the particle sputtering enable the Al atoms to overcome the energy barrier to form Al–O bonds with the O atoms on the Al₂O₃ ceramic surface, thereby improving the wettability of Al/Al₂O₃.     

Al2O3/ZrO2/Y3Al5O12 Composites: A High-Temperature Mechanical Characterization

An Al₂O₃/5 vol%·ZrO₂/5 vol%·Y₃Al₅O₁₂ (YAG) tri-phase composite was manufactured by surface modification of an alumina powder with inorganic precursors of the second phases. The bulk materials were produced by die-pressing and pressureless sintering at 1500 °C, obtaining fully dense, homogenous samples, with ultra-fine ZrO₂ and YAG grains dispersed in a sub-micronic alumina matrix. The high temperature mechanical properties were investigated by four-point bending tests up to 1500 °C, and the grain size stability was assessed by observing the microstructural evolution of the samples heat treated up to 1700 °C. Dynamic indentation measures were performed on as-sintered and heat-treated Al₂O₃/ZrO₂/YAG samples in order to evaluate the micro-hardness and elastic modulus as a function of re-heating temperature. The high temperature bending tests highlighted a transition from brittle to plastic behavior comprised between 1350 and 1400 °C and a considerable flexural strength reduction at temperatures higher than 1400 °C; moreover, the microstructural investigations carried out on the re-heated samples showed a very limited grain growth up to 1650 °C.     

New Insights into the Mechanism of Nucleation of ZrO2 Inclusions at High Temperature

It is difficult to observe the nucleation mechanism of inclusions in real-time. In this study, the nucleation process of zirconium oxide inclusions was systematically studied by classical nucleation theory and first principles. Zr deoxidized steel with 100 ppm Zr addition was processed into metallographic samples for scanning electron microscopy energy-dispersive spectroscopy observation. The electrolytic sample was analyzed by micro X-ray diffraction and transmission electron microscopy, and the zirconium oxide in the sample was determined to be ZrO₂. The nucleation rate and radius of the ZrO₂ inclusions were calculated by classical nucleation theory, and they were compared with the experimental values. There was a considerable difference between the experimental and theoretical values of the nucleation rate. The effect of the nucleation size was analyzed by first-principles calculation, and the thermodynamic properties of ZrO₂ clusters and nanoparticles were analyzed by constructing (ZrO₂)_n (n = 1–6) clusters. The thermodynamic properties of ZrO₂ calculated by first principles were consistent with the values in the literature. Based on two-step nucleation theory, the nucleation pathway of ZrO₂ is as follows: Zr_atom + O_atom → (ZrO₂)_n → (ZrO₂)₂ → core (ZrO₂ particle)–shell ((ZrO₂)₂ cluster) nanoparticle → (ZrO₂)_bulk.     

A Low Temperature Growth of Cu2O Thin Films as Hole Transporting Material for Perovskite Solar Cells

Copper oxide thin films have been successfully synthesized through a metal–organic chemical vapor deposition (MOCVD) approach starting from the copper bis(2,2,6,6-tetramethyl-3,5-heptanedionate), Cu(tmhd)₂, complex. Operative conditions of fabrication strongly affect both the composition and morphologies of the copper oxide thin films. The deposition temperature has been accurately monitored in order to stabilize and to produce, selectively and reproducibly, the two phases of cuprite Cu₂O and/or tenorite CuO. The present approach has the advantages of being industrially appealing, reliable, and fast for the production of thin films over large areas with fine control of both composition and surface uniformity. Moreover, the methylammonium lead iodide (MAPI) active layer has been successfully deposited on the ITO/Cu₂O substrate by the Low Vacuum Proximity Space Effusion (LV-PSE) technique. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and atomic force microscopy (AFM) analyses have been used to characterize the deposited films. The optical band gap (E_g), ranging from 1.99 to 2.41 eV, has been determined through UV-vis analysis, while the electrical measurements allowed to establish the p-type conductivity behavior of the deposited Cu₂O thin films with resistivities from 31 to 83 Ω cm and carrier concentration in the order of 1.5–2.8 × 10¹⁶ cm⁻³. These results pave the way for potential applications of the present system as a hole transporting layer combined with a perovskite active layer in emergent solar cell technologies.     

