Effects of pH value on the microstructure and magnetic properties of solution combusted Fe3O4 powders

Magnetite (Fe₃O₄) powders were prepared by solution combustion synthesis method using conventional and microwave ignition at various pH values of starting solution, adjusted by NH₄OH. The chelated species in dried gels were predicted by theoretical calculations and Fourier transform infrared spectroscopy. The combustion reaction rate strongly depended on pH values as investigated by thermal analysis. Phase evolution and structure characterized by X-ray diffraction method showed single phase and well-crystalline Fe₃O₄ powders which were achieved using conventional ignition at pH ≥ 7. However, the microwave ignition led to the formation of impure FeO phase together with Fe₃O₄. The microwave combusted powders exhibited the disintegrated structure in comparison with the bulky microstructure for conventionally combusted powders, as observed by scanning electron microscopy. Magnetic properties of the as-combusted powders studied by vibration sample magnetometry showed the highest saturation magnetization of 81.3 emu/g for conventional ignition at pH of 7, due to the high purity and large crystallite size.     

Effect of fuel type on the microstructure and magnetic properties of solution combusted Fe3O4 powders

Porous magnetite (Fe₃O₄) powders were synthesized by solution combustion method using the glycine and urea at different fuel to oxidant ratios (ϕ). The combustion behavior depended on the fuel type as characterized by thermal analysis. The structure and phase evolution investigated by X-ray diffraction method showed nearly single phase Fe₃O₄ powders which were achieved only by using the glycine fuel at ϕ=1. The specific surface area and porous structures of the as-combusted Fe₃O₄ powders were characterized by N₂ adsorption-desorption isotherms and scanning electron microscopy, respectively. The surface area using the glycine fuel (62.6 m²/g) was higher than that of urea fuel (42.5 m²/g), due to different combustion reactions. Magnetic properties of the as-combusted powders were studied by vibration sample magnetometry which exhibited the highest saturation magnetization of 74 emu/g using the glycine fuel at ϕ=1 on account of its high purity and large crystallite size.     

Effects of the fuel type and fuel content on the specific surface area and magnetic properties of solution combusted CoFe2O4 nanoparticles

In this work, the different fuels (citric acid, glycine and urea) at the various fuel to oxidant ratios (ϕ=0.5, 0.75, 1 and 1.25) were used for solution combustion synthesis of CoFe₂O₄ nanoparticles. The phase evolution, microstructure, specific surface area and magnetic properties of the solution combusted CoFe₂O₄ nanoparticles were investigated by X-ray diffraction, thermal analysis, electron microscopy, adsorption-desorption isotherms and vibrating sample magnetometry techniques. The specific surface area of the combusted products decreased with the increase of fuel to oxidant ratio (ϕ), irrespective of the fuel type. However, the specific surface area for the glycine fuel was higher than the others, due to the higher combustion rate for releasing gaseous products. Furthermore, the solution combusted CoFe₂O₄ powders by the glycine fuel exhibited the higher saturation magnetization (63.6 emu/g) on account of their higher crystallinity and particle size.     

Properties of NiFe2O4 ceramics from powders obtained by auto-combustion synthesis with different fuels

Nickel ferrite (NiFe₂O₄) powders derived by auto-combustion synthesis using three different fuels (citric acid, glycine and dl-alanine) have been characterized. The sintering behavior of ceramics using these powders has been compared. Oxygen balance (OB) setting for the chemical reaction is found to regulate the combustion reaction rate. A rapid reaction rate and a high flame temperature are achieved with dl alanine fuel yielding single phase NiFe₂O₄ powder in the as-burnt stage, whereas powders derived with citric acid and glycine fuels show poor crystallinity and necessitate post-annealing. The powder particles are largely agglomerated with a non-uniform distribution in shape and size, and the average particle size is estimated in the range ~ 54–71 nm. Powders derived from dl-alanine fuel show better phase purity, smaller crystallite size, larger surface area and superior sintering behavior. Additional Raman modes discerned for dl-alanine derived powder support a 1:1 ordering of Ni²⁺ and Fe³⁺ at the octahedral sites relating to microscopic tetragonal P4₁22 symmetry expected theoretically for the formation of NiFe₂O₄ with inverse spinel structure. Microstructure of sintered ceramics depends on the precursor powders that are used and sintering at 1200 °C is found to be optimum. Citric acid and glycine derived powders yield high saturation magnetization (M_s~47–49 emu/g), but poor dielectric properties, whereas dl-alanine derived powders yield ceramics with high resistivity (~3.4×10⁸ Ω cm), low dielectric loss (tan δ~0.003 at 1 MHz) and high magnetization (46 emu/g). Dielectric dispersion and impedance analysis show good correlation with the changes in the ceramic microstructure.     

