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1.
Mössbauer, ESR and magnetization measurements have been carried out on a basalt glass heat-treated at different temperatures (600, 650, 700, 800 and 900°C for 8 h). The as-annealed glass and the above five samples showed two-doublet Mössbauer spectra, while the last two samples also showed a six line magnetic hyperfine pattern at 300 K. At 4 K, the last four samples showed magnetic hyperfine patterns, while the as-annealed glass showed that there was already short range magnetic ordering present. High field Mössbauer data at 4 K showed that the surface spins are canted. The minimum quadrupole splitting and the maximum isomer shift around 700°C are related to the improved symmetry of the magnetite lattice. ESR spectra showed paramagnetic resonances at g = 4.3 and g = 2.0 for the first two samples, while the last four samples showed superparamagnetic resonance centred around g = 2.0 at 300 K. At lower temperatures, the 650 and 700°C samples showed ferrimagnetic resonance. Magnetization curves against H/T superpose well both at 300 and 77 K, showing the typical superparamagnetic behaviour of the small magnetite particles. The saturation magnetization (at 270 K) showed a sharp change around 700°C, showing the formation of magnetite. The magnetic structure of the small magnetite particles are discussed in terms of the above results.  相似文献   

2.
ZnO crystals doped with Cr, Mn, Fe and Co were grown by the flux method. The prepared crystals revealed no phase separation detectable by X-ray diffraction. Structure properties were characterized by Raman and photoluminescence spectroscopy. For ZnO:Co, Mn and Cr, no spontaneous ferromagnetic moment was observed up to T=2 K whereas for the ZnO:Fe crystals the m(H) curves suggest the existence of 5 nm superparamagnetic iron clusters. At low temperatures the m(H) curves can be interpreted as a superposition of major paramagnetic and minor antiferromagnetic contribution. The paramagnetic part corresponds to the presence of Co2+, Fe3+, Mn2+ ions and small Cr atom clusters.  相似文献   

3.
The magnetic field dependence of magnetization M(B) at the temperature 1.72 K in magnetic fields up to 5 T and the temperature dependence of magnetic susceptibility (MS) χ(T) in the temperature range 1.7–400 K of six PbTe:Eu samples with the concentration of Eu impurity of the order of 1×1019–1×1020 cm?3, prepared from the doped crystals grown from the melt by the Bridgman method, have been investigated. It is shown that the dependence of M(B) and χ(T) can be quantitatively explained by the contribution of the single centers of Eu ions, their pairs, and the matrix of the doped crystals using the same set of parameters for each sample. This is true provided we use in our analysis the values of the exchange integrals between Eu ions in EuO normalized with the lattice constant of PbTe, i.e., J1/kB=0.056 K for the ferromagnetic interaction of the NN (nearest neighbor) pairs and J2/kB=?0.13 K for the antiferromagnetic interaction of the NNN (next nearest neighbor) pairs, as well as different values of the MS of crystal χmatrix. It is revealed that the probability of the formation of complexes based on the magnetic impurity pairs is higher in the incipient section of a doped ingot, and it decreases towards the ingot end where the single centers of Eu ions become the only centers of the impurity. We conclude that the pairs of Eu2+ ions, which are formed during the growth of the PbTe:Eu ingots from melt by the Bridgman method, are the constituents of the complexes of the magnetic impurities with the background Oxygen impurities in the crystal matrix of the doped lead telluride. It is shown that the formation of the complexes leads to an increase of the MS of crystal matrix χmatrix and can even cause the change of its sign from minus to plus, i.e., it can convert the crystal matrix from the diamagnetic to paramagnetic state. The possible causes of this effect are analyzed.  相似文献   