Sintering Behavior,Thermal Expansion,and Environmental Impacts Accompanying Materials of the Al2O3/ZrO2 System Fabricated via Slip Casting

This work focuses on research on obtaining and characterizing Al₂O₃/ZrO₂ materials formed via slip casting method. The main emphasis in the research was placed on environmental aspects and those related to the practical use of ceramic materials. The goal was to analyze the environmental loads associated with the manufacturing of Al₂O₃/ZrO₂ composites, as well as to determine the coefficient of thermal expansion of the obtained materials, classified as technical ceramics. This parameter is crucial in terms of their practical applications in high-temperature working conditions, e.g., as parts of industrial machines. The study reports on the four series of Al₂O₃/ZrO₂ materials differing in the volume content of ZrO₂. The sintering process was preceded by thermogravimetric measurements. The fabricated and sintered materials were characterized by dilatometric study, scanning electron microscopy, X-ray diffraction, and stereological analysis. Further, life cycle assessment was supplied. Based on dilatometric tests, it was observed that Al₂O₃/ZrO₂ composites show a higher coefficient of thermal expansion than that resulting from the content of individual phases. The results of the life cycle analysis showed that the environmental loads (carbon footprint) resulting from the acquisition and processing of raw materials necessary for the production of sinters from Al₂O₃ and ZrO₂ are comparable to those associated with the production of plastic products such as polypropylene or polyvinyl chloride.     

Hf1−xSixO2 Nanocomposite Coatings Prepared by Ion-Assisted Co-Evaporation Process for Low-Loss and High-LIDT Optics

Hf_1−xSi_xO₂ nanocomposites with different SiO₂ doping ratios were synthesized using an ion-assisted co-evaporation process to achieve dense amorphous Hf_1−xSi_xO₂ coatings with low loss and a high laser-induced damage threshold (LIDT). The results showed that the Hf_1−xSi_xO₂ nanocomposites (x ≥ 0.20) exhibited excellent comprehensive performance with a wide band gap and a dense amorphous microstructure. High-temperature annealing was carried out to ensure better stoichiometry and lower absorption. Precipitation and regrowth of HfO₂ grains were observed from 400 °C to 600 °C during annealing of the Hf_0.80Si_0.20O₂ nanocomposites, resulting in excessive surface roughness. A phenomenological model was proposed to explain the phenomenon. The Hf_1−xSi_xO₂ nanocomposites (x = 0.3 and 0.4) maintained a dense amorphous structure with low absorption after annealing. Finally, a 1064-nm Hf_0.70Si_0.30O₂/SiO₂ high-performance reflector was prepared and achieved low optical loss (15.1 ppm) and a high LIDT (67 J/cm²).     

Calculation of Thermal Expansion Coefficient of Rare Earth Zirconate System at High Temperature by First Principles

Compounds of rare earth zirconates with pyrochlore structure are candidates for the application of thermal barrier coatings of next generation. In order to modify the mechanic properties and maintain the low thermal conductivity, other trivalent rare-earth element substitution is commonly used. Presently, investigation on the evaluation of the property of thermal expansion is attracting more attention. In this paper, a feature parameter of thermal expansion coefficient at high temperature (α_∞) was proposed by combining Grüneisen’s equation and the Debye heat capacity model. Using α_∞ model, the thermal expansion property of different compounds can be easily figured out by first principles. Firstly, α_∞ of ZrO₂, HfO₂, were calculated, and results are in good agreement with the experimental data from the literature. Moreover, α_∞ of La₂Zr₂O₇, Pr₂Zr₂O₇, Gd₂Zr₂O₇, and Dy₂Zr₂O₇ were calculated, and results demonstrated that the model of α_∞ is a useful tool to predict the thermal expansion coefficient at high temperature. Finally, Gd₂Zr₂O₇ with 4 different Yb dopant concentrations (Gd_1-xYb_x)₂Zr₂O₇ (x = 0, 0.125, 0.3125, 0.5) were calculated. Comparing with the experimental data from the literature, the calculation results showed the same tendency with the increasing of Yb concentration.     

Characterization of Ionic Transport in Li2O-(Mn:Fe)2O3-P2O5 Glasses for Li Batteries

We present a systematic study of the lithium-ion transport upon the mixed manganese-iron oxide phosphate glasses 3Li₂O-xMn₂O₃-(2-x)Fe₂O₃-3P₂O₅(LM_xF_2−xPO; 0≤ x ≤2.0) proposed for the use in a cathode for lithium secondary batteries. The glasses have been fabricated using a solid reaction process. The electrical characteristics of the glass samples have been characterized by electrical impedance in the frequency range from 100 Hz to 30 MHz and temperature from 30 °C to 240 °C. Differential thermal analysis and X-ray diffraction were used to determine the thermal and structural properties. It has been observed that the dc conductivity decreases, but the activation energies of dc and ac and the glass-forming ability increase with the increasing Mn₂O₃ content in LM_xF_2−xPO glasses. The process of the ionic conduction and the relaxation in LM_xF_2−xPO glasses are determined by using power–law, Cole–Cole, and modulus methods. The Li⁺ ions migrate via the conduction pathway of the non-bridging oxygen formed by the depolymerization of the mixed iron–manganese–phosphate network structure. The mixed iron–manganese content in the LM_xF_2−xPO glasses constructs the sites with different depths of the potential well, leading to low ionic conductivity.     

