High heat generation ability in AC magnetic field for nano-sized magnetic Y3Fe5O12 powder prepared by bead milling

Nano-sized magnetic Y₃Fe₅O₁₂ ferrite having a high heat generation ability in an AC magnetic field was prepared by bead milling. A commercial powder sample (non-milled sample) of ca. 2.9 μm in particle size did not show any temperature enhancement in the AC magnetic field. The heat generation ability in the AC magnetic field improved with a decrease in the average crystallite size for the bead-milled Y₃Fe₅O₁₂ ferrites. The highest heat ability in the AC magnetic field was for the fine Y₃Fe₅O₁₂ powder with a 15-nm crystallite size (the samples were milled for 4 h using 0.1 mm? beads). The heat generation ability of the excessively milled Y₃Fe₅O₁₂ samples decreased. The main reason for the high heat generation property of the milled samples was ascribed to an increase in the Néel relaxation of the superparamagnetic material. The heat generation ability was not influenced by the concentration of the ferrite powder. For the samples milled for 4 h using 0.1 mm? beads, the heat generation ability (W g⁻¹) was estimated using a 3.58×10⁻⁴ fH² frequency (f/kHz) and the magnetic field (H/kA m⁻¹), which is the highest reported value of superparamagnetic materials.     

Heat generation ability in AC magnetic field of nano MgFe2O4-based ferrite powder prepared by bead milling

Nanosized MgFe₂O₄-based ferrite powder having heat generation ability in an AC magnetic field was prepared by bead milling and studied for thermal coagulation therapy applications. The crystal size and the particle size significantly decreased by bead milling. The heat generation ability in an AC magnetic field improved with the milling time, i.e. a decrease in crystal size. However, the heat generation ability decreased for excessively milled samples with crystal sizes of less than 5.5 nm. The highest heat ability (ΔT=34 °C) in the AC magnetic field (370 kHz, 1.77 kA/m) was obtained for fine MgFe₂O₄ powder having a ca. 6 nm crystal size (the samples were milled for 6-8 h using 0.1 mm ? beads). The heat generation of the samples was closely related to hysteresis loss, a B-H magnetic property. The reason for the high heat generation properties of the samples milled for 6-8 h using 0.1 mm ? beads was ascribed to the increase in hysteresis loss by the formation of a single domain. Moreover, the improvement in heating ability was obtained by calcination of the bead-milled sample at low temperature. In this case, the maximum heat generation (ΔT=41 °C) ability was obtained for a ca. 11 nm crystal size sample was prepared by crystal growth during the sample calcination. On the other hand, the ΔT value for Mg_0.5Ca_0.5Fe₂O₄ was synthesized using a reverse precipitation method decreased by bead milling.     

Electrochemical behaviour of sputtered c-V2O5 and LiCoO2 thin films for solid state lithium microbatteries

Here are reported for the first time electrochemical data on all-solid-state lithium microbatteries using crystalline sputtered V₂O₅ thin films as cathode materials and LiPON as solid electrolyte. The stable specific capacity of 30 µAh/cm² found with a 2.4 µm thick film competes very well with the best values obtained for solid state microbatteries using amorphous films. With the challenge of decreasing the temperature of heat treatment for sputtered LiCoO₂ thin films, we show that a temperature of 500 °C combined with an optimized bias sputtering (-50 V) allows to get highly crystalline deposits, to minimize the presence of Co₃O₄ and to suppress any trace of the cubic phase. At the same time the theoretical specific capacity is reached in the 4.2 V-3 V range and a good cycling behaviour is achieved with a high capacity of 50 µAh/cm²/µm after 140 cycles at 10 µA.cm².     

Luminescence in trivalent rare earth activated Sr4Al2O7 phosphor

In this paper we report the combustion synthesis of trivalent rare-earth (RE³⁺ = Dy, Eu and Ce) activated Sr₄Al₂O₇ phosphor. The prepared phosphors were characterized by the X-ray powder diffraction (XRD) and photoluminescence (PL) techniques. Photoluminescence emission peaks of Sr₄Al₂O₇:Dy³⁺ phosphor at 474 nm and 578 nm in the blue and yellow region of the spectrum. The prepared Eu³⁺ doped phosphors were excited by 395 nm then we found that the characteristics emission of europium ions at 615 nm (⁵D₀?⁷F₂) and 592 nm (⁵D₀?⁷F₁). Photoluminescence (PL) peaks situated at wavelengths of 363 and 378 nm in the UV region under excitation at around 326 nm in the Sr₄Al₂O₇:Ce³⁺ phosphor.     

