Study on the optically linear birefringence and dichroism properties of Fe3O4 magnetic nanoparticles

We adopt an improved co-precipitation method to prepare the Fe₃O₄ magnetic nanoparticles (MNPs). Influence factors such as the reaction temperature, the pH value of the solution, and the Fe³⁺/Fe²⁺ molar concentration are considered. Via the transmission electronic microscope and X-ray diffractometry, we characterize the dispersibility and size of the products. The reaction temperature and the pH value of the solution have a great influence in the dispersibility and size of MNPs. The diameter of Fe₃O₄ MNP, produced under Fe³⁺/Fe²⁺ molar concentration of 0.25 mole/l and molar ratio of 1.9:1, the reaction temperature is 80 °C, and the pH value reaches 9, is close to 11 nm. Above all, considering the variation of molar concentrations in Fe³⁺/Fe²⁺, the linear birefringence and dichroism of the kerosene-based ferrofluids are investigated by a Stokes polarimeter.     

Sonochemical assisted synthesis of SrFe12O19 nanoparticles

We present the synthesis of M-type strontium hexaferrite by sonochemistry and annealing. The effects of the sonication time and thermal energy on the crystal structure and magnetic properties of the obtained powders are presented. Strontium hexagonal ferrite (SrFe₁₂O₁₉) was successfully prepared by the ultrasonic cavitation (sonochemistry) of a complexed polyol solution of metallic acetates and diethylene glycol. The obtained materials were subsequently annealed at temperatures from 300 to 900 °C. X-ray diffraction analysis shows that the sonochemical process yields an amorphous phase containing Fe³⁺, Fe²⁺ and Sr²⁺ ions. This amorphous phase transforms into an intermediate phase of maghemite (γ-Fe₂O₃) at 300 °C. At 500 °C, the intermediate species is converted to hematite (α-Fe₂O₃) by a topotactic transition. The final product of strontium hexaferrite (SrFe₁₂O₁₉) is generated at 800 °C. The obtained strontium hexaferrite shows a magnetization of 62.3 emu/g, which is consistent with pure hexaferrite obtained by other methods, and a coercivity of 6.25 kOe, which is higher than expected for this hexaferrite. The powder morphology is composed of aggregates of rounded particles with an average particle size of 60 nm.     

Soft chemistry routes for synthesis of rare earth oxide nanoparticles with well defined morphological and structural characteristics

Phosphors of (Y_0.75Gd_0.25)₂O₃:Eu³⁺ (5 at.%) have been prepared through soft chemistry routes. Conversion of the starting nitrates mixture into oxide is performed through two approaches: (a) hydrothermal treatment (HT) at 200 °C/3 h of an ammonium hydrogen carbonate precipitated mixture and (b) by thermally decomposition of pure nitrate precursor solution at 900 °C in dispersed phase (aerosol) within a tubular flow reactor by spray pyrolysis process (SP). The powders are additionally thermally treated at different temperatures: 600, 1000, and 1100 °C for either 3 or 12 h. HT—derived particles present exclusively one-dimensional morphology (nanorods) up to the temperatures of 600 °C, while the leaf-like particles start to grow afterward. SP—derived particles maintain their spherical shape up to the temperatures of 1100 °C. These submicron sized spheres were actually composed of randomly aggregated nanoparticles. All powders exhibits cubic Ia-3 structure (Y_0.75Gd_0.25)₂O₃:Eu and have improved optical characteristics due to their nanocrystalline nature. The detailed study of the influence of structural and morphological powder characteristics on their emission properties is performed based on the results of X-ray powder diffractometry, scanning electron microscopy, X-ray energy dispersive spectroscopy, transmission electron microscopy, and photoluminescence measurements.     

