Effects of Co substitution on structural and magnetic properties of R3(Fe1−xCox)29−yVy (R=Tb,Dy)

Synthesis of two novel series of intermetallic compounds Tb₃(Fe_1−xCo_x)_27.4V_1.6 (x=0,0.1, 0.2, 0.3, 0.4) and Dy₃(Fe_1−xCo_x)_27.8V_1.2 (x=0, 0.1, 0.2, 0.3) with the monoclinic Nd₃(Fe,Ti)₂₉-type structure (3:29) is presented. In the Dy series for x=0.4 a disordered variant of the hexagonal Th₂Ni₁₇-type structure is formed. The cell parameters decrease and the Curie temperature increases with increasing of the Co content. In the case of the Tb₃(Fe_1−xCo_x)_27.4V_1.6 series in the M(T) curve a magnetic transition is observed which is attributed to spin reorientation phenomena. This critical temperature decreases with increasing Co from 473 K for x=0.1 to 393 K for x=0.3, and was not observed in the case of 0.4. XRD patterns of magnetically aligned powder samples reveal the presence of a tilted magnetic structure.     

Magnetic properties of GdCo12B6 compound under high pressures

The effects of hydrostatic pressure up to 10 kbar on Curie temperature T_C, compensation temperature T_COMP and spontaneous magnetization M_S of ferrimagnetic GdCo₁₂B₆ compound have been studied. Two antiferromagnetically coupled sublattices that are carrying magnetization of typically 0.42 μ_B/Co atom and 7 μ_B/Gd cancel out at compensation temperature at about 50 K and magnetic ordering temperature T_C=163±2 K. The volume dependence of intrinsic magnetic properties of the GdCo₁₂B₆ compound has been determined by studying it under hydrostatic pressure. The observed increase of M_S with pressure (dM_S/dp=+0.005 μ_B kbar^?1 at 5 K) is attributed predominantly to the pressure induced decrease of Co magnetic moments. The crucial role of Co in this behavior is confirmed by the change of sign of the pressure slope at temperatures above T_COMP and by the fact that the estimated decrease of m_Co is also quite comparable with pressure induced decrease of M_S in YCo₁₂B₆ (dM_S/dp=?0.007 μ_B kbar^?1). The decrease of m_Co is also responsible for the increase of T_COMP with pressure (dT_COMP/dp=+0.06 K kbar^?1). The decrease of T_C with pressure (dT_C/dp=?0.55 K kbar^?1) is comparable to the decrease observed on RCo₁₂B₆ compounds with non-magnetic R and can be attributed to the volume dependence of Co–Co exchange interactions. The remarkable role of the hybridization as a consequence of small distances between Co and B atoms could be a background of this rather unexpected volume stability of magnetic properties.     

Pressure effect on magnetic properties of RCo12B6 (R=Y,Ce) compounds

The effect of pressure on magnetic properties of YCo₁₂B₆ and CeCo₁₂B₆ was studied in temperature range 5–300 K at pressures up to 9 kbar. The Curie temperature T_C and spontaneous magnetization M_S decrease with pressure for both compounds. The decrease can be attributed mostly to the volume dependence of both, the Co magnetic moment and the exchange interactions. The hybridization of the p–d states as a consequence of small distances between the Co and B atoms can be one reason of the relatively low pressure effects (ΔT_C/Δp=?0.39±0.02 K/kbar, d ln M_S/dp=?0.0013±0.0002 kbar^?1) in YCo₁₂B₆. Higher volume sensitivity of magnetic properties of CeCo₁₂B₆ in comparison with YCo₁₂B₆ can be attributed to the pressure induced changes of the Ce f- and Co d-states.     

Ferromagnetic order and spin-glass behavior in multi-metallic compound Ni1.125Co0.375[Fe(CN)6] · 6.8H2O

Multi-metallic Prussian blue compound Ni_1.125Co_0.375[Fe(CN)₆] · 6.8H₂O has been synthesized. The Mössbauer spectroscopy at room temperature and IR spectra study revealed that the metal ions are bonded through cyanide ligand and the presence of low spin Fe^III(S = 1/2) and high spin Fe^III(S = 5/2) ions, as showed in these structure: Fe^III(S = 1/2)-CN-(Co^II/Ni^II)(96%) and Fe^III(S = 5/2)-NC-(Co^II/Ni^II) (4%). The Curie constant of C = 3.00 cm³ K mol⁻¹ and Weiss paramagnetic Curie temperature of θ = 16.43 K were observed in fitting according to Curie–Weiss law. These results indicate that there existed a ferromagnetic exchange interaction in the complexes. The observed value of coercive field (H_c) and remanent magnetization (M_r) at 4 K for the compound are 497 Oe and 1.03 Nβ. The presence of spin-glass behaviours in the compound is ascribed mainly to domain mobility or domain growth under different cooling conditions.     

Synthesis and optical properties of Co2+ and Ni2+ ions doped β-BaB2O4 nanopowders

Co²⁺ and Ni²⁺ ions doped β-BaB₂O₄ nanopowders have been prepared by co-precipitation method and their structural properties are studied by spectroscopic techniques. Powder XRD data reveals that the crystal structure belongs to monoclinic and the average crystallite size is calculated. Optical absorption spectra data reveal octahedral site symmetry for Co²⁺ and Ni²⁺ ions. Crystal field (Dq) and inter-electron repulsion (B and C) parameters are evaluated for Co²⁺ doped β-BaB₂O₄ nanopowders as Dq=960, B=900 and C=3850 cm^?1 and for Ni²⁺ doped β-BaB₂O₄ nanopowders, Dq=900, B=850 and C=3500 cm^?1. FT-IR spectra showed the characteristic vibrational bands related to BO₃ and BO₄ molecules. Photoluminescence spectra contain the emission bands in ultraviolet and blue regions.     