Preparation and photoluminescence characteristics of Eu-doped MgAl1.8Y0.2O4 nanocrystals

A simple combustion route was employed for the preparation of Eu³⁺-doped MgAl_1.8Y_0.2−xO₄ nanocrystals using metal nitrates as precursors and urea as a fuel in a preheated furnace at 500 °C. The powders thus obtained were then fired at 1000 °C for 3 h to get better luminescent properties. The incorporation of Eu³⁺ activator in these nanocrystals was checked by luminescence characteristics. These nanocrystals displayed bright red color on excitation under 254 nm UV source. The main emission peak was assigned to the transition [⁵D₀→⁷F₂] at 615 nm. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) studies were carried out to understand surface morphological features and the particle size. Crystal structures of the nanocrystals were investigated by the X-ray diffraction (XRD) technique. The crystallite size of the as-prepared nanocrystals was around 29 nm, which was evaluated from the broad XRD peaks. The crystallite size increased to ∼45 nm on further heat treatment at 1000 °C.     

Green synthesis and characterization of superparamagnetic Fe3O4 nanoparticles

In this paper, we have first demonstrated a facile and green synthetic approach for preparing superparamagnetic Fe₃O₄ nanoparticles using α-d-glucose as the reducing agent and gluconic acid (the oxidative product of glucose) as stabilizer and dispersant. The X-ray powder diffraction (XRD), X-ray photoelectron spectrometry (XPS), and selected area electron diffraction (SAED) results showed that the inverse spinel structure pure phase polycrystalline Fe₃O₄ was obtained. The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results exhibited that Fe₃O₄ nanoparticles were roughly spherical shape and its average size was about 12.5 nm. The high-resolution TEM (HRTEM) result proved that the nanoparticles were structurally uniform with a lattice fringe spacing about 0.25 nm, which corresponded well with the values of 0.253 nm of the (3 1 1) lattice plane of the inverse spinel Fe₃O₄ obtained from the JCPDS database. The superconducting quantum interference device (SQUID) results revealed that the blocking temperature (T_b) was 190 K, and that the magnetic hysteresis loop at 300 K showed a saturation magnetization of 60.5 emu/g, and the absence of coercivity and remanence indicated that the as-synthesized Fe₃O₄ nanoparticles had superparamagnetic properties. Fourier transform infrared spectroscopy (FT-IR) spectrum displayed that the characteristic band of Fe-O at 569 cm⁻¹ was indicative of Fe₃O₄. This method might provide a new, mild, green, and economical concept for the synthesis of other nanomaterials.     

Structural and cathodoluminiscent properties of Zr0.95Ce0.05O2 nanopowders prepared by sol-gel and template methods

Nanopowders of Zr_0.95Ce_0.05O₂ composition have been prepared by a standard Pechini-type sol-gel process and by means of a colloidal crystal template approach. In the latter method, inverse opal Zr_0.95Ce_0.05O₂ powders were fabricated employing poly(methyl methacrylate) (PMMA) colloidal crystals as a template. The effects of the two different synthesis routes on the structure and microstructural characteristics of the prepared nanopowders were evaluated by X-ray diffraction and scanning electron microscopy. For both preparation routes, the X-ray diffraction analysis has shown that a tetragonal fluorite structure is formed with a crystallite size of ∼35-40 nm. The scanning electron microscopy measurements indicate that the powder obtained by the sol-gel Pechini-type process is comprised of nanoparticles that are arranged in agglomerates with shape and size relatively uniform whereas the inverse opal Zr_0.95Ce_0.05O₂ nanopowders exhibit the formation of macropores with a mean size of ∼100 nm. The cathodoluminescence spectra of the prepared Zr_0.95Ce_0.05O₂ nanomaterials have been measured in the 300-800 nm wavelength range. The powder prepared by sol-gel method yields a broad emission band centered at 482 nm whereas the emission from the inverse opal preparation is considerably less intense.     

Effect of sintering temperature and the particle size on the structural and magnetic properties of nanocrystalline Li0.5Fe2.5O4

Sintering temperature and particle size dependent structural and magnetic properties of lithium ferrite (Li_0.5Fe_2.5O₄) were synthesized and sintered at four different temperatures ranging from 875 to 1475 K in the step of 200 K. The sample sintered at 875 K was also treated for four different sintering times ranging from 4 to 16 h. Samples sintered at 1475 K have the cubic spinel structure with a small amount of α-Fe₂O₃ (hematite) and γ-Fe₂O₃ (maghemite). The samples sintered at≤1275 K do not show hematite and maghemite phases and the crystals form the single phase spinel structure with the cation ordering on octahedral sites. Particle size of lithium ferrite is in the range of 13-45 nm, and is depend on the sintering temperature and sintering time. The saturation magnetization increased from 45 to 76 emu/g and coercivity decreases from 151 to 139 Oe with an increase in particle size. Magnetization temperature curve recorded in ZFC and FC modes in an external magnetic field of 100 Oe. Typical blocking effects are observed below about 244 K. The dielectric constant increases with an increase in sintering temperature and particle size.     

