Precipitation of zinc ferrite nanoparticles in the Fe2O3–ZnO–SiO2 glass system

Glass materials in the ZnO–Fe₂O₃–SiO₂ system, containing zinc ferrite nanoparticles, were prepared by the sol–gel method and characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), Mössbauer spectroscopy, AC- and DC-magnetization techniques. The gel samples, dried at 130 °C, were further heat treated in air at 500 and 800 °C. At 500 °C zinc ferrite and hematite nanoparticles, with an average size of approximately 24 nm, were precipitated in the brown and opaque 10ZnO–10Fe₂O₃–80SiO₂ and in the ruby colored transparent 5ZnO–5Fe₂O₃–90SiO₂ and 2.5ZnO–2.5Fe₂O₃–95SiO₂ glass matrices. In the 5ZnO–5Fe₂O₃–90SiO₂ sample the nanoparticles exhibited ferro or ferrimagnetic interactions combined with superparamagnetism with a blocking temperature of approximately 14 K. Heating at 800 °C seems to cause partial dissolution of the zinc ferrite and hematite particles in all the investigated compositions. Accordingly at 800 °C the 5ZnO–5Fe₂O₃–90SiO₂ glass shows a paramagnetic behavior down to 2 K.     

Synthesis and magnetic properties of monodisperse Fe3O4 nanoparticles with controlled sizes

Monodisperse magnetite nanoparticles coated with organic ligands have been chemically synthesised by using the poliol method. Modifying the synthetic conditions, particle diameter can be tuned from 3.5 to 7.1 nm. In order to investigate the critical size effects on the magnetic behavior of the samples, Fe₃O₄ nanoparticles have been fully characterized by X-ray diffraction, thermogravimetric analysis, transmission electron microscopy, SQUID magnetometry and electron paramagnetic resonance spectroscopy.     

Ultrafine Co1−xZnxFe2O4 particles synthesized by hydrolysis: Effect of thermal treatment and its relationship with magnetic properties

Co_1−xZn_xFe₂O₄ (x = 0, 0.2 and 0.4) fine powders with particles size of 3 nm were prepared by hydrolysis method. The powders were annealed at 500 °C for 3 h. With heat treatment, the average particles size increased to 12 nm with corresponding increase in blocking temperature, saturation magnetization and reduced remanence. A significant increase in coercive field was found only for the pure CoFe₂O₄.     

Structural impact of iron ions on BaBiBO4 glasses: Spectroscopic and dielectric investigations

Transparent glasses of composition 10BaO.20Bi₂O₃.(70 ? x)B₂O₃.xFe₂O₃ (wt.%) where 0 ≤ x ≤ 2.0, were characterized by XRD and SEM. Physical, spectroscopic and dielectric properties were investigated. At higher dopant of Fe₂O₃, EPR results revealed that, the number of Fe³⁺ ions participate in the resonance is decreased by forming a new signal at g ≈ 3.015 due to increase of antiferromagnetic interaction of Fe³⁺ ions and/or formation of low spin Fe³⁺ ions in the glass matrix. With initial 0.5 wt.% doping of Fe₂O₃, less dense glass is formed with colloids of metallic Bi⁰ atoms. The absorption bands at 604 and 712 nm in F5 glass are ascribed to Bi⁰ and Bi⁺ radicals respectively. No characteristic Fe³⁺ absorption bands (spin-forbidden) are found. Fe²⁺ ions are increased at higher concentration of Fe₂O₃. Higher concentration of Fe₂O₃ is favorable for BO₂O^?, BO₃, BiO₆ and FeO₆ symmetry unit leads to low band gap and high Urbach energy. By doping of Fe₂O₃ the dielectric parameters like dielectric constant (ε′), loss (tanδ and ac electrical conductivity (σ_ac) are found to increase.     

