Magnetic and structural properties of CaO–SiO2–P2O5–Na2O–Fe2O3 glass ceramics

Magnetic properties of glass ceramics derived from glasses with composition 41CaO·(52−x)SiO₂·4P₂O₅·xFe₂O₃·3Na₂O (2?x?10 mol% iron oxide (Fe₂O₃)) are reported. Structural investigation revealed the presence of nanocrystalline magnetite phase in the heat-treated samples containing x?2 mol% Fe₂O₃. Magnetic hysteresis cycles of the glass-ceramic samples were obtained with a maximum applied field of ±20 kOe as well as a low field of ±500 Oe, in order to evaluate the potential of these glass ceramics for hyperthermia treatment of cancer. Samples with x>2 mol% of iron oxide exhibited magnetic behavior similar to soft magnetic materials with low coercivity. The evolution of magnetic properties in these samples as a function of iron oxide molar concentration is correlated with the amount and crystallite size of magnetite phase present in them.     

Compositional dependence of in-vitro bioactivity in sodium calcium borate glasses

Borate glasses with composition xCaO (100−x) B₂O₃ (20≤x≤50), where x is in mole percent) and 50CaO·45B₂O₃·5Na₂O have been prepared using conventional melt quench technique. Samples were submerged in simulating body fluid solution (SBF) at 37 °C for various periods of time. After storage the samples were analyzed in order to investigate if a surface layer of hydroxyl carbonate apatite layer (HCA layer/Ca-P layer) had formed. The analysis technique used included Fourier-Transform Infrared Spectroscopy (FTIR). The rate of HCA layer formation on the surface of exposed glass samples is determined by FTIR, percentage weight loss measurements of glass samples in SBF and variation of pH of SBF as a function of time. Increase in calcium content in the glass matrix has shown to decrease the rate of HCA formation on glass surfaces. The borate glass with x=20 has shown HCA layer formation on glass surface within two days of dipping. The bone like apatite formation of glass surface demonstrates the potential of glass for integration with bone.     

Static susceptibility and heat capacity studies on V3O7·H2O7 nanobelts

V₃O₇·H₂O nanobelts were prepared by a hydrothermal method at 190 °C using V₂O₅·nH₂O gel and H₂C₂O₄·2H₂O as starting agents. The obtained nanobelts have diameters ranging from 40 to 70 nm with lengths up to several micrometers. Measurements of the static magnetic susceptibility and the specific heat show a discontinuous phase transition at around T=145 K, which separates two regions of paramagnetic behavior.     

A facile method to the cube-like MnSe2 microcrystallines via a hydrothermal process

A convenient hydrothermal process was applied to prepare the cube-like MnSe₂ microcrystallines through the reaction of MnSO₄·H₂O with Se and NaH₂PO₂·H₂O in aqueous solution at 160 °C for 12 h. Powder X-ray diffraction (XRD) analysis confirmed that the product was the cubic phase of MnSe₂ with cell parameter a=6.440 Å. The chemical composition of the MnSe₂ was determined by XPS. The Raman spectrum of MnSe₂ presented the peaks of the Se-Se stretching mode at 232.44 and 266.58 cm⁻¹. The images of scanning electron microscope (SEM) and transmission electron microscope (TEM) showed the cube-like morphology of the product with the edge length ranging from 20 to 30 μm. The formation mechanism of the MnSe₂ microcrystallines was discussed as well.     

α-Fe2O3-In2O3 mixed oxide nanoparticles synthesized under hydrothermal supercritical conditions

α-Fe₂O₃-In₂O₃ mixed oxide nanoparticles system has been synthesized by hydrothermal supercritical and postannealing route, starting with (1−x)Fe(NO₃)₃·9H₂O·xIn(NO₃)₃·5H₂O aqueous solution (x=0-1). X-ray diffraction and Mössbauer spectroscopy have been used to study the phase structure and substitutions in the nanosized samples. The concentration regions for the existence of the solid solutions in the α-Fe₂O₃-In₂O₃ nanoparticle system together with the solubility limits of In³⁺ ions in the hematite lattice and of Fe³⁺ ions in the cubic In₂O₃ structure have been evidenced. In general, the substitution level is considerably lower than the nominal concentration x. A justification of the processes leading to the formation of iron and indium phases in the investigated supercritical hydrothermal system has been given.     

