Reactive flash sintering and electrical transport properties of high-entropy (MgCoNiCuZn)1-xLixO oxides

In this paper, high-entropy (MgCoNiCuZn)_1-xLi_xO oxides (x = 0, 0.1, 0.15, 0.2, and 0.3) were synthesized via reactive flash sintering (RFS), and the effect of RFS process on the microstructure and electrical property of the materials were studied. The Li-doped materials exhibited a mixed ionic–electronic transport behavior. The oxidation of Co²⁺ into Co³⁺ upon Li incorporation into the materials synthesized via the conventional solid-state reaction route was not evidenced in the flash sintered materials. Instead, the charge unbalance in the Li-doped materials synthesized via RFS was compensated by oxygen vacancies and holes in the valence band of the oxides, which were accounted for the ionic conduction and electronic conduction, respectively. The ionic conductivity increased upon increasing the Li concentration as more oxygen vacancies were formed. The attraction between defects with different charges (Li_M^/ and V_O^••), which formed defect complexes, led to a decrease in the mobility of the defects, thus resulting in a less pronounced increase in the ionic conductivity at high Li concentrations. The change in the charge compensation mechanism of the materials indicates that the microstructure of such kind of oxides could be altered through RFS, and thus the property may be manipulated.     

Electrical Properties of Triethylene Glycol Stabilized MnxCo1-xFe2O4 Nanoparticles

We reported on the synthesis and analysis of the composition, micro-structure, ac–dc conductivity performance and dielectric permittivity of triethylene glycol (TEG) stabilized Mn_xCo_1-xFe₂O₄ nanoparticles obtained by polyol method. Crystallite size from XRD and particle size from TEM micrographs are consistent with each other. Conductivity measurements were performed to investigate the influence of the coating with TEG on the conduction characteristics of Mn_xCo_1-xFe₂O₄ NP’s. The frequency-dependency of the ac conductivity shows electrode polarization effect. The dc conductivity is strongly temperature dependent and shows maximum conductivity of about 5 × 10^?5 S cm^?1 for x = 1.0 at 120 °C. Analysis of dielectric permittivity functions suggests that ionic and polymer segmental motions are strongly coupled.     

Zinc substitution effect on the structural,spectroscopic and electrical properties of nanocrystalline MnFe2O4 spinel ferrite

This paper reports the structural, morphological, spectroscopic, dielectric, ac conductivity, and impedance properties of nanocrystalline Mn_1-xZn_xFe₂O₄. The nanocrystalline Mn–Zn ferrites were synthesized using a solvent-free combustion reaction method. The structural analysis using X-ray diffraction (XRD) pattern reveals the single-phase of all the samples and the Rietveld refined XRD patterns confirmed the cubic-spinel structure. The calculated crystallite size values increase from 8.5 nm to 19.6 nm with the Zn concentration. The surface morphological analysis using field emission scanning electron microscopy and the transmission electron microscopy confirms the nano size of the prepared ferrites. X-ray photoelectron spectroscopy was used to study the ionic state of the atoms present in the samples. Further, the high-resolution Mn 2p, Zn 2p, Fe 2p, and O 1s spectra of Mn_1-xZn_xFe₂O₄ does not result in the appearance of new peaks with Zn content, indicating that the Zn substitution does not change the ionic state of Mn, Zn, Fe, and O present in nanocrystalline Mn_1-xZn_xFe₂O₄. The investigated electrical properties show that the dielectric constant, tan δ and ac conductivity gradually decrease with increasing Zn substitution and the sample Mn_0·2Zn_0·8Fe₂O₄ has the lowest value of conductivity at 303 K. The ac conductivity measured at different temperatures shows the semiconducting nature of the ferrites. The impedance spectra analysis shows that the contribution of grain boundary is higher compared with the grain to the resistance. The obtained results suggest that the Zn substituted manganese ferrite nanoparticles can act as a promising candidate for high-frequency electronic devices applications.     