The Use of ZrO2 Waste for the Electrolytic Production of Composite Ni–P–ZrO2 Powder

Ni–P–ZrO₂ composite powder was obtained from a galvanic nickel bath with ZrO₂ powder. Production was conducted under galvanostatic conditions. The Ni–P–ZrO₂ composite powder was characterized by the presence of ZrO₂ particles covered with electrolytical nanocrystalline Ni–P coating. The chemical composition (XRF method), phase structure (XRD method) and morphology (SEM) of Ni–P–ZrO₂ and the distribution of elements in the powder were all investigated. Based on the analyses, it was found that the obtained powder contained about 50 weight % Zr and 40 weight % Ni. Phase structure analysis showed that the basic crystalline component of the tested powder is a mixed oxide of zirconium and yttrium Zr_0.92Y_0.08O_1.96. In addition, the sample contains very large amounts of amorphous compounds (Ni–P). The mechanism to produce the composite powder particles is explained on the basis of Ni²⁺ ions adsorption process on the metal oxide particles. Current flow through the cell forces the movement of particles in the bath. Oxide grains with adsorbed nickel ions were transported to the cathode surface. Ni²⁺ ions were discharged. The oxide particles were covered with a Ni–P layer and the heavy composite grains of Ni–P–ZrO₂ flowed down to the bottom of the cell.     

(Cr1−xAlx)N Coating Deposition by Short-Pulse High-Power Dual Magnetron Sputtering

The paper deals with the (Cr_1−xAl_x)N coating containing 17 to 54 % Al which is deposited on AISI 430 stainless steel stationary substrates by short-pulse high-power dual magnetron sputtering of Al and Cr targets. The Al/Cr ratio in the coating depends on the substrate position relative to magnetrons. It is shown that the higher Al content in the (Cr_1−xAl_x)N coating improves its hardness from 17 to 28 GPa. Regardless of the Al content, the (Cr_1−xAl_x)N coating manifests a low wear rate, namely (4.1–7.8) × 10⁻⁹ and (3.9–5.3) × 10⁻⁷ mm³N⁻¹m⁻¹ in using metallic (100Cr6) and ceramic (Al₂O₃) counter bodies, respectively. In addition, this coating possesses the friction coefficient 0.4–0.7 and adhesive strength quality HF1 and HF2 indicating good interfacial adhesion according to the Daimler-Benz Rockwell-C adhesion test.     

Influence of Conditioning Temperature on Defects in the Double Al2O3/ZnO Layer Deposited by the ALD Method

In this work, we present the results of defects analysis concerning ZnO and Al₂O₃ layers deposited by atomic layer deposition (ALD) technique. The analysis was performed by the X-band electron paramagnetic resonance (EPR) spectroscopy, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) methods. The layers were either tested as-deposited or after 30 min heating at 300 °C and 450 °C in Ar atmosphere. TEM and XPS investigations revealed amorphous nature and non-stoichiometry of aluminum oxide even after additional high-temperature treatment. EPR confirmed high number of defect states in Al₂O₃. For ZnO, we found the as-deposited layer shows ultrafine grains that start to grow when high temperature is applied and that their crystallinity is also improved, resulting in good agreement with XPS results which indicated lower number of defects on the layer surface.     

Impact of Li3BO3 Addition on Solid Electrode-Solid Electrolyte Interface in All-Solid-State Batteries