A comparative study of the magnetic and microwave properties of Al3+ and In3+ substituted Mg–Mn ferrites

The effect of substitution of diamagnetic Al³⁺ and In³⁺ ions for partial Fe³⁺ ions in a spinel lattice on the magnetic and microwave properties of magnesium–manganese (Mg–Mn) ferrites has been studied. Three kinds of Mg–Mn based ferrites with compositions of Mg_0.9Mn_0.1Fe₂O₄, Mg_0.9Mn_0.1Al_0.1Fe_1.9O₄, and Mg_0.9Mn_0.1In_0.1Fe_1.9O₄ were prepared by the solid-state reaction route. Each mixture of high-purity starting materials (oxide powders) in stoichiometric amounts was calcined at 1100 °C for 4 h, and the debinded green compacts were sintered at 1350 °C for 4 h. XRD examination confirmed that the sintered ferrite samples had a single-phase cubic spinel structure. The incorporation of Al³⁺ or In³⁺ ions in place of Fe³⁺ ions in Mg–Mn ferrites increased the average particle size, decreased the Curie temperature, and resulted in a broader resonance linewidth as compared to un-substituted Mg–Mn ferrites in the X-band. In this study, the In³⁺ substituted Mg–Mn ferrites exhibited the highest saturation magnetization of 35.7 emu/g, the lowest coercivity of 4.1 Oe, and the highest Q×f value of 1050 GHz at a frequency of 6.5 GHz.     

Synthesis of BSCF perovskites using a microwave-assisted combustion method

Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−Δ (BSCF) perovskite-type oxide was synthesized using a microwave-assisted combustion method. Following about 10 min of exposure to microwave, the combustion reaction was self-ignited and it produced a porous powder. For comparison, BSCF perovskite powders were also synthesized by conventional heating. Two different fuel types were used in the two heating methods. The crystalline BSCF powders were characterized using scanning calorimetry and thermogravimetry (DSC/TG), X-ray diffraction (XRD), BET surface area measurement, scanning electron microscopy (SEM), and dilatometric analysis. The microwave heating method resulted in a powder with nanometric crystallites, submicrometric particles, and a specific surface area of 9.93 m²/g, which corresponds to a BET diameter of approximately 100 nm. The dilatometric analysis showed that the microwave-synthesized BSCF powder has the maximum sintering rate at 970 °C, but the sintering process initiates at lower temperatures.     

Microwave sintering of CeO2 and Y2O3 co-stabilised ZrO2 from stabiliser-coated nanopowders

Tetragonal ZrO₂ polycrystalline (TZP) composites with 2 wt.% Al₂O₃ and co-stabilised with 1 mol% Y₂O₃ and (4, 6 or 8) mol% CeO₂ were sintered at 1450 °C for 20 min in a single mode 2.45 GHz microwave furnace. For comparison, conventional sintering was performed in air at 1450 °C for 20 min. The starting powder mixture was obtained by a suspension coating technique using yttrium nitrate, cerium nitrate and pure m-ZrO₂ nanopowder. Fully dense material grades were obtained by both sintering methods. The influence of the composition and the sintering methods on the final phase composition and microstructure were investigated by X-ray diffraction and scanning electron microscopy. Finer and more uniform microstructures were observed in the microwave sintered ceramics when compared to the conventionally sintered samples. The fracture toughness increases with decreasing stabiliser content, whereas a reverse relation was found for the Vickers hardness. Comparable toughness and hardness values were obtained for the microwave and conventionally sintered samples.     