Emission analysis of Pr and Tm: Ca2Gd2W3O14 phosphors

5 mol% of Pr³⁺ and Tm³⁺ ions activated calcium gadolinium tungstate (Ca₂Gd₂W₃O₁₄₎ phosphors were synthesized by traditional solid state reaction method. Crystalline phase structure was identified from the X-ray diffraction (XRD) profiles. From the scanning electron microscopy (SEM) images, we have observed the agglomeration of the particles, and average grain size is around 40-300 nm. Using the energy dispersive X-ray analysis (EDAX) and Fourier transform infrared (FTIR) spectra, identified the elements and functional groups present in the prepared phosphors. The emission spectrum of Pr³⁺: Ca₂Gd₂W₃O₁₄ powder phosphors have shown an intense red emission at 615 nm with the excitation wavelength λ_exci=450 nm and thus these red color emitting powder phosphors are used as one of the components in the preparation of WLEDs. The excitation spectrum of Tm³⁺: Ca₂Gd₂W₃O₁₄ powder phosphor has shown a ligand to metal charge transfer (W-O) band (LMCT) within the WO₄²⁻ group. Emission spectrum of Tm³⁺: Ca₂Gd₂W₃O₁₄ phosphors have shown blue emissions at 453 nm (¹D₂→³F₄).     

Synthesis of nanocrystalline Zn0.5Mn0.5Fe2O4 via in situ polymerization technique

Nanocrystalline Zn_0.5Mn_0.5Fe₂O₄ was synthesized through the pyrolysis of polyacrylate salt precursors prepared via in situ polymerization of the metal salts and acrylic acid. The pyrolysis behavior of the polymeric precursors was studied by use of thermal analysis. The as-obtained product was characterized by powder X-ray diffraction (XRD), transmission electron microscope (TEM), electron diffraction (ED) pattern, scanning electron microscopy (SEM) and electron dispersive X-ray (EDX) analysis. The results revealed that the particle size is in the range of 15–25 nm for Zn-Mn ferrites with good crystallinity. Magnetic properties of the sample at 300 K were measured using a vibrating sample magnetometer, which showed that the sample exhibited characteristics of superparamagnetism.     

Electronic structure studies of the spinel CoFe2O4 by X-ray photoelectron spectroscopy

The spinel CoFe₂O₄ has been synthesized by combustion reaction technique. X-ray photoelectron spectroscopy shows that samples are near-stoichiometric, and that the specimen surface both in the powder and bulk sample is most typically represented by the formula (Co_0.4Fe_0.6)[Co_0.6Fe_1.4]O₄, where cations in parentheses occupy tetrahedral sites and those within square brackets in octahedral sites. The results demonstrate that most of the iron ions are trivalent, but some Fe²⁺ may be present in the powder sample. The Co 2p_3/2 peak in powder sample composed three peaks with relative intensity of 45%, 40% and 15%, attributes to Co²⁺ in octahedral sites, tetrahedral sites and Co³⁺ in octahedral sites. The O 1s spectrum of the bulk sample is composed of two peaks: the main lattice peak at 529.90 eV, and a component at 531.53 eV, which is believed to be intrinsic to the sample surface. However, the vanishing of the O 1s shoulder peak of the powder specimen shows significant signs of decomposition.     

Synthesis and ion conductivity of (Bi2O3)0.75(Dy2O3)0.25 ceramics with grain sizes from the nano to the micro scale

Using (Bi₂O₃)_0.75(Dy₂O₃)_0.25 nano-powder synthesized by reverse titration co-precipitation method as raw material, dense ceramics were sintered by both Spark Plasma Sintering (SPS) and pressureless sintering. According to the predominance area diagram of Bi-O binary system, the sintering conditions under SPS were optimized. (Bi₂O₃)_0.75(Dy₂O₃)_0.25 ceramics with relative density higher than 95% and an average grain size of 20 nm were sintered in only 10 min up to 500 °C. During the pressureless sintering process, the grain growth behavior of (Bi₂O₃)_0.75(Dy₂O₃)_0.25 followed a parabolic trend, expressed as D² − D₀² = Kt, and the apparent activation energy of grain growth was found to be 284 kJ mol^− 1. Dense (Bi₂O₃)_0.75(Dy₂O₃)_0.25 ceramics with different grain sizes were obtained, and the effect of grain size on ion conductivity was investigated by impedance spectroscopy. It was shown that the total ion conductivity was not affected by the grain size down to 100 nm, however lower conductivity was measured for the sample with the smallest grain size (20 nm). But, although only the δ phase was evidenced by X-ray diffraction for this sample, a closer inspection by Raman spectroscopy revealed traces of α-Bi₂O₃.     