Phase transformation of strontium hexagonal ferrite

The phase transformation of strontium hexagonal ferrite (SrFe₁₂O₁₉) to magnetite (Fe₃O₄) as main phase and strontium carbonate (SrCO₃) as secondary phase is reported here. SrFe₁₂O₁₉ powder was obtained by a heat treatment at 250 °C under controlled oxygen flow. It was observed that the phase transformation occurred when the SrFe₁₂O₁₉ ferrite was heated up to 625 °C in confinement conditions. This transformation took place by a combination of three factors: the presence of stresses in the crystal lattice of SrFe₁₂O₁₉ due to a low synthesis temperature, the reduction of Fe³⁺ to Fe²⁺ during the heating up to 625 °C, and the similarity of the coordination spheres of the iron atoms present in the S-block of SrFe₁₂O₁₉ and Fe₃O₄. X-ray diffraction analysis confirmed the existence of strain and crystal deformation in SrFe₁₂O₁₉ and the absence of them in the material after the phase transformation. Dispersive X-ray absorption spectroscopy and Fe⁵⁷ Mössbauer spectroscopy provided evidences of the reduction of Fe³⁺ to Fe²⁺ in the SrFe₁₂O₁₉ crystal.     

YIG formation in annealed iron implanted YAG

YAG and YIG crystals implanted respectively with 100 keV⁵⁷Fe²⁺ ions (1 × 10¹⁷ ions.cm^?2) and 50 keV²⁷Al ions (1.1 × 10¹⁷ ions.cm^?2) have been studied by conversion electron Mössbauer spectroscopy (CEMS) directly after implantation and after annealings in air at temperatures up to 1100°C. In both as-implanted samples iron is found mainly in three states: Fe²⁺, Fe³⁺ and small metallic precipitates. Annealing behaviour is divided into two stages: (i) up to 400°C the iron has become completely oxidized and (ii) between 400 and 850°C the epitaxial regrowth of the implanted layer takes place. During this process a part of iron ions are incorporated into octahedral and tetrahedral sites, thus making a Y₃ (Al Fe)₅ O₁₂ compound. The remaining iron part precipitates in the form of Fe₂O₃ particles.     

Effect of Ti4+ ions doping on microstructure and dc resistivity of nickel ferrites

Nanostructured nickel ferrites (NiFe₂O₄) were prepared by doping with Ti⁴⁺ ions using solid-state reaction route. Lowest grain size of 55 nm was achieved in the specimens with 20 mole% TiO₂ doping. Magnetization in the specimens decreases with decreasing grain sizes. Lower volume fractions of ferrite phase due to dissociation of the magnetic phase into smaller particles by the disruption of super exchange interaction by the titanium substitution results a decrease in magnetizations. Coercivity showed an increasing trend. This was explained as arising due to multidomain/monodomain magnetic behavior of magnetic nanoparticles. Small polaron hopping conduction between Fe²⁺ and Fe³⁺ sites controls the dc electrical properties of the specimens. The presence of an interfacial amorphous phase between the sites is evident from Mott's analysis. Specimens containing 10 mole or more TiO₂ and sintered at 1350 °C contain NiTiO₃ as a secondary phase and show unusual dc conductivity.     

Preparation of CuO nanoparticles by metal salt-base reaction in aqueous solution and their metallic bonding property

This article describes a method for preparing CuO nanoparticles in aqueous solution, and a demonstration of feasibility of metallic bonding with the use of the CuO particles. Colloid solution of CuO nanoparticles was prepared from Cu(NO₃)₂ aqueous solution (0.01 M) and NaOH aqueous solution (0.019 M) at 5–80 °C. Leaf-like aggregates with an average size of 567 nm composed of CuO nanoparticles were produced at 20 °C. The size of leaf-like aggregates decreased with increasing reaction temperature. Metallic copper discs could be bonded using the CuO nanoparticles under annealing at 400 °C and pressurizing at 1.2 MPa for 5 min in H₂ gas. A shear strength required for separating the bonded discs was 25.4 MPa for the CuO nanoparticles prepared at 20 °C, whose aggregates were the largest among the CuO particles examined. These results indicated that the formation of leaf-like aggregates of CuO nanoparticles led to efficient metallic bonding.     

