Nanocrystalline LaFeO3 preparation and thermal process of precursor

Nanocrystalline LaFeO₃ was synthesized by calcining precursor La₂(CO₃)₂(OH)₂–Fe₂O₃?1.5H₂O in air. XRD analysis showed that precursor dried at 80 °C was a mixture containing orthorhombic La₂(CO₃)₂(OH)₂ and amorphous Fe₂O₃?1.5H₂O. Orthorhombic LaFeO₃ with highly crystallization was obtained when La₂(CO₃)₂(OH)₂–Fe₂O₃?1.5H₂O was calcined at 900 °C in air for 2 h. Magnetic characterization indicated that the calcined product at 900 °C behaved weak magnetic behavior at room temperature. The thermal process of La₂(CO₃)₂(OH)₂–Fe₂O₃?1.5H₂O experienced five steps, which involves, at first, dehydration of 0.8 absorption water, then dehydration of 0.7 crystal water, decomposition of orthorhombic La₂(CO₃)₂(OH)₂ into orthorhombic LaCO₃OH, reaction of two LaCO₃OH into hexagonal La₂O₂CO₃ and crystallization of tetragonal Fe₂O₃, at last, reaction of hexagonal La₂O₂CO₃ with tetragonal Fe₂O₃ into orthorhombic LaFeO₃. In the DTG curve, four DTG peaks indicated the precursor experienced mass loss of four steps.     

Room temperature multiferroic properties of (Bi0.95La0.05)(Fe0.97Mn0.03)O3/NiFe2O4 double layered thin film

(Bi_0.95La_0.05)(Fe_0.97Mn_0.03)O₃/NiFe₂O₄ double layered thin film was prepared on a Pt(111)/Ti/SiO₂/Si(100) substrate by a chemical solution deposition method. X-ray diffraction and Raman scattering spectroscopy studies confirmed the formation of the distorted rhombohedral perovskite and the inverse spinel cubic structures for the (Bi_0.95La_0.05)(Fe_0.97Mn_0.03)O₃/NiFe₂O₄ double layered thin film. The (Bi_0.95La_0.05)(Fe_0.97Mn_0.03)O₃/NiFe₂O₄ double layered thin film exhibited well saturated ferromagnetic (2 M_r of 18.1 emu/cm³ and 2H_c of 0.32 kOe at 20 kOe) and ferroelectric (2P_r of 60 μC/cm² and 2E_c of 813 kV/cm at 866 kV/cm) hysteresis loops with low order of leakage current density (4.5 × 10⁻⁶ A/cm² at an applied electric field of 100 kV/cm), which suggest the ferroelectric and ferromagnetic multi-layers applications in real devices.     

Synthesis and magnetocaloric properties of La0.85K0.15MnO3 nanoparticles

In this paper, La_0.85K_0.15MnO₃ nanoparticles were successfully synthesized at relatively low calcinated temperature from a polyaminocarboxylate complex precursor with diethylenetriaminepentaacetic acid (H₅DTPA) as ligand, and the magnetocaloric properties were investigated. The phase transformation, chemical composition, and microstructure of La_0.85K_0.15MnO₃ nanoparticles were characterized by X-ray diffraction (XRD), thermogravimetric (TG), differential scanning calorimetry (DSC), transmission electron microscopy (TEM) and electron diffraction (ED). The results revealed that La_0.85K_0.15MnO₃ nanoparticles calcined at temperatures within the range of 600–1000 °C are of pure single-phase rhombohedral structure and the grain sizes were precisely controlled by varing the calcined temperature. The relationship between magnetocaloric properties and the calcined temperature of La_1?xK_xMnO₃ nanoparticles was also investigated systematically. From the magnetic measurements as function of temperature and magnetic applied field, we have discovered that the Curie temperature T_C is 274.5 K and is independent of the calcined temperature. From the measurements and calculation of isothermal magnetization at different temperatures, the maximum magneticentropy changes close to T_C (274 K) of the samples calcined at 600 °C, 800 °C and 1000 °C are 2.02, 3.06 and 3.56/kg K at H = 2T, respectively. Also La_0.85K_0.15MnO₃ nanoparticle displays a second-order phase transition. These results suggest that this material is a candidate for use as an active for magnetic refrigerent around the room temperature.     