4.
Silica substrates were implanted with Ni+ ions to nominal fluences (F) ranging from 1015 to 6×1016 cm−2 at energy E=160 keV. The anisotropic spectrum of electron paramagnetic resonance with g||=2.49±0.03 and g=2.17±0.03 was observed at 77 and 295 K for the samples implanted to F=(1-3)×1015 cm−2 and was attributed to Ni+ ions with ground state |xy〉 or |x2y2〉. The single line with g=2.29 and ΔHpp∼14 mT was found at 77 and 295 K for the samples implanted to F=(4-8)×1015 cm−2 and was assigned to clusters of Ni+ ions coupled by exchange interactions. Starting from F=8×1015 cm−2 and at higher fluences the single line with g∼2.2 and ΔHpp∼30-40 mT was observed at room temperature. The behavior of this line as function of measurement temperature indicates its superparamagnetic origin earlier studied by Isobe et al. Optical absorption spectra and transmission electron microscopy confirm the results obtained by other authors concerning the formation of particles of metallic nickel of nanometer size in silica glass implanted with Ni+ to F>1016 cm−2.  相似文献   

5.
Two coordination polymers, {[Ln(2-stp)(4,4′-bipy)(H2O)].(H2O)}, [Ln = Dy (1) and Eu (2), 2-stp = 2-sulfoterephthalate and 4,4′-bipy = 4,4′-bipyridine] have been characterized by solid state UV-vis, FTIR spectra, X-ray single crystal diffraction and solid state photoluminescence. Variable-temperature magnetic susceptibility and isothermal magnetization as function of external magnetic field is also studied for both complexes. After ligand-mediated excitation, both complexes show the characteristic visible and NIR luminescence of the corresponding LnIII ions (Ln = Dy, Eu) which is due to efficient energy transfer from the ligands to the central LnIII ions via an antenna effect. The indirect energy transfer in both complexes has been investigated and discussed in detail.  相似文献   

6.
The local glass structure of tellurite glasses containing CuO with the nominal composition x(CuO) · (1−x)(TeO2), where x=0.10, 0.20, 0.30, 0.40, and 0.50, as well as the valence state of the copper ions have been investigated by X-ray photoelectron spectroscopy (XPS) and magnetization measurements. The Te 3d core level spectra for all glass samples show symmetrical peaks (Te 3d5/2 and Te 3d3/2) at essentially the same binding energies as measured for TeO2 indicating that the chemical environment of the Te atoms in the glasses does not vary significantly with the addition of CuO. The O 1s spectra, however, show slight asymmetry for all glass samples which results from two contributions, one from the presence of oxygen atoms in the Te-O-Te environment (bridging oxygen BO) and the other from oxygen atoms in an Te-O-Cu environment (non-bridging oxygen NBO). The ratio of NBO to total oxygen was found to increase with CuO content and to be in good agreement with calculated values for the TeO4 trigonal bipyramid structure. Moreover, the appearance of a satellite peak in the Cu 2p spectra provides definitive evidence for the presence of Cu2+ ions in these glass samples where the asymmetry and broadening of the Cu 2p3/2 and Cu 2p1/2 peaks are indicative of the presence of both Cu2+ and Cu+ ions. The relative concentration Cu2+ determined from XPS is in good qualitative agreement with the determinations of Cu2+ from magnetic susceptibility measurements on the same glass samples. Furthermore the susceptibility data follow a Curie-Weiss temperature-dependent behavior (χ=C/(Tθ)) with negative Curie temperatures indicating that the predominant magnetic interactions between the Cu2+-Cu2+ exchange pairs are antiferromagnetic in nature.  相似文献   

