Effect of Gd-doping on thermoelectric properties of Ca<Subscript>3</Subscript>Co<Subscript>4</Subscript>O<Subscript>9+δ</Subscript> ceramics

A series of Ca_3−x Gd _x Co₄O_9+δ precursor powders were synthesized by the polyacrylamide gel method, and their ceramics were obtained by the Spark Plasma Sintering (SPS). There were lots of defects in the sheet-like grains from SEM and TEM observations. The electrical and the thermal transport properties were obviously affected by the material microstructure. The small polaron hopping conduction mechanism was determined above 600 K, and the hopping activation energy increased with the increase of doping contents. It was found that the Seebeck coefficient and the resistivity of doped samples were markly enhanced due to the impurity compensation effect, and their thermal conductivities were decreased due to the defects scattering. The maximum figure of merit of ZT = 0.24 at 973 K was obtained for Ca_2.7Gd_0.3Co₄O_9+δ.     

Synthesis and properties of Ca<Subscript>2.8</Subscript>Ln<Subscript>0.2</Subscript>Co<Subscript>4</Subscript>O<Subscript>9 + δ</Subscript> (Ln = La,Nd, Sm,Tb-Er) solid solutions

Ca_2.8Ln_0.2Co₄O_{9 + δ} (Ln = La, Nd, Sm, Tb-Er) solid solutions have been prepared via a citrate route and their structural parameters have been determined. Their thermal expansion, thermoelectric power, thermal conductivity, and electrical conductivity have been measured above room temperature. The results demonstrate that all of the materials obtained are p-type semiconductors. Their unit-cell parameters decrease with a decrease in the ionic radius of the Ln³⁺ cation substituted for Ca²⁺, and their thermoelectric power increases with an increase in the number of f electrons of the Ln³⁺ cation. We have determined the electron and phonon contributions to the thermal conductivity of the materials and evaluated the thermoelectric power factor and thermoelectric figure of merit of the oxide ceramics. The highest thermoelectric power factors are offered by the Ca_2.8Tb_0.2Co₄O_{9 + δ} and Ca_2.8Er_0.2Co₄O_{9 + δ} solid solutions: 0.27 and 0.29 mW/(m K²), respectively, at T = 1100 K.     

Effect of refractory nitride nanoadditives on the properties of (Bi,Pb)<Subscript>2</Subscript>Sr<Subscript>2</Subscript>Ca<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>10+δ</Subscript>

We have investigated the interaction between (Bi,Pb)₂Sr₂Ca₂Cu₃O_10+δ (Bi-2223) and small additions (0.05–0.3 wt %) of nitride powders (TaN, AlN, HfN, NbN, Si₃N₄, TiN, and ZrN) with a particle size from 0.02 to above 0.5 μm and the effect of these nitrides on the microstructure, phase composition, distribution, and morphology of the resulting second-phase inclusions. The concentration and particle size of the nitrides and sintering conditions are shown to influence the superconducting transition temperature T _c, critical current density j _c, irreversible remanent magnetization, bulk density, and mechanical properties of the Bi-2223/nitride composites.     

Influence of Bi substitution on microwave dielectric properties of BaO–La<Subscript>2</Subscript>O<Subscript>3</Subscript>–Sm<Subscript>2</Subscript>O<Subscript>3</Subscript>–TiO<Subscript>2</Subscript> ceramics

The influences of Bi substitution on microwave dielectric properties of Ba₄(La_0.5Sm_0.5)_9.33Ti₁₈O₅₄ solid solutions were investigated. Dielectric ceramics with general formula Ba₄(La_(0.5−z)Sm_0.5Bi _z )_9.33Ti₁₈O₅₄, z = 0.0–0.2 were prepared by conventional solid state route. The structural analysis of all the samples was carried out by X-ray diffraction and scanning electron microscopy. The dielectric properties were investigated as a function of Bi contents using open-ended coaxial probe method in the frequency range 0.3–3.0 GHz at room temperature. Dielectric constant varies from 83 to 88 and loss tangent from 2.1 × 10⁻³ to 5.5 × 10⁻³ at 3 GHz with temperature coefficient of resonant frequency changing from 106.7 to −8.4 ppm/oC as Bi contents increases from z = 0.00–0.20. It has been found that dielectric constant and temperature coefficient of resonant frequency improve whereas loss tangent is adversely affected with increase in Bi substitution.     