No room temperature ferromagnetism in Mn over-doped Zn1−xMnxO (x>0.02)

Mn-doped ZnO samples having composition Zn_1−xMn_xO (x=0.02, 0.04 and 0.05) were synthesized by solid state reaction technique with varying concentration of Mn from 0.02 to 0.05. Evidence of room temperature ferromagnetism was observed only in the composition Zn_0.98Mn_0.02O sintered at 500 °C. Our XRD pattern confirms the presence of Mn₃O₄ impurity phase in all the Zn_1−xMn_xO samples with the exception of Zn_0.98Mn_0.02O. We emphasize that the appearance of Mn₃O₄ phase in the system forbids the exchange type of interaction between the Mn ions and suppresses the ferromagnetism in all the Mn over-doped Zn_1−xMn_xO (x>0.02) system. SEM microstructure study also supports the interruption of exchange type of interaction inside the system with the increase in Mn concentration in the sample. Interestingly, for this particular composition, Zn_0.98Mn_0.02O sintered at 500 °C, glassy ferromagnetism type of transition is observed at low temperature. This type of transition is attributed to the formation of the oxides of Mn clusters at low temperature.     

Synthesis of Fe-doped NiO nanofibers using electrospinning method and their ferromagnetic properties

To make p-type diluted magnetic semiconductor (DMS), Ni_1−xFe_xO nanofibers with different Fe doping concentrations have been successfully synthesized by electrospinning method using polyvinyl alcohol (PVA) and Ni(CH₃COO)₂·4H₂O as starting materials. The nanofibers were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, superconductivity quantum interference device (SQUID) and X-ray photoelectron spectroscopy (XPS) test. The results show that Fe doping has no influence on the diameter and surface morphology of NiO nanofibers, and the nanofibers are polycrystalline with NaCl structure. All Fe-doped samples show obvious ferromagnetic properties and the saturation magnetization is enhanced with increase of the doping concentration of Fe, which indicates that the doped Fe has been incorporated into the NiO host and results in room-temperature ferromagnetism in the Ni_1−xFe_xO nanofibers.     

Influence of Co doping content on its valence state in Zn1−xCoxO (0 ≤ x ≤ 0.15) thin films

Zn_1−xCo_xO (0 ≤ x ≤ 0.15) thin films grown on Si (1 0 0) substrates were prepared by a sol-gel technique. The effects of Co doped on the structural, optical properties and surface chemical valence states of the Zn_1−xCo_xO (0 ≤ x ≤ 0.15) films were investigated by X-ray diffraction (XRD), ultraviolet-visible spectrometer and X-ray photoelectron spectroscopy (XPS). XRD results show that the Zn_1−xCo_xO films retained a hexagonal crystal structure of ZnO with better c-axis preferred orientation compared to the undoped ZnO films. The optical absorption spectra suggest that the optical band-gap of the Zn_1−xCo_xO thin films varied from 3.26 to 2.79 eV with increasing Co content from x = 0 to x = 0.15. XPS studies show the possible oxidation states of Co in Zn_1−xCo_xO (0 ≤ x ≤ 0.05), Zn_0.90Co_0.10O and Zn_0.85Co_0.15O are CoO, Co₃O₄ and Co₂O₃, with an increase of Co content, respectively.     

Micromechanical and thermal behaviour of gel grown pure- and sodium-modified copper tartrate crystals

Results regarding micromechanical characteristics of gel grown pure- and sodium-modified copper tartrate crystals, bearing composition CuC₄H₄O₆·3H₂O, (Cu)_0.77(Na)_0.23C₄H₄O₆·3H₂O and (Cu)_0.65(Na)_0.35C₄H₄O₆·H₂O, as obtained on using indentation induced hardness testing technique are reported. Thermal behaviour of these crystals in the temperature ranging from room temperature (∼25 °C) to about 600 °C is also reported. Pure copper tartrate crystals are found to be thermally more stable than the sodium-modified ones. Dependence of Vickers’ hardness number H_v on load ranging from 0.049 to 2.94 N on two different planes for all the three compositions is analyzed. It is shown that after initial rise in the value of H_v, the same achieves saturation at a load of 0.49 N. Modification of copper tartrate crystal by introducing sodium in its lattice brings about a change in the micromechanical characteristics. The saturation value of H_v decreases with increase in the concentration of sodium ions. The results on (0 0 1) and (1 1 1) planes for both pure and modified copper tartrate crystals suggest hardness anisotropy. Relative difference of hardness between the two planes and yield strength for both pure and modified copper tartrate crystals is worked out. The experimental results are analyzed for applicability of Meyer’s law and Proportional Specimen Resistance Model. It is suggested that the experimental results indicating reverse ISE phenomenon may be explained in terms of the existence of a distorted zone near the crystal-medium interface. The integral method of Coats and Redfern approximation applied to the thermoanalytical data suggests “Random Nucleation Model” for the reaction kinetics of these crystals. Non-isothermal kinetic parameters such as activation energy, frequency factor and order of reaction are calculated.     