Structural,magnetic and magnetostrictive properties of Co1-xLixFe2O4 synthesized by cathode materials of spent Li-ion batteries

In this study, we investigated the effects of substituting Li⁺ for Co²⁺ at the B sites of the spinel lattice on the structural, magnetic and magnetostrictive properties of cobalt ferrites. The Li⁺ substituted cobalt ferrites, Co_1-xLi_xFe₂O₄, with x varying from 0 to 0.7 in 0.1 increments, were synthesized with a sol-gel auto-combustion method using the cathode materials of spent Li-ion batteries. X-ray diffraction analysis revealed that all the Co_1-xLi_xFe₂O₄ nanopowders had a single-phase spinel structure and the lattice parameters decreased with increasing Li⁺ content, which can be proved by slight shifts towards higher diffraction angle values of the (311) peak. Field emission scanning electron microscopy was used to observe the fractured inner surface of the sintered cylindrical rods and the increased porosity resulted in a decreased magnetostriction. The oxidation states of Co and Fe in the cobalt ferrite samples were examined by X-ray photoelectron spectroscopy. High resolution transmission electron microscopy micrographs showed that most particles were roughly spherical and with sizes of 25–35?nm. Li⁺ substitution had a strong effect on the saturation magnetization and coercivity, which were characterized with a vibrating sample magnetometer. The Curie temperature was reduced due to the decrease in magnetic cations and the weakening of the exchange interactions. The magnetostrictive properties were influenced by the incorporation of Li⁺ at the B sites of the spinel structure and correlated with the changes in porosity, magnetocrystalline anisotropy and the cation distribution.     

Zirconium substituted spinel nano-ferrite Mg0.2Co0.8Fe2O4 particles and their hybrids with reduced graphene oxide for photocatalytic and other potential applications

Zirconium substituted magnesium cobalt ferrite (Zr_xMg_0.2-xCo_0.8-xFe₂O₄) nanoparticles and their nano-heterostructures with graphene were synthesized by co-precipitation and ultra-sonication route respectively. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopic (SEM) analysis was done to study the effect of Zr⁴⁺ substitution on structural properties, surface morphology, dielectric and current-voltage properties of nanoparticles. The crystallite size of nanoparticles was found in the range of 23–28 nm. XRD pattern analysis confirmed the spinel structure of nanoparticles. Graphene synthesized by modified Hummer's method was utilized as substrate to prepare the heterostructures with ferrite particles. Dispersion of nanoparticles on the surface of rGO sheets was confirmed by SEM analysis. Enhanced photocatalytic activity of nanoparticles and graphene based nano-heterostructures was observed under visible light irradiation. During the current-voltage measurements, decrease in electrical resistivity of nanoparticles was observed. Dielectric measurements were performed within the frequency range 1 MHz–3 GHz. Electrochemical impedance spectroscopy was done to evaluate the kinetic parameters and charge-transfer resistance (R_ct) at electrode interface. Enhanced photocatalytic applications, suggested that Zr_xMg_0.2-xCo_0.8-xFe₂O₄ nanoparticles and graphene based nano-heterostructures can be used for degradation of various organic based pollutants in drinking water.     

Nanostructured quaternary Ni1-xCuxFe2-yCeyO4 complex system: Cerium content and copper substitution dependence of cation distribution and magnetic-electric properties in spinel ferrites

Quaternary Ni_1-xCu_xFe_2-yCe_yO₄ complex nano-ferrites system with different cerium content ratio and copper substitution degree were synthesized via co-precipitation wet chemical technique. The newly obtained nanoparticles, with general formula Ni_1-xCu_xFe_2-yCe_yO₄ (where x = 0.0, 0.3, 0.6 and y = 0.00, 0.03, 0.05, 0.08 and 0.10) were heated up to 600 °C to stabilize the specific crystalline spinel structure. The limit of cerium content was quantitively determined to be around 0.08 and up to 0.10. Furthermore, the powders were pelletized in a 13 mm wide pellets and thermally treated at 950 °C. The thermal treatment affected even more the phases segregation process, as CeO₂ was identified in the sample with lowest degree of cerium insertion – 0.03. Also, a difference in color and size of pelletized samples was noticed after the 950 °C thermal treatment. The Rietveld refinement, crystal structure confirmation, morphology magnetic and electrical properties of samples have been deeply studied. The cation distribution carried out from Rietveld refinement confirms the occupancy of (Fe³⁺) on tetrahedral sites and [Ni²⁺], [Cu²⁺], [Fe³⁺] and [Ce²⁺] on octahedral sites in the crystal lattice. Preliminary information regarding the cation distribution in spinel structures were suggested by FTIR spectral results, precisely in the 650-520 cm^?1 region, as a consequence of peak shape and lack of shiftiness of M^Td – O bond. Spherical-shaped quaternary nano-ferrites of 17–28 nm were determined from FE-SEM analysis and the samples composition was confirmed by EDX analysis. Hysteresis loops shows modifications in coercivity, magnetization and magnetic remanence with Ni²⁺ and Cu²⁺ ions doping in Ni_1-xCu_xFe_2-yCe_yO₄ complex systems with typical ferrimagnetic behavior. Dielectric measurements were employed in order to determine the electrical permittivity, dielectric losses and conductivity values in a 10 Hz – 1 MHz frequency range.     