Reaction of CaAl<Subscript>4</Subscript>O<Subscript>7</Subscript> with (0001)-oriented α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

Reactions between thin films of CA₂ and (0001)-oriented α-Al₂O₃ have been studied using a combination of microscopy techniques. Thin films of amorphous CA₂ were deposited on sapphire substrates by pulsed-laser deposition at 900 °C in an oxygen ambient atmosphere. After deposition, the reaction couples were heat treated in air for various times either at 1300 or 1400 °C. Atomic-force microscopy was used to monitor changes in the microstructure of the films. Interfaces between the different regions were examined by transmission electron microscopy (TEM) of cross-sectional samples prepared by focused ion-beam milling. The CA₂ films had dewetted the substrate surface as a result of the heat treatment. An interfacial reaction layer was observed between the dewetted CA₂ droplets and the substrate. The structure of this reaction layer was found to be consistent with γ-Al₂O₃ by computer analysis of high-resolution TEM images. There is a perfect epitaxy between the interfacial layer and the substrate. For the samples heat treated for longer times, hexagonal features were found on the substrate surface. The presence of these features on (0001)-oriented α-Al₂O₃ suggests that CA₆ platelets form by the transformation of the interfacial reaction layer. The results are discussed in relation to the crystallization behavior of the various calcium aluminate phases and the equilibrium-phase diagram of the CaO–Al₂O₃ system.     

BaFe<Subscript>12</Subscript>O<Subscript>19</Subscript> films produced from BaFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> heterostructures

BaFe₁₂O₁₉ hexaferrite films have been produced on thermally oxidized single-crystal silicon (SiO₂/Si) substrates by sequential ion-beam sputtering of BaFe₂O₄ and α-Fe₂O₃ targets in an argon-oxygen atmosphere. Their crystal structure has been studied, and the origin of the impurity phases forming during heat treatment has been identified. The results show that heat treatment may lead to the formation of eutectic melts. As a result, the hexaferrite films may contain spherulites.     

Thermodynamic and structural properties of PrBaCo<Subscript>2</Subscript>O<Subscript>5 + δ</Subscript>

The oxygen content of the double cobaltite PrBaCo₂O_{5 + δ} was determined by coulometric titration in broad temperature and oxygen pressure ranges, and the partial thermodynamic functions of oxygen were evaluated. The results on the nonstoichiometry and structural properties of PrBaCo₂O_{5 + δ} demonstrate that, at 5 + δ < 5.3, this cobaltite has a high-temperature phase with lattice parameters a = 11.774 Å, b = 11.932 Å, and c = 7.609 Å. The composition dependences of \(\Delta \bar H(O)\) and \(\Delta \bar S(O)\) indicate that the 3a_p × 3a_p × 2a_p orthorhombic structure persists in the range 5.15 ≤ 5 + δ ≤ 5.30. Some of the Co³⁺ ions are shown to disproportionate according to the scheme 2Co³⁺=Co²⁺+Co⁴⁺.     

Spectroscopic characterisation of local structure in Y<Subscript>2</Subscript>O<Subscript>3</Subscript>–B<Subscript>2</Subscript>O<Subscript>3</Subscript>–Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> glasses doped with gadolinium

Gadolinium doped bismuth borate glasses containing up to 30 mol% Y₂O₃ were prepared by fast melt quenching method. The effect of yttrium on the local order in 3B₂O₃ · Bi₂O₃ and B₂O₃ · Bi₂O₃ glass matrices, particularly on the bismuth sites, was investigated by infrared (IR) spectroscopy and electron paramagnetic resonance (EPR) of Gd³⁺ ions. The IR results show that the local structure is more ordered in the glass system with higher bismuth content and the progressive addition of yttrium increases the local disorder in both bismuth–borate glass matrices. The EPR results indicate that Gd³⁺ ions occupy both bismuth and yttrium sites and reflect the same structural disorder like that suggested by IR results.     