Synthesis of (Mg0.476Mn0.448Zn0.007)(Fe1.997Ti0.002)O4 powder and sintered ferrites by high energy ball-milling process

(Mg_0.476Mn_0.448Zn_0.007)(Fe_1.997Ti_0.002)O₄ nanocrystalline powder prepared by high energy ball-milling process were consolidated by microwave and conventional sintering processes. Phases, microstructure and magnetic properties of the ferrites prepared by different processes were investigated. The (Mg_0.476Mn_0.448Zn_0.007)(Fe_1.997Ti_0.002)O₄ nanocrystalline powder could be prepared by high energy ball-milling process of raw Fe₃O₄, MnO₂, ZnO, TiO₂ and MgO powders. Prefired and microwave sintered ferrites could achieve the maximum density (4.86 g/cm⁻³), the average grain size (15 μm) was larger than that (10 μm) prepared by prefired and conventionally sintered ferrites with pure ferrite phase, and the saturation magnetization (66.77 emu/g) was lower than that of prefired and conventionally sintered ferrites (88.25 emu/g), the remanent magnetization (0.7367 emu/g) was higher than that of prefired and conventionally sintered ferrites (0.0731 emu/g). Although the microwave sintering process could increase the density of ferrites, the saturation magnetization of ferrites was decreased and the remanent magnetization of ferrites was also increased.     

Organic acid assisted solid-state synthesis of Li1.2Ni0.16Co0.08Mn0.56O2 nanoparticles as lithium ion battery cathodes

Lithium-rich layered oxide Li_1.2Ni_0.16Co_0.08Mn_0.56O₂ can be referred as a crystalline mixture of Li₂MnO₃ and LiNi_0.4Co_0.2Mn_0.4O₂ at equal molar ratio. In the paper, the solid state reaction of M(AC)₂·4H₂O (M = Mn, Co and Ni) and LiOH·H₂O has been performed to obtain nanocrystalline Li_1.2Ni_0.16Co_0.08Mn_0.56O₂ using a small molecular organic acid (i.e., oxalic acid (OA), citric acid (CA) or tartaric acid (TA)) as additive. The introduction of organic acids can help to improve the layered structure and inhibit the particle growth of Li_1.2Ni_0.16Co_0.08Mn_0.56O₂, and the different organic acids exert distinct influences on the structural and electrochemical properties of Li_1.2Ni_0.16Co_0.08Mn_0.56O₂. In detail, the nanoparticles obtained in the presence of OA have the smallest average size of 50–150 nm, which correspondingly exhibit the highest initial discharge capacity of 267.52 mAh g⁻¹ at 0.1C and the best high-rate capability (e.g., 152.22 mAh g⁻¹, 5C) when applied as a lithium ion battery cathode. Furthermore, the active substance obtained from TA shows the best cycling stability and a discharge capacity of 202.42 mAh g⁻¹ can be retained after 50 cycles at 0.5C.     

Preparation and magnetic properties of the conductive Co(1−x)NixFe2O4/polyaniline microsphere composites

Core-shell Co_(1−x)Ni_xFe₂O₄/polyaniline nanoparticles, where the core was Co_(1−x)Ni_xFe₂O₄ and the shell was polyaniline, were prepared by the combination of sol-gel process and in-situ polymerization methods. Nanoparticles were investigated by Fourier transform spectrometer, X-ray diffraction diffractometer, Scanning electron microscope, Differential thermal analysis and Superconductor quantum interference device. The results showed that the saturation magnetization of pure Co_(1−x)Ni_xFe₂O₄ nanoparticles were 57.57 emu/g, but Co_(1−x)Ni_xFe₂O₄/polyaniline composites were 37.36 emu/g. It was attributed to the lower content (15 wt%), smaller size and their uneven distribution of Co_(1−x)Ni_xFe₂O₄ nanoparticles in the final microsphere composites. Both Co_(1−x)Ni_xFe₂O₄ and PANI/Co_(1−x)Ni_xFe₂O₄ showed superparamagnetism.     