Formation of nickel and nickel,zinc-bearing ferrite in aqueous suspension by air oxidation

Stoichiometric Ni-bearing ferrite was formed by air oxidation of an iron(II) hydroxide suspension at an initial Ni : Fe_tot mol ratio (r_Ni) of 0.20 : 2.80 at pH 10.0 and 65°C. Most of products formed at r_Ni=0.40 : 2.60 and 0.60 : 2.40 were Ni-bearing ferrites, of which vacancies of Fe³⁺ ion on the lattice points may be considered. Only Ni, Zn-bearing ferrites were formed in the suspensions at initial (Ni + Zn)  : Fe_tot mol ratios (r_{Ni + Zn}) of 0.20 : 2.80–0.60 : 2.40 at pH 10.0 and 65°C. At higher r_Ni or r_{Ni + Zn} by-products containing Ni, Fe and O₄²⁻ were formed. The formation of the by-products was depressed in the suspensions containing chloride ions in the place of sulfate ions.     

Sono-assisted preparation of highly-efficient peroxidase-like Fe3O4 magnetic nanoparticles for catalytic removal of organic pollutants with H2O2

Fe₃O₄ magnetic nanoparticles (Fe₃O₄ MNPs) with much improved peroxidase-like activity were successfully prepared through an advanced reverse co-precipitation method under the assistance of ultrasound irradiation. The characterizations with XRD, BET and SEM indicated that the ultrasound irradiation in the preparation induced the production of Fe₃O₄ MNPs possessing smaller particle sizes (16.5 nm), greater BET surface area (82.5 m² g^?1) and much higher dispersibility in water. The particle sizes, BET surface area, chemical composition and then catalytic property of the Fe₃O₄ MNPs could be tailored by adjusting the initial concentration of ammonia water and the molar ratio of Fe²⁺/Fe³⁺ during the preparation process. The H₂O₂-activating ability of Fe₃O₄ MNPs was evaluated by using Rhodamine B (RhB) as a model compound of organic pollutants to be degraded. At pH 5.4 and temperature 40 °C, the sonochemically synthesized Fe₃O₄ MNPs were observed to be able to activate H₂O₂ and remove ca. 90% of RhB (0.02 mmol L^?1) in 60 min with a apparent rate constant of 0.034 min^?1 for the RhB degradation, being 12.6 folds of that (0.0027 min^?1) over the Fe₃O₄ MNPs prepared via a conventional reverse co-precipitation method. The mechanisms of the peroxidase-like catalysis with Fe₃O₄ MNPs were discussed to develop more efficient novel catalysts.     

Annealing Behavior of 57Fe Implanted in ZrO2(Y)

Using conversion electron Mossbauer spectroscopy(CEMS) and slow positron beam, the chemical states of the implanted ⁵⁷Fe (100KeV,3 × 10 ¹⁶ ions/cm ²) in ZrO₂ containing 3 mol% Y ₂O ₃( ZY ₃) and its thermodynamic behavior during annealing process with the temperature from 200 to 500°C were studied. After annealing at 400°C the complex of Fe³⁺-V has been mostly dissolved, and the prior phase to α-Fe and α-Fe nano-crystalline cluster were present in the sample. Meanwhile the mixed conducting of oxygen-ions and electrons in the ZY₃ containing Fe sample appeared. This revised version was published online in August 2006 with corrections to the Cover Date.     

Domain state–dependent magnetic formation of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles analyzed via magnetic resonance