Investigation of La3 + Doped Yb2Sn2O7 as new thermal barrier materials

Low thermal conductivity is one of the key requirements for thermal barrier coating materials. From the consideration of crystal structure and ion radius, La^3 + Doped Yb₂Sn₂O₇ ceramics with pyrochlore crystal structures were synthesized by sol–gel method as candidates of thermal barrier materials in aero-engines. As La^3 + and Yb^3 + ions have the largest radius difference in lanthanoid group, La^3 + ions were expected to produce significant disorders by replacing Yb^3 + ions in cation layers of Yb₂Sn₂O₇. Both experimental and computational phase analyses were carried out, and good agreement had been obtained. The lattice constants of solid solution (La_xYb_1 − x)₂Sn₂O₇ (x = 0.3, 0.5, 0.7) increased linearly when the content of La^3 + was increased. The thermal properties (thermal conductivity and coefficients of thermal expansion) of the synthesized materials had been compared with traditional 8 wt.% yttria stabilized zirconia (8YSZ) and La₂Zr₂O₇ (LZ). It was found that La^3 + Doped Yb₂Sn₂O₇ exhibited lower thermal conductivities than un-doped stannates. Amongst all compositions studied, (La_0.5Yb_0.5)₂Sn₂O₇ exhibited the lowest thermal conductivity (0.851 W·m^− 1·K^− 1 at room temperature), which was much lower than that of 8YSZ (1.353 W·m^− 1·K^− 1), and possessed a high coefficient of thermal expansion (CTE), 13.530 × 10^− 6 K^− 1 at 950 °C.     

Synthesis of Co3(OH)2V2O7·1.7H2O nanosheets and its application in lithium ion batteries

Cobalt vanadium oxide hydroxide hydrate (Co₃(OH)₂V₂O₇·nH₂O) nanosheets are successfully synthesized by a simple hydrothermal method. The composition of Co₃(OH)₂V₂O₇·nH₂O is studied by thermal gravity (TG) analysis in N₂ atmosphere and subsequent X-ray powder diffraction (XRD) characterization of the sample obtained via annealing Co₃(OH)₂V₂O₇·nH₂O nanosheets in N₂ atmosphere at 800 °C for 6 h. The results indicate that there are 1.7 water molecules in a Co₃(OH)₂V₂O₇·nH₂O molecular formula. Electrochemical properties of Co₃(OH)₂V₂O₇·1.7H₂O nanosheets as negative electrode of lithium ion batteries are studied by conventional charge/discharge test, which show an initial capacity of 730 mAh g^?1 with steady plateau near 0.9 V at a current density of 0.05 mA cm^?2.     

Electromagnetic and microwave absorption performance of some transition metal doped La0.7Sr0.3Mn1−xTMxO3±δ (TM = Fe,Co or Ni)

In this study the transition metal doped La_0.7Sr_0.3Mn_1?xTM_xO_3±δ (TM = Fe, Co or Ni, x = 0, 0.2) powders were fabricated by the conventional solid state reaction method. The compositions, morphologies and crystal structures were characterized using different method. The influences of the incorporation of TM into La_0.7Sr_0.3MnO_3±δ on the complex permittivity, complex permeability and microwave absorption performance were investigated in the range of 5.85–18 GHz. It is found that the electromagnetic loss has been enhanced after TM doping. And the microwave absorption properties have been significantly improved. In present study La_0.7Sr_0.3Mn_0.8Fe_0.2O_3±δ had the best microwave absorption properties. The maximum reflection loss was 27.67 dB at 10.97 GHz, and the absorbing bandwidth above 6 dB was 6.80 GHz with 2 mm thickness.     