Dielectric and magnetic properties of Nickel ferrite ceramics using crystalline powders derived from DL alanine fuel in sol–gel auto-combustion

Dielectric and magnetic properties of NiFe₂O₄ ceramics prepared with powders using DL-alanine fuel in the sol–gel auto combustion technique are studied. DL-alanine fuel yields crystalline as-burnt powders, and when used for ceramic processing yields varying microstructure at different sintering temperatures. The dielectric properties are influenced by the resulting microstructure and the magnetic properties show slight change in saturation magnetization M_s (~44 – 46 emu/g). The coercive fields, dielectric losses and dispersion are reduced considerably at higher sintering temperatures (1200–1300 °C). The influence of changing microstructure is analyzed through dielectric response, complex impedance analysis and electrical modulus spectroscopy in the frequency range (10⁻²–10⁷ Hz) to understand the interactions from the grain and grain boundary phases. Sintering at 1200 °C, is found to be optimum, yields lower losses & reduced dielectric dispersion, and high resistivity (3.4×10⁸ Ω cm).     

Effect of Pb excess in sol–gel process on phase composition in PFN ceramics

Lead iron niobate Pb(Fe_0.5Nb_0.5)O₃ (PFN) precursors were prepared using sol–gel synthesis by mixing acetates Pb and Fe with Nb-ethylene glycol–tartarate (Pechini) complex at 80 °C and calcination of gels at 600 °C. Single pyrochlore phase with structure close to Pb₃Nb₄O₁₃ was formed in stoichiometric precursor and Pb₃Nb₄O₁₃ with small amount of perovskite phase Pb(Fe_0.5Nb_0.5)O₃ in nonstoichiometric precursor prepared with the excess of Pb in molar ratio (Pb:Fe:Nb = 1.2:0.5:0.5). Average particle sizes of PFN calcined powders were ～120 nm. The metastable pyrochlore phase was partially decomposed to perovskite phase at sintering temperature of 1150 °C for 2, 4 and 6 h. Excess of Pb caused increasing of the density (7.4 g/cm³) and content of the perovskite phase (～53 vol.%) in ceramics sintered for 4 h. In microstructures of PFN ceramics sintered at 1150 °C for different times, the bimodal grain size distribution was observed with small spherical grains of perovskite phase and larger octahedral grains, which represent the pyrochlore phase. Results of EDX analysis confirm that complex types of pyrochlore phases that differ in iron content were present in ceramics.     

The effect of Si–Bi2O3 on the ignition of the Al–CuO thermite

The ignition temperature of the Al–CuO thermite was measured using DTA at a scan rate of 50 °C min^?1 in a nitrogen atmosphere. Thermite reactions are difficult to start as they require very high temperatures for ignition, e.g. for Al–CuO thermite comprising micron particles it is ca. 940 °C. It was found that the ignition temperature is significantly reduced when the binary Si–Bi₂O₃ system is added as sensitizer. Further improvement is achieved when the reagents are nano-sized powders. For the composition Al + CuO + Si + Bi₂O₃ (65.3:14.7:16:4 wt.%), with all components nano-sized, the observed ignition temperature is ca. 613 °C and a thermal runaway reaction is observed in the DTA.     

Synthesis of CoFe2O4 powders with high surface area by solution combustion method: Effect of fuel content and cobalt precursor

High surface area cobalt ferrite (CoFe₂O₄) powders were synthesized by solution combustion method. The dependence of the adiabatic temperature and the released gases during combustion reaction on the fuel content and cobalt precursor type, cobalt nitrate and cobalt acetate, was thermodynamically calculated. Thermal analysis, infrared spectroscopy, X-ray diffractometry, nitrogen adsorption–desorption, electron microscopy and vibrating sample magnetometer were used for investigation of the phase evolution, surface areas, morphology and magnetic properties of the synthesized CoFe₂O₄ powders. The specific surface area decreased from 285.4 to 35.7 m²/g with increasing of fuel to oxidant molar ratio, ϕ, from 0.5 to 1.25 for the cobalt nitrate precursor, while the maximum surface area of 182.1 m²/g was attained at ϕ=1 for the cobalt acetate precursor. The synthesized CoFe₂O₄ powders from the cobalt nitrate precursor exhibited the higher saturation magnetization and coercivity on account of the higher purity and crystallinity.     