All-solid-state lithium-ion batteries raise the issue of high resistance at the interface between solid electrolyte and electrode materials that needs to be addressed. The article investigates the effect of a low-melting Li₃BO₃ additive introduced into LiCoO₂- and Li₄Ti₅O₁₂-based composite electrodes on the interface resistance with a Li₇La₃Zr₂O₁₂ solid electrolyte. According to DSC analysis, interaction in the studied mixtures with Li₃BO₃ begins at 768 and 725 °C for LiCoO₂ and Li₄Ti₅O₁₂, respectively. The resistance of half-cells with different contents of Li₃BO₃ additive after heating at 700 and 720 °C was studied by impedance spectroscopy in the temperature range of 25–340 °C. It was established that the introduction of 5 wt% Li₃BO₃ into LiCoO₂ and heat treatment at 720 °C led to the greatest decrease in the interface resistance from 260 to 40 Ω cm² at 300 °C in comparison with pure LiCoO₂. An SEM study demonstrated that the addition of the low-melting component to electrode mass gave better contact with ceramics. It was shown that an increase in the annealing temperature of unmodified cells with Li₄Ti₅O₁₂ led to a decrease in the interface resistance. It was found that the interface resistance between composite anodes and solid electrolyte had lower values compared to Li₄Ti₅O₁₂|Li₇La₃Zr₂O₁₂ half-cells. It was established that the resistance of cells with the Li₄Ti₅O₁₂/Li₃BO₃ composite anode annealed at 720 °C decreased from 97.2 (x = 0) to 7.0 kΩ cm² (x = 5 wt% Li₃BO₃) at 150 °C.     

Effect of Sintering Process on Ionic Conductivity of Li7-xLa3Zr2-xNbxO12 (x = 0, 0.2, 0.4, 0.6) Solid Electrolytes

Garnet-type Li₇La₃Zr₂O₁₂ (LLZO) is considered as a promising solid electrolyte. Nb-doped LLZO ceramics exhibit significantly improved ion conductivity. However, how to prepare the Nb-doped LLZO ceramics in a simple and economical way, meanwhile to investigate the relationship between process conditions and properties in Li_7-xLa₃Zr_2-xNb_xO₁₂ ceramics, is particularly important. In this study, Li_7-xLa₃Zr_2-xNb_xO₁₂ (LLZN_xO, x = 0, 0.2, 0.4, 0.6) ceramics were prepared by conventional solid-state reaction. The effect of sintering process on the structure, microstructure, and ionic conductivity of LLZN_xO (x = 0, 0.2, 0.4, 0.6) ceramics was investigated. Due to the more contractive Nb-O bonds in LLZN_xO ceramics, the cubic structures are much easier to form and stabilize, which could induce the decreased preparation time. High-performance garnet LLZN_xO ceramics can be obtained by optimizing the sintering process with lower calcining temperature and shorter holding time. The garnet samples with x = 0.4 calcined at 850 °C for 10 h and sintered at 1250 °C for 4 h exhibit the highest ionic conductivity of 3.86 × 10⁻⁴ S·cm⁻¹ at room temperature and an activation energy of 0.32 eV, which can be correlated to the highest relative density of 96.1%, and good crystallinity of the grains.     

Intrinsic Properties of Multi-Layer TiO2/V2O5/TiO2 Coatings Prepared via E-Beam Evaporation

Nanocomposite multi-layer TiO₂/V₂O₅/TiO₂ thin films were prepared via electron-beam evaporation using high-purity targets (TiO₂ and V₂O₅ purity > 99.9%) at substrate temperatures of 270 °C (TiO₂) and 25 °C (V₂O₅) under a partial pressure of oxygen of 2 × 10⁻⁴ mbar to maintain the stoichiometry. Rutherford backscattering spectrometry was used to confirm the layer structure and the optimal stoichiometry of the thin films, with a particle size of 20 to 40 nm. The thin films showed an optical transmittance of ~78% in the visible region and a reflectance of ~90% in the infrared. A decrease in transmittance was observed due to the greater cumulative thickness of the three layers and multiple reflections at the interface of the layers. The optical bandgap of the TiO₂ mono-layer was ~3.49 eV, whereas that of the multi-layer TiO₂/V₂O₅/TiO₂ reached ~3.51 eV. The increase in the optical bandgap was due to the inter-diffusion of the layers at an elevated substrate temperature during the deposition. The intrinsic, structural, and morphological features of the TiO₂/V₂O₅/TiO₂ thin films suggest their efficient use as a solar water heater system.     

