Neutron and X-ray diffraction studies on the Tb2Ni3Si5 single crystal

Neutron and X-ray diffraction studies on the Tb₂Ni₃Si₅ single crystal have been done to investigate its crystal modulation and magnetic properties. The modulated single crystal is constructed by the TbNiSi₂ (CeNiSi₂-type Cmcm) and the Tb₂Ni₃Si₅ (U₂Co₃Si₅-type Ibam) lattices. The relationship between the two lattices is described as direction of the b₁₁₂-axis coincides with the a₂₃₅-axis. The crystal modulation gives significant effects on magnetism. Each of the two lattices takes complex antiferromagnetism with multiplex propagation vectors.     

Experimental system for X-ray magnetic diffraction under extreme conditions

An experimental system for X-ray magnetic diffraction (XMD) under extreme conditions was constructed on the beamline BL39XU at SPring-8. This system aims at studying magnetic properties of ferromagnets through the measurements of magnetic form factors under the conditions of low temperature (5 K), high magnetic field (6 T) and high pressure (10 GPa). This system consists of a superconducting magnet (SCM), a diamond anvil cell (DAC), a two-axis manipulator for the DAC, a five-axis goniometer for the SCM, and an X-ray polarizer with a phase plate. Details of this system are presented. Experimental results on uranium telluride are shown as a performance test with this instrumentation.     

Immiscibility in the nickel ferrite-zinc ferrite spinel binary

Immiscibility in the trevorite (NiFe₂O₄)-franklinite (ZnFe₂O₄) spinel binary is investigated by reacting 1:1:2 molar ratio mixtures of NiO, ZnO and Fe₂O₃ in a molten salt solvent at temperatures in the range 400-1000 °C. Single phase stability is demonstrated down to about 730 °C (the estimated consolute solution temperature, T_cs). A miscibility gap/solvus exists below T_cs. The solvus becomes increasingly asymmetric at lower temperatures and extrapolates to stoichiometric parameters = 0.15, 0.8 at 300 °C. A thermodynamic analysis, which accounts for changes in configurational and magnetic ordering entropies during cation mixing, predicts solvus phase compositions at room temperature in reasonable agreement with those determined by extrapolation of experimental results. The delay between disappearance of magnetic ordering above (for NiFe₂O₄) and disappearance of a miscibility gap at T_cs is explained by the persistence of long-range ordering correlations in a quasi-paramagnetic region above T_C.     

Effects of the substitution of gadolinium for neodymium on the crystal and magnetic properties of the Nd1−xGdxCo4B compounds

The crystal and magnetic properties of the Nd_1−xGd_xCo₄B compounds for 0?x?1 have been studied by X-ray powder diffraction, magnetization and differential scanning calorimetry (DSC) measurements. These compounds crystallize in a hexagonal CeCo₄B-type structure with the P6/mmm space group. The substitution of Gd for Nd leads to a decrease of the unit-cell parameter a and the unit-cell volume V, while the unit-cell parameter c remains almost constant. Magnetic measurements indicate that all samples are ordered magnetically below room temperature. The Curie temperatures determined by the DSC technique increase linearly as Nd is substituted by Gd. The saturation magnetization at 5 K decreases upon the Gd substitution up to x=0.6, and then increases again.     

Observation of ordered orbital of YTIO3 by the X-ray magnetic diffraction experiments

X-ray magnetic diffraction (XMD) experiments of ferromagnetic YTiO₃ were performed. The orbital-magnetic form factor (L) and the spin-magnetic form factor (S) were individually measured by utilizing the LS separation method of the XMD. The experiments consisted of two parts. The first was the measurement of the orbital-magnetic form factor to examine whether the orbital moment of this compound was quenched or not. The second was the measurement of the spin-magnetic form factor to examine whether the ordered orbital of Ti-3d electrons was observed by the XMD. The result of the first experiment suggested quenching of the orbital moment. In the second experiment, the spin-magnetic form factor was observed for the total 22 reciprocal-lattice points. Calculated spin-magnetic form factor with a model wave function of the ordered orbital reproduced the observed one well. This result shows that the ordered orbital of Ti-3d electrons can be observed by the XMD.     