Structural and electrochemical characteristics of Li4−xAlxTi5O12 as anode material for lithium-ion batteries

Al-doped Li₄Ti₅O₁₂ in the form of Li_4−xAl_xTi₅O₁₂ (x = 0, 0.05, 0.1 and 0.2) was synthesized via solid state reaction in an Ar-flowing atmosphere. Al-doping does not change the phase composition and particle morphology, but easily results in the lattice distortion and thus the poor crystallinity of Li₄Ti₅O₁₂. Al-doping decreases the specific capacity of Li₄Ti₅O₁₂, while improves remarkably its cycling stability at high charge/discharge rate. The substitution of Al for Li site can enhance the electronic conductivity of Li₄Ti₅O₁₂ via the generation of mixing Ti⁴⁺/Ti³⁺, whereas impede the Li-ion diffusion in the lattice. Excessive Al causes large electrode polarization due to the lower Li-ion conductivity, and thus leads to low specific capacity at high current densities. Li_3.9Al_0.1Ti₅O₁₂ exhibits a relatively high specific capacity and an excellent cycling stability.     

Ca and Pr substitution promoted the cell performance in LnSr3Fe3O10-δ cathode for solid oxide fuel cells

The substitution of Ca for Sr in the LnSr_3-xCa_xFe₃O_10-δ (x = 0–1.5, Ln = La, Pr, and Sm), Ruddlesden-Popper (RP) intergrowth structure was investigated to determine how the physical and electrochemical properties of this potential cathode material in solid oxide fuel cells (SOFCs) are impacted. A small amount of Ca incorporated into the structure reduced the thermal expansion coefficient, improved the electrical conductivity, and increased power density by up to 30% of a La_0.8Sr_0.2Ga_0.8Mg_0.2O₃ electrolyte-supported single cell. The microstructure and oxygen permeability of the materials were independent of Ca substitution. A phase transformation of LaSr_3-xCa_xFe₃O_10-δ to perovskite was observed when the Ca composition of x > 1.0. Among the substitution of Pr and Sm for La in LaSr_2.7Ca_0.3Fe₃O_10-δ, only PrSr_2.7Ca_0.3Fe₃O_10-δ was pure with no phase transformation found. The co-substitution of Pr and Ca promoted the reduction of Fe, enhanced the oxygen permeation and active surface, and diminished the contact resistance at the cathode-electrolyte interlayer. The co-substitution of Ca and Pr delivered good electrochemical performance of approximately 354 mWcm⁻² at 800 °C on a 0.3 mm thick La_0.8Sr_0.2Ga_0.8Mg_0.2O₃ electrolyte-supported cell and the lowest area specific resistance (ASR).     