Synthesis of nanoparticle zinc phosphate dihydrate by solid state reaction at room temperature and its thermochemical study

Nanoparticle zinc phosphate dihydrate was prepared by solid-state reaction at ambient temperature from Na₃PO₄·12H₂O and ZnSO₄·7H₂O, and characterized by X-ray, Raman, FT-IR spectra and TEM. Thermochemical study was performed by a RD496-III microcalorimeter at 298.15 K. The results reveal that the obtained product is Zn₃(PO₄)₂·2H₂O with spherical shape and particle size is between 40–50 nm. The standard enthalpy value for above reaction is calculated as − 45.793 kJ·mol^− 1. The standard enthalpy of formation for zinc phosphate dihydrate is recommended as − 3788.607 kJ·mol^− 1.     

Microwave-assisted hydrothermal synthesis of zinc oxide particles starting from chloride precursor

Zinc oxide (ZnO) was synthesized using a microwave assisted hydrothermal (MAH) process based on chloride/urea/water solution and under 800 W irradiation for 5 min. In the bath, Zn²⁺ ions reacted with the complex carbonate and hydroxide ions to form zinc carbonate hydroxide hydrate (Zn₄CO₃(OH)₆·H₂O), and the conversion from Zn₄CO₃(OH)₆·H₂O to ZnO was synchronously achieved by a MAH process. The as-prepared ZnO has a sponge-like morphology. However, the initial sponge-like morphology of ZnO could change to a net-like structure after thermal treatment, and compact nano-scale ZnO particles were finally obtained when the period of thermal treatment increased to 30 min. Pure ZnO nanoparticles was obtained from calcination of loose sponge-like ZnO particles at 500 °C. The analysis of optical properties of these ZnO nanoparticles showed that the intensity of 393 nm emission increased with the calcination temperature because the defects were reduced and the crystallinity was improved.     

Novel highly luminescent europium dinitrosalicylates

A series of lanthanide dinitrosalicylates M₃Ln(3,5-NO₂-Sal)₃ · nH₂O (Ln = Eu, Gd; M = Li, Na, K, Cs) was synthesized. It was found that the luminescence efficiency of some M₃Eu(3,5-NO₂-Sal)₃ · nH₂O compounds was near to the high efficiency of europium dibenzoylmethanate with 1,10-phenanthroline, Eu(DBM)₃ · Phen. The luminescence excitation spectra, electron-vibrational luminescence spectra, and vibrational IR spectra were investigated. The energy of the lowest excited triplet state of the ligand was obtained from phosphorescence spectra of M₃Gd(3,5-NO₂-Sal)₃ · nH₂O, M(3,5-NO₂-HSal) · nH₂O, and M₂(3,5-NO₂-Sal) · nH₂O. The details of the structure of compounds were discussed. The influence of different M-cations on the Eu³⁺ luminescence efficiency and on the processes of excitation energy transfer to a Eu³⁺ ion was analyzed. The presence of large alkali metal cations in lanthanide dinitrosalicylates and an increase in the temperature weaken the network of hydrogen bonds and, to some extent, the “ligand–metal” bonds. This is a cause of a long-wavelength shift of the intraligand charge transfer (ILCT) band in Eu³⁺ excitation spectra arising at inclusion of Cs⁺ instead of Li⁺ cations in the crystal lattice and at the heating of compounds. A change of the energies of ligand electronic states at substitution of Li⁺ and Na⁺ for Cs⁺ can give a tenfold enhancement of the Eu³⁺ luminescence efficiency at 300 K.     

