Magnetic and structural characterization of silver-iron oxide nanoparticles obtained by the microemulsion technique

In the present paper we report the magnetic characterization of silver-iron oxide nanocomposite obtained by the chemical microemulsion method. TEM images and X-ray diffractograms show that the nanocomposite consists of Ag nanoparticles of ～ 7 nm surrounded by a quasiamorphous matrix. The ZFC–FC curves and Mössbauer spectra obtained at different temperatures show a typical evolution of a system composed of weakly interacting nanoparticles with a blocking temperature (T_b) of ～50 K. The analysis of the magnetic data reveals that the matrix is formed by γ-Fe₂O₃ phase with a structural range order of ～2 nm.     

Mössbauer study of multiphase iron oxide composites

A representative nanocomposite made of ferrimagnetic γ-Fe₂O₃ and antiferromagnetic α-Fe₂O₃ nanoparticles with estimated weight fractions of ～90 and ～10%, respectively, and grown in transparent silica xerogels has been characterized by Mössbauer spectroscopy with respect to the temperature. The changes of the hyperfine parameters of the different subspectral components have been compared with other macroscopic magnetic and structural measurements. This comparison has allowed us to identify two different superparamagnetic transitions, located at ～50 K and at ～250 K, as well as the phases involved in each transition.     

Structural study of undoped and (Mn, In)-doped SnO2 thin films grown by RF sputtering

Undoped and 5%(Mn, In)-doped SnO₂ thin films were deposited on Si(1 0 0) and Al₂O₃ (R-cut) by RF magnetron sputtering at different deposition power, sputtering gas mixture and substrate temperature. X-ray reflectivity was used to determine the films thickness (10–130 nm) and roughness (～1 nm). The combination of X-ray diffraction and Mössbauer techniques evidenced the presence of Sn⁴⁺ in an amorphous environment, for as-grown films obtained at low power and temperature, and the formation of crystalline SnO₂ for annealed films. As the deposition power, substrate temperature or O₂ proportion are increased, SnO₂ nanocrystals are formed. Epitaxial SnO₂ films are obtained on Al₂O₃ at 550 °C. The amorphous films are quite uniform but a more columnar growth is detected for increasing deposition power. No secondary phases or segregation of dopants were detected.     

Iron environment in calcium-soda-phosphate glasses and vitroceramics

The structure of calcium-soda-phosphate glasses and vitroceramics with relatively high iron content was investigated by X-ray diffraction, electron paramagnetic resonance (EPR) and Mössbauer spectroscopy. The X-ray diffraction analysis proves the vitreous state of the as prepared samples and the development of crystalline phases in the annealed samples. The ferric ions disposed in sites that give rise to the absorption line with g_ef ≈ 4.3 in the EPR spectra of vitreous samples are not more evidenced in the spectra of the annealed samples, from which only of a symmetric and narrowed line with g_ef ≈ 2 is recorded. The room temperature ⁵⁷Fe Mössbauer spectra both of glass and vitroceramic samples consist of two quadrupole doublets characteristic for octahedral sites of Fe²⁺ and Fe³⁺ ions. The isomer shift for glass samples decreases and for vitroceramic samples increases with the iron oxide content.     