New Li solid electrolytes

New Li-ion conductors with several different structure types are reported. Li₄B₇O₁₂(Cl,Br) and LiM₂P₃O₁₂ (MZr, Hf) have framework structures. The others are based on structures with isolated polyhedra in a network of edge-linked Li polyhedra and include Li_2+xC_1?xB_xO₃, Li_3?x B_1?xC_xO₃, Li_4+xSi_1?xSi_1?xAl_xO₄, Li_4?xSi_1?xP_xO₄, Li_4?2xSi_1?xS_xO₄ and Li _5?xAl_1?xSi_xO₄. Li_0.8Zr_1.8 Ta_0.2P₃O₁₂ has the best room temperature conductivity, ～5 × 10^?6 (Ωcm)_?1. At 300°C, the conductivities of Li_3.75Si_0.75P_0.25O₄, Li_3.4Si_0.3O₄ and Li_2.25C_0.75B_0.25O₃ are 1 × 10^?2 (Ωcm)^?1. These compositions resist attack by molten li at 200°C and some can be easily prepared as dense ceramics.     

Thermal radiation and cycling properties of (Ca,Fe) or (Sr,Mn) co-doped La2Ce2O7 coatings

La₂Ce₂O₇ with low thermal conductivity as a potential candidate of thermal barrier coatings (TBCs) was co-doped with (Ca, Fe) or (Sr, Mn) in order to further improve its thermal radiation at high temperatures. The microstructure, chemical composition, infrared emission properties (reflection and absorption properties) and thermal cycling lifetime of the coatings were respectively investigated. The results revealed that La_2-xCa_xCe_2-xFe_xO₇₊δ and La_2-xSr_xCe_2-xMn_xO₇₊δ coatings had defected fluorite structure and their infrared emittances were much higher than that of the parent La₂Ce₂O₇. The superior infrared emission could be ascribed to the enhancement of the intrinsic absorption (electron transition absorption), free-carrier absorption and impurity absorption as well as lattice vibration absorption. However, the thermal cycling lifetime of La₂Ce₂O₇ coatings presented a reduction after the (Ca, Fe) or (Sr, Mn) substitution, primarily due to the decrease in the fracture toughness and the increase in the thermal conductivity.     

Enhanced Li-ion conductivity of strontium doped Li-excess garnet-type Li7+xLa3-xSrxZr2O12

The mechanism underlying the enhancement of the conductivity of Li₇La₃Zr₂O₁₂ (LLZO), an oxide-based solid electrolyte that contains excess Li, was experimentally investigated through subvalent cation substitution. We prepared Sr-substituted Li-rich LLZO with high conductivity of the order of 10⁻⁴ S/cm by using a solid-state method. We investigated the mechanism underlying the conductivity enhancement via detailed structural analysis through Sr K-edge X-ray absorption near edge spectroscopy and X-ray diffraction and neutron powder diffraction analyses. The results suggested that the conductivity enhancement is due to the change in Li⁺ arrangement caused by the incorporation of excess Li into the LLZO lattice.     

Novel Bi4O5Br2/MnxZn1-xFe2O4 magnetic composite with an enhanced photodegradation activity and excellent recyclability

Bi₄O₅Br₂/Mn_xZn_1-xFe₂O₄ nanocomposites with impressive photocatalytic and recyclability properties were synthesised using a microemulsion method. In addition to the photocatalytic effect, the crystal structure and morphology, photoelectrochemical characteristics, magnetic effect and photocatalytic mechanism of Bi₄O₅Br₂/Mn_xZn_1-xFe₂O₄ were also investigated. As the best sample, the removal rate of the Bi₄O₅Br₂/Mn_xZn_1-xFe₂O₄ photocatalyst with 7.5 wt% Mn_xZn_1-xFe₂O₄ to rhodamine B (RhB) reached up to 99.4% within 60 min. The enhanced photocatalyst activity was mainly attributed to the type-II heterojunction formed between Bi₄O₅Br₂ and Mn_xZn_1-xFe₂O₄, which not only optimised the energy band structure, but also led to the building of an interior electromagnetic field within the Bi₄O₅Br₂/Mn_xZn_1-xFe₂O₄ heterojunction. Meanwhile, the constantly producing and migrating h⁺ and ·O₂^? were the main active components. In particular, the results of the saturation magnetization tests and magnetic recovery experiments revealed that the magnetic composite photocatalyst can be recovered effectively. The results of the removal rate of RhB remaining at 85.2% after five uses reflected the advantages of the stability of the Bi₄O₅Br₂/Mn_xZn_1-xFe₂O₄ photocatalyst. In brief, this paper presented an original idea to develop a novel composite magnetic photocatalyst and research the enhancement mechanism of photocatalysis.     