Structural and electrical properties of Dy3+ substituted NiFe2O4 ceramics prepared from powders derived by combustion method

Dysprosium (Dy) substituted nickel ferrite (NiDy_xFe_2-xO₄) powders with varying Dy content (x=0.0, 0.025, 0.05, 0.075, 0.1, 0.2) have been prepared by combustion method using DL-alanine fuel. Sintering characteristics of the powders and electrical properties of ceramics have been studied. Effective substitution of Dy³⁺ for Fe³⁺ is seen up to x=0.075 yielding improved properties, and a higher Dy content (x≥0.1) leads to partial substitution, disturbed stoichiometry, and diffusion of Dy to the grain boundaries and segregation as a secondary phase. Increasing Dy content reduces the crystallite size, powder particle size, and grain size in sintered ceramics, and the changing microstructural evolution is better resolved with back scattered electron imaging and compositional analysis. Raman spectroscopy confirms inverse spinel structure formation and substantiates the presence of secondary phase evidenced through X-ray diffraction and electron microscopy. A marginal increase in the electrical resistivity (ρ_dc) and magnetization are observed due to effectual substitution of Dy³⁺ for Fe³⁺ at the octahedral sites up to x=0.075. For x≥0.1, the increasing influence of highly resistive DyFeO₃ secondary phase at the inter-granular boundaries leads to a rapid increase in resistivity and reduction in dielectric losses, and the magnetization is reduced due to the anti-ferromagnetic nature of the secondary phase (DyFeO₃). Dense ceramics with high resistivity (~10⁹ Ω cm), low dielectric loss (tan δ ~0.002) at 1 MHz, and high magnetization (50.07 emu/g) are obtained for an optimum Dy content of x=0.075. Dielectric response, complex impedance, and electrical modulus spectroscopy in the frequency range (10⁻²–10⁶ Hz) reflect the changes in the microstructure, and suggests a non-Debye type relaxation.     

PVA assisted coprecipitation synthesis and characterization of MgFe2O4 nanoparticles

Single phase magnesium ferrite (MgFe₂O₄) nanoparticles were prepared by the coprecipitation method followed by calcination at 700 °C for 1 h. The effects of polyvinyl alcohol (PVA) agent on the structural, microstructure, magnetic properties and AC magnetically induced heating characteristics of MgFe₂O₄ nanoparticles were investigated. The structure and cation distributions investigated by X-ray diffraction method showed single phase MgFe₂O₄ powders had partially inverse spinel structure in which the inversion coefficient increased by adding more PVA. The small particle size and narrow size distribution of the coprecipitated MgFe₂O₄ powders characterized by scanning electron microscopy were achieved using PVA agent. Magnetic properties of MgFe₂O₄ nanoparticles studied by vibrating sample magnetometry showed ferrimagnetic characteristics with the highest saturation magnetization and coercivity of 24.6 emu/g and 17 Oe, respectively. The coprecipitated MgFe₂O₄ nanoparticles assisted by PVA exhibited the lower AC heating temperature of 5.6 °C and specific loss power of 2.4 W/g in comparison with 6.1 °C and 2.7 W/g for the powders coprecipitated without using PVA.     

Promoting role of transition metal oxide on ZnTiO3–TiO2 nanocomposites for the photocatalytic activity under solar light irradiation

Transition metal oxide (Fe₂O₃, Co₃O₄ and CuO) loaded ZnTiO₃–TiO₂ nanocomposites were successfully prepared by solid state dispersion method. The structural, morphological and optical properties of samples were characterized by TGA/DTA, XRD, BET, FT-IR, DRS, PL, XPS and SEM techniques. The photocatalytic activity of samples was investigated by degradation of 4-chlorophenol in water under sunlight. The Fe₂O₃ loaded sample was found to exhibit much higher photocatalytic activity than the other composite powders. 7Fe₂O₃/ZnTi sample has the highest percentage of 4-chlorophenol degradation (100%) and highest reaction rate (1.27 mg L⁻¹ min⁻¹) was obtained in 45 min. The enhancement of photocatalytic activity for ZnTiO₃–TiO₂ sample with Fe₂O₃ addition may be attributed to its small particle size, the presence of more surface OH groups, lower band gap energy than other samples in this paper and the presence of more hexagonal ZnTiO₃ phase in the morphology.     