Preparation and characterization of polyaniline (PANI)-Mn3O4 nanocomposite

Polyaniline (PANI)-Mn₃O₄ nanocomposite was synthesized by a combination of sonochemical synthesis of Mn₃O₄ NP's and in-situ polymerization of aniline. Structural characteristics were evaluated by XRD, FT-IR, TGA, VSM, TEM and SEM analysis, and conduction characteristics were evaluated by total conductivity measurements in the temperature range of 20-100 °C and frequency range of 0.1 Hz-1 MHz. Our findings show that PANI is successfully coated on nanoparticles surface and overall conductivity of nanocomposite is approximately 50-1000 times higher than that of uncapped Mn₃O₄ or PANI base with increase in temperature. Morphology of the synthesized powder was observed to be thin nanosheets with a thickness of 2-3 nm based on SEM analysis. Room temperature magnetization curves for nanocomposite show no hysteresis, indicating the super-paramagnetic character of the sample in the region of measured field strength. σ_AC increased after polyaniline coating.     

Oxide coatings on Y3Al5O12:Tb particles

A coating method with precipitating process was developed to reduce the particle size and to improve the particle dispersion of Y₃Al₅O₁₂:Tb³⁺ phosphor prepared by sol-gel method. The particle morphology was observed by using SEM and TEM; and the particle size and its dispersion was measured by using laser scattering technique. Several coating materials were tested. Among them, Al₂(SiO₃)₃ coating not only reduced the particle size from several micrometers to ∼1 μm and improved the particle dispersion, but also well kept luminescent intensities and improved the duration of the phosphor under the bombardment of cathode ray. The mechanism of the particle size reduction was proposed.     

Bulk and surface properties of spinel Co3O4 by density functional calculations

DFT calculations are employed to bulk and surface properties of spinel oxide Co₃O₄. The bulk magnetic structure is calculated to be antiferromagnetic, with a Co²⁺ moment of 2.631 μ_B in the antiferromagnetic state. There are three predicted electron transitions O(2p) → Co²⁺(t_2g) of 2.2 eV, O(2p) → Co³⁺(e_g) of 2.9 eV and Co³⁺(t_2g) → Co²⁺(t_2g) of 3.3 eV, and the former two transitions are close to the corresponding experimental values 2.8 and 2.4 eV. The naturally occurring Co₃O₄ (1 1 0) and (1 1 1) surfaces were considered for surface calculations. For ideal Co₃O₄ (1 1 0) surfaces, the surface relaxations are not significant, while for ideal Co₃O₄ (1 1 1) surfaces the relaxation of Co²⁺ cations in the tetrahedral sites is drastic, which agrees with the experiment observation. The stability over different oxygen environments for possible ideal and defect surface terminations were explored.     

Synthesis of Y2Si2O7:Eu nanocrystal and its optical properties

Nanocrystalline Y₂Si₂O₇:Eu phosphor with an average size about 60 nm is easily prepared using silica aerogel as raw material under ultrasonic irradiation and annealing temperature at 300-600 °C and this nanocrystalline decomposes into Y₂O₃:Eu and silica by heat treatment at 700-900 °C. The excitation broad band centered at 283 and 254 nm results from Eu³⁺ substituting for Y³⁺ in Y₂Si₂O₇ and Y₂O₃/SiO₂, respectively. Compared with Y₂O₃:Eu/SiO₂ crystalline, the PL excitation and emission peaks of Y₂Si₂O₇:Eu nanocrystalline red-shift and lead to the enhance of its luminescence intensity due to the different chemical surroundings of Eu³⁺ in above nanocrystallines. The decrease of PL intensity may be ascribed to quenching effect resulting from more defects in Y₂O₃:Eu/SiO₂ crystalline.     

Synthesis, characterization, and luminescent properties of Lu2O3:Eu phosphors

Eu-doped lutetia (Lu₂O₃:Eu) nano-phosphors were synthesized by the sol-gel combustion process from a mixed aqueous solution of europium and lutetium nitrates, using organic glycine as the fuel. Powder X-ray diffraction shows that cubic Lu₂O₃:Eu crystallites are directly obtained by the sol-gel combustion process without further calcination. Electron microscopy reveals that the as-prepared phosphors are agglomerated and have a fluffy, fine, and porous morphology, consisting of primary particle size of 8-10 nm. The excitation spectrum is characterized by three dominant bands centered at 395, 466, and 534 nm, respectively. Both the photoluminescent and radioluminescent spectra are very similar and exhibit intense emission peaks centered at 612 nm due to ⁵D₀→⁷F₂ transition of Eu³⁺ ions. The energy transfer from Lu₂O₃ host to Eu³⁺ activator is more efficient in the case of calcined phosphors than for the as-prepared phosphors due to their improved lattice perfection.