Synthesis and characterization of room-temperature ferromagnetism in Fe- and Ni-co-doped In2O3

Observation of room-temperature ferromagnetism in Fe- and Ni-co-doped In₂O₃ samples (In_0.9Fe_0.1−xNi_x)₂O₃ (0?x?0.1) prepared by citric acid sol-gel auto-igniting method is reported. All of the samples with intermediate x values are ferromagnetic at room-temperature. The highest saturation magnetization (0.453 μ_B/Fe+Ni ions) moment is reached in the sample with x=0.04. The highest solubility of Fe and Ni ions in the In₂O₃ lattice is around 10 and 4 at%, respectively. The 10 at% Fe-doped sample is found to be weakly ferromagnetic, while the 10 at% Ni-doped sample is paramagnetic. Extensive structure including Extended X-ray absorption fine structure (EXAFS), magnetic and magneto-transport including Hall effects studies on the samples indicate the observed ferromagnetism is intrinsic rather than from the secondary impurity phases.     

Superhydrophilic stability enhancement of RF co-sputtered TixSi1−xO2 thin films in dark

Ti_xSi_1−xO₂ compound thin-film systems were deposited by reactive RF magnetron co-sputtering technique. The effect of Ti concentration on the hydrophilicity of Ti_xSi_1−xO₂ compound thin films was studied and it was shown that the films with Ti_0.6Si_0.4O₂ composition possess the best hydrophilic property among all the grown samples. Surface ratio and average roughness of the thin films were measured by atomic force microscopy (AFM). Surface chemical states and stoichiometry of the films were determined by X-ray photoelectron spectroscopy (XPS). In addition, XPS revealed that the amount of Ti-O-Si bonds in nanometer depth from the surface of the Ti_0.6Si_0.4O₂ films was the maximum, which resulted in the most stable superhydrophilic property. According to XRD data analysis for the pure TiO₂ films, the polycrystalline anatase phase was formed with an average grain size of about 15 nm. Moreover, amorphous phase was also formed for the Ti_xSi_1−xO₂ compound systems due to presence of silicon in the films. Finally, optical properties of the films such as transmission, reflection and band gap energy were investigated using UV-vis spectrophotometry. It was found that the transmittance of the films was decreased with increasing Ti concentration in the films.     

Effect of Bi2O3 on EPR, optical transmission and DC conductivity of vanadyl doped alkali bismuth borate glasses

Glasses with composition xBi₂O₃·(30−x)M₂O·70B₂O₃ (M=Li, Na) containing 2 mol% V₂O₅ have been prepared over the range 0≤x≤15 (x is in mol%). The electron paramagnetic resonance spectra of VO²⁺ of these glasses have been recorded in the X-band (≈9.3 GHz) at room temperature (RT≈300 K). Spin Hamiltonian parameters, g_∥, g_⊥, A_∥, A_⊥, dipolar hyperfine coupling parameter, P, and Fermi contact interaction parameter, K, have been calculated. The molecular orbital coefficients, α² and γ², have been calculated by recording the optical transmission spectra. In xBi₂O₃·(30−x)Li₂O·70B₂O₃ glasses there is decrease in the tetragonality of the V⁴⁺O₆ complex for x up to 6 mol% whereas for x≥6 mol%, tetragonality increases. In xBi₂O₃·(30−x)Na₂O·70B₂O₃ glasses there is increase in the tetragonality of the V⁴⁺O₆ complex with increasing x. The 3d_xy orbit expands with increase in Bi₂O₃:M₂O ratio. Values of the theoretical optical basicity, Λ_th, have also been reported. The DC conductivity increases with increase in temperature. The order of conductivity is 10⁻⁵ ohm⁻¹ m⁻¹ at low temperature and 10⁻³ ohm⁻¹ m⁻¹ at high temperature. The DC conductivity decreases and the activation energy increases with increase in Bi₂O₃:M₂O ratio.     