Magnetic properties, arising from surface exchange and interparticle interactions of the Fe₃O₄ (magnetite) nanoparticles, were investigated in the temperature range of 5–300 and 120–300 K using vibrating sample magnetometer technique and electron spin resonance spectroscopy, respectively. The research was based on to figure out the origin of intraparticle interactions and the change of interparticle interactions in wide size range Fe₃O₄ nanoparticles. The analyses were done for samples having almost same particle size distributions. The average particle sizes were changed in between 30 ± 2 and 34 ± 2 nm. The observed magnetization values were demonstrated the mixture of single-domain size particles, exhibiting both single-domain (SD) and superparamagnetic (SPM) states. The symmetry of resonance curves changed according to the ratio of SD and SPM-stated particles in mixture under located temperature. The changes of anisotropy up to domain state were understood by freezing magnetic moment in glycerol matrix from room temperature to 120 K under 5-kG field. The shift of H _R values to higher magnetic fields and the more symmetric resonance spectrum proved the effect of anisotropy and interparticle interactions fields on magnetic behave. In addition, the origin of intra-interaction was exposed from Fe³⁺ centers and exchange coupling in between Fe²⁺, Fe³⁺, and O⁻, and Fe³⁺ centers found from g factor (g).     

Influence of pH on the preparation of dispersed Ag–TiO<Subscript>2</Subscript> nanocomposite

In this paper, data concerning the effect of pH on the morphology of Ag–TiO₂ nanocomposite during photodeposition of Ag on TiO₂ nanoparticles is reported. TiO₂ nanoparticles prepared by sol–gel method were coated with Ag by photodeposition from an aqueous solution of AgNO₃ at various pH levels ranging from 1 to 10 in a titania sol, under UV light. The as-prepared nanocomposite particles were characterized by UV–vis absorption spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), and N₂ adsorption/desorption method at liquid nitrogen temperature (−196 °C) from Brunauer–Emmett–Teller (BET) measurements. It is shown that at a Ag loading of 1.25 wt.% on TiO₂, a high-surface area nanocomposite morphology corresponding to an average of one Ag nanoparticle per titania nanoparticle was achieved. The diameter of the titania crystallites/particles were in the range of 10–20 nm while the size of Ag particles attached to the larger titania particles were 3 ± 1 nm as deduced from crystallite size by XRD and particle size by TEM. Ag recovery by photo harvesting from the solution was nearly 100%. TEM micrographs revealed that Ag-coated TiO₂ nanoparticles showed a sharp increase in the degree of agglomeration for nanocomposites prepared at basic pH values, with a corresponding sharp decrease in BET surface area especially at pH > 9. The BET surface area of the Ag–TiO₂ nanoparticles was nearly constant at around a value of 140 m² g⁻¹ at all pH from 1–8 with an anomalous maximum of 164 m² g⁻¹ when prepared from a sol at pH of 4, and a sharp decrease to 78 m² g⁻¹ at pH of 10.     

Luminescence and defect studies of YAlO3:Dy3+, Sm3+ single crystals exposed to 100 MeV Si7+ ion beam

Ionoluminescence (IL) and photoluminescence (PL) spectra for different rare earth ions (Sm³⁺ and Dy³⁺) activated YAlO₃ single crystals have been induced with 100 MeV Si⁷⁺ ions with fluence of 7.81×10¹² ions cm^?2. Prominent IL and PL emission peaks in the range 550–725 nm in Sm³⁺ and 482–574 nm in Dy³⁺ were recorded. Variation of IL intensity in Dy³⁺ doped YAlO₃ single crystals was studied in the fluence range 7.81×10¹²–11.71×10¹² ions cm^?2. IL intensity is found to be high in lower ion fluences and it decreases with increase in ion fluence due to thermal quenching as a result of an increase in the sample temperature caused by ion beam irradiation. Thermoluminescence (TL) spectra were recorded for fluence of 5.2×10¹² ions cm^?2 on pure and doped crystals at a warming rate of 5 °C s^?1 at room temperature. Pure crystals show two glow peaks at 232 (Tg₁) and 328 °C (Tg₂). However, in Sm³⁺ doped crystals three glow peaks at 278 (Tg₁), 332 (Tg₂) and 384 °C (Tg₃) and two glow peaks at 278 (Tg₁) and 331 °C (Tg₂) in Dy³⁺ was recorded. The kinetic parameters (E, b s) were estimated using glow peak shape method. The decay of IL intensity was explained by excitation spike model.     