Microstructure and properties of the Ba<Subscript>0.75−x</Subscript>Ca<Subscript>x</Subscript>La<Subscript>0.25</Subscript>Fe<Subscript>11.6</Subscript>Co<Subscript>0.25</Subscript>Ti<Subscript>0.15</Subscript>O<Subscript>19</Subscript> hexaferrites

In the case of Ti⁴⁺ remain unchanged, the Ca²⁺ substituted Ba_0.75?xCa_xLa_0.25Fe_11.6Co_0.25Ti_0.15O₁₉ (0?≤?x?≤?0.05) were prepared by conventional solid-state reaction method at temperature of 1280 °C. A ball-to-power weight ratio of 10:1. Their crystal structure and magnetic properties were mainly investigated. The results show that the single magnetoplumbite phase structure transformed into the multiphase structure. Meanwhile, the small amount of α-Fe₂O₃ phase existed in M-type phase. The micrographs were observed by a field emission scanning electron microscopy (SEM). Vibrating sample magnetometer (VSM) was used to analyze the magnetic properties. The saturation magnetization (M _s ) first increases then decreases when x from 0 to 0.03. But, when x from 0.03 to 0.05, the saturation magnetization (M _s ) first increases then decreases too. The maximum value is at x?=?0.04 (M _s ?=?70.73 emu/g). The value of coercivity (H _c ) first increases then decreases when x from 0 to 0.04. But, the value increased when x from 0.04 to 0.05. The maximum value is at x?=?0.02 (H _c ?=?1691 Oe).     

Mechanical and acid-etching properties of Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–ZnO–B<Subscript>2</Subscript>O<Subscript>3</Subscript> glass-containing ceramic fillers

The properties of the composite, having a complicated microstructure, are decided by many factors such as those of glass matrix, crystal phases, fillers, and holes. We investigated how the addition of ceramic fillers to the glass matrix affects the mechanical and etching properties of the glass composite by forming new crystal phases. Different amounts of two fillers, ZnO and Al₂O₃, were added to a glass frit consisting of Bi₂O₃–ZnO–B₂O₃. It was sintered at 550 °C for 30 min. Based on the results of this study, the porosity and degree of crystallization of the composites could be controlled by adjusting the content of the ZnO and Al₂O₃ fillers. Therefore, porosity and degree of crystallization formed by the reaction between a glass matrix and fillers influence the mechanical and etching properties of the composite.     

Synthesis and Magnetic Properties of Bi<Subscript>1.7</Subscript>Pb<Subscript>0.3</Subscript>Sr<Subscript>2</Subscript>Ca<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>10+<Emphasis Type="Italic">δ</Emphasis></Subscript> Added with Nano Y

Bi₁₇Pb_0.3Sr₂Ca₂Cu₃O_10+δ superconductor samples were synthesized by the conventional solid-state reaction method. To study the effects of the addition of yttrium nanoparticles to the superconducting system, nano Y₂O₃ was introduced by small weight percentages (0.2, 0.4, 0.6, 0.8, and 1.0 wt%) in the first step of the synthesis process. Phase identification and microstructural characterization of the samples were investigated using X-ray diffraction and scanning electronic microscopy (SEM). Energydispersive X-ray spectroscopy (EDX) analysis was utilized to confirm the presence of the desired elements in the chemical composition of the samples. Moreover, DC electrical resistivity as a function of the temperature, critical current density (J _c), AC magnetic susceptibility, and DC magnetization measurements were carried to evaluate the relative performance of samples. XRD analysis showed that both (Bi,Pb)-2223 and Bi-2212 phases coexist in the samples having an orthorhombic crystal structure. Both the onset critical temperatures (T _c) (onset) and zero electrical resistivity critical temperatures (T _c) (R = 0) of the samples were determined from the DC electrical resistivity measurements. An improvement of the superconducting transition temperature of 3.0 % was obtained with increasing Y₂O₃ nanoparticles to x = 1.0 wt%, while the critical current density is improved by 200 %. AC magnetic susceptibility measurement showed that the diamagnetic fraction and intergranular coupling of the x = 1.0 wt% sample are greater than those of the others. The variation of magnetization with temperature (M–T curve) of the samples was measured by cooling the sample in zero fields (ZFC) and an applied field of 10 Oe (FC). The results of AC magnetic susceptibility and DC magnetization measurements were in good agreement with DC electrical resistivity measurement.     