Electronic structure and ferromagnetism of polycrystalline Zn1−xCoxO (0≤x≤0.15)

The electronic structure of polycrystalline ferromagnetic Zn_1−xCo_xO (0.05≤x≤0.15) and the oxidation state of Co in it, have been investigated. The Co-doped polycrystalline samples are synthesized by a combustion method and are ferromagnetic at room temperature. XPS and optical absorption studies show evidence for Co²⁺ ions in the tetrahedral symmetry, indicating substitution of Co²⁺ in the ZnO lattice. However, powder XRD and electron diffraction data show the presence of Co metal in the samples. This give evidence to the fact that some Co²⁺ ion are incorporated in the ZnO lattice which gives changes in the electronic structure whereas ferromagnetism comes from the Co metal impurities present in the samples.     

In vitro evaluation of bioactivity of CaO-SiO2-P2O5-Na2O-Fe2O3 glasses

Glasses with compositions 41CaO(52 − x)SiO₂4P₂O₅·xFe₂O₃3Na₂O (2 ≤ x ≤ 10 mol.%) were prepared by melt quenching method. Bioactivity of the different glass compositions was studied in vitro by treating them with simulated body fluid (SBF). The glasses treated for various time periods in SBF were evaluated by examining apatite formation on their surface using grazing incidence X-ray diffraction, Fourier transform infrared reflection spectroscopy, scanning electron microscopy and energy dispersive spectroscopy techniques. Increase in bioactivity with increasing iron oxide content was observed. The results have been used to understand the evolution of the apatite surface layer as a function of immersion time in SBF and glass composition.     

Magnetic and bioactivity evaluation of ferrimagnetic ZnFe2O4 containing glass ceramics for the hyperthermia treatment of cancer

Glass ceramics of the composition xZnO·25Fe₂O₃·(40−x)SiO₂·25CaO·7P₂O₅·3Na₂O were prepared by the melt-quench method using oxy-acetylene flame. Glass-powder compacts were sintered at 1100 °C for 3 h and then rapidly cooled at −10 °C. X-ray diffraction (XRD) revealed 3 prominent crystalline phases: ZnFe₂O₄, CaSiO₃ and Ca₁₀(PO₄)₆(OH)₂. Vibrating sample magnetometer (VSM) data at 10 KOe and 500 Oe showed that saturation magnetization, coercivity and hence hysteresis area increased with the increase in ZnO content. Nano-sized ZnFe₂O₄ crystallites were of pseudo-single domain structure and thus coercivity increased with the increase in crystallite size. ZnFe₂O₄ exhibited ferrimagnetism due to the random distribution of Zn²⁺ and Fe³⁺ cations at tetrahedral A sites and octahedral B sites. This inversion/random distribution of cations was probably due to the surface effects of nano-ZnFe₂O₄ and rapid cooling of the material from 1100 °C (thus preserving the high temperature state of the random distribution of cations). Calorimetric measurements were carried out using magnetic induction furnace at 500 Oe magnetic field and 400 KHz frequency. The data showed that maximum specific power loss and temperature increase after 2 min were 26 W/g and 37 °C, respectively for the sample containing 10% ZnO. The samples were immersed in simulated body fluid (SBF) for 3 weeks. Scanning electron microscope (SEM), energy dispersive spectroscopy (EDX) and XRD results confirmed the growth of precipitated hydroxyapatite phase after immersion in SBF, suggesting that the ferrimagnetic glass ceramics were bioactive and could bond to the living tissues in physiological environment.     

Effects of Fe doping and Fe-N-codoping on magnetic properties of SnO2 prepared by chemical co-precipitation

The effects of Fe-doping and Fe-N-codoping on the magnetic properties of SnO₂, prepared by chemical co-precipitation technique, are investigated in details. We found that the paramagnetism is the dominant magnetic interaction in Fe doped SnO₂. A weak antiferromagnetic coupling between Fe²⁺ ions is also confirmed through Zero field-cooled (ZFC) and field-cooled (FC) magnetization studies. On the other hand, hystersis behavior is observed for Fe-N-codoped SnO₂ samples with coercivity H_c∼420 and 352 Oe for x=0.05 and 0.10, respectively. As no other secondary or impurity phase is detected by XRD study and the presence of N is confirmed by EDX analysis, this observed ferromagnetism is originated due to the substitution of N in Sn_1−xFe_xO₂. N doping at the oxygen site can be regarded as defect and introduces a hole in this system. As a result, a hole-induced ferromagnetism might be the origin of the observed ferromagnetism in Fe-N-codoped SnO₂ samples.     