Thermal expansion behavior and chemical compatibility of BaxSr1−xCo1−yFeyO3−δ with 8YSZ and 20GDC

Perovskite oxides of the composition Ba_xSr_1−xCo_1−yFe_yO_3−δ(BSCF) were synthesized via a modified Pechini method and characterized by X-ray diffraction, dilatometry and thermogravimetry. Investigations revealed that single-phase perovskites with cubic structure can be obtained for x ≤ 0.6 and 0.2 ≤ y ≤ 1.0. The as-synthesized BSCF powders can be sintered in several hours to nearly full density at temperatures of over 1180 °C. Thermal expansion curves of dense BSCF samples show nonlinear behavior with sudden increase in thermal expansion rate between about 500 °C and 650 °C, due mainly to the loss of lattice oxygen caused by the reduction of Co⁴⁺ and Fe⁴⁺ to lower valence states. Thermal expansion coefficients (TECs) of BSCF were measured to be 19.2–22.9 × 10^− 6 K^− 1 between 25 °C and 850 °C. Investigations showed further that Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ is chemically compatible with 8YSZ and 20GDC for temperatures up to 800 °C, above which severe reactions were detected. After being heat-treated with 8YSZ or 20GDC for 5 h above 1000 °C, Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ was completely converted to phases like SrCoO_3−δ, BaCeO₃, BaZrO₃, etc.     

Effect of the concentration of precursors on the microwave absorbent properties of Zn/Fe oxide nanopowders

Zn/Fe oxide compound powders were obtained by the hydrothermal method using ferric nitrate Fe(NO₃)₃·9H₂O and zinc nitrate Zn(NO₃)₂·6H₂O at 200 °C and different precursor molar ratios x = Fe³⁺/Zn²⁺ equal to 2.8/0.2, 2.5/0.5, 1.8/1.2 and 1.5/1.5. The samples were characterized by X-ray diffraction (XRD) and scanning electron microscopy/energy dispersive X-ray analysis (SEM–EDAX). Room temperature measurements of the frequency dependence of the complex magnetic permeability and complex dielectric permittivity, over the frequency range from 0.1 to 6 GHz, were performed. For precursor molar ratios x = 2.8/0.2, x = 1.8/1.2 and x = 1.5/1.5 the obtained samples showed a ferromagnetic-like resonance behaviour. This behaviour was assigned to the prevalent compounds in the obtained samples, Fe₂O₃ (for x = 2.8/0.2) and ZnFe₂O₄ (for x = 1.8/1.2 and x = 1.5/1.5). Based on the magnetic and dielectric measurements, the microwave absorbent properties of the four samples were analysed, and the sample containing mostly of ZnFe₂O₄ (for x = 1.8/1.2) was found to be the best electromagnetic absorber in the frequency range 1.36–6 GHz.     

In situ Mössbauer spectroscopic study on cobalt and iron molybdates and their mixtures with Bi2(MoO4)3 during propene mild oxidation

Several Co and Fe and mixed Co, Fe molydates have been studied by Mössbauer spectroscopy at 360–415°C in a flow C₃H₆+O₂+N₂ 100/100/560 Torr, with and without adding Bi₂ (MoO₄)₃. It is concluded that cobalt stabilizes Fe²⁺ sites and Bi₂(MoO₄)₃ stabilizes Fe³⁺ in solid solution and it is proposed that Fe²⁺?Fe³⁺ pairs act as active sites in propene mild oxidation.     

Fabrication and characterization of solid state proton conductor (NH4)2SiP4O13–NH4PO3 for fuel cells operated at 150–250 °C

NH₄PO₃–(NH₄)₂SiP₄O₁₃ composite, a potential electrolyte for intermediate temperature fuel cells that operated around 250 °C, was synthesized with a solid-state reaction method. Electromotive forces (emfs) as measured with hydrogen concentration cells showed that the composite was a pure proton conductor at hydrogen partial pressure from 10² to 10⁵ Pa. Its proton transference numbers were determined to be 1.0 at 150 °C, 0.99 at 200 °C, and 0.99 at 250 °C. Fuel cells that used NH₄PO₃–(NH₄)₂SiP₄O₁₃ as electrolytes were also fabricated. Maximum power density was 6.6 mW/cm² at 250 °C when dry hydrogen and dry oxygen were used as the fuel and oxidant, respectively. Improved cell performance is expected by increasing cathode activity, increasing the electrolyte density, and decreasing the electrolyte thickness.     