7.
《Journal of Non》2006,352(32-35):3414-3422
The crystallization of fluoroindate glasses doped with Gd3+, Mn2+ and Cu2+ heat treated at different temperatures, ranging from the glass transition temperature (Tg) to the crystallization temperature (Tc), are investigated by electron paramagnetic resonance (EPR) and 19F nuclear magnetic resonance (NMR). The EPR spectra indicate that the Cu2+ ions in the glass are located in axially distorted octahedral sites. In the crystallized glass, the g-values agreed with those reported for Ba2ZnF6, which correspond to Cu2+ in a tetragonal compressed F octahedron and to Cu2+ on interstitial sites with a square-planar F co-ordination. The EPR spectra of the Mn2+ doped glasses exhibit a sextet structure due to the Mn2+ hyperfine interaction. These spectra suggest a highly ordered environment for the Mn2+ ions (close to octahedral symmetry) in the glass. The EPR spectra of the recrystallized sample exhibit resonances at the same position, suggesting that the Mn2+ ions are located in sites of highly symmetric crystalline field. The increase of the line intensity of the sextet and the decrease of the background line in the thermal treated samples suggest that the Mn2+ ions move to the highly ordered sites which contribute to the sextet structure. The EPR spectra of the Gd3+ doped glasses exhibit the typical U-spectrum of a s-state ion in a low symmetry site in disordered systems. The EPR of the crystallized glasses, in contrast, have shown a strong resonance in g  2.0, suggesting Gd3+ ions in environment close to cubic symmetry. The 19F NMR spin–lattice relaxation rates were also strongly influenced by the crystallization process that takes over in samples annealed above Tc. For the glass samples (doped or undoped) the 19F magnetization recoveries were found to be adjusted by an exponential function and the spin–lattice relaxation was characterized by a single relaxation time. In contrast, for the samples treated above Tc, the 19F magnetization-recovery becomes non-exponential. A remarkable feature of our results is that the changes in the Cu2+, Mn2+, Gd3+ EPR spectra and NMR relaxation, are always observed for the samples annealed above Tc.  相似文献   

8.
The rate of dissolution and growth of settling crystals of spinel was measured optically in a borosilicate melt that was pre-heated at a temperature above liquidus to erase the effects of previous history. The Hixson-Crowell equation, which is based on Fick's first law, was used to determine mass-transfer coefficients (kH) for dissolution and growth; both were found to fit the same Arrhenius function of temperature (T). An attempt was made to estimate the diffusion coefficient (D) and the concentration-boundary-layer thickness (δ). The calculated values of δ compared well with experimental results and observations. The D vs. T function was similar to a literature function obtained for the dissolution of magnetite in sodium disilicate glass.  相似文献   

9.
The magnetic susceptibility χ(T) at 4.2 K < T < 293 K; the dependence of the magnetic moment on the magnetic field strength, M(H), at 4.2, 77, and 293 K; and the electrical resistivity ρ(T) at 4.2 K < T < 293 K are studied for samples of perovskite-phase KTaO3 obtained by both solid-phase synthesis (KTaO 3 s ) and deposition on a cathode during electrolysis of melts (KTaO 3 e ). Yellowish white KTaO 3 s powders are diamagnetic and reveal dielectric properties. Dark polycrystalline KTaO 3 e samples with metallic luster are characterized by the dependence ρ(T) typical of metals and additional paramagnetic contribution to the paramagnetic susceptibility as compared with KTaO 3 e . Changes in the properties of KTaO3 during electrocrystallization are attributed to partial reduction of tantalum. They are revealed in the structural features of KTaO 3 e (excess of tantalum as compared to the stoichiometric composition of KTaO 3 e , deficiency of the oxygen sublattice, and clearly pronounced anharmonicity of atomic vibrations). A change of the cation-anion-cation interactions, occurring owing to the overlapping of oxygen p orbitals with tantalum t2g orbitals and the formation of impurity levels near the conduction band, leads to the generation of free carriers, which make a paramagnetic contribution to the magnetic susceptibility.  相似文献   

10.
A combination of Langevin and hyperbolic tangent functions weighted by a log-normal particle size distributions were used to fit the magnetization curves of Fe10Ag90 granular alloys, produced by a sol–gel process under different chemical conditions. The fitting technique allows one to get both the superparamagnetic and the blocked particle size distributions. The average size of the Fe particles obtained from the fit were in good agreement with those obtained by X-ray diffraction. The correlation between the coercive field and the particle distribution was also investigated. Zero-field cooling dc magnetic susceptibility measurements were fitted using a similar technique to that used for fitting the magnetization curves. The saturation magnetization and mean Fe particle size values obtained from the two fittings were in good agreement.  相似文献   