Protein dynamics on different timescales

Structure and dynamics determine the function of proteins. This contribution discusses two aspects of protein dynamics, the structural fluctuation and the structural relaxation connected with conformational changes. Myoglobin and haemoglobin were investigated. To cover a wide time range different experimental techniques had to be used. Moreover, measurements in a large temperature regime were used to separate contributions from different modes of motions. Phonon assisted Mössbauer effect using synchrotron radiation allowed the study of the harmonic vibrations which have characteristic times of 1 fs to 0.6 ps. They are present in the whole temperature range from cryogenic to room temperature. With a combination of neutron structure analysis and incoherent neutron scattering it was possible to distinguish three types of hydrogen mean square displacements which are present only above a characteristic temperature T_c: These are the backbone-like (slower than about 100 ps), methyl-like (partly slower partly faster than about 100 ps) and lysine-like (faster than about 100 ps) displacements. The exceptional high energy resolution of Mössbauer absorption on ⁵⁷Fe allowed the measurement of quasi diffusive modes of molecular segments which have characteristic times slower than 1 ns and are present only above T_c. Conformational changes from the ligated to the unligated structure of myoglobin and haemoglobin were investigated by creating a metastable intermediate and observing the relaxation into the equilibrium conformation. A metastable state was obtained by X-ray irradiation. Structural relaxation was investigated as a function of time and temperature using the Mössbauer hyperfine interactions as indicator. Furthermore it was possible to measure intermediates created by photolysis of a ligand with temperature dependent X-ray structure analysis or time dependent X-ray structure analysis with the Laue technique. It was shown that the quasi diffusive structural fluctuations above T_c strongly facilitate structural relaxations.     

Exchange interactions in hydrogen-induced amorphous YFe2

The magnetic properties of hydrogen-induced amorphous (HIA) YFe₂H_x (x = 1.8, 3.0 and 3.4) alloys have been investigated by means of ⁵⁷Fe Mössbauer spectroscopy and atomic pair distribution analysis. The exchange integral (J) estimated from the temperature dependence of the average ⁵⁷Fe hyperfine field shows a tendency to decrease with decreasing the average Fe–Fe interatomic separation. Moreover, an abrupt drop of J is evident at an average Fe–Fe interatomic separation of about 0.25 nm, which is the empirical threshold where the magnetic interaction between Fe moments changes from ferromagnetic to antiferromagnetic. The absence of a spin-glass state in HIA YFe₂(H) is well understood by the enhancement of J through the volume expansion induced by the absorption of hydrogen.     

Thermal behavior of substituted FeCo-based metallic glasses

Three compositions of metallic glasses, Fe₅₈Co₂₄Nb₃Ta₁Mo₁B₁₃, Fe_61.5Co_20.5Nb₃Ta₁Mo₁B₁₃ and Fe₆₆Co₁₈Si₁B₁₅ were prepared by rapid quenching from the melt and subsequently annealed for 1 hour at 450, 650 and 750 °C. The samples were analyzed by X-ray diffraction (XRD) and Mössbauer spectroscopy. All Mössbauer spectra were fitted with a six-line pattern corresponding to the crystalline α-(FeCo) phase and a hyperfine magnetic field distribution representing the amorphous component. The Mössbauer spectra of annealed Fe₆₆Co₁₈Si₁B₁₅ revealed the presence of a secondary crystalline phase, namely (FeCo)₃(BSi). Moreover, the last Mössbauer spectrum in the set was fitted with an additional sextet, corresponding to the appearance of hematite in the system. It is inferred that the addition of Nb, Ta and Mo considerably delays the onset of bulk crystallization and iron oxidation in these systems. The XRD patterns are in qualitative agreement with the Mössbauer results and are consistent with a surface layer of hematite nanoparticles in the system. The activation energy of 4.34 eV for oxidation was estimated from the Mössbauer results.     

Phase evolution and magnetic properties of Co/α-Fe2O3 powder mixtures with different molar ratios treated by mechanical alloying