On the enzymatic formation of platinum nanoparticles

A dimeric hydrogenase enzyme (44.5 and 39.4 kDa sub units) was isolated in a 39.5% yield from the fungus Fusarium oxysporum and purified 4.64-fold by ion exchange chromatography on Sephacryl S-200. Characterisation of the enzyme afforded pH and temperature optima of 7.5 and 38 °C, respectively, a half-life stability of 36 min and a V _max and K _m of 3.57 nmol min⁻¹ mL⁻¹ and 2.25 mM, respectively. This enzyme was inhibited (non-competitively) by hydrogen hexachloroplatinic acid (H₂PtCl₆) at 1 or 2 mM with a K _i value of 118 μM. Incubation of the platinum salt with the pure enzyme under an atmosphere of hydrogen and optimum enzyme conditions (pH 7.5, 38 °C) afforded <10% bioreduction after 8 h while at conditions suitable for platinum nanoparticle formation (pH 9, 65 °C) over 90% reduction took place after the same length of time. Cell-free extract from the fungal isolates produced nearly 90% bioreduction of the platinum salt under both pH and temperature conditions. The bioreduction of the platinum salt by a hydrogenase enzyme takes place by a passive process and not an active one as previously understood.     

Thermoluminescence study of aluminum oxide doped with therbium and thulium

In this work, α-Al₂O₃ doped either with Tb³⁺ or Tm³⁺ was prepared by combustion synthesis techniques for thermoluminescent (TL) ionizing radiation dosimetry applications. In this method, the reactants (aluminum nitrate, urea and therbium or thulium nitrate) are ignited in a muffle furnace at temperatures as low as 500 °C. This synthesis route is an alternative technique to the conventional fabrication methods of materials based on α-Al₂O₃ (Czochralsky, Vernuil), where high melting temperatures and reducing atmospheres are required. After combustion, the samples were annealed at temperatures ranging from 1000 to 1400 °C for 4 h in order to obtain the pure α-phase structure and were then irradiated with a Co-60 gamma radiation source. The annealed samples present a well defined TL glow peak with a maximum at approximately 200 °C and linear TL response in the dose range 0.5–5 Gy. It was observed that a 0.1 mol% concentration of Tb³⁺ or Tm³⁺ and annealing at 1400 °C optimize the TL sensitivity. The highest sensitivity was found for Tm³⁺ doped samples which were approximately 25 times more sensitive than Tb³⁺ doped samples. These results strongly suggest that combustion synthesis is a suitable technique to prepare doped aluminum oxide material and that Tm³⁺ doped aluminum oxide is a potential material for TL radiation dosimetry.     

Effect of Eu and Pb doping on the dosimetric properties of LiCAF

LiCaAlF₆ (LiCAF) crystals doped with two different ions (europium and lead) have been investigated as potential new dosimetric materials. The stability of thermally stimulated luminescence (TSL) glow peaks in LiCAF:Eu was evaluated by means of the initial rise technique. The decay times at room temperature of the traps related to the dosimetric glow peaks were found to range between 40 and 2 × 10⁴ years confirming the good dosimetric characteristics of this crystal. The glow curve of LiCAF:Pb is dominated by a peak at approximately 300 °C emitting in the UV region (³P_0,1–¹S₀ transition of Pb²⁺) superimposed to a very broad structure at lower temperature (20–200 °C) featuring recombination at an intrinsic defect centre. The anomalous behavior of the low temperature structure during thermal cleaning procedures prevented any reliable numerical analysis of the TSL glow peak at 300 °C.