Local order and structural transitions in the molecule-based layer ferrimagnet (n-C4H9)4N FeFe(C2O4)3

Local structural order and temperature-dependent structural variation have been studied in the molecular-based layer ferrimagnet (n-C₄H₉)₄N Fe^IIFe^III(C₂O₄)₃ by EXAFS and high resolution X-ray powder diffraction. The EXAFS spectra measured at the Fe K-edge are successfully modelled by successive O, C, O and metal shells, showing that even when there is extensive structural disorder due to stacking faults, the local structural order in this class of ferrimagnets is fully retained. In this salt, which shows remarkable negative magnetisation at low temperature (Néel class Q), the EXAFS Debye-Waller factor has a discontinuity at 40 K, corresponding to one found in the magnetisation. At the same temperature there is also a change in the expansion of the lattice as evidenced by the high resolution X-ray powder diffraction.     

Effect of K doping on the physical properties of La0.65Ca0.35−xKxMnO3 (0?x?0.2) perovskite manganites

The effects of K doping in the A-site on the structural, magnetic and magnetocaloric properties in La_0.65Ca_0.35−xK_xMnO₃ (0?x?0.2) powder samples have been investigated. Our samples have been synthesized using the solid-state reaction method at high temperature. The parent compound La_0.65Ca_0.35MnO₃ is an orthorhombic (Pbnm space group) ferromagnet with a Curie temperature T_C of 248 K. X-ray diffraction analysis using the Rietveld refinement show that all our synthesized samples are single phase and crystallize in the orthorhombic structure with Pbnm space group for x?0.1 and in the rhombohedral system with R3¯c space group for x=0.2 while La_0.65Ca_0.2K_0.15MnO₃ sample exhibits both phases with different proportions. Magnetization measurements versus temperature in a magnetic applied field of 50 mT indicate that all our investigated samples display a paramagnetic-ferromagnetic transition with decreasing temperature. Potassium doping leads to an enhancement in the strength of the ferromagnetic double-exchange interaction between Mn ions, and makes the system ferromagnetic at room temperature. Arrott plots show that all our samples exhibit a second-order magnetic-phase transition. The value of the critical exponent, associated with the spontaneous magnetization, decreases from 0.37 for x=0.05 to 0.3 for x=0.2. A large magnetocaloric effect (MCE) has been observed in all samples, the value of the maximum entropy change, |ΔS_m|_max, increases from 1.8 J/kg K for x=0.05 to 3.18 J/kg K for x=0.2 under a magnetic field change of 2 T. For x=0.15, the temperature dependence of |ΔS_m| presents two maxima which may arise from structural inhomogeneity.     

Influence of solvothermal growth condition on morphological formation of hematite spheroid and pseudocubic micro structures and its magnetic coercivity

Influence of solvothermal growth condition on morphological formation and population of defects of hematite spheroid and pseudocubic micro structures and its magnetic properties were studied. Spheroid shaped crystals with different size were obtained from growth solution made of methanol, methanol-water, propanol and pseudocubic crystallites with dimension of 1.281 μm size were obtained with propanol-water solution combination at a growth temperature of 200 °C. UV absorption and magnetic properties of spheroid and pseudocubic micro structures were size and shape dependant. Spheroid shaped sample grown from precursor solution made of methanol gives intense UV absorption peaks at 360 nm and high coercivity (5.23 KOe) at room temperature. Reduction in magnetic coercivity and remanence of all samples at 5 K with respect to 300 K is attributed to antiferromagnetic nature of hematite with spheroid and pseudocubic morphology. High coercivity (6.2 KOe) at room temperature was observed from micro pseudocubic sample grown with propanol-water combination which is contributed to high aspect ratio, inter particle interaction and crystalline defects.     

