Hydrothermal phase transformation of hematite to magnetite

Different phases of iron oxide were obtained by hydrothermal treatment of ferric solution at 200°C with the addition of either KOH, ethylenediamine (EDA), or KOH and EDA into the reaction system. As usually observed, the α-Fe₂O₃ hexagonal plates and hexagonal bipyramids were obtained for reaction with KOH and EDA, respectively. When both KOH and EDA were added into the reaction system, we observed an interesting phase transformation from α-Fe₂O₃ to Fe₃O₄ at low-temperature hydrothermal conditions. The phase transformation involves the formation of α-Fe₂O₃ hexagonal plates, the dissolution of the α-Fe₂O₃ hexagonal plates, the reduction of Fe³⁺ to Fe²⁺, and the nucleation and growth of new Fe₃O₄ polyhedral particles.     

Hematites Precipitated in Alkaline Precursors: Comparison of Structural and Textural Properties for Methane Oxidation

Hematite (α-Fe₂O₃) catalysts prepared using the precipitation methods was found to be highly effective, and therefore, it was studied with methane (CH₄), showing an excellent stable performance below 500 °C. This study investigates hematite nanoparticles (NPs) obtained by precipitation in water from the precursor of ferric chloride hexahydrate using precipitating agents NaOH or NH₄OH at maintained pH 11 and calcined up to 500 °C for the catalytic oxidation of low concentrations of CH₄ (5% by volume in air) at 500 °C to compare their structural state in a CH₄ reducing environment. The conversion (%) of CH₄ values decreasing with time was discussed according to the course of different transformation of goethite and hydrohematites NPs precursors to magnetite and the structural state of the calcined hydrohematites. The phase composition, the size and morphology of nanocrystallites, thermal transformation of precipitates and the specific surface area of the NPs were characterized in detail by X-ray powder diffraction, transmission electron microscopy, infrared spectroscopy, thermal TG/DTA analysis and nitrogen physisorption measurements. The results support the finding that after goethite dehydration, transformation to hydrohematite due to structurally incorporated water and vacancies is different from hydrohematite α-Fe₂O₃. The surface area SBET of Fe₂O₃_NH-70 precipitate composed of protohematite was larger by about 53 m²/g in comparison with Fe₂O₃_Na-70 precipitate composed of goethite. The oxidation of methane was positively influenced by the hydrohematites of the smaller particle size and the largest lattice volume containing structurally incorporated water and vacancies.     

Progress toward Room-Temperature Synthesis and Functionalization of Iron-Oxide Nanoparticles

Novel magnetic nanohybrids composed of nanomaghemite covered by organic molecules were successfully synthesized at room temperature with different functionalization agents (sodium polystyrene sulfonate, oxalic acid, and cetyltrimethylammonium bromide) in low and high concentrations. Structural, vibrational, morphological, electron energy-loss spectroscopy, magnetic, and Mössbauer characterizations unraveled the presence of mainly cubic inverse spinel maghemite (γ-Fe₂O₃), whilst X-ray diffraction and ⁵⁷Fe Mössbauer spectroscopy showed that most samples contain a minor amount of goethite phase (α-FeOOH). Raman analysis at different laser power revealed a threshold value of 0.83 mW for all samples, for which the γ-Fe₂O₃ to α-Fe₂O₃ phase transition was observed. Imaging microscopy revealed controlled-size morphologies of nanoparticles, with sizes in the range from 8 to 12 nm. Organic functionalization of the magnetic nanoparticles was demonstrated by vibrational and thermogravimetric measurements. For some samples, Raman, magnetic, and Mössbauer measurements suggested an even more complex core-shell-like configuration, with a thin shell containing magnetite (Fe₃O₄) covering the γ-Fe₂O₃ surface, thus causing an increase in the saturation magnetization of approximately 11% against nanomaghemite. Field cooling hysteresis curves at 5 K did not evidence an exchange bias effect, confirming that the goethite phase is not directly interacting magnetically with the functionalized maghemite nanoparticles. These magnetic nanohybrids may be suitable for applications in effluent remediation and biomedicine.     