Preparation and characterization of polymer coated superparamagnetic magnetite nanoparticle agglomerates

In order to produce magnetic microparticles (agglomerates), magnetite (Fe₃O₄) particles were synthesized using coprecipitation of FeSO₄·7H₂O and FeCl₃·6H₂O with the presence of poly(methacrylic acid) (PMAA) in aqueous solution.. Transmission electron microscopy (TEM), X-ray diffraction, and vibrating sample magnetometry (VSM) methods were used to characterize the PMAA coated superparamagnetic agglomerates. The influences of various processing parameters such as the process temperature, PMAA content, and the addition of surfactant on the agglomerate size and size distribution of produced magnetic microparticles were investigated. The particle size and size distribution characteristics, (the volume weighted mean size (D[4,3], surface weighted mean size D[3,2], the geometric standard deviation, and span value) of the magnetic agglomerates were determined using the laser diffraction technique. The PMAA coated magnetic agglomerates with surface weighted mean sizes ranging from 1.5 to 3 μm were produced successfully.     

Structural, transport, and magnetic properties in the Ti-doped manganites LaMn1−xTixO3 (0≤x≤0.2)

The magnetism and transport properties of the samples LaMn_1−xTi_xO₃ (0≤x≤0.2) were investigated. All samples show a rhombohedral structure () at room temperature. The sample with x=0 undergoes the paramagnetic-ferromagnetic (PM-FM) transition accompanied by an insulator-metal (I-M) transition due to the oxygen excess. The doped samples show ferromagnetism and cluster behavior at low temperatures. Though no I-M transition associated with the PM-FM transition appears, the magnetoresistance (MR) effect was observed especially at low temperatures under the applied fields of 0.5 T. Due to the fact that the oxygen content in the Ti-doped samples is nearly stochiometry (3.01) and the Hall resistivity at room temperature is negative, the ferromagnetism in LaMn_1−xTi_xO₃ (0.05≤x≤0.2) is believed to be consistent with the Mn²⁺-O-Mn³⁺ double exchange (DE) mechanism. These results suggest that DE can be obtained by direct Mn-site doping.     

The influence of hydrogen annealing on magnetism of Co-doped TiO2 films prepared by sol–gel method

Co-doped TiO₂ (Co_xTi_1−xO₂, 0.05?x?0.2) films have been prepared on Si (0 0 1) substrates by sol–gel method. When heat treated in air, Co_xTi_1−xO₂ films are non-ferromagnetic at room temperature. However, after further annealed in a flowing hydrogen atmosphere, Co_xTi_1−xO₂ films show room-temperature ferromagnetism (RTFM). Measurements of magnetization (M) vs. temperature (T), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) fail to detect Co clusters in the hydrogenated Co_0.1Ti_0.9O₂ films, suggesting that RTFM in the hydrogenated Co_0.1Ti_0.9O₂ films may be intrinsic. But, metal Co appears in the hydrogenated Co_0.2Ti_0.8O₂ films, showing that RTFM in the hydrogenated Co_0.2Ti_0.8O₂ films is as least partly due to metal Co. These results indicate that hydrogen annealing can produce room-temperature ferromagnetism in Co_xTi_1−xO₂ films, but it should be carefully designed to avoid the formation of metal Co in the hydrogenated Co_xTi_1−xO₂ films.     

Synthesis and characterization of the SnO2-pillared layered titanate nanohybrid

SnO₂-pillared titanate nanohybrid has been prepared by reacting the exfoliated layered titanate sheets with the nanosized SnO₂ sol particles. The stable two-dimensional colloidal nanosheets could be obtained by intercalating tetrabutylammonium cation into the layered protonic titanate, H_xTi_2−x/4□_x/4O₄·H₂O (x=0.67) with a lepidocrocite-like structure, and by successive exfoliation process in an aqueous solution. Monodispersed SnO₂ nano sol particles were prepared by hydrolysis of SnCl₄·5H₂O in the presence of sodium hydroxide, and then the exfoliated titanate suspension was mixed with SnO₂ nano sol solution until the flocculated products formed. The final product was heated at various temperatures in order to complete the grafting reaction of intercalated SnO₂ nano sol on the interlayer surface of layered titanate. Inductive coupled plasma, X-ray diffraction, thermal analysis and N₂-adsorption-desorption isotherms were carried out to study the hybridizing process and the structure of SnO₂-pillared titanate nanohybrid.