Porosity of microporous zeolites A, X and ZSM-5 studied by small angle X-ray scattering and nitrogen adsorption

Small-angle X-ray scattering (SAXS) using synchrotron radiation and nitrogen adsorption have been applied to characterizations of porosities and microporous structures for the zeolites of NaA, KA, CaA, NaX and ZSM-5. Besides the information on the external morphology of the particles of the zeolites, the complementation of the two techniques has revealed rich and consistent structural and surface information on the molecular scale crystalline pores of these zeolites. Analyses of the data suggest that the determined sizes of the micropores imply the pore spaces occupied by the probe molecules of water in the SAXS and nitrogen in adsorption techniques, respectively. The microporous information of NaA and KA are difficult to obtain from nitrogen adsorption, due to the blocking of nitrogen by their narrow channels, but have been satisfactorily measured by SAXS. The factors causing variations of the measured values of the parameters in different analysis methods have been discussed.     

BaCO3 mediated modifications in structural and magnetic properties of natural nanoferrites

Preparing M-type barium hexaferrite and improving the magnetic response of natural ferrites by incorporating barium carbonate (BaCO₃) is ever-demanding. Series of barium carbonate doped ferrites with composition (100−x)Fe₃O₄·xBaCO₃ (x=0, 10, 20, 30 wt%) are prepared through solid state reaction method and sintered gradually at temperatures of 800 and 1000 °C. Nanoparticles of natural ferrite and commercial BaCO₃ are used as raw materials. Impacts of BaCO3 on structural and magnetic properties of these synthesized ferrites are inspected. The obtained ferrites are characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD) and vibrating sample magnetometer (VSM) at room temperature. Uniform barium hexaferrite particles in terms of both morphology and size are not achieved. The average crystallite size of BaFe₁₂O₁₉ is observed to be within 30–600 nm. The sintering process results phase transformation from Fe₃O₄ (magnetite) to α-Fe₂O₃ (hematite) and the formation of hexagonal barium ferrite crystals. The occurrence of barium crystal is found to enhance with the increase of BaCO₃ concentrations up to 20 wt% and suddenly drop at 30 wt%. Saturation and remanent magnetization of the doped ferrites are significantly augmented up to 16.37 and 8.92 emu g⁻¹, respectively compared to their pure counterpart. Furthermore, the coercivity field is slightly decreased as BaCO₃ concentrations are increased. BaCO₃ mediated improvements in the magnetic response of natural ferrites are demonstrated.     

Low temperature synthesis of Mn0.4Zn0.6In0.5Fe1.5O4 nanoferrite for high-frequency applications

In the present study, nanoferrite of composition Mn_0.4Zn_0.6In_0.5Fe_1.5O₄ has been synthesized by co-precipitation method. Decomposition of residue at a temperature as low as 200 °C gives the ferrite powder. The ferrite has been, finally, sintered at 500 °C. The structural studies have been made by using X-ray diffraction (XRD) technique and scanning electron microscopy (SEM), which confirm the formation of single spinel phase and nanostructure. The dc resistivity is studied as a function of temperature and values found are more than twice those for the samples prepared by the other chemical methods. It is found that the resistivity decreases with increase in temperature. The initial permeability value is found to be higher as compared to the other chemical routes. The initial permeability value is found to increase with increase in temperature. At a certain temperature called Curie temperature, it attains a maximum value, after which the initial permeability decreases sharply. Even at nanolevel, appreciable value of initial permeability is obtained and low magnetic losses make these ferrites especially suitable for high-frequency applications. The particle size is calculated using Scherrer's equation for Lorentzian peak, which comes out between 35 and 49 nm. Possible mechanisms contributing to these processes have been discussed.     

Structural and magnetic ordering in the VxNb1+yS2 system

The influence of composition on the structural ordering and magnetism in the V_xNb_1+yS₂ system has been investigated by X-ray diffraction and magnetic measurements. Stoichiometric V_1/3NbS₂ did not exhibit the structural ordering of vanadium between the NbS₂ layers. In the ordered structure, the vanadium composition deviated from the ideal value of to both higher and lower values, while the niobium composition was in the range of 0.05?y?0.18. Excess niobium, y>0, is thought to play an essential role in the structural ordering in this system. For samples with excess niobium and ordered structures, a magnetic transition was observed at 20-50 K, depending on the composition. The spontaneous magnetization of 3-5×10⁻³ μ_B/V atom is thought to be intrinsic to this system. The magnetization curves consisted of a constant and a proportional parts of the magnetic field, which correspond to the spontaneous magnetization and high-field susceptibility, respectively. The magnetization curves and the temperature dependencies of the high-field susceptibility were quite similar to those of the canted antiferromagnetic NiS₂. A correlation between the structural and magnetic ordering is suggested.     

