In situ 2D mapping of hydrogen entry into an Fe sheet under a droplet of NaCl solution using a hydrogenochromic sensor

The distribution of hydrogen entering an Fe sheet under a droplet of NaCl solution was successfully visualized using a hydrogenochromic sensor consisting of a polyaniline layer and a Ni intermediate layer. At the initial stage of corrosion, the hydrogen entry was barely confirmed. The hydrogen entry was observed as the corrosion proceeded, and the preferential hydrogen entry site corresponded to the rust-formed area. It was postulated that the hydrogen entry is promoted by the decrease in pH due to the hydrolysis reactions of Fe ions under the rust. The hydrogenochromic sensor paves the way for the visualization of the hydrogen entry into metals under corrosion conditions.     

Magnetic properties,phase evolution,hollow structure and biomedical application of hematite (α-Fe2O3) and QUAIPH

We investigate synthesis, phase evolution, hollow and porous structure and magnetic properties of quasi-amorphous intermediate phase (QUAIPH) and hematite (α-Fe₂O₃) nanostructure synthesized by annealing of akaganeite (β-FeOOH) nanorods. It is found that the annealing temperature determines the phase composition of the products, the crystal structure/size dictates the magnetic properties whereas the final nanorod morphology is determined by the starting material. Annealing of β-FeOOH at ～300 °C resulted in the formation of hollow QUAIPH nanorods. The synthesized material shows low-cytotoxicity, superparamagnetism and good transverse relaxivity, which is rarely reported for QUAIPH. The QUAIPH nanorods started to transform to porous hematite nanostructures at ～350 °C and phase transformation was completed at 600 °C. During the annealing, the crystal structure changed from monoclinic (akaganeite) to quasi-amorphous and rhombohedral (hematite). Unusually, the crystallite size first decreased (akaganeite → QUAIPH) and then increased (QUAIPH → hematite) during annealing whereas the nanorods retained particle shape. The magnetic properties of the samples changed from antiferromagnetic (akaganeite) to superparamagnetic with blocking temperature T_B = 84 K (QUAIPH) and finally to weak-ferromagnetic with the Morin transition at T_M = 244 K and high coercivity H_C = 1652 Oe (hematite). The low-cytotoxicity and MRI relaxivity (r₂ = 5.80 mM^?1 s^?1 (akaganeite), r₂ = 4.31 mM^?1 s^?1 (QUAIPH) and r₂ = 5.17 mM^?1 s^?1 (hematite)) reveal potential for biomedical applications.     

Ammonia production using iron nitride and water as hydrogen source under mild temperature and pressure

Ammonia generation was studied in the reaction between water and nitrogen-containing iron at 323 K and atmospheric pressure. Similar to metallic Fe, the interstitial compound Fe₃N reduced water through Fe oxidation to produce hydrogen gas, while the N combined with atomic hydrogen to produce ammonia as a byproduct. The addition of carbon dioxide to this system accelerated the reaction with concomitant consumption of carbon dioxide. The promoted ammonia production upon addition of carbon dioxide can be attributed to the generation of atomic hydrogen from the redox reaction of carbonic acid and Fe, as well as removal of used Fe from the reaction system through the formation of a soluble carbonato complex. When carbonate was added to the reaction system, the production rates of ammonia and hydrogen increased further. The results here confirmed that ammonia can be synthesized from iron nitride under mild conditions by utilizing carbon dioxide.     

Microstructure and coloring mechanism of iron spots on bluish white porcelain from Jingdezhen of the Song Dynasty

Jingdezhen is famous for its bluish white (Qingbai) porcelains of the Song Dynasty, and those decorated with iron spots are distinctive among them. Herein, iron spots on a bluish white porcelain were investigated using a series of microscopic and spectroscopic characterizations. We found the decreasing iron content from more than 8 wt% to about 2 wt% during the glaze color transition from rusty to brown and finally into green, which built a connection on the coloring mechanism of iron-rich crystallized glaze and celadon glaze. We identified the rare ε-Fe₂O₃, a promising magnetic material, in both the dark brown crystals and the triangular crystals in the rusty area, which is its first discovery among bluish white porcelains. Based on these findings, we discussed the coloring mechanism of iron-spot decoration along with the physical form of the iron oxide crystals, indicating the partially reducing atmosphere during firing process.     