Epoxide assisted sol–gel synthesis of perovskite-type LaMxFe1−xO3 (M = Ni, Co) nanoparticles

Perovskite-type LaM_xFe_1−xO₃ (M = Ni, Co) nanoparticles were synthesized by a sol–gel method using propylene oxide as a gelation agent. The resulting nanoparticles show a narrow size distribution with particles in the 30–50 nm range. A highly homogeneous wet gel was formed during the hydrolysis and condensation of the precursor salts. This high homogeneity allows a substantial reduction of the calcination temperature and time required for the formation of the perovskite phase as compared with the solid-state and other wet solution routes, reducing drastically the aggregation of the particles during calcination.     

Synthesis,characterization and application of magnetic-zirconia nanocomposites

In the present study, a magnetic-zirconia nanocomposite was successfully synthesized by a single-step co-precipitation method. The as-prepared nanocomposite was characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, powder X-ray diffraction, and nitrogen sorption measurements. The ultimate material was found to be Fe₃O₄–ZrO₂ nanoparticles with average diameter of 80 nm, high surface area up to 166 m²/g, and strong magnetic property. The application of this new nanocomposite was herein demonstrated by the adsorption of ethyl methylphosphonic acid, a degradation product of nerve agent in water, followed by mass spectrometry detection. Excellent adsorption could be observed, indicating the as-synthesized material was effective to remove phosphonic acid compound from water. Apart from adsorption, the Fe₃O₄–ZrO₂ nanocomposite is promising in various applications such as catalysis and bioseparation.     

Synthesis and characterization of CoFe2O4–PVP nanocomposites

Cobalt ferrite–poly(N-vinyl-2-pyrrolidone) nanocomposites were prepared by drying a dispersion of cobalt ferrite (CoFe₂O₄) nanoparticles and poly(N-vinyl-2-pyrrolidone). Magnetic measurements indicate a superparamagnetic behavior. Zero-field-cooling magnetization experiments at 100 Oe show different trends depending on the CoFe₂O₄ nanoparticles size. For the smaller ones (3.9 nm), the blocking temperatures shift to lower temperatures with increasing concentration; however, this shift is not observed for the larger ones (6.6 nm). These differences can be related to the anisotropy constant of the CoFe₂O₄ nanoparticles and the interparticle dipolar interactions.     

Multiferroic behavior in silicate glass nanocomposite having a core–shell microstructure

Nanosized iron core and barium titanate shell microstructure was generated within a silicate glass of composition 23.1 Na₂O, 23.1 BaO, 23.0 TiO₂, 7.6 B₂O₃, 5.8 Fe₂O₃, 17.4 SiO₂ by first reducing it at 893 K for ½ h and then subjecting it to heat treatment at 759 K for 4 h. Transmission electron microscopy showed the composite particles to have a mean diameter of 3.9 nm. The nanocomposite exhibited both ferroelectric and ferromagnetic behavior. The dielectric constant peak was not prominent because of a small thickness of the barium titanate phase. The magnetic hysteresis loop showed an asymmetric behavior giving rise to a small exchange bias field. This is believed to arise due to exchange interaction between the ferromagnetic iron core and the thin layer of Fe₃O₄ on the core surface with a spin glass-like behavior. The magnetization under zero-field cooled (ZFC) and field cooled (FC) conditions indicated superparamagnetic behavior at temperatures higher than 300 K. The optical absorption spectra exhibited a peak at around 325 nm. This was analyzed satisfactorily on the basis of a metal core–oxide shell nanoconfiguration. The extracted values of metal core conductivity showed a metal insulator transition for iron core diameters less than 2.4 nm. The present synthesis approach will lead to newer multiferroic nanocomposites and glasses with multifunctionalities.     