Preparation and characterization of surface modified γ-Fe2O3 (maghemite)-silica nanocomposites used for the purification of benzaldehyde lyase

γ-Fe₂O₃ (maghemite)-silica nanocomposite particles were synthesized using a sol-gel method. The condensation products of 3-glycidoxy propyltrimethoxy silane (GPTMS) and nitrilotriacetic acid (NTA) were introduced onto the surfaces of the γ-Fe₂O₃-silica nanocomposite particles and subsequently, these modified surfaces were complexed with cobalt (Co⁺²) metal ions. A possibility of using these surface modified γ-Fe₂O₃-silica particles for the purification of 6×histidine tagged recombinant benzaldehyde lyase (BAL, EC 4.1.2.38) based on magnetic separation was investigated. X-ray diffraction (XRD), thermal analysis, and vibrating sample magnetometry (VSM) methods were used to characterize the surface modified superparamagnetic γ-Fe₂O₃ (maghemite)-silica nanoparticles. XRD (Scherer's equation) results indicate that the primary particle size of maghemite was around 11 nm. Magnetic characterization results confirmed that the γ-Fe₂O₃ (maghemite)-silica nanoparticles were superparamagnetic. According to sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) results, these superparamagnetic nanoparticles specifically capture 6×His-tagged BAL from crude extract of Escherichia coli (E. coli) BL21(DE3)pLysS/BAL_HIS. This study shows that the surface modified γ-Fe₂O₃ (maghemite)-silica nanoparticles are eligible for immobilized metal-ion affinity adsorption for histidine tagged recombinant proteins with its high capacity (3.16±0.4 mg/g) and selectivity.     

Enhanced multiferroic properties in La and Ce co-doped BiFeO3 nanoparticles

Room temperature multiferroic properties of BiFeO₃ (BFO), Bi_0.9La_0.1FeO₃ ((La)BFO) and Bi_0.9La_0.075Ce_0.025FeO₃ ((La,Ce)BFO) nanoparticles have been reported in this paper. XRD (X-ray diffraction) analyses of the nanoparticles show a decrease in the lattice constants and cell volume with the substitution of La and Ce. It is evident from the SEM (scanning electron microscope) micrographs that the (La,Ce) co-doped sample possesses dense microstructure made of smaller particles. Raman study accounts for the weakening of the strong hybridization between Bi-O by the substitution of La and Ce ions. This is also accompanied by an increase in the remanent magnetization, dielectric constant, and ferroelectric polarization. BFO nanoparticles show exchange bias effect under an applied magnetic field while the (La)BFO and (La,Ce)BFO samples show no trace of such effect. Ac-conductivity of (La,Ce) co-doped sample is observed to be several orders lesser in magnitude than bulk BFO ceramics. These results are interpreted by means of the subtle change in the structure, suppression of the spin cycloid and reduction of oxygen vacancies in the doped samples.     

Study of structural and ferromagnetic properties of pure and Cd doped copper ferrite

This report presents the synthesis of copper cadmium ferrite (Cu_1−xCd_xFe₂O₄, x=0.3, 0.4, 0.5, 0.6 and 0.7) by the citrate precursor method and its subsequent characterization by X-ray diffraction (XRD), differential scanning calorimetry, infrared spectroscopy and ferromagnetic resonance. XRD results confirm the single cubic spinel phase formation with the particle size of 40 nm, which decreased up to 20 nm with increase in Cd content, while the lattice parameter increased with increase in Cd content. A significant change in the magnetic properties was observed in the CuFe₂O₄ system with Cd doping. The line width and resonance field variation against change in temperature is noted and the data is fitted to the linearlized model (LM) and Smit and Beljers (SB) model to find out the parameters. The results recorded from the SB approach are in good agreement with those observed in the magnetic measurements carried out by vibrating sample magnetometer (VSM) techniques.     