Synthesis and electrochemical characterization of Li2MnO3–LiNixCOyMnzO2 cathode for lithium battery using co-precipitation method

The Li_xNi_0.23Co_0.12Mn_0.65O₂ electrode system with various compositions (x = 1.19, 1.33, 1.46, 1.58) was synthesized from a metal oxide precursor synthesized by co-precipitation method. The XRD patterns of the prepared powders revealed a hexagonal α-NaFeO₂ structure (space group: R-3m, 166) and the existence of a Li₂MnO₃ phase in the composite structure. In particular, the low Li content sample shows a three integrated structure (spinel, Li₂MnO₃, LiMO₂) for a Li/Metal(Ni/Co/Mn) mol ratio of 1.2. Scanning electron microscopy showed that all the synthesized samples contained spherical agglomerates with a size of 8–10 μm. Among the samples tested, Li_1.46Ni_0.23Co_0.12Mn_0.65O₂ shows relatively high charge and discharge capacity for the first cycle is 287, 192.9 mA h g^?1, respectively. Also, charge transfer resistance was also significantly improved compare with other samples.     

Hydrothermal synthesis of mesoporous VO2·½(H2O) nanosheets and study of their electrical properties

Layered sheet-like nanocrystalline VO₂·½(H₂O) has been synthesized by hydrothermal process using V₂O₅ as vanadium source and 2-phenylethylamine as a reducing agent and a structure-directing template. Techniques X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR) and nitrogen adsorption/desorption isotherms have been used to characterize the structure, morphology and composition of the materials. Electrical conductivity measurements showed that the as synthesized VO₂·½(H₂O) nanosheets has a conductivity value which goes from 75 × 10^?6 Ω^?1 cm^?1 at 298 K, to 68 10^?5 Ω^?1 cm^?1 at 386 K with activation energy of 0.24 eV.     

Synthesis and adsorption property of zinc rust of zinc hydroxynitrate

In order to clarify the formation condition of zinc rusts such as layered zinc hydroxynitrate (Zn₅(OH)₈(NO₃)₂·2H₂O: ZHN), ZnO particles were aged with aqueous Zn(NO₃)₂·6H₂O solution at 6–140 °C for 48 h. Further, adsorption of H₂O and CO₂ on ZHN was examined for simulating study of atmospheric corrosion of galvanized steel. The ZHN was formed at 6 °C and the ZnO completely disappeared, meaning the hydrolysis of ZnO particles in aqueous Zn(NO₃)₂·6H₂O solution to recrystallize as ZHN. Increasing the aging temperature improved the crystallinity of layered structure of ZHN, showing a maximum at 85 °C. The formed ZHN was hexagonal plate-like particles. The particle size was dependent of the crystallinity of layered structure of ZHN. The specific surface area of ZHN was decreased on elevating the aging temperature, showing a minimum at 85 °C. The adsorption of H₂O and CO₂ was enhanced on increasing the crystallinity of layered structure of ZHN, meaning that these molecules are adsorbed not only on particle surface but also in interlayer of ZHN. These facts infer that the preferred orientation of plate-like ZHN particles leads to the formation of compact rust layer on galvanized steel and to the enhancement of corrosion resistance.     

Effect of Air Annealing on the Structural and Magnetic Properties of LaMnO3 Perovskite Produced by Reactive Spark Plasma Sintering Route

Perovskite-type lanthanum manganite (LaMnO₃) was synthesized from Mn₂O₃ and La₂O₃ precursor powders using the Spark Plasma Sintering technique (SPS). The in situ reaction proceeds in a few minutes at 1000 °C under 50 MPa with a very high heating rate of 100 °C/min. The Rietveld refinement of the X-ray powder diffraction shows that LaMnO₃ sample crystallizes in a perovskite structure of O′-type orthorhombic symmetry with Pbnm space group. After annealing at 1000 °C in air for 10 hrs, the symmetry changes to rhombohedral with R-3c space group. For the as prepared sample, two critical temperature points in the temperature dependence of the ZFC and FC magnetization occurring at 125 K and 145 K are observed. They are suggested to be related to A-type antiferromagnetic Néel temperature and ferromagnetic short range order, respectively. The ferromagnetic component in the annealed sample increases indicating the expected variation in the concentration of Mn³⁺ and Mn⁴⁺ ions, which was attributed to the oxygen stoichiometry effects.     