Transport properties of p-type Ca3-xLnxCo4O9-Ag (Ln = Lu,Yb; 0.1≤x≤0.2) oxides

Thermoelectric transport properties of p-type Ca_3-xLn_xCo₄O₉/yAg oxides (Ln = Lu & Yb; 0.1 ≤ x ≤ 0.2; 0.05 ≤ y ≤ 0.1) synthesized by sol-gel methodology were investigated in this paper. The structural analyses (SEM, XRD and TEM) confirmed the presence of two phases, viz, Ca_3-xLn_xCo₄O₉ and Ag-metallic phases. The contribution of rare earth doping in one hand and presence of Ag as secondary phase on the other hand were studied. The resistivity measurements indicated the reduction of electrical resistance at the grain boundary leading to an overall decrease in electrical resistivity with increasing Ag-concentration. The enhancement of Seebeck coefficient is attributed to the substitution of Ln³⁺ at Ca²⁺ sites that in turn reduces hole concentration through formation Co³⁺ for charge concentration counter balance in Ca_3-xLn_xCo₄O₉/yAg matrix. The tuning of electrical transport properties through Ca_3-xLn_xCo₄O₉ and Ag-metallic bi-phasic formation resulted high power factor of 582 μW m⁻¹ K⁻² for Ca_2.8Ln_0.2Co₄O₉/0.05Ag and 548 μW m⁻¹ K⁻² for Ca_2.8Yb_0.2Co₄O₉/0.05Ag at 950 K highlighting its potential application on small scale energy harvesting to power sensor and wireless sensor network where requirement of power is in the milliwatt range.     

Effects of W6+ substitution on crystal structure and microwave dielectric properties of Li3Mg2NbO6 ceramics

Li₃Mg₂(Nb_1-xW_x)O_6+x/2 (0 ≤ x ≤ 0.08) ceramics were synthesized by the solid-state reaction route. The effects of W⁶⁺ substitution on the phase composition, microstructure and microwave dielectric properties of Li₃Mg₂NbO₆ ceramics were investigated systematically. The XRD results showed that all the samples formed a pure solid solution in the whole doping range. The SEM iamges and relative density revealed the dense structure of Li₃Mg₂(Nb_1-xW_x)O_6+x/2 ceramics. The relationship between the crystal structure and dielectric properties of Li₃Mg₂(Nb_1-xW_x)O_6+x/2 ceramics was researched through polarizability, average bond valence, and bond energy. The substitution of W⁶⁺ for Nb⁵⁺ in Li₃Mg₂(Nb_1-xW_x)O_6+x/2 ceramics significantly promoted the Q × f values. In addition, the increase of W⁶⁺ content improved the thermal stability of the Li₃Mg₂(Nb_1-xW_x)O_6+x/2 ceramics. The Li₃Mg₂(Nb_0.94W_0.06)O_6.03 ceramics sintered at 1175 °C for 6h possessed excellent properties: ε_r ~ 15.82, Q × f ~ 124,187 GHz, τ_f ~ −18.28 ppm/°C.     

Mn1-xCuxO2/ reduced graphene oxide nanocomposites: Synthesis,characterization, and evaluation of visible light mediated catalytic studies

The narrow optical band gap, higher electrical conductivity, and wider-absorption range are three key features that a good photocatalyst must possess. Herein, we have fabricated Cu-doped MnO₂ (Mn_1-xCu_xO₂) nanostructure by facile wet chemical approach and formed its nanocomposite with r-GO (Mn_1-xCu_xO₂/r-GO) via ultra-sonication approach. The successful replacement of host metal ions (Mn⁴⁺) with the dopant metal ions (Cu²⁺) was supported with the PXRD, FT-IR, and EDX characterizations. The effect of Cu-doping on the band gap and r-GO matrix on the conductivity of the fabricated nanocomposite was also evaluated via Tauc plots and I–V tests, respectively. The photocatalytic efficiency of the fabricated photocatalysts was tested and compared against the methylene blue (MB) under visible light irradiation. The photocatalytic experiments revealed that Mn_1-xCu_xO₂/r-GO photocatalyst exhibited superior photocatalytic aptitude than that of pristine MnO₂ and Mn_1-xCu_xO₂ photocatalysts. More precisely, the Mn_1-xCu_xO₂ photocatalysts degraded 86.89% MB dye at the rate of 0.021 min^?1 after a 90-min exposure to the visible light. Observed superior catalytic activity of the nanocomposite can be attributed to the synergistic effects between the Cu doped MnO₂ and r-GO nanosheets that resulted in its narrow band-gap (2.19 eV) and excellent conductivity (2.217 × 10^?2 Scm^?1).     