Deformation of single crystal sample using D-DIA apparatus coupled with synchrotron X-rays: In situ stress and strain measurements at high pressure and temperature

We present a technique for high pressure and high temperature deformation experiment on single crystals, using the Deformation-DIA apparatus at the X17B2 beamline of the NSLS. While deformation experiments on polycrystalline samples using D-DIA in conjunction with synchrotrons have been previously reported, this technical paper focuses on single crystal application of the technique. Our single crystals are specifically oriented such that only [1 0 0] slip or [0 0 1] slip in (0 1 0) plane is allowed. Constant applied stress (sigma <300 MPa) and specimen strain rates were monitored using in situ time-resolved X-ray diffraction and radiography imaging, respectively. Rheological properties of each activated slip system in the crystals can be revealed using this technique. In this paper, we describe the principle of sample preparation (e.g. [1 1 0]_c and [0 1 1]_c orientations) to activate specific slip systems (i.e. [1 0 0](0 1 0) and [0 0 1](0 1 0), respectively), stress measurement and procedures of the deformation experiments.     

Magnetic and dielectric properties of Ni0.8Co0.1Cu0.1Fe2O4+PZT composites

Magnetoelectric composites of Ni_0.8Co_0.1Cu_0.1Fe₂O₄ and Lead Zirconate Titanate (PZT) were prepared by using conventional ceramic method. The measured values of saturation magnetization (M_s) and magnetic moments (μ_B) are in accordance with the volume fraction of ferrite content in the composite. The dielectric constant of the composites decreases with frequency. The plots of dielectric constant () against temperature (T) show a peak at their respective transition temperatures. The ME output was measured by varying dc bias magnetic field. A large ME output signal of 776 mV/cm was observed for 35% ferrite +65% ferroelectric composite. The magnetoelectric (ME) response is found to be dependent on the content of ferrite phase.     

Hard magnetic properties of nanosized Sr(Fe,Al)12O19 hexaferrites obtained by Pechini method

In this work, we report the magnetic properties of isotropic M-type SrFe_12−xAl_xO₁₉ (x=0.0,1.5) hexaferrites synthesized by means of Pechini method. A polycrystalline distribution of fine grains was verified by Transmission Electron Microscopy for both compositions, with average sizes below 60 nm. Remarkable coercivity values within the range 500–850 kA/m were attained as a consequence of a combined effect of grain size refinement together with an enhancement of the anisotropy field afforded by the incorporation of the Al³⁺ cations into the hexagonal crystal structure.     

In situ high-pressure X-ray diffraction study of densification of a molecular chalcogenide glass

Structural mechanisms of densification of a molecular chalcogenide glass of composition Ge_2.5As_51.25S_46.25 have been studied in situ at pressures ranging from 1 atm to 11 GPa at ambient temperature as well as ex situ on a sample quenched from 12 GPa and ambient temperature using high-energy X-ray diffraction. The X-ray structure factors display a reduction in height of the first sharp diffraction peak and a growth of the principal diffraction peak with a concomitant shift to higher Q-values with increasing pressure. At low pressures of at least up to 5 GPa the densification of the structure primarily involves an increase in the packing of the As₄S₃ molecules. At higher pressures the As₄S₃ molecules break up and reconnect to form a high-density network with increased extended-range ordering at the highest pressure of 11 GPa indicating a structural transition. This high-density network structure relaxes only slightly on decompression indicating that the pressure-induced structural changes are quenchable.     

Study of dielectric behaviour of Mn-Zn nano ferrites

Dielectric properties of Mn_0.4Zn_0.6Fe₂O₄ ferrites synthesised by co-precipitation method have been investigated as a function of frequency (up to 30 MHz) at different temperatures. Dispersion in dielectric constant has been observed between temperatures 450-500 K. DC resistivity was found to increase up to 100 times greater than those for the samples prepared by the conventional ceramic methods. Resistivity variation with temperature is also reported in the present work. The particle size is calculated using Scherrer equation for Lorentzian peak, which comes out between 9 and 19 nm. Possible mechanisms contributing to these processes have been discussed.