11.
E. Vanea  M. Tămăşan  C. Albon  V. Simon 《Journal of Non》2011,357(22-23):3791-3796
Sol–gel derived 60SiO2·20Al2O3·10Fe2O3·10Dy2O3 (mol%) glass and vitro-ceramic samples obtained after high temperature treatment were investigated with respect to structure, magnetic behaviour, response to simulated body fluid (SBF) and bovine serum albumin (BSA). After heat treatment, the iron preponderantly crystallises as magnetite and hematite. The field-dependent magnetisation measurements support a soft ferrimagnetic, nearly superparamagnetic behaviour. After soaking in SFB/BSA solutions, the analysis of the outermost surface layer by X-ray photoelectron spectroscopy shows the attachment of the protein and the self-assembly of a calcium containing phase.  相似文献   

12.
Some physical properties (such as lattice parameter, density and porosity) and magnetic properties of the system Mg1‐xZnxFe2O4; where x=0,0.1,0.2,0.3,0.4,0.5and 0.6 have been studied. It was found that the lattice parameter increases with increasing the zinc concentration. The composition dependence of the physical properties is divided into two regions. The first one is for x ≤ 0.3 and the second one is for x > 0.3. From the magnetization measurements, the basic composition (MgFe2O4) shows the lowest magnetization, while the composition of x=0.4 shows the highest one. The behaviour of magnetization M versus composition shows also two regions for x <>0.3. The behaviour of M versus x was discussed in the bases of cation distribution. From the B‐H loops, the remanence induction Br, saturation induction Bs and the coercive force Hc were determined and studied with x. The Curie temperature TC was determined from the measurements of the initial permeability μi versus temperature. It was found TC decreases with increasing Zn‐content. Also paramagnetic temperature TP was determined from the behaviour of MS vs. T. In general it was found TP > TC by about 7‐10 K.  相似文献   

13.
Rare‐earth substituted strontium ferrite nanopowders SrFe12‐xRxO19 (R = La, Gd and Er; x = 0.2, 0.5 and 1) were prepared by sol‐gel‐autocombustion method and subsequent heat treatments. Structural and magnetic properties of SrFe12‐xRxO19 powders heat treated at 800, 900 and 10000C, for various times, were characterized with an X‐ray diffractometer, a vibrating sample magnetometer and a scanning electron microscope. The results of X‐ray diffraction measurements showed the M‐type hexagonal structure formation by heat treatments. Magnetic properties, such as specific saturation magnetization σs, specific remanent magnetization σr and coercivity Hc, as well as microstructure depend on the heat treatment conditions (temperature and time). The coercivity Hc exhibits a great increase after a critical heat treatment time. When the heat treatment time increases, one obtains an increase in Hc after a shorter heat treatment time. This jump of Hc was explained by a transition from the superparamagnetic state to normal state of the single domain nanoparticles. The occurrence of an agglomerated structure composed of magnetically interacting ultrafine crystallites also contributes to the increase of Hc.The heat treatment determines a reduced grain growth due to the internal stress generated by R ions. With increasing R content the σs and σr decrease due to the dissolution of R ions into the hexaferrite lattice. We believe that by selecting the time and temperature of the heat treatment, microstructure and magnetic properties suitable for magnetic recording media application can be obtained. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)  相似文献   

14.
《Journal of Non》2007,353(22-23):2263-2271
The system of equations describing the formation of silver nanoclusters through the reduction of ionic silver in the course of thermal processing of silver containing glasses in hydrogen is formulated and solved numerically. The processes of the clusterization of neutral silver within the glass and at the surface, and the growth of the nanoclusters are modeled with the account of different mobilities and concentrations of the participating species. The influence of the variation of diffusion coefficients of Ag0 atoms, Ag+ and H+ ions as well as concentration of Ag+ ions in the glass matrix. It is shown that concentration distribution of neutral hydrogen (H0) strongly depends on the relationship between concentration of Ag+ ions (CAg+) and concentration of neutral hydrogen at the glass surface (C1), as well as between diffusion coefficients of silver and hydrogen ions. When DAg+  DH+ and CAg+  C1, the total hydrogen concentration profile (CHtot = CH0 + CH+) is defined by silver ion diffusion coefficient DAg+. Concentration of neutral silver, CAg0, represents a bell-shaped depth distribution, whose maximum moves to the depth linearly with t1/2 with the rate depending both on the diffusion coefficient of neutral silver, DAg0, and neutral hydrogen, DH0. It is shown that the depth position of the maximum coincides with the frontier of the layer filled by clusters. The kinetics of the cluster radius growth in the bulk of the glass also depends both on DAg0 and DH0 and essentially deviated from the kinetic law R2  t predicted earlier in the assumption of time-independent oversaturation. The kinetics of Ag cluster growth on the glass surface turned out independent of the DAg0 diffusion coefficient.  相似文献   