In this work, we report the phase formation and magnetic properties of Co–hematite powder mixtures with two different molar ratios: Co/α-Fe₂O₃: 1/0.7 and 1/1.3 subjected to high-energy mechanical milling using metallic cobalt and hematite powder as the initial raw material in ambient air atmosphere. The samples were activated with a ball to powder weight ratio (BPR) of 10 and the milled powders were collected after 0, 1, 5, 15, 25 and 30 h. Various characterization techniques such as XRD, HRTEM, VSM and Mössbauer spectroscopy were utilized to study the prepared samples. For the samples with Co/α-Fe₂O₃: 1/0.7 milled for 1 and 5 h the formation of cobalt ferrite was confirmed. However, this was not the case for the samples milled above 5 h for whose both Mössbauer and XRD results confirmed the phase decomposition taken place for the previously formed cobalt ferrite phase. Further, the formation of superparamagnetic nanoclusters of iron oxide, a wustite-like Fe_1?XCo_XO phase and the existence of small amounts of metallic Fe/Fe_1?XCo_X phase/s were also detected for these samples. The presence of the latter phase is not believed to be solely related to contamination from the steel vial/balls used. A mechanochemical-reduction process is assumed to be also possibly responsible for the formation of the observed reduced phases. For the powder mixture with Co/α-Fe₂O₃: 1/1.3, however, increased formation of cobalt ferrite phase was observed by increasing the milling time. The highest maximum magnetization (53 e.m.u/g) and coercive field (500 Oe) was obtained for the sample milled for 25 h among various samples of this series of powder mixture. The lower magnetization obtained for this sample compared to that of the bulk is attributed to the size effect. Furthermore, the structural–magnetic properties relationship of the various powders prepared is discussed in detail.     

Effect of OH-content on thermal and chemical properties of SnOP2O5 glasses

Glasses with 55–60 mol% SnO and 40–45 mol% P₂O₅ have shown extremely large differences in the chemical and thermal properties depending on the temperature at which they were melted. Glasses prepared at low melting temperature, 450–550 °C, had low T_g, 150–200 °C, and low chemical stability. Glasses prepared at high melting temperature, 800–1200 °C, had much higher T_g, 250–300 °C, and much higher chemical stability. No significant differences were found by ¹¹⁹Sn Mössbauer and ³¹P Nuclear Magnetic Resonance spectroscopy. Large differences in the OH-content could be detected as the reason by infrared absorption spectroscopy, thermal analyses, and ¹H Nuclear Magnetic Resonance spectroscopy. In samples with low T_g, a broad OH – vibration band around 3000 nm with an absorption intensity >20 cm^?1, bands at 2140 nm with intensity ～5 cm^?1, at 2038 nm with intensity ～2.7 cm^?1, and at 1564 nm with intensity ～0.4 cm^?1 were measured. These samples have shown a mass loss of 3–4 wt% by thermal gravimetric analyses under argon in the temperature range 400–1000 °C. No mass loss and only one broad OH-band with a maximum at 3150 nm and low absorption intensity <4 cm^?1 could be detected in samples melted at high temperature, 1000–1200 °C, which have much higher T_g, ～300 °C, and much higher chemical stability.     

Exchange-bias and superparamagnetic behaviour of Fe nanoparticles embedded in a porous carbon matrix

Combining different experimental techniques, the physical properties of Fe nanoparticles (NPs) randomly dispersed in a porous carbon have been investigated. From the analysis of TEM images and the broad maximum observed in ZFC–FC magnetization measurements under an applied magnetic field of 2.5 mT, a broad-size distribution NPs (5–50 nm) is estimated. The nature of these NPs (α-Fe and γ-Fe) was determined from X-ray diffraction. Furthermore, magnetization measurements suggest that these Fe-NPs remain completely blocked below 60 K due to a magnetic exchange-bias coupling induced on the surface of these NPs. However, the true nature of the core–shell responsible for this exchange bias within the NPs, is not totally understood yet. In addition, the system begins to be magnetically unblocked above 60 K, becoming almost superparamagnetic above 200 K. Room temperature Mössbauer spectroscopy confirms the existence of both α- and γ-Fe phases; an additional quadrupole component is required to properly fit the spectrum, which could be associated with the NP’s shell or to an oxide phase probably located on the surface of the NPs.     