Low-Temperature Rapid Sintering of Dense Cubic Phase ZrW2−xMoxO8 Ceramics by Spark Plasma Sintering and Evaluation of Its Thermal Properties

In this study, we report a low-temperature approach involving a combination of a sol–gel hydrothermal method and spark plasma sintering (SPS) for the fabrication of cubic phase ZrW_2−xMo_xO₈ (0.00 ≤ x ≤ 2.00) bulk ceramics. The cubic-ZrW_2−xMo_xO₈ (0.00 ≤ x ≤ 1.50) bulk ceramics were successfully synthesized within a temperature range of 623–923 K in a very short amount of time (6–7 min), which is several hundred degrees lower than the typical solid-state approach. Meanwhile, scanning electron microscopy and density measurements revealed that the cubic-ZrW_2−xMo_xO₈ (0.00 ≤ x ≤ 1.50) bulk ceramics were densified to more than 90%. X-ray diffraction (XRD) results revealed that the cubic phase ZrW_2−xMo_xO₈ (0.00 ≤ x ≤ 1.5) bulk ceramics, as well as the sol–gel-hydrothermally synthesized ZrW_2−xMo_xO₇(OH)₂·2H₂O precursors correspond to their respective pure single phases. The bulk ceramics demonstrated negative thermal expansion characteristics, and the coefficients of negative thermal expansion were shown to be tunable in cubic-ZrW_2−xMo_xO₈ bulk ceramics with respect to x value and sintering temperature. The cubic-ZrW_2−xMo_xO₈ solid solution can thus have potential applications in electronic devices such as heat sinks that require regulation of thermal expansion.     

Structural Morphology and Optical Properties of Strontium-Doped Cobalt Aluminate Nanoparticles Synthesized by the Combustion Method

The study of structural morphology and the optical properties of nanoparticles produced by combustion methods are gaining significance due to their multifold applications. In this regard, in the present work, the strontium-doped cobalt aluminate nanoparticles were synthesized by utilizing Co_1−xSr_xAl₂O₄ (0 ≤ x ≤ 0.5) L-Alanine as a fuel in an ignition cycle. Subsequently, several characterization studies viz., X-ray diffraction (XRD), energy-dispersive X-ray (EDX) analysis, high-resolution scanning electron microscopy (HRSEM), Fourier transform infrared spectroscopy (FTIR), ultraviolet (UV) spectroscopy and vibrating sample magnetometry (VSM) were accomplished to study the properties of the materials. The XRD analysis confirmed the cubic spinel structure, and the average crystallite size was found to be in the range of 14 to 20 nm using the Debye–Scherrer equation. High-resolution scanning electron microscopy was utilized to inspect the morphology of the Co_1−xSr_xAl₂O₄ (0 ≤ x ≤ 0.5) nanoparticles. Further, EDS studies were accomplished to determine the chemical composition. Kubelka–Munk’s approach was used to determine the band gap, and the values were found to be in the range of 3.18–3.32 eV. The energy spectra for the nanoparticles were in the range of 560–1100 cm⁻¹, which is due to the spinel structure of Sr-doped CoAl₂O₄ nanoparticles. The behavior plots of magnetic induction (M) against the magnetic (H) loops depict the ferromagnetic behavior of the nanomaterials synthesized.     

Cobalt Minimisation in Violet Co3P2O8 Pigment

This study considers the limitations of cobalt violet orthophosphate, Co₃P₂O₈, in the ceramic industry due to its large amount of cobalt. Mg_xCo_3−xP₂O₈ (0 ≤ x ≤ 3) solid solutions with the stable Co₃P₂O₈ structure were synthesised via the chemical coprecipitation method. The formation of solid solutions between the isostructural Co₃P₂O₈ and Mg₃P₂O₈ compounds decreased the toxically large amount of cobalt in this inorganic pigment and increased the melting point to a temperature higher than 1200 °C when x ≥ 1.5. Co₃P₂O₈ melted at 1160 °C, and compositions with x ≥ 1.5 were stable between 800 and 1200 °C. The substitution of Co(II) with Mg(II) decreased the toxicity of these materials and decreased their price; hence, the interest of these materials for the ceramic industry is greater. An interesting purple colour with a* = 31.6 and b* = −24.2 was obtained from a powdered Mg_2.5Co_0.5P₂O₈ composition fired at 1200 °C. It considerably reduced the amount of cobalt, thus improving the colour of the Co₃P₂O₈ pigment (a* = 16.2 and b* = −20.1 at 1000 °C). Co₃P₂O₈ is classified as an inorganic pigment (DCMA-8-11-1), and the solid solutions prepared were also inorganic pigments when unglazed. When introducing 3% of the sample (pigment) together with enamel, spreading the mixture on a ceramic support and calcining the whole in an electric oven, a colour change from violet to blue was observed due to the change in the local environment of Co(II), which could be seen in the UVV spectra of the glazed samples with the displacement of the bands towards higher wavelengths and with the appearance of a new band assigned to tetrahedral Co(II). This blue colour was also obtained with Co₂SiO₄, MgCoSiO₄ or Co₃P₂O₈ pigments containing a greater amount of cobalt.