Effects of B-site ion (M) substitution on the ionic conductivity of (Li3xLa2/3−x)1+y/2(MyTi1−y)O3 (M=Al, Cr)

Effect on the ionic conductivity of B-site ion (M) substitution in (Li_3xLa_2/3−x)_1+y/2M_yTi_1−yO₃ (M=Al, Cr) has been investigated. It has been found that partial substitution of smaller Al³⁺ for Ti⁴⁺ is effective to enhance the ionic conductivity of Li_3xLa_2/3−xTiO₃. At 300 K, the maximum bulk conductivity of (1.58±0.01)×10⁻³ S cm⁻¹ is observed from the composition of (Li_0.39La_0.54)_1−y/2Al_yTi_1−yO₃ with y=0.02 (x=0.13), that is the highest yet reported for known perovskite solutions at room temperature. The conductivity enhancement is interpreted as being due to the substitution-induced bond-strength change rather than due to bottleneck size change for Li migration, TiO₆-octahedron tilting or A-site cation ordering.     

Effect of doping on dielectric and optical properties of barium hexaferrite: Photocatalytic performance under solar light irradiation

A series of Co-doped and Cr-doped Ba_1-xCo_xFe_12-yCr_yO₁₉ nanoparticles (NPs) were synthesized via the microemulsion route. The effects of Co and Cr substitution on the structural, dielectric, optical, and photocatalytic properties of the NPs were investigated. The Ba_1-xCo_xFe_12-yCr_yO₁₉ NPs were characterized using Fourier-transform infrared spectroscopy, X-ray diffraction analysis, scanning electron microscopy, Raman scattering, and dielectric measurements. The Ba_1-xCo_xFe_12-yCr_yO₁₉ NPs were obtained in a single phase with an average crystallite size of 18 nm. The dielectric constant of the NPs decreased, while the dielectric loss and tangent loss increased with increasing dopant (Co and Cr) contents. The photocatalytic activities (PCAs) of the Ba_1-xCo_xFe_12-yCr_yO₁₉ and BaFe₁₂O₁₉ NPs were appraised by carrying out the degradation of CV (crystal violet) dye under solar light irradiation. The doping improved the PCA of BaFe₁₂O_19, and up to 64.23% of the CV dye could be degraded within 60 min under visible light irradiation. The Ba_1-xCo_xFe_12-yCr_yO₁₉ NPs showed great potential for application as an economic photocatalyst as they required solar light irradiation for the degradation of CV.     

Rietveld refinement,Raman, optical,dielectric, Mössbauer and magnetic characterization of superparamagnetic fcc-CaFe2O4 nanoparticles