Sol–gel derived Co<Subscript>3</Subscript>O<Subscript>4</Subscript> thin films: effect of annealing on structural,morphological and optoelectronic properties

Nanocrystalline Co₃O₄ thin films were prepared on glass substrates by using sol–gel spin coating technique. The effect of annealing temperature (400–700 °C) on structural, morphological, electrical and optical properties of Co₃O₄ thin films were studied by X-ray diffraction (XRD), Scanning Electron Microscopy, Electrical conductivity and UV–visible Spectroscopy. XRD measurements show that all the films are nanocrystallized in the cubic spinel structure and present a random orientation. The crystallite size increases with increasing annealing temperature (53–69 nm). These modifications influence the optical properties. The morphology of the sol–gel derived Co₃O₄ shows nanocrystalline grains with some overgrown clusters and it varies with annealing temperature. The optical band gap has been determined from the absorption coefficient. We found that the optical band gap energy decreases from 2.58 to 2.07 eV with increasing annealing temperature between 400 and 700 °C. These mean that the optical quality of Co₃O₄ films is improved by annealing. The dc electrical conductivity of Co₃O₄ thin films were increased from 10⁻⁴ to 10⁻² (Ω cm)⁻¹ with increase in annealing temperature. The electron carrier concentration (n) and mobility (μ) of Co₃O₄ films annealed at 400–700 °C were estimated to be of the order of 2.4–4.5 × 10¹⁹ cm⁻³ and 5.2–7.0 × 10⁻⁵ cm² V⁻¹ s⁻¹ respectively. It is observed that Co₃O₄ thin film annealing at 700 °C after deposition provide a smooth and flat texture suited for optoelectronic applications.     

Study of structural and magnetoelectric properties of 1−x(Ba<Subscript>0.96</Subscript>Ca<Subscript>0.04</Subscript>TiO<Subscript>3</Subscript>)–x(ZnFe<Subscript>2</Subscript>O<Subscript>4</Subscript>) ceramic composites

Multiferroic ceramic composites of (1?x)Ba_0.96Ca_0.04TiO₃–(x)ZnFe₂O₄ (BCT-ZF) were prepared from ferroelectric (FE) barium calcium titanate (BCT) and ferromagnetic (FM) zinc ferrite (ZF) by using the solid state reaction method with different mol% fractions of x (x?=?0.1 and 0.2). The preliminary structural studies carried out by X-ray diffraction at room temperature reveals that the samples have a tetragonal structure along with the cubic spinel ferrite phase. Raman spectra of the composites also confirm the existence of BCT phase and ZF phase. The room temperature ferroelectric polarization measurements as a function of magnetic field show the existence strong magnetoelectric coupling of 10.85 (mV/(cm.Oe).     

Optical properties and crystallization of glasses in the system Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–MoO<Subscript>3</Subscript>–B<Subscript>2</Subscript>O<Subscript>3</Subscript>

The purpose of this work is to study the optical properties and crystallization of glasses in the ternary system Bi₂O₃–MoO₃–B₂O₃. In order to verify the obtaining of bismuth borate crystal phases several glass compositions have been selected for crystallization. The obtained samples were characterized by X-ray diffraction, scanning electron microscopy and UV–Vis spectroscopy. The UV–Vis spectroscopy showed that the obtained glasses are transparent in the visible region. The values of optical band gap (E _opt) and changes in cut-off (λ_c) depending on composition are reported. It was established that the increase in the MoO₃ content led to decreasing the transmittance of the glasses. Moreover, the absorption edge shifts towards longer wavelength.     

Facile Synthesis of Co<Subscript>3</Subscript>O<Subscript>4</Subscript>/CoO Nanoparticles by Thermal Treatment of Ball-Milled Precursors

Co₃O₄/CoO nanoparticles have been synthesized by a simple method which is based on the ball-milling and calcination of cobalt acetate and citric acid. The samples were characterized using X-ray diffraction, transmission electron microscope, and Fourier transform infrared spectroscopy. The results show that Co₃O₄ nanoparticles with an average particle size of ∼40 nm can be obtained by calcination of ball-milled precursors at relatively low temperature (350 °C) for 3 hours. It should be noted that it is possible to control the size of Co₃O₄ particles by calcination temperature, calcination time and also by ball-milling duration using this method. Meanwhile, the pure CoO nanoparticles were obtained successfully by thermal decomposition of Co₃O₄ at 950 °C and quickly quenching to liquid nitrogen.     