15.
The current study aimed at the assessment of CuO gradual addition on the crystallization behavior and magnetic properties of ferromagnetic glass ceramic in the system Fe2O3·CaO·ZnO·SiO2. Ferromagnetic glass–ceramics with a high quantity of magnetite were designed to be crystallized in the system Fe2O3·CaO·ZnO·SiO2. The influences of gradual addition of CuO and melting temperature on the sequence of crystallization and magnetic properties were studied. The X-ray diffraction patterns showed the presence of nanometric magnetite crystals in a glassy matrix after direct cooling from the melt without any additional heat treatments. Increasing the melting temperature resulted in an increase in the magnetite crystallization. The addition of up to 20 g CuO/100 g batch composition revealed a decreasing effects in both endo- and exothermic values, whereas, the same values were inversely increased with increasing the CuO addition to 30 g. In general, increasing the CuO amounts greatly enhanced the crystallization of magnetite. A significant amount of delaffosite (CuFeO2) was unexpectedly detected and increased by increasing both the added amount of CuO and the treatment temperature. The XRD results detected some traces of cuprite (Cu2O) in the samples of high CuO content. The TEM results reflected the precipitation of nano-magnetite crystals in the 2–10 nm size range. Magnetic hysteresis cycles were analyzed using a vibrating sample magnetometer with a maximum applied field of 20 kOe at room temperature in quasi-static conditions. From the obtained hysteresis loops, the saturation magnetization (Ms), remanence magnetization (Mr) and coercivity (Hc) were determined.  相似文献   

16.
Copper ions incorporated into alkaline earth zinc borate glasses 10RO + 30ZnO + 60B2O3 (R = Mg, Ca and Sr) and 10SrO + (30 ? x)ZnO + 60B2O3 + xCuO (x = 0, 0.1, 0.3, 0.5, and 0.7 wt.%) were characterized by electron paramagnetic resonance (EPR), optical absorption and FTIR techniques. The EPR spectra of all the glass samples exhibit resonance signals characteristic of Cu2+ ions. The values of spin-Hamiltonian parameters indicate that the Cu2+ ions in alkaline earth zinc borate glasses were present in octahedral sites with tetragonal distortion. The spin concentration (N) participating in resonance was calculated as a function of temperature for strontium zinc borate (SrZB) glass sample containing 0.7 wt.% of Cu2+ ions and the activation energy was calculated. From the EPR data, the paramagnetic susceptibility (χ) was calculated at different temperatures and the Curie constant was evaluated from the 1/χ-T graph. The optical absorption spectra of these samples show only one absorption band. The optical band gap energies (Eg) and Urbach energy (ΔE) are calculated from their ultraviolet edges. The FTIR studies show different stretching and bending vibrations of alkaline earth zinc borate glasses.  相似文献   