On the coordination environment of Fe- and Pb-rich solidified industrial waste: An X-ray absorption and Mössbauer study

The oxidation state and coordination environment of Fe and Pb atoms in a series of homogeneous vitrified Pb- and Fe-rich industrial waste glasses is investigated by means of X-ray absorption fine structure (XAFS) and ⁵⁷Fe Mössbauer spectroscopies. The waste content in the studied samples varies between 10 and 60 wt.%. The Mössbauer analysis reveals that even though all the glasses contain both Fe³⁺ and Fe²⁺ ions, the concentration of Fe²⁺ decreases with increasing waste content. The XAFS results demonstrate that the structural role of Fe depends on the waste content and the Fe³⁺ ion occupies increasingly tetrahedral at the expense of octahedral sites as the waste content increases. On the other hand, the Pb²⁺ coordination environment remains unaffected by the waste content. In order to determine the percentage of FeO₆ and FeO₄ polyhedra, we propose a mixed model for the analysis of the Fe-K edge extended-XAFS (EXAFS) spectra according to which X% of the Fe atoms occupy tetrahedral sites while the rest (1 − X)% constitute octahedra. The EXAFS results disclose that when the waste content increases from 10 to 40 wt.%, the percentage of FeO₆ octahedra decreases from 55 to 13 wt.%. When the waste content exceeds 50 wt.%, Fe is predominantly a glass former. The importance of this finding relies with the fact that stabilized products can be produced using a higher amount of Fe-containing toxic waste and a smaller amount of vitrifying agents.     

Conversion of tin and alkali chlorides to phosphates and vitrification into silicate glasses

Mixtures of tin(II) chloride and tin(II)-sodium–potassium chlorides were converted into phosphate salts by reaction with ammonium dihydrogen-phosphate at 400 °C. Element analyses showed that no loss occurred during the treatment, and Mössbauer and wet analyses indicated no change in tin valence. The converted tin phosphate and tin–sodium–potassium phosphates were then dissolved into silicate glasses at 1350 °C without loss. Structural analyses were realized with ³¹P, ²⁹Si, ¹¹⁹Sn NMR and ¹¹⁹Sn Mössbauer, which revealed a complete dissociation of tin phosphate into the silicates. Phosphate units consisted in ortho- and pyro-phosphates. Tin(II) was partially oxidized into tin(IV), but there was no evidence for a phase separation into SnO₂ or SnP₂O₇, tin being mainly bonded to silicate units. These results are discussed in terms of O²⁻ exchange between phosphate and silicate units during the melting process.     

Spin disorder in Fe-doped manganites

Ln_0.7M_0.3MnO₃ compounds are well-known ferromagnets mediated by a double exchange mechanism. As Mn atoms are substituted by Fe in the ratio Mn_1−xFe_x the magnetic structure dramatically changes, because the ferromagnetic double exchange chain is broken. At low Fe concentrations all compounds are magnetically ordered. For intermediate values ferro (FM), antiferro (AF) and paramagnetic (PM) phases co-exist in a large temperature range, and at x ≈ 0.2 spin or cluster-glass behavior is found. Magnetization, Mössbauer, polarized and low angle neutron scattering as well as muon spin relaxation experiments have been performed on 0 ⩽ x ⩽ 0.30 compounds showing the transit from long range ferromagnetism to spin glass. Co-existence of FM and AF clusters of different size has been found for all doped compounds.     

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.     

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.     

Electronic states of SnO-ZnO–P2O5 glasses and photoluminescence properties

SnO–ZnO–P₂O₅ glasses with 30 and 40 mol% P₂O₅ were prepared by a melting process in an air atmosphere. The glass transition temperature, refractive index, and photoluminescence of the glasses were investigated. The electronic states of Sn(II) and Sn(IV) were determined by Mössbauer spectroscopy. The PO₄ units were investigated by Raman spectroscopy. The glass transition temperature was lower than 450 °C, and decreased as the Sn concentrations increased, so that the minimum was about 250 °C. The refractive index increased as the Sn concentration increased. The emission spectra of the glasses peaked at around 2.0–3.0 eV and depended on the glass compositions.     