A comparison of results obtained using different methods to assess the elastic properties of ceramic materials exemplified for Ba<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>Co<Subscript>0.8</Subscript>Fe<Subscript>0.2</Subscript>O<Subscript>3−δ</Subscript>

Different mechanical testing methods have been used to assess the elastic behavior of the mixed ion electron conducting perovskite Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF). Although the main aim is the comparison of the testing techniques for ceramic material in general, experiments have been performed at RT and up to 900 °C to illustrate the capabilities of the utilized methods for a perovskite with a stiffness anomaly. BSCF specimens in disc shape and tubular geometry provided by different suppliers were tested in biaxial bending by ring-on-ring testing and under uniaxial stress in O-ring and under compression loading. The elastic modulus was determined as a function of temperature up to 900 °C. In addition, the room temperature elastic modulus was measured using depth-sensitive indentation.     

Variable—Range hopping in Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-K<Subscript>2</Subscript>B<Subscript>4</Subscript>O<Subscript>7</Subscript> glasses

The dc conductivity of the glasses in the Fe₂O₃-Bi₂O₃-K₂B₄O₇ system was studied at temperatures between 223 and 393 K. At temperatures from 300 to 223 K, T^–1/4 (T is temperature) dependence of the conductivity was found, however, both Mott variable-range hopping and Greaves intermediate range hopping models are found to be applicable. Mott and Greaves parameters analysis gave the density of states at Fermi level N (E_F) = 3.13 × 10²⁰–21.01 × 10²⁰ and 1.93 × 10²¹–16.39 × 10²¹ cm^–3eV^–1 at 240 K, respectively. The variable-range hopping conduction occurred in the temperature range T = 300–223 K, since W_D was found to be large (W_D = 0.08–0.14 eV for these glasses) and dominated the conduction at T < 300 K.     

Enhanced antibacterial performance of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>–Ag and MnFe<Subscript>2</Subscript>O<Subscript>4</Subscript>–Ag nanocomposites

In this work, we have described the antibacterial activities of Fe₃O₄ nanoparticles with different organic parts, including Humic acid (HA), Nicotinic acid (Nico) and Histidine (His), and the antibacterial activity of MnFe₂O₄ nanoparticles coated with PANI and SiO₂ against different bacteria and some standard antibacterial drugs. The present study revealed that the newly fabricated various Fe₃O₄ and MnFe₂O₄ nanocomposites, when combined with some different organic parts, are superiour antibacterial agents. Also, the synthesized nanocomposites can be easily separated from aqueous solution by magnetic filtration without any contamination of the medium.     

Hydrothermal process fabrication of NiO–NiCoO<Subscript>2</Subscript>–Co<Subscript>3</Subscript>O<Subscript>4</Subscript> composites used as supercapacitor materials

A composite consisting of Co₃O₄, NiCoO₂ and NiO is prepared by a simple and easy hydrothermal method followed by calcining at 300?°C. The composition, morphology and microstructure of NiO–NiCoO₂–Co₃O₄ composites are examined by X-ray diffraction, field emission scanning electron microscope and transmission electron microscopic. The electrochemical performances of NiO–NiCoO₂–Co₃O₄ composites are characterized by cyclic voltammetry, galvanostatic charge–discharge and electrochemical impedance spectroscopy in 3 M KOH electrolyte. The results of electrochemical measurements show that the NiO–NiCoO₂–Co₃O₄ composites exhibit a high specific capacitance of 990 and 580 F/g at the current densities of 1.0 and 10 A/g, respectively. About 50% of the maximum specific capacitance can still be retained after 1000 continuous CD cycles at 10 A/g. It reveals a great potential of NiO–NiCoO₂–Co₃O₄ composites used in high-performance energy-storage systems.     

Structure and properties of CaF<Subscript>2</Subscript>–B<Subscript>2</Subscript>O<Subscript>3</Subscript> glasses

FTIR spectroscopy has been employed to investigate the structure of CaF₂–B₂O₃ glasses. It is proposed that CaF₂ partially modifies the borate network forming \textCa _{1 / 2} ²⁺ [\textBO _{3 / 2} \textF] ^- {\text{Ca}}_{ 1 / 2}^{ 2+ } [{\text{BO}}_{ 3 / 2} {\text{F]}}^{ - } units. The rest of CaF₂ is assumed to build an amorphous network formed of CaF₄ tetrahedra. Analysis of density and molar volume revealed that the volume of CaF₄ tetrahedron in the studied glasses is slightly greater than that in the crystalline form. Data of density, molar volume, and electric conductivity have been correlated with the glass structure. As far as the authors know, CaF₂–B₂O₃ glasses are investigated for the first time.