Characterization of iron phosphate glasses prepared by microwave heating

Phosphate glasses have been prepared by melting batch materials in electric furnaces, induction furnaces, and in microwave ovens. In the present work mixtures of (NH₄)₂HPO₄ and Fe₃O₄ or Fe₂O₃ were exposed to microwave energy, heated to 1200 °C, and cast to produce iron phosphate glasses. Glasses were also produced in electric furnaces for comparison. The material was analyzed by X-ray diffraction, Mössbauer spectroscopy, and differential thermal analysis. For magnetite-based glasses produced in an electric furnace, the Fe²⁺/(Fe²⁺ + Fe³⁺) ratio is compatible with the value in the batch material. The Fe²⁺/(Fe²⁺ + Fe³⁺) ratio is higher for glasses produced in a microwave oven. Glasses with nominal composition 55Fe₃O₄–45P₂O₅ (mol%) produced in an electric furnace present an arranged magnetic phase with hyperfine field that could be associated to hematite (estimated to be 21%). All the glasses submitted to heat treatments for crystallization present the following crystalline phases: FePO₄, Fe₃(PO₄)₂, Fe(PO₃)₃, Fe(PO₃)₂ and Fe₇(PO₄)₆. The amount of these phases depends on the glass composition, and glass preparation procedure. Microwave heating allows to reach melting temperatures at high heating rates, making the procedure easy and economical, but care should be taken concerning the final Fe²⁺/(Fe²⁺ + Fe³⁺) ratio.     

Preparation,crystallization behavior and magnetic properties of nanoparticles magnetic glass–ceramics in the systems Fe2O3 CoO MnO2, Fe2O3 NiO MoO3 and Fe2O3 CoO V2O5

Ferrimagnetic glass–ceramics were prepared in the systems Fe₂O₃ CoO MnO₂ (S1), Fe₂O₃ NiO MoO₃ (S2) and Fe₂O₃ CoO V₂O₅ (S3). Small amount of H₃BO₄ was added to make the melting process easier. The samples were characterized using DTA, XRD, TEM and EDX. Sequence of crystallization was studied by applying heat-treatment at 800 and 1000 °C for 4 h. CoFe₂O₄ with crystallite sizes of ≈ 14–20 nm was successfully prepared beside FeCoOBO₃ and Co₃BO₅ in S1. NiMoO₄, (FeNi₂)O₂(BO₃) and NiO with crystallite size ≈ 56–79 nm were crystallized in S2. CoFe₂O₄, FeCoOBO₃ and Co₃BO₅ with crystallite size ≈ 6–8 nm were crystallized in S3. Magnetic hysteresis cycles were analyzed with a maximum applied field of 20 kOe at room temperature. From the obtained hysteresis loops Ms records higher values for S1 and S3 and lower value for S2, while coercivity reach maximum for S2. The variable, magnetic, data range gives a wide range for different applications.     

Structural properties of Cr2O3–Fe2O3–P2O5 glasses,Part I

The structural properties of xCr₂O₃–(40 − x)Fe₂O₃–60P₂O₅, 0 ⩽ x ⩽ 10 (mol%) glasses have been investigated by Raman and Mössbauer spectroscopies, X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The Raman spectra show that the addition of up to 5.3 mol% Cr₂O₃ does not produce any changes in the glass structure, which consists predominantly of pyrophosphate, Q¹, units. This is in accordance with O/P ≈ 3.5 for these glasses. The increase in glass density and T_g that occurs with increasing Cr₂O₃ suggests the strengthening of glass network. The Mössbauer spectra indicate that the Fe²⁺/Fe_tot ratio increases from 0.13 to 0.28 with increasing Cr₂O₃ content up to 5.3 mol%, which can be related to an increase in the melting temperature from 1423 to 1473 K. After annealing, the 10Cr₂O₃–30Fe₂O₃–60P₂O₅ (mol%) sample was partially crystallized and contained crystalline β-CrPO₄ and Fe₃(P₂O₇)₂. The SEM and AFM micrographs of the partially crystallized sample revealed randomly distributed crystals embedded in a homogeneous glass matrix. EDS analysis indicated that the glass matrix was rich in Fe₂O₃ (39.6 mol%) and P₂O₅ (54.9 mol%), but contained only 5.5 mol% of Cr₂O₃. These results suggest that the maximum solubility of chromium in these iron phosphate melts is 5.5 mol% Cr₂O₃.     