This article describes synthesis of superparamagnetic fcc-CaFe₂O₄ nanoparticles by a metal nitrate-citrate monohydrate sol–gel route and characterization using X-ray diffractometry, Raman spectroscopic, UV–Vis–NIR optical absorption spectroscopic, Mössbauer spectroscopy, dielectric and SQUID magnetometry measurements. Rietveld refinement of the X-ray diffraction pattern and observation of active A_1?g, T_2?g & E_g modes in the Raman spectrum confirmed formation of single phase CaFe₂O₄ nanoparticles in the spinel ferrite type fcc structure without impurity. Mössbauer and Rietveld data analysis revealed that nanocrystalline CaFe₂O₄ is dominantly an inverse ferrite in which 85% Ca atoms preferentially occupy the octahedral site in the fcc symmetry and the Fe ions are in high spin Fe⁺³ state. Nanocrystalline CaFe₂O₄ significantly absorbs optical light below 500?nm and the direct band gap energy is estimated to ~1.83?eV, which is higher than 1.26?eV reported for orthorhombic CaFe₂O₄. Temperature and field dependent magnetic studies showed that fcc-CaFe₂O₄ nanoparticles exhibit superparamagnetism at room temperature with high saturation magnetization of 1.07μ_B. The blocking temperature is ~53?K at 1000?Oe and ~72?K at 500?Oe clearly shows lowering of blocking temperature at higher magnetic field. Interestingly below the blocking temperature at 20?K, CaFe₂O₄ nanoparticles behave as non collinear soft-ferrimagnetic material with a saturation magnetization of 1.16 μ_B, coercivity of 150?Oe and remanence of 4.45?emu/g. The magnetic momenta of Fe⁺³ ions residing at the octahedral sub-lattice are canted at ~25?°.     

Synthesis and analysis of structural,compositional, morphological,magnetic, electrical and surface charge properties of Zn-doped nickel ferrite nanoparticles

Zn-doped nickel ferrite nanoparticles (Zn_xNi_(1-x)Fe₂O₄) were synthesized using the co-precipitation technique. The structural and compositional studies of the Zn_xNi_(1-x)Fe₂O₄ nanoparticles revealed their face-centred cubic spinel structure and an appropriate amount of Zn doping in nickel ferrite nanoparticles, respectively. The morphological analysis had been carried out to obtain the particle size of the synthesized nanoparticles. The magnetic studies revealed the superparamagnetic nature of the Zn_xNi_(1-x)Fe₂O₄ nanoparticles, and the maximum magnetization of 30 emu/g for the Zn_0.2N_0.8Fe₂O₄ sample. The M ? H curves were fitted with the Langevin function to obtain the magnetic particle diameter of Zn_xNi_(1-x)Fe₂O₄ nanoparticles. The electrical conduction in Zn_xNi_(1-x)Fe₂O₄ nanoparticles was explained through the Verway hopping mechanism. The Zn_0.2N_0.8Fe₂O₄ nanoparticle exhibited a higher electrical conductivity of 42 μS/cm and surface charge of ?29/7 mV due to the enhanced hopping of Fe³⁺ ions in the octahedral sites. Owing to this nature, they were identified as the suitable candidates in the applications such as thermoelectrics, hyperthermia, magnetic coating and for the preparation of conducting ferrofluids.     

Synthesis and characterization of Ca3-xLaxCo4-yCuyO9+δ cathodes for intermediate temperature solid oxide fuel cells

The calcium cobaltite Ca_3-xLa_xCo_4-yCu_yO_9+δ with x and y = 0 and 0.1 were synthesized and the electrical, thermal, and catalytic behaviors for the oxygen reduction reaction (ORR) for use as air electrodes in intermediate-temperature solid oxide fuel cells (IT-SOFCs) were evaluated. X?ray diffraction confirms the Ca_3-xLa_xCo_4-yCu_yO_9+δ samples were crystallized in a monoclinic structure and scanning electron microscopic image shows lamella-like grain formation. Introduction of dopants decreases slightly the loss of lattice oxygen and thermal expansion co-efficient. The Ca_3-xLa_xCo_4-yCu_yO_9+δ samples exhibit good phase stability for long-term operation, thermal expansion, and chemical compatibility with the Ce_0.8Gd_0.2O_2-δ electrolyte. Among the studied samples, Ca_2.9La_0.1Co₄O_9+δ shows a maximum conductivity of 176 Scm^?1 at 800 °C. Although the doped samples exhibit a higher total electrical conductivity, an improved symmetrical cell performance is displayed by the undoped sample. Comparing the sintering temperatures, the composite cathode Ca₃Co₄O_9+δ + Ce_0.8Gd_0.2O_2-δ sintered at 800 °C exhibit the lowest area specific resistance of 0.154 Ω cm² at 800 °C in air. In the Ca_3-xLa_xCo_4-yCu_yO_9+δ + GDC composite cathodes, the charge-transfer process at high frequencies presents a major rate limiting step for the oxygen reduction reaction.