Electrical characterization of La9.33Si2Ge4O26 oxyapatite for prospective intermediate-temperature solid oxide fuel cells

La_9.33Si₂Ge₄O₂₆ materials have been fabricated from La₂O₃, SiO₂ and GeO₂ powders by high speed mechanical alloying followed by conventional and microwave hybrid sintering at different temperatures and holding times. XRD data showed that the apatite phase is formed after 1 h of mechanical alloying at 850 rpm. This phase remained stable after conventional sintering in an electric furnace with density increasing as sintering temperatures and holding times were increased. However, the highest density was achieved for samples sintered in the microwave furnace (5.44 g cm⁻³), corresponding to a relative density of 98%. The electrical conductivity of the samples microwave sintered at 700 and 800 ºC are 4.72×10⁻³ and 1.93×10⁻² S.cm⁻¹, respectively, with a correspondent activation energy of 0.952 eV.     

Mechanical properties of 2.45 GHz microwave sintered Si3N4–Y2O3–MgO–ZrO2 system

Mechanical properties of 2.45 GHz microwave sintered Si₃N₄–Y₂O₃–MgO–ZrO₂ system have been investigated. Microwave sintered samples exhibited higher hardness compared to conventionally sintered samples. SEM microstructures of microwave sintered samples revealed lower average grain length and width than those of the conventionally sintered samples. Fracture toughness increased with increasing sintering temperature in the case of conventionally sintered samples whereas microwave sintered samples exhibited no variation despite differences in microstructure. The results of present study demonstrated that microwave sintering could influence the microstructure and thereby improve the mechanical properties.     

Capillary rise properties of porous mullite ceramics prepared by an extrusion method using organic fibers as the pore former

Porous mullite ceramics with unidirectionally oriented pores were prepared by an extrusion method to investigate their capillary rise properties. Rayon fibers 16.5 μm in diameter and 800 μm long were used as the pore formers by kneading with alumina powder, kaolin clay, China earthen clay and binder with varying Fe₂O₃ contents of 0, 5 and 7 mass%. The resulting pastes were extruded into cylindrical tubes (outer diameter (OD) 30–50 mm and inner diameter (ID) 20–30 mm), dried at room temperature and fired at 1500 °C for 4 h. The bulk densities of the resulting porous ceramics ranged from 1.31 to 1.67 g/cm³, with apparent porosities of 43.2–59.3%. The pore size distributions measured by Hg porosimetry showed a sharp peak at 10.0 μm in the sample without Fe₂O₃ and at 15.6 μm in the samples containing Fe₂O₃; these pores, which arose from the burnt-out rayon fibers, corresponded to total pore volumes ranging from 0.24 to 0.34 ml/g. SEM showed a microstructure consisting of unidirectionally oriented pores in a porous mullite matrix. Prismatic mullite crystals were well developed on the surfaces of the pore walls owing to the liquid phase formed by the Fe₂O₃ component added to color the samples. The bending strengths of the tubular samples ranged from 15.6 to 26.3 MPa. The height of capillary rise, measured under controlled relative humidities (RH) of 50, 65 and 85%, was greater in the ceramics containing Fe₂O₃ than in those without Fe₂O₃, especially in the thinner samples. The maximum capillary rise reached about 1300 mm, much higher than previously reported. This excellent capillary rise ability is thought to be due to the controlled pore size, pore distribution and pore orientation in these porous mullite ceramics.     