Dielectric behavior and impedance spectroscopy of bismuth iron phosphate glasses

The electrical and dielectrical properties of Bi₂O₃–Fe₂O₃–P₂O₅ glasses were measured by impedance spectroscopy in the frequency range from 0.01 Hz to 4 MHz and over the temperature range from 303 to 473 K. It was shown that the dc conductivity strongly depends on the Fe₂O₃ content and Fe(II)/Fe_tot ratio. With increasing Fe(II) ion content from 17% to 34% in the bismuth-free 39.4Fe₂O₃–59.6P₂O₅ and 9.8Bi₂O₃–31.7Fe₂O₃–58.5P₂O₅ glasses, the dc conductivity increases. On the other hand, the decrease in dc conductivity for the glasses with 18.9 mol% Bi₂O₃ is attributed to the decrease in Fe₂O₃ content from 31.7 to 23.5 mol%, which indicates that the conductivity for these glasses depends on Fe₂O₃ content. The conductivity for these glasses is independent of the Bi₂O₃ content and arises mainly from polaron hopping between Fe(II) and Fe(III) ions suggesting an electronic conduction. The evolution of the complex permittivity as a function of frequency and temperature was investigated. At low frequency the dispersion was investigated in terms of dielectric loss. The thermal activated relaxation mechanism dominates the observed relaxation behavior. The relationship between relaxation parameters and electrical conductivity indicates the electronic conductivity controlled by polaron hopping between iron ions. The Raman spectra show that the addition of up to 18.9 mol% of Bi₂O₃ does not produce any changes in the glass structure which consists predominantly of pyrophosphate units.     

Nd5Fe64B23Mo4Y4 bulk nanocomposite permanent magnets produced by crystallizing amorphous precursors

The glass forming ability and magnetic properties of Nd₅Fe_68 ? xB₂₃Mo₄Y_x (x = 0, 2, 4, 6) alloys prepared by copper mold casting technique have been studied. Amorphous rods with a diameter of 2 mm were obtained in the Nd₅Fe₆₄B₂₃Mo₄Y₄ alloy. After annealing for 10 min at 1013 K, the Nd₅Fe₆₄B₂₃Mo₄Y₄ alloy showed optimal hard magnetic properties with the coercivity of 764.2 kA/m, remanence of 0.6 T and maximum energy product of 57.3 kJ/m³, respectively. The enhanced magnetic properties can be ascribed to the strong exchange coupling among the magnetically soft α-Fe (25–30 nm), Fe₃B (30–35 nm) and hard Nd₂Fe₁₄B (40–50 nm) grains present in the magnet microstructure. Large size bulk nanocomposite magnets with sound magnetic properties make the Nd–Fe–B–Mo–Y alloy system a promising candidate for industrial applications.     

Square-wave voltammetry and impedance spectroscopy in iron-doped melts of the system Li2O/Al2O3/SiO2

Glass melts with the basic compositions xLi₂O · 15Al₂O₃ · (85 − x)SiO₂ (x = 8.5, 11, 13.5, 16 and 18.5) doped with 0.25 mol% Fe₂O₃ were studied by square-wave voltammetry and impedance spectroscopy at temperatures in the range from 1100 to 1600 °C. The square-wave voltammograms show a pronounced peak attributed to the reduction of Fe³⁺ to Fe²⁺. The attributed peak potentials which are equal to the standard potentials of the redox pair decrease linearly with the temperature. Impedance spectra measured could be simulated using an equivalent circuit attributed to a simple electron transfer reaction controlled by diffusion.     

The effect of fluoride on the Fe2+/Fe3+-redox equilibrium in glass melts in the system Na2O/NaF/CaO/Al2O3/SiO2

Liquids with the base compositions (16 − x/2)Na₂O · xNaF · 10CaO · 74SiO₂ (x = 0, 1, 3, and 4) and (10 − x/2) · Na₂O · xNaF · 10CaO · yAl₂O₃ · (80 − y)SiO₂ (x = 0, 1, 3, 5 and y = 5 and 15) doped with 0.25 mol% Fe₂O₃ were studied by means of square-wave voltammetry in the temperature range from 1000 to 1500 °C. With increasing temperature, the redox equilibria were shifted to the reduced state. Also while increasing the alumina concentration, the Fe²⁺/Fe³⁺-redox equilibrium is shifted to the reduced state. In the soda-lime–silica melt the addition of fluoride shifts the equilibrium to the oxidized state, while in the aluminosilicate melts with 15 mol% Al₂O₃, the equilibrium is shifted to the reduced state. In the aluminosilicate melts with 5 mol% Al₂O₃, the equilibrium was not affected by the fluoride concentration. This is explained by the structure of the respective glass compositions.     