Ferromagnetism and optical properties of La1???x Al x FeO3 nanopowders

La_{1 − x} Al _x FeO₃ (x = 0.0, 0.05, 0.1, 0.2, 0.3, 0.4, and 0.5) nanopowders were prepared by polymerization complex method. All prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), and UV-vis spectrophotometry (UV-vis). The magnetic properties were investigated using a vibrating sample magnetometer (VSM). The X-ray results of all samples show the formation of an orthorhombic phase with the second phase of α-Fe₂O₃ in doped samples. The crystallite sizes of nanoparticles decreased with increasing Al content, and they are found to be in the range of 58.45 ± 5.90 to 15.58 ± 4.64 nm. SEM and TEM images show the agglomeration of nanoparticles with average particle size in the range of 60 to 75 nm. The FT-IR spectra confirm the presence of metal oxygen bonds of O-Fe-O and Fe-O in the FeO₆ octahedra. The UV-vis spectra show strong absorption peaks at approximately 285 nm, and the calculated optical band gaps are found to be in the range of 2.05 to 2.09 eV with increasing Al content. The M-H loop of the pure sample is antiferromagnetic, whereas those of the doped samples tend to be ferromagnetic with increasing Al content. The magnetization, remanent magnetization, and coercive field of the Al-doped sample with x = 0.5 are enhanced to 1.665 emu/g, 0.623 emu/g, and 4,087.0 Oe, respectively.     

Preparation and characterization of spindle-like Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> mesoporous nanoparticles

Magnetic spindle-like Fe₃O₄ mesoporous nanoparticles with a length of 200 nm and diameter of 60 nm were successfully synthesized by reducing the spindle-like α-Fe₂O₃ NPs which were prepared by forced hydrolysis method. The obtained samples were characterized by transmission electron microscopy, powder X-ray diffraction, attenuated total reflection fourier transform infrared spectroscopy, field emission scanning electron microscopy, vibrating sample magnetometer, and nitrogen adsorption-desorption analysis techniques. The results show that α-Fe₂O₃ phase transformed into Fe₃O₄ phase after annealing in hydrogen atmosphere at 350°C. The as-prepared spindle-like Fe₃O₄ mesoporous NPs possess high Brunauer-Emmett-Teller (BET) surface area up to ca. 7.9 m² g^-1. In addition, the Fe₃O₄ NPs present higher saturation magnetization (85.2 emu g^-1) and excellent magnetic response behaviors, which have great potential applications in magnetic separation technology.     

CO Adsorption on FeO x Nanoclusters Supported on HOPG—Effect of Oxide Formation on Catalytic Activity

CO adsorption on FeO _x clusters has been characterized by thermal desorption spectroscopy (TDS) and molecular beam scattering. Iron was vapor deposited and oxidized by annealing in O₂. The TDS curves consist initially of two peaks indicating formation of γ-Fe₂O₃/Fe₃O₄. Increasing the O₂ exposure results in one TDS peak and the dominance of α-Fe₂O₃.     

Enhanced Sensing Ability of Brush-Like Fe2O3-ZnO Nanostructures towards NO2 Gas via Manipulating Material Synergistic Effect

Brush-like α-Fe₂O₃–ZnO heterostructures were synthesized through a sputtering ZnO seed-assisted hydrothermal growth method. The resulting heterostructures consisted of α-Fe₂O₃ rod templates and ZnO branched crystals with an average diameter of approximately 12 nm and length of 25 nm. The gas-sensing results demonstrated that the α-Fe₂O₃–ZnO heterostructure-based sensor exhibited excellent sensitivity, selectivity, and stability toward low-concentration NO₂ gas at an optimal temperature of 300 °C. The α-Fe₂O₃–ZnO sensor, in particular, demonstrated substantially higher sensitivity compared with pristine α-Fe₂O₃, along with faster response and recovery speeds under similar test conditions. An appropriate material synergic effect accounts for the considerable enhancement in the NO₂ gas-sensing performance of the α-Fe₂O₃–ZnO heterostructures.     