17.
G.D. Khattak  A. Mekki  L.E. Wenger 《Journal of Non》2009,355(43-44):2148-2155
Vanadium phosphate glasses with the nominal chemical composition [(V2O5)x(P2O5)1?x], where x = 0.30, 0.40, 0.50, and 0.60, have been prepared and investigated by X-ray photoelectron spectroscopy (XPS) and magnetization measurements. Asymmetries found in the O 1s, P 2p, and V 2p core level spectra indicate the presence of primarily P–O–P, P–O–V, and V–O–V structural bonds, a spin–orbit splitting of the P 2p core level, and more than one valence state of V ions being present. The magnetic susceptibility data for these glasses follow a Curie–Weiss behavior which also indicates the presence of some V ions existing in a magnetic state, i.e., a valence state other than that of the non-magnetic V5+. From qualitative comparisons of the abundance of the bridging oxygen or P–O–P sites as determined from the areas under the various O 1s peaks with the abundances of differing phosphate structural groups associated with the presence of different valence states of the vanadium ions, a glass structure model consisting of a mixture of vanadate phosphate phases is proposed for these glass samples. These include V2O5, VOPO4, (VO)2P2O7, VO(PO3), and V(PO3)3 with the abundance of orthophosphate (PO4)3? units increasing with increasing vanadium content.  相似文献   

18.
Zero-field and in-field (at 8 T) conductivity vs temperature (σ-T), magneto-resistance (Δρ/ρ), magnetization vs temperature (M-T) and magnetization vs field (M-H) of unannealed Al70Pd20Mn10 and annealed Al70Pd20Mn10, Al70Pd21Mn9 and Al70Pd22Mn8 quasicrystalline alloys have been studied in the temperature range of 1.4-300 K. Room temperature resistivity and the low-temperature magneto-resistance show a correlation with the corresponding magnetization. The σ-T for all the studied samples shows a pair of minima and maxima. The σ-T maxima show a correlation with the total magnetization. The analysis shows that σ-T is dominated by weak-localization effects. The minima are arising due to competing inelastic scattering times τi (e-ph scattering in the dirty metallic limit, τi ∝ T−2) and the Kondo-type spin-flip scattering time τsf whereas the maxima has been attributed to ‘Kondo-maxima’, occurring due to maxima in the spin-flip rate . The magneto-resistance of these samples shows a changeover from negative to positive where the negative component shows a correlation with the magnetization of the sample. The values of parameters derived from refinement give spin-flip scattering fields, which are found to be correlated with the total sample magnetization.  相似文献   

19.
The structural aspects of clustering of Yb3+ ions and the paramagnetic behavior of these clusters have been investigated in GeO2 glasses doped with 140-1100 ppm by weight of Yb2O3 using time-domain electron paramagnetic resonance (EPR) spectroscopic techniques. The echo-detected EPR (EDEPR) spectra of Yb3+ ions and their unusual dependencies on microwave power and magnetic field have been found to be indicative of the formation of clusters of these rare earth ions in GeO2 glass that behave as non-Kramers type spin systems. The magnetic field and concentration dependence of phase relaxation rates of Yb3+ in these glasses further substantiate such a scenario and indicate the formation of clusters of Yb3+ ions. A comparison of the EDEPR spectra with calculated cw-EPR line shapes yields a semi-quantitative measure of the typical cluster size of ?3 Yb atoms and intra-cluster Yb-Yb distances of 3.5-4.0 Å in these glasses at doping levels of ?350 ppm of Yb2O3.  相似文献   

20.
The basicity of an oxide glass can be measured experimentally from the frequency shifts in the ultra-violet (UV) (s-p) spectra of probe ions such as Pb2+ and can be expressed on the numerical scale of optical basicity Λ (ideally Λ lies between zero and unity). It is possible to relate Λ with (i) the constitution, and (ii) the electronegativity of the cations (e.g. Na+, Si4+, etc.) of the glass, and the relationship allows microscopic optical basicities λ to be assigned to individual oxides and oxy-groups in the glass. These microscopic optical basicities are used for interpreting various aspects of the physics and chemistry of glass including refractivity, network coordination number changes, chemical durability, the glass electrode, UV transparency and the host behaviour of glass towards metal ions generally. Changes in glass basicity in going from one alkali metal oxide to another are also discussed. Finally, the concept of optical basicity, both as an experimentally obtained quantity and as a number calculated from glass constitution and electronegativity, is discussed in relation to the traditional approach to acid-base behaviour in glass.  相似文献   

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