Structure and properties of nanostructured Fe(AlCr)2O4–Cr–(AlCr)2O3–Fe composite coating prepared by plasma spraying

In-situ nanostructured Fe(AlCr)₂O₄-based composite coating (FACr_52.5 coating) was prepared by reactive plasma spraying with micro-sized Al–Fe₂O₃–Cr₂O₃ powders. The microstructure, toughness and Vickers hardness, and adhesive strength of the coating were investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and mechanical tests. The results indicated that the interlamellar spacing of the FACr_52.5 coating is only 1 μm. The coating exhibited nanostructured microstructure. The in-situ Cr (20 nm) and Fe (50–200 nm) particles were uniformly distributed in an Fe(AlCr)₂O₄ matrix, while the grain size of the Fe(AlCr)₂O₄ matrix is about 60 nm. The FACr_52.5 composite nano-coating exhibited much higher hardness, better wear resistance, stronger adhesive strength and toughness as compared to those of the composite nano-coating sprayed with Fe₂O₃–Al powders. Excellent mechanical properties of the FACr_52.5 coating were attributed to the uniform distribution of the in-situ nano-sized Cr particles in the coating matrix.     

Enhancement of the interfacial polarization resistance of La0.6Sr0.4Co0.2Fe0.8O3-δ cathode by microwave-assisted combustion method

Thermogravimetry, phase formation, microstructural evolution, specific surface area, and electrical properties of La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF) cathode were studied as functions of its preparation technique. The pure perovskite LSCF cathode powder was synthesized through glycine–nitrate process (GNP) using microwave heating technique. Compared with conventional heating technique, microwave heating allows the rapid combustion to occur simultaneously between the nitrates and glycine in a controllable manner. The resulting powder is a single-phase nanocrystallite with a mean particle size of 113 nm and a high specific surface area of 12.2 m²/g, after calcination at 800 °C. Impedance analysis indicates that microwave heating has significantly reduced the polarization resistance of LSCF cathode. The area specific resistance (ASR) value of 0.059 and 0.097 Ω cm² at 800 °C and 750 °C, respectively, were observed. These values were twofold lower than the corresponding ASR of the cathode (0.133 and 0.259 Ω cm² at 800 °C and 750 °C, respectively) prepared through conventional heating. Results suggest that the microwave heating GNP strongly contributes to the enhancement of the LSCF cathode performance for intermediate temperature solid oxide fuel cells.     

Red-brown ceramic pigments based on chromium doped ferrian armalcolite,effect of mineralizers

A new red-brown ceramic pigment based on chromium-doped ferrian armalcolite have been synthesized and characterized. (MgFe)(Cr_xTi_3−xFe)O₁₀ powders (x=0–0.3) fired at 1200 °C crystallize ferrian armalcolite as the only crystalline phase detected. Samples fired at 1000 °C show red-brown shades in glazes that darken and bluish (b* turns to negative values) at 1200 °C. The x=0.2 sample fired at 1000 °C shows the best red colour (L*a*b*=49.5/15.2/10.3). Assignment of bands in the UV–Vis–NIR spectra is difficult due to the overlapping of Cr³⁺, Cr⁴⁺ and Fe³⁺ absorptions in octahedral coordination. Analysis of UV–Vis–NIR spectra of powders shows that these spectra are dominated by the strong absorption associated to Fe³⁺ ions in octahedral sites. In contrast, an intense band at 520 nm dominates the UV–Vis–NIR spectra of glazed samples, which should be associated to Cr⁴⁺ in octahedral coordination. This absorption increases when the amount of chromium increases, indicating that chromium is the real chromophore of the system. Finally, the weak shoulder at 600 nm and the double weak band at 700 nm, detected more evidently when chromium amount in sample increases, indicate the progressive presence of Cr³⁺ in octahedral sites. The entrance of Cr⁴⁺ in x=0.1 sample shrinks the crystalline cell, but when chromium amount in the samples increases, both Cr⁴⁺ and Cr³⁺enter simultaneously and the unit cell remains practically stable. The microstructure of the powders analysed by SEM microscopy indicates aggregates of 6–10 fine particles of 200–400 nm of diameter. The addition of mineralizers (boric acid, sodium perborate, NaF and a mixture BaF₂.4MgF₂) does not modify significantly the reactivity of the system; at 1000 °C hematite and rutile remain as residual crystalline phases, except in NaF additions where the crystallization of NaFeTi₃O₈ is detected. SEM-EDX mapping analyses of pigment powders confirm in all cases a homogeneous distribution of ions in the particles.