Effect of composition change of metals in transition metal sites on electrochemical behavior of layered Li[Co1 −2x(Li1 / 3Mn2 / 3)x(Ni1 / 2Mn1 / 2)x]O2 solid solutions

Five compositions of Li[Co_1 −2x(Li_1 / 3Mn_2 / 3)_x(Ni_1 / 2Mn_1 / 2)_x]O₂ solid solutions ( x = 0.1, 0.2, 0.3, 0.4, and 0.5) were synthesized using a sol–gel method with three end members of LiCoO₂, Li₂MnO₃(Li[Li_1 / 3Mn_2 / 3]O₂), and Li[Ni_0.5Mn_0.5]O₂. The compositions of metals in transition metal sites were changed to see the effect of them on electrochemical behavior of the solid solutions. All the samples were nano-sized semi-spherical shaped particles with a layered structure. The reduction of cobalt content (the increase of other metals) in the sites increases the lattice parameters, a and c, resulting in the shift of Raman and XRD peak positions. The discharge capacity fading turned serious at higher Co contents, but it was significantly diminished with the decrease of Co content. At lower Co contents, the capacity increased with cycle numbers. The most stable voltage profile was obtained from the composition of Li[Li_1 / 15Co_3 / 5Ni_1 / 10Mn_7 / 30]O₂ (x = 0.2).     

Enhanced magnetocaloric effect in a Co-doped Heusler Mn50Ni37Co3In10 unidirectional crystal

A high-pressure optical zone-melting technique was employed to grow a Mn-rich Heusler Mn₅₀Ni₃₇Co₃In₁₀ unidirectional crystal in the present study. It was found that the Co-doped Mn₅₀Ni₃₇Co₃In₁₀ unidirectional crystal showed a low magnetic hysteretic loss and a widened working temperature interval in the vicinity of the martensitic transformation. The inverse magnetic entropy change (∆S_M) reached 7.84 Jkg⁻¹K⁻¹ around 237.5 K under a magnetic field change of 30 kOe, and the corresponding effective refrigeration capacity (RC_eff) was about 127.2 Jkg⁻¹. The experimental results demonstrated a high potential to develop high-performance Mn-rich Heusler Mn–Ni–In magnetocaloric materials by means of Co doping in combination with the high-pressure optical zone-melting fabrication technique.     

Mixed conductivity,stability and thermomechanical properties of Ni-doped La(Ga,Mg)O3−δ

Perovskite-type LaGa_0.65Mg_0.15Ni_0.20O_3−δ exhibiting oxygen transport comparable to that in K₂NiF₄-type nickelates was characterized as a model material for ceramic membrane reactors, employing mechanical tests, dilatometry, oxygen permeability and faradaic efficiency measurements, thermogravimetry (TG), and determination of the total conductivity and Seebeck coefficient in the oxygen partial pressure range from 10^− 15 Pa to 40 kPa. Within the phase stability domain which is similar to La₂NiO_4+δ, the defect chemistry of LaGa_0.65Mg_0.15Ni_0.20O_3−δ can be adequately described by the ideal solution model with oxygen vacancies and electron holes to be the only mobile defects, assuming that Ni²⁺ may provide two energetically equivalent sites for hole location. This assumption is in agreement with the density of states, estimated from thermopower, and the coulometric titration and TG data suggesting Ni⁴⁺ formation in air at T < 1150 K. The hole conductivity prevailing under oxidizing conditions occurs via small-polaron mechanism as indicated by relatively low, temperature-activated mobility. The ionic transport increases with vacancy concentration on reducing p(O₂) and becomes dominant at oxygen pressures below 10^− 7–10^− 5 Pa. The average thermal expansion coefficients in air are 11.9 × 10^− 6 and 18.4 × 10^− 6 K^− 1 at 370–850 and 850–1270 K, respectively. The chemical strain of LaGa_0.65Mg_0.15Ni_0.20O_3−δ ceramics at 1073–1123 K, induced by the oxygen partial pressure variations, is substantially lower compared to perovskite ferrites. The flexural strength determined by 3-point and 4-point bending tests is 167–189 MPa at room temperature and 85–97 MPa at 773–1173 K. The mechanical properties are almost independent of temperature and oxygen pressure at p(O₂) = 1–2.1 × 10⁴ Pa and 773–1173 K.     

BaT2As2 single crystals (T = Fe,Co, Ni) and superconductivity upon Co-doping

The crystal structure and physical properties of BaFe₂As₂, BaCo₂As₂, and BaNi₂As₂ single crystals are surveyed. BaFe₂As₂ gives a magnetic and structural transition at T_N = 132(1) K, BaCo₂As₂ is a paramagnetic metal, while BaNi₂As₂ has a structural phase transition at T₀ = 131 K, followed by superconductivity below T_c = 0.69 K. The bulk superconductivity in Co-doped BaFe₂As₂ below T_c = 22 K is demonstrated by resistivity, magnetic susceptibility, and specific heat data. In contrast to the cuprates, the Fe-based system appears to tolerate considerable disorder in the transition metal layers. First principles calculations for BaFe_1.84Co_0.16As₂ indicate the inter-band scattering due to Co is weak.     

Superconducting property of Zr–Co–Al–Nb metallic glasses

The superconducting property of Zr₅₅Co_(30?x)Al₁₅Nb_x (x = 0–20 at.%) metallic glasses fabricated by rapid solidification was investigated. The Zr₅₅Co_(30–