Electronic conductivity in zinc iron phosphate glasses

The electrical properties of (40−x)ZnO–xFe₂O₃–60P₂O₅ (x = 10, 20, 30 mol%) glasses were measured by impedance spectroscopy in the frequency from 0.01 Hz to 4 MHz and the temperature range from 303 to 473 K. It was shown that the dc conductivity strongly depends on the Fe₂O₃ content and Fe(II)/Fe_tot ratio. The increase in dc conductivity for these glasses is attributed to the increase in Fe₂O₃ content from 10 to 30 mol%. With increasing Fe(II) ion content from 6% to 17% the dc conductivity increases. This indicated that the conductivity arises mainly from polaron hopping between Fe(II) and Fe(III) ions suggesting an electron conduction in these glasses. By applying scaling on conductivity data measured at different temperatures, single master curve was obtained for each glass. On the other hand, deviation from the master curve at high frequencies was observed for glasses with different compositions. This deviation originates from a various mobility of charge carriers in different glass structures. Raman spectra showed the change of structure, from metaphosphate to pyrophosphate, with increasing Fe₂O₃ content from 10 to 30 mol%.     

Low temperature dielectric dispersion and electrical conductivity studies on Fe2O3 mixed lithium yttrium silicate glasses

Lithium yttrium silicate glasses mixed with different concentrations of Fe₂O₃ of the composition (40 ? x) Li₂O–10Y₂O₃–50SiO₂: x Fe₂O₃, with x = 0.3, 0.5, 0.8, 1.0, 1.2 and 1.5 (all in mol%) were synthesized. Electrical and dielectric properties including dielectric constant, ε′(ω), loss, tan δ, ac conductivity, σ_ac, impedance spectra as well as electric moduli, M(ω), over a wide continuous frequency range of 40 Hz to 10⁶ Hz and in the low temperature range 100 to 360 K were measured as a function of the concentration of Fe₂O₃. The dc conductivity is also evaluated in the temperature range 100 … 360 K. The temperature and frequency dispersions of dielectric constant as well as dielectric loss have been analyzed using space charge polarization model. The ac and dc conductivities have exhibited increasing trend with increasing Fe₂O₃ content beyond 0.5 mol%, whereas the activation energy for the conductivity demonstrated decreasing tendency in this dopant concentration range. Both quantum mechanical tunneling (QMT) and correlated barrier hopping models (CBH) were used for clarification of ac conductivity origin and the corresponding analysis has indicated that CBH model is more appropriate for this glass system. For the better understanding of relaxation dynamics of the electrical properties we have drawn the scaling plots for ac conductivity and also electric moduli. The plots indicated that the relaxation dynamics is independent on temperature but depends on concentration of Fe₂O₃. The dc conductivity is analyzed using small polaron hoping model. The increase of conductivity with the concentration of Fe₂O₃ beyond 0.5 mol% is explained in terms of variations in the redox ratio of iron ions in the glass network. The results were further analyzed quantitatively with the support of experimental data from IR, optical absorption and ESR spectral studies. The overall analysis has indicated that Li₂O–Y₂O₃–SiO₂ glasses containing more than 0.5 mol% of Fe₂O₃ are more suitable for achieving good electrical conductivity in these glasses.     