Structure and properties of nanocrystalline Cu70Fe18Co12 obtained by mechanical alloying

Cu₇₀Fe₁₈Co₁₂ alloy is prepared by mechanical alloying of pure Cu, Fe, Co powder using a high energy ball mill, with increasing milling time ranging from 4 to 8, 24, 36 and 54 h. The variation of the morphology and the elemental distribution were measured at these different stages on various grains of the alloy using a scanning electron microscope with a dispersive energy analyzer. Atomic clusters of iron were observed on some grains after 8 h of milling, confirming the non-homogenisation of the powder at this stage. Beyond 12 h, the homogenisation is ensured over a volume of one cube micron. Microstructural changes during the mechanical alloying have been studied by X-ray diffractometry (XRD) and Mössbauer spectroscopy. X-ray diffraction measurements confirm the dissolution of iron and cobalt phases in the FCC matrix of copper after 24 h of milling with increase of the structural parameter. This same dissolution was also measured by Mössbauer spectroscopy, confirming that after 4 h of milling the CuFe phase begins to form and iron dissolution is incomplete with partial amount of alpha Fe phase surviving after 36 h of milling.     

Study of hyperfine interactions in Fe–Co nanocomposite films by Mössbauer spectroscopy and NMR

Nanogranular magnetic films were produced by the specially designed UHV plasma-jet system with DC hollow-cathode discharge. We investigated the properties of these ferromagnetic FeCo-AlN films. The samples were studied by nuclear magnetic resonance, Mössbauer spectroscopy, and transmission electron microscopy. The films are composed of nanoparticles of cubic FeCo, 2–10 nm in size, embedded in amorphous matrix containing Al, N and O. The Mössbauer spectra indicate that the orientation of local magnetic moments on the surface is random for the sample with 1:1 Fe/Co ratio, while the magnetization lays in the plane of the layer for samples with Fe/Co smaller than 1 (0.91–0.95).     

Influence of Ag nanoparticles on luminescent performance of SiO2:Tb3 + nanomaterials

Tb^3 + single-doped SiO₂ (SiO₂:Tb^3 +) and Tb^3 +, Ag co-doped SiO₂ (SiO₂:Tb^3 +–Ag) nanostructured luminescent materials were prepared by a modified Stöber method. Their microstructure and optical property were investigated using scanning electron microscopy, ultraviolet visible absorption and photoluminescence spectrophotometry. Results show that the samples are composed of well-dispersed near-spherical particles with a diameter about 50 nm, the highest fluorescence intensity is obtained when the doping concentration of Tb^3 + is 4.86 mol%, the corresponding internal quantum efficiency is 13.6% and the external quantum efficiency is 8.2%. The experimental results indicate that Ag nanoparticles can greatly enhance the light absorption at 226 nm and the light emission at 543 nm of SiO₂:Tb^3 +–Ag, and the fluorescence lifetime reduces with increasing Ag concentration in SiO₂:Tb^3 +–Ag. Additionally, the present results indicate that fluorescence enhancement is attributed to the local field enhancement and the increased radiative decay rates induced by Ag nanoparticles.     

Synthesis and characterization of nanocrystalline Fe60X20B10P10 (X = Co,Ni) alloys

In this work, two nanocrystalline alloys, Fe₆₀Ni₂₀P₁₀B₁₀ and Fe₆₀Co₂₀P₁₀B₁₀, were produced by mechanical alloying processing them at milling times of 5, 40 and 100 h. Structural properties were determined by X-ray diffraction and transmission Mössbauer spectroscopy. The 100-h milled alloys consisted primarily of metastable bcc Fe(Co, Ni) nanocrystals (11–17 nm) with different Fe-rich environments. Differential scanning calorimetry measurements were performed in order to study the thermal stability of the nanocrystalline phases and their crystalline growth. The values for the apparent activation energy of the main crystallization processes were 2.1 ± 0.1 and 2.4 ± 0.1 eV, respectively, which were associated with grain growth mechanisms.