Colossal dielectric response and relaxation behavior in novel system of Zr4+ and Nb5+ co-substituted CaCu3Ti4O12 ceramics

In this work, we developed a novel system of isovalent Zr⁴⁺ and donor Nb⁵⁺ co-doped CaCu₃Ti₄O₁₂ (CCTO) ceramics to enhance dielectric response. The influences of Zr⁴⁺ and Nb⁵⁺ co-substituting on the colossal dielectric response and relaxation behavior of the CCTO ceramics fabricated by a conventional solid-phase synthesis method were investigated methodically. Co-doping of Zr⁴⁺ and Nb⁵⁺ ions leads to a significant reduction in grain size for the CCTO ceramics sintered at 1060 °C for 10 h. XRD and Raman results of the CaCu₃Ti_3.8-xZr_xNb_0.2O₁₂ (CCTZNO) ceramics show a cubic perovskite structure with space group Im-3. The first principle calculation result exhibits a better thermodynamic stability of the CCTO structure co-doped with Zr⁴⁺ and Nb⁵⁺ ions than that of single-doped with Zr⁴⁺ or Nb⁵⁺ ion. Interestingly, the CCTZNO ceramics exhibit greatly improved dielectric constant (~10⁵) at a frequency range of 10²–10⁵ Hz and at a temperature range of 20–210 °C, indicating a giant dielectric response within broader frequency and temperature ranges. The dielectric properties of CCTZNO ceramics were analyzed from the viewpoints of defect-dipole effect and internal barrier layer capacitance (IBLC) model. Accordingly, the immensely enhanced dielectric response is primarily ascribed to the complex defect dipoles associated with oxygen vacancies by co-doping Zr⁴⁺ and Nb⁵⁺ ions into CCTO structure. In addition, the obvious dielectric relaxation behavior has been found in CCTZNO ceramics, and the relaxation process in middle frequency regions is attributed to the grain boundary response confirmed by complex impedance spectroscopy and electric modulus.     

Ammonia gas sensing and magnetic permeability of enhanced surface area and high porosity lanthanum substituted Co–Zn nano ferrites

This work reports magnetic permeability and ammonia gas sensing characteristics of La³⁺ substituted Co–Zn nano ferrites possessing chemical formula Co_0.7Zn_0.3La_xFe_2-2xO₄ (x = 0–0.1) synthesized by a sol-gel route. Refinement of X-ray diffraction (XRD) patterns of the ferrite powders by the Rietveld technique has revealed the creation of single-phase spinel structure. The tenancy of constituent cations at tetrahedral/octahedral sites was obtained from the refinement of XRD. The crystallite sizes calculated from the W–H method vary from 20 to 24 nm. The scanning electron microscope (SEM) profiles of the ferrite samples were analyzed for the morphological details. The energy dispersive X-ray analysis (EDAX) patterns of the samples were obtained to test the elemental purity of the ferrites within their stoichiometry. The transmission electron microscope (TEM) image of the ferrite (x = 0.1) exhibits the spherical and oval shaped particles with a mean size of 20 nm. Fourier transform infra-red (FTIR) spectra were analyzed to confirm the superseding of La³⁺ cations at octahedral sites. The Brunauer-Emmett-Teller (BET) analysis of nitrogen adsorption-desorption isotherms of the ferrites was performed to investigate the porous structure and to determine the surface area of the nanocrystalline ferrites. The oxidation states of the constituent ions were confirmed by means of X-ray photoelectron spectroscopy (XPS). The complex permeability as a function of frequency was studied to explore the effects of structural parameters on the magnetic behaviour of the ferrites. Analysis of gas sensing properties of the ferrites have proved that the Co–Zn–La ferrite with controlled La composition can be utilized as an effective ammonia gas sensing material in commercial gas sensors.     