Effect of niobium valence on the mechanochemical activation of niobium oxides–hematite magnetic ceramic nanoparticles

Three types of nanostructured systems: xNbO·(1?x)α-Fe₂O₃, xNbO₂·(1?x)α-Fe₂O₃, and xNb₂O₅·(1?x)α-Fe₂O₃ were synthesized by ball milling at different molar concentrations (x=0.1, 0.3, 0.5, and 0.7). The effect of Nb valence and milling time on mechanochemical activation of these systems were studied by X-ray diffraction and the Mössbauer spectroscopy measurements. In general, Nb-substituted hematite was obtained at lower molar concentrations for all Nb oxides. For the NbO–Fe₂O₃ system the favorable substitution of Fe²⁺ for Nb²⁺ in the octahedral sites in the NbO lattice was observed after 12 h milling for x=0.7. In the case of the NbO₂–Fe₂O₃ and Nb₂O₅–Fe₂O₃ systems a formation of orthorhombic FeNbO₄ compound was observed, in which Fe³⁺ cations were detected. For the highest concentration of NbO₂ (x=0.7) iron was completely incorporated into the FeNbO₄ phase after 12 h milling. The molar concentrations of x=0.3 and 0.5 were the most favorable for the formation of ternary FeNbO₄ compound in the Nb₂O₅–Fe₂O₃ system. Influence of ball milling on thermal behavior of the powders was investigated by simultaneous DSC–TG measurements up to 800 °C.     

Study on an iron–manganese Fischer–Tropsch synthesis catalyst prepared from ferrous sulfate

A systematic study was undertaken to investigate the effects of the initial oxidation degree of iron on the bulk phase composition and reduction/carburization behaviors of a Fe–Mn–K/SiO₂ catalyst prepared from ferrous sulfate. The catalyst samples were characterized by powder X-ray diffraction (XRD), Mössbauer spectroscopy, X-ray photoelectron spectroscopy (XPS) and H₂ (or CO) temperature-programmed reduction (TPR). The Fischer–Tropsch synthesis (FTS) performance of the catalysts was studied in a slurry-phase continuously stirred tank reactor (CSTR). The characterization results indicated that the fresh catalysts are mainly composed of α-Fe₂O₃ and Fe₃O₄, and the crystallite size of iron oxides is decreased with the increase of the initial oxidation degree of iron. The catalyst with high content of α-Fe₂O₃ in its as-prepared state has high content of iron carbides after being reduced in syngas. However, the catalyst with high content of Fe₃O₄ in its as-prepared state cannot be easily carburized in CO and syngas. FTS reaction study indicates that Fe-05 (Fe³⁺/Fe_total = 1.0) has the highest CO conversion, whereas Fe-03 (Fe³⁺/Fe_total = 0.55) has the lowest activity. The catalyst with high CO conversion has a high selectivity to gaseous hydrocarbons (C₁–C₄) and low selectivity to heavy hydrocarbons (C₅₊).     

Enzymatic Synthesis of Magnetic Nanoparticles

We report the first in vitro enzymatic synthesis of paramagnetic and antiferromagnetic nanoparticles toward magnetic ELISA reporting. With our procedure, alkaline phosphatase catalyzes the dephosphorylation of l-ascorbic-2-phosphate, which then serves as a reducing agent for salts of iron, gadolinium, and holmium, forming magnetic precipitates of Fe_45±14Gd_5±2O_50±15 and Fe_42±4Ho_6±4O_52±5. The nanoparticles were found to be paramagnetic at 300 K and antiferromagnetic under 25 K. Although weakly magnetic at 300 K, the room-temperature magnetization of the nanoparticles found here is considerably greater than that of analogous chemically-synthesized Ln_xFe_yO_z (Ln = Gd, Ho) samples reported previously. At 5 K, the nanoparticles showed a significantly higher saturation magnetization of 45 and 30 emu/g for Fe_45±14Gd_5±2O_50±15 and Fe_42±4Ho_6±4O_52±5, respectively. Our approach of enzymatically synthesizing magnetic labels reduces the cost and avoids diffusional mass-transfer limitations associated with pre-synthesized magnetic reporter particles, while retaining the advantages of magnetic sensing.     