Low-temperature synthesis,structural and magnetic properties of self-dopant LaMnO3+δ nanoparticles from a metal-organic polymeric precursor

Self-dopant LaMnO_3+δ nanoparticles have been successfully synthesized by metal citrate complex method based on Pechini-type reaction route, at low temperature (773 K). Powder X-ray diffraction and transmission electron microscope revealed pure and nanostructured phase of LaMnO_3+δ (δ = 0.125) with an average grain size of ∼72 nm (773 K) and ∼80 nm (1173 K). DC-magnetization measurements under an applied magnetic field of H = ±60 kOe showed an increase in the magnetization with the increase of calcination temperature. Ferromagnetic nature shown by non-stoichiometric LaMnO_3+δ was verified by well-defined hysteresis loop with large remanent magnetization (M_r) and coercive field (H_c). Surface areas of LaMnO_3+δ nanoparticles were found to be 157.4 and 153 m² g⁻¹ for the samples annealed at 773 K and 1173 K, respectively.     

Fabrication of CuO/Fe2O3 hollow hybrid microspheres

CuO/Fe₂O₃ hollow hybrid spheres with the size of 3–5 μm were successfully synthesized by a convenient hydrothermal method, using FeSO₄·7H₂O and CuSO₄·5H₂O as the starting materials and urea as the homogeneous precipitant. The samples were characterized by XRD, TEM, ED, SEM, EDX, IR and XPS measurements. XRD and XPS analyses indicated that the nanostructured materials consisted of CuO and α-Fe₂O₃. TEM and SEM measurements showed that the morphology of binary metal oxide was in the shape of hollow sphere. Careful observation from SEM measurements could find that CuO/Fe₂O₃ hollow microsphere shell was composed of uniform and dense metal oxide nanorods with about 20–40 nm in diameter and 100–200 nm in length. Moreover, the influence of calcination temperature on the thermal stability of the hollow structures was investigated. It showed that the hollow structure was stable after being calcined at 300 °C for 2 h. The formation mechanism of the CuO/Fe₂O₃ hollow spheres under hydrothermal condition was discussed.     

Crystal structure,thermal analysis and IR spectrometric investigation of l-tyrosine hydrazide diphosphate monohydrate

The monoclinic crystal structure of (C₉H₁₅N₃O₂)₂P₂O₇·H₂O denoted DLTHDP [a = 14.626(1), b = 6.1990(2), c = 14.562(1) Å, β = 97.289(3)°, Z = 2, monoclinic P2₁, D_cal = 1.508, D_mes = 1.49 g cm⁻³] has been solved using direct methods and refined to a reliability factor R = 4.37% for 2079 independent reflections. The DLTHDP structure can be described by infinite polyanions [P₂O₇·H₂O]_n⁴ⁿ⁻ organized in chains parallel to the b-direction and located at z = 1/2, alternating with organic cations associated in ribbons spreading along the a-direction. Multiple hydrogen bonds originating from amine, hydroxyl groups and water molecules donors [NH…O(N) and O(W)H…O] connect the different components of the lattice. The IR data of DLTHDP is reported and discussed according to the theoretical group analysis and by comparison with IR results of similar compounds. The coupled thermogravimetric analysis (TGA)–differential thermal analysis (DTA) thermal study shows the departure of one water molecule, confirming the hydrated character of this compound.     

Low-temperature synthesis of Li7La3Zr2O12 with cubic garnet-type structure

In this paper, we report the direct synthesis of Li₇La₃Zr₂O₁₂ with the cubic garnet-type structure at low temperature with a lattice constant of 13.0035 Å. The synthesis condition is optimized to be at 750 °C for 8 h with 30 wt% excess lithium salt. No intermediate grinding was involved in this straightforward route. Without the adventitious of Al³⁺, the cubic Li₇La₃Zr₂O₁₂ is unstable above 800 °C and has an ionic conductivity of the order of 10^?6 S cm^?1.     