Enhanced electromagnetic microwave absorption of Fe/C/SiCN composite ceramics targeting in integrated structure and function

The Fe/C/SiCN composite ceramics were synthesized by polymer-derived method to obtain the integration of structure and functions. The electromagnetic waves (EMW) absorption properties at X and Ku bands were investigated. The addition of nano-sized Fe particles improved the magnetic loss and impedance matching, and the carbon nanotubes generated by the iron in-situ catalysis increased the internal relaxation polarization and interfacial polarization, which together improved the EMW absorption properties significantly. In particular, the Fe/C/SiCN-9 showed the optimum reflection loss (RL) of ?31.06 dB at 10.03 GHz with an effective absorption bandwidth (EAB, RL < ?10 dB) of 3.03 GHz at 2.51 mm, indicating the excellent EMW absorption properties of Fe/C/SiCN composite ceramics.     

Electrical and magnetic properties of double perovskite: Y2CoMnO6

In this communication, the structural, micro-structural, dielectric, electrical, magnetic, and leakage-current characteristics of a double perovskite (Y₂CoMnO₆) ceramic material have been reported. The material was synthesized via a high-temperature mixed-oxide route. The compound crystallizes in a monoclinic structure which is confirmed from preliminary X-ray structural study. The morphological study by using scanning electron micrograph reveals the almost homogeneous distribution of grains throughout the surface of the sample. The nature of frequency-dependence of dielectric constant has been described by the Maxwell-Wagner model. The occurrence of a dielectric anomaly in the temperature dependence of dielectric permittivity study demonstrates the ferroelectric-paraelectric phase transition in the material. From the Nyquist plots, we found the existence of both grain and grain boundary effects. The frequency dependence of conductivity was studied by the Jonscher’s Power law, and the conduction phenomenon obeys the large overlapping polaron tunneling model. By using the Arrhenius equation, the activation energy has been calculated which is nearly equal to the energy required for the hoping of the electron. Both impedance and conductivity analysis demonstrate that the sample exhibits negative temperature coefficient of resistance (NTCR) properties indicating the semiconducting type of material at high temperatures. The anti-ferromagnetic character of the material is observed from the nature of magnetic hysteresis loop. The leakage current analysis suggests that the conduction process in the material follows the space charge limited conduction phenomenon. Such material will be helpful for modern electronic devices and spintronic applications.     

Iron(II) Sulfate(VI) from Titania Production as a Raw Material for Preparation of Hydrogen Sulfide Sorbents

A hybrid sorbent material for removal of hydrogen sulfide from air was developed. The material is based on activated carbon and iron compounds obtained from waste iron(II) sulfate(VI) heptahydrate. The iron salt is deposited on the carbonaceous support and subjected to oxidation (Fe²⁺ to Fe³⁺) using atmospheric oxygen under alkaline conditions. An effect of H₂O₂ addition to the process on the composition of the resultant material was also examined. X-ray diffraction (XRD) analyses confirmed easy conversion of waste FeSO₄·7H₂O to iron oxides Fe₃O₄ and FeOOH. The activated carbon supporting iron oxides revealed a higher efficiency in H₂S elimination from air compared to the commercial activated carbon, without any modification.     

A simulation study of reduction kinetics for sponge iron production in a rotary hearth furnace

ABSTRACT

A mathematical model has been developed by coupling genetic algorithm (GA) with heat and material balance equations to estimate rate parameters and solid-phase evolution related to the reduction of iron ore-coal composite pellets in a multi-layer bed Rotary hearth Furnace (RHF). The present process involves treating iron ore-coal composite pellets in a crucible over the hearth in RHF. The various solid phases evolved at the end of the process are estimated experimentally, and are used in conjunction with the model to estimate rate parameters. The predicted apparent activation energy for the wustite reduction step is found to be lower than those of the reduction of higher oxides. The thermal efficiency is found to decrease significantly with an increase in the carbon content of the pellet. Thermal efficiency was also found to increase mildly up to three layers. Multilayer bed remains as a potential design parameter to increase thermal efficiency.