Synthesis of new type of Au-magnetic nanocomposite and application for protein separation thereof

We present a different strategy for synthesizing the Au-γ-Fe₂O₃ bifunctional nanoparticle by using a larger (50 nm) Au nanoparticle as the core surrounded by smaller (10 nm) γ-Fe₂O₃ nanoparticles. The synthesis of the composite nanoparticles is quite facile based on a simple redox process whereby Fe²⁺ is used to reduce Au³⁺. The morphology and composition of the product is measured by transmission electron microscopy, X-ray powder diffraction and UV–vis spectroscopy. We demonstrate the utility of these as-prepared Au-γ-Fe₂O₃ nanoparticles by showing they can be used to separate proteins in solution. For example, bovine serum is efficiently removed from an aqueous solution with the simple addition of the NPs and application of a small magnet. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis is performed to evaluate the fidelity and efficiency of the protein separation procedure.     

Synthesis and Characterization of Poly(Acrylonitrile-co-Vinylacetate)/Fe2O3@PEDOT Core-Shell Nanocapsules and Nanofibers

P(AN-co-VAc)/Fe₂O₃ core-shell nanocapsules were synthesized by miniemulsion polymerization and P(AN-co-VAc)/Fe₂O₃@PEDOT core-shell structure was constituted by oxidative polymerization. Homogeneous nanofibers were obtained from the core-shell nanocapsules. Characterizations were performed by XRD, GPC, UV-vis, and FTIR-ATR. SEM, AFM, and TEM. Molecular weight and Tg of the nanocapsules were effected by the increase in γ-Fe₂O₃ NPs. Nanofiber resistance (Rnfb) drastically decreased from 2700 to 110 kΩ.cm² by the inclusion of γ-Fe₂O₃ NPs into the nanocapsules 8.3 kΩ.cm² obtained after coating with PEDOT. The electrochemical Impedance results were fitted to models of [R (Q(R (CR)))] and [R (Q(R (QR)))], respectively.     

Structural and magnetic properties of porous FexOy nanosheets and nanotubes fabricated by electrospinning

2D porous α-Fe₂O₃ nanosheets and 1D porous Fe_xO_y nanotubes were synthesized using electrospinning technique under different conditions. XRD results show that the α-Fe₂O₃ nanosheets are pure α-Fe₂O₃ phase, and the Fe_xO_y nanotubes are mainly composed of α-Fe₂O₃ phase accompanied by weak Fe₃O₄ phase. The EDX mappings demonstrate that the elements of O and Fe were uniformly distributed in nanosheets and nanotubes. The valence of iron ion is pure 3?+ in the α-Fe₂O₃ nanosheets, and it shows 3?+ with a small amount of 2?+ in the Fe_xO_y nanotubes. Magnetic properties of the synthesized samples were studied by vibrating sample magnetometer and Mössbauer spectrometer, the results show that the α-Fe₂O₃ nanosheets have the room temperature ferromagnetism and the Fe_xO_y nanotubes have a higher saturation magnetization of 18.91?emu/g. Mössbauer spectrometer proved further the microstructure of nanosheets and nanotubes, which are consistent with the results of XPS. Our results will be helpful for the application of nanoporous materials.     

Influence of Ce3+ Substitution on Antimicrobial and Antibiofilm Properties of ZnCexFe2−xO4 Nanoparticles (X = 0.0, 0.02, 0.04, 0.06, and 0.08) Conjugated with Ebselen and Its Role Subsidised with γ-Radiation in Mitigating Human TNBC and Colorectal Adenocarcinoma Proliferation In Vitro

Cancers are a major challenge to health worldwide. Spinel ferrites have attracted attention due to their broad theranostic applications. This study aimed at investigating the antimicrobial, antibiofilm, and anticancer activities of ebselen (Eb) and cerium-nanoparticles (Ce-NPs) in the form of ZnCe_xFe_2−XO₄ on human breast and colon cancer cell lines. Bioassays of the cytotoxic concentrations of Eb and ZnCe_xFe_2−XO₄, oxidative stress and inflammatory milieu, autophagy, apoptosis, related signalling effectors, the distribution of cells through the cell-cycle phases, and the percentage of cells with apoptosis were evaluated in cancer cell lines. Additionally, the antimicrobial and antibiofilm potential have been investigated against different pathogenic microbes. The ZOI, and MIC results indicated that ZnCe_xFe_2−XO₄; X = 0.06 specimen reduced the activity of a wide range of bacteria and unicellular fungi at low concentration including P. aeruginosa (9.5 mm; 6.250 µg/mL), S. aureus (13.2 mm; 0.390 µg/mL), and Candida albicans (13.5 mm; 0.195 µg/mL). Reaction mechanism determination indicated that after ZnCe_xFe_2−xO₄; X = 0.06 treatment, morphological differences in S. aureus were apparent with complete lysis of bacterial cells, a concomitant decrease in the viable number, and the growth of biofilm was inhibited. The combination of Eb with ZFO or ZnCe_xFe_2−XO₄ with γ-radiation exposure showed marked anti-proliferative efficacy in both cell lines, through modulating the oxidant/antioxidant machinery imbalance, restoring the fine-tuning of redox status, and promoting an anti-inflammatory milieu to prevent cancer progression, which may be a valuable therapeutic approach to cancer therapy and as a promising antimicrobial agent to reduce the pathogenic potential of the invading microbes.     

Fabrication of mesoporous Cr2O3 with highly distributed α-Fe2O3 and Pt nanoparticles for ultrafast H2 evolution rate

In the present contribution, p-n type heterojunction α-Fe₂O₃/Cr₂O₃ S-scheme system photocatalyst has been fabricated utilizing a sol-gel approach with assisted nonionic surfactant for a highly effective H₂ evolution rate under visible illumination. Pt NPs have been reduced by photodeposition during the photocatalytic reaction to collect Pt@α-Fe2O3/Cr2O3 finally. XRD analysis of Fe₂O₃/Cr₂O₃ nanocomposites verified the construction of Fe₂O₃ and Cr₂O₃ with rhombohedral phases. TEM images of Cr₂O₃ NPs were almost spherical and uniform in shape and size (20 ± 5 nm), and very small Fe₂O₃ NPs (3-5 nm) were distributed on the mesoporous Cr₂O₃ networks. The obtained α-Fe₂O₃/Cr₂O₃ photocatalyst exhibited noteworthy photocatalytic H₂ evolution with high efficiency and stability for 45 h. Interestingly, the photocatalytic H₂ evolution rate gradually boosted with the extent of Fe₂O₃ percentage up to 15% and its rate of 2215.4 μmol g^-1h^-1, which was fostered 7.25 folds larger than that of Cr₂O₃ NPs (305.7 μmol g^-1h^-1). The enhancement H₂ evolution rate of Fe₂O₃/Cr₂O₃ photocatalyst in comparison with bare Cr₂O₃ NPs was ascribed to facilitate the separation of photocarriers and existing considerable reactive sites. In addition, constructing n-type Fe₂O₃ and p-type Cr₂O₃ with close contact is essential in improving the H₂ evolution rate. The possible photocatalytic mechanism over Fe₂O₃/Cr₂O₃ nanocomposite was addressed based on electrochemical measurements. The construction of the S-scheme system of Fe₂O₃/Cr₂O₃ nanocomposite could be suggested to improve the separation of photocarriers through optimal transfer channels owing to the formation of synergistic characteristics. Our results provide avenues for constructing stable photocatalysts with high efficiency for H₂ evolution through visible exposure.     

Crystallization and magnetic property of iron oxide nanoparticles precipitated in silica glass matrix

Crystallization and magnetic property of Fe₂O₃ nanoparticle precipitated in SiO₂ matrix was investigated. Fe₂O₃/SiO₂ nanocomposite thin film was obtained by annealing of the amorphous Fe-Si-O thin film deposited by RF-magnetron sputtering of (α-Fe₂O₃)_1−x/(SiO₂)_x composite targets. The Fe₂O₃ crystallite size increased with decreasing SiO₂ area ratio, x of the target and increasing annealing temperature. ?-Fe₂O₃ with the crystallite size of 20-30 nm was obtained after annealing the film deposited in SiO₂ area ratio, x = 0.33-0.42 at 900 °C. Lower SiO₂ area ratio (x) than 0.25 and higher annealing temperature resulted in precipitation of α-Fe₂O₃ with the larger crystallite size than 40 nm. In the case of SiO₂ area ratio, x ≥ 0.50, the annealed film was amorphous and showed higher magnetization and smaller coercivity due to the precipitation of very small crystalline γ-Fe₂O₃. The ?-Fe₂O₃/SiO₂ composite thin film showed ferromagnetic hysteresis with coercive force of 0.14 T.     

Role of vanadium ions,oxygen vacancies,and interstitial zinc in room temperature ferromagnetism on ZnO-V2O5 nanoparticles

In this work, we present the role of vanadium ions (V⁺⁵ and V⁺³), oxygen vacancies (V_O), and interstitial zinc (Zn_i) to the contribution of specific magnetization for a mixture of ZnO-V₂O₅ nanoparticles (NPs). Samples were obtained by mechanical milling of dry powders and ethanol-assisted milling for 1 h with a fixed atomic ratio V/Zn?=?5% at. For comparison, pure ZnO samples were also prepared. All samples exhibit a room temperature magnetization ranging from 1.18?×?10⁻³ to 3.5?×?10⁻³ emu/gr. Pure ZnO powders (1.34?×?10⁻³ emu/gr) milled with ethanol exhibit slight increase in magnetization attributed to formation of Zn_i, while dry milled ZnO powders exhibit a decrease of magnetization due to a reduction of V_O concentration. For the ZnO-V₂O₅ system, dry milled and thermally treated samples under reducing atmosphere exhibit a large paramagnetic component associated to the formation of V₂O₃ and secondary phases containing V⁺³ ions; at the same time, an increase of V_O is observed with an abrupt fall of magnetization to σ?~?0.7?×?10⁻³ emu/gr due to segregation of V oxides and formation of secondary phases. As mechanical milling is an aggressive synthesis method, high disorder is induced at the surface of the ZnO NPs, including V_O and Zn_i depending on the chemical environment. Thermal treatment restores partially structural order at the surface of the NPs, thus reducing the amount of Zn_i at the same time that V₂O₅ NPs segregate reducing the direct contact with the surface of ZnO NPs. Additional samples were milled for longer time up to 24 h to study the effect of milling on the magnetization; 1-h milled samples have the highest magnetizations. Structural characterization was carried out using X-ray diffraction and transmission electron microscopy. Identification of V_O and Zn_i was carried out with Raman spectra, and energy-dispersive X-ray spectroscopy was used to verify that V did not diffuse into ZnO NPs as well to quantify O/Zn ratios.     

Investigation of Structural,Morphological and Magnetic Properties of MFe2O4 (M = Co,Ni, Zn,Cu, Mn) Obtained by Thermal Decomposition

The structural, morphological and magnetic properties of MFe₂O₄ (M = Co, Ni, Zn, Cu, Mn) type ferrites produced by thermal decomposition at 700 and 1000 °C were studied. The thermal analysis revealed that the ferrites are formed at up to 350 °C. After heat treatment at 1000 °C, single-phase ferrite nanoparticles were attained, while after heat treatment at 700 °C, the CoFe₂O₄ was accompanied by Co₃O₄ and the MnFe₂O₄ by α-Fe₂O₃. The particle size of the spherical shape in the nanoscale region was confirmed by transmission electron microscopy. The specific surface area below 0.5 m²/g suggested a non–porous structure with particle agglomeration that limits nitrogen absorption. By heat treatment at 1000 °C, superparamagnetic CoFe₂O₄ nanoparticles and paramagnetic NiFe₂O₄, MnFe₂O₄, CuFe₂O₄ and ZnFe₂O₄ nanoparticles were obtained.     

Enhanced negative thermal expansion of (KMg)3+-substituted Fe2Mo3O12 ceramics

Herein, we report the solid-state synthesis of (KMg)_xFe_2-xMo₃O₁₂ (0 = x ≤ 1.5) ceramics. Phase composition, crystal structure, morphology, phase transition and thermal expansion behavior of the (KMg)_xFe_2-xMo₃O₁₂ ceramics were investigated by XRD, Raman, XPS, HRTEM, EDX, SEM, TMA and high-temperature XRD. Results indicate that (KMg)³⁺ dual-cations have successfully replaced Fe³⁺ in Fe₂Mo₃O₁₂ ceramics and single-phase monoclinic (KMg)_xFe_2-xMo₃O₁₂ ceramics were prepared for 0.25 = x ≤ 1. (KMg)³⁺ introduction can increase the density of (KMg)_xFe_2-xMo₃O₁₂ ceramics and effectively improve their negative thermal expansion (NTE) performance. In addition, the phase transition temperature (Tc) of Fe₂Mo₃O₁₂ was reduced from 508.1 °C to room temperature with the increase of (KMg)³⁺-substitution. Monoclinic KMgFeMo₃O₁₂ ceramics was observed to show stronger NTE in a wider temperature range of 30–700 °C for the first time. Its corresponding coefficient of thermal expansion (CTE) is as high as ?17.21 × 10^?6 °C^?1. The distortion of [FeO₆/MgO₆] polyhedra in (KMg)_xFe_2-xMo₃O₁₂ caused by (KMg)³⁺-substitution contributed to the stronger NTE.     

Phase equilibria in the Fe-V-O system near “FeO”-V2O3 isopleth

Phase equilibria in the “FeO”-V₂O₃ system from 1273 to 1808 K and in the range of oxygen partial pressure from 10⁻¹⁵ to 10⁻⁴ atm are investigated. High-temperature quenching, XRD, SEM-EDS, and DSC are used to determine the phase relations. Stable regions of (FeO)_s.s., (V₂O₃)_s.s., and spinel phases are considerably effected by the oxygen partial pressure, and structural models are proposed as (Fe²⁺, Fe³⁺, V²⁺)_1-xO, (V²⁺, V³⁺, V⁴⁺, Fe³⁺)₂O_3+x, and (Fe²⁺, Fe³⁺, V³⁺)(Fe²⁺, Fe³⁺, V³⁺, Va)₂O₄. Continuous solid solution FeV₂O₄-Fe₃O₄ is formed. The nonstoichiometry of FeV₂O₄ is attributed to the appearance of vanadium vacancies for electroneutrality due to the oxidation of Fe²⁺. The standard Gibbs energy of formation for FeV₂O₄ and component activities in FeV₂O₄-Fe₃O₄ solid solution at 1623 and 1773 K are derived based on the equilibrium oxygen partial pressure. The cation distribution in FeV₂O₄ at different temperatures is obtained according to site preference energy.