Characterization of M(H2PO4)2·2H2O (M = Mn,Co, Ni) and their in situ thermal decomposition by magnetic measurements

It has been established that M(H₂PO₄)₂·2H₂O (M = Mn, Co, Ni) are paramagnetics between 173 and 353 K with weak antiferromagnetic exchange interaction between the metal ions. In situ magnetic measurements during the thermal decomposition of the salts show that the oxidation state and the octahedral coordination of M²⁺ are preserved. From the data obtained it could be supposed that in M(H₂PO₄)₂·2H₂O (M = Co, Ni) this process is topotactic with no long-range diffusion transport. In Mn(H₂PO₄)₂·2H₂O, the formation of the large variety of intermediate products probably requires more drastic rearrangement and diffusion of the manganese ions during the complex transformations, which reflect on both the value and the sign of the θ constants. M₂P₄O₁₂ (M = Mn, Co, Ni), which are the final decomposition products of the corresponding dihydrogen phosphates are paramagnetics in the temperature range of 295–573 K with antiferomagnetic interactions between the metal ions. The lattice parameters of Ni(H₂PO₄)₂·2H₂O have been calculated. It crystallizes in the monoclinic system with a = 7.228(1) Å; b = 9.778(1) Å; c = 5.306(1) Å; β = 94.50(1)°, SG P2₁/n with Z = 2.     

Surface characteristics and electrochemical corrosion behavior of NiTi alloy coated with IrO2

The aim of this work is to investigate the surface characteristics and corrosion behavior of NiTi (50.6 at.% Ni) shape memory alloy coated by a ceramic-like and highly biocompatible material, iridium oxide (IrO₂). IrO₂ coatings were prepared by thermal decomposition of H₂IrCl₆ · 6H₂O precursor solution at the temperature of 300 °C, 400 °C and 500 °C, respectively. The surface morphology and microstructure of the coatings were investigated by scanning electron microscope (SEM) and glancing angle X-ray diffraction (GAXRD). X-ray photoelectron spectroscopy (XPS) was employed to determine the surface elemental composition. Corrosion resistance property of the coated samples was studied in a simulated body fluid at 37 ± 1 °C by electrochemical method. It was found that the morphology and microstructure of the coatings were closely related to the oxidizing temperatures. A relatively smooth, intact and amorphous coating was obtained when the H₂IrCl₆·6H₂O precursor solution (0.03 mol/L) was thermally decomposed at 300 °C for 0.5 h. Compared with the bare NiTi alloy, IrO₂ coated samples exhibited better corrosion resistance behavior to some extent.     

Crystal structure and thermal expansion of LaCr1−xMgxO3, 0 < x ≤ 0.25

Solid solution LaCr_1?xMg_xO₃, 0 < х ≤ 0.25 was prepared by heating stoichiometric amounts of appropriate oxides in air at 1400 °C, 48 h. At room temperature it crystallizes in orthorhombically distorted GdFeO₃-type structure (a ≈ √2 × a_per; b ≈ √2 × a_pe; c ≈ 2 × a_per, where a_per – perovskite subcell parameter). High-temperature X-ray powder diffraction (HT XRPD) and dilatometry revealed first order phase transition to rhombohedral perovskite phase (R-3c, a ≈ √2 × a_per, c ≈ 2√3 × a_per) at 260–311 °C (OR phase transition). Crystal structures of room-temperature orthorhombic and high-temperature rhombohedral phases for LaCr_0.75Mg_0.25O₃ were refined using HT XRPD data. Temperature of OR phase transition increases gradually with increasing of magnesium content. Low-temperature orthorhombic phase exhibits TEC lower in comparison with high-temperature rhombohedral one (e.g. for LaCr_0.85Mg_0.15O₃ TEC(O) = 8.8 ppm K^?1; TEC(R) = 11.6 ppm K^?1). TEC for rhombohedral phase increases with increasing magnesium content from 10.4 ppm K^?1 for LaCr_0.95Mg_0.05O₃ to 12.1 ppm K^?1 for LaCr_0.75Mg_0.25O₃.