Efficient plasmonic coupling between Er3 +:(Ag/Au) in tellurite glasses

We report a systematic study of the localized surface plasmon resonance effects on the photoluminescence of Er^3 +-doped tellurite glasses containing Silver or Gold nanoparticles. The Silver and Gold nanoparticles are obtained by means of reduction of Ag ions (Ag⁺ → Ag⁰) or Au ions (Au^3 + → Au⁰) during the melting process followed by the formation of nanoparticles by heat treatment of the glasses. Absorption and photoluminescence spectra reveal particular features of the interaction between the metallic nanoparticles and Er^3 + ions. The photoluminescence enhancement observed is due to dipole coupling of Silver nanoparticles with the ⁴I_13/2 → ⁴I_15/2 Er^3 + transition and Gold nanoparticles with the ²H_11/2 → ⁴I_13/2 (805 nm) and ⁴S_3/2 → ⁴I_13/2 (840 nm) Er^3 + transitions. Such process is achieved via an efficient coupling yielding an energy transfer from the nanoparticles to the Er^3 + ions, which is confirmed from the theoretical spectra calculated through the decay rate.     

Studies of lead–iron phosphate glasses by Raman,Mössbauer and impedance spectroscopy

The effect of Fe₂O₃ content on electrical conductivity and glass stability against crystallization in the system PbO–Fe₂O₃–P₂O₅ has been investigated using Raman, XRD, Mössbauer and impedance spectroscopy. Glasses of the molar composition (43.3 − x)PbO–(13.7 + x)Fe₂O₃–43P₂O₅ (0 ⩽ x ⩽ 30), were prepared by quenching melts in the air. With increasing Fe₂O₃ content and molar O/P ratio there is corresponding reduction in the length of phosphate units and an increase in the Fe(II) ion concentration, which causes a higher tendency for crystallization. Raman spectra of the glasses show that the interaction between Fe sites, which is essential for electron hopping, strongly depends on the cross-linking of the glass network. The electronic conduction of these glasses depends not only on the Fe(II)/Fe_tot ratio, but also on easy pathways for electron hopping in a non-disrupted pyrophosphate network. The Raman spectra of crystallized glasses indicate a much lower degree of cross-linking since more non-bridging oxygen atoms are present in the network. Despite the significant increase in the Fe₂O₃ content and Fe(II) ion concentration, there is a considerable weakening in the interactions between Fe sites in crystalline glasses. The impedance spectra reveal a decrease in conductivity, caused by poorly defined conduction pathways, which are result of the disruption and inhomogeneity of the crystalline phases that are formed during melting.     

Sodium tracer diffusion in sodium boroaluminosilicate glasses

Sodium tracer diffusion coefficients, D*_Na, have been measured using the radioactive isotope Na-22 in sodium boroaluminosilicate (NBAS) glasses containing either a small amount of As₂O₃ or Fe₂O₃. The chemical compositions of the first type of glasses are given by the formula [(Na₂O)_0.71(Fe₂O₃)_0.05(B₂O₃)_0.24]_0.2[(SiO₂)_x(Al₂O₃)_1 ? x]_0.8 and those of the second type of glasses correspond to the formula [(Na₂O)_0.73(B₂O₃)_0.24(As₂O₃)_0.03]_0.18[(SiO₂)_x(Al₂O₃)_1 ? x]_0.82. Tracer diffusion measurements were performed at different temperatures between 198 and 350 °C. Pre-annealing of the glass samples at their glass transition temperatures in common air was found to lead to changes in the values of sodium tracer diffusion coefficients. For the NBAS glasses containing Fe₂O₃, after pre-annealing for 5 h, the activation enthalpy derived for the sodium tracer diffusion increases almost linearly from 57.5 to 71.3 kJ/mol with a decrease in the alumina content while the pre-exponential factor of the sodium tracer diffusion coefficient increases from 2.1 · 10^? 4 to 5.3 · 10^? 4 cm²/s. For the iron-free NBAS glasses pre-annealed for 5 h, the activation enthalpy varies between 63.9 and 71.4 kJ/mol while the pre-exponential factor varies between 1.5 · 10^? 4 and 1.2 · 10^? 3 cm²/s. In addition, it was observed that the considered glasses take up water when annealed at 300 °C in wet air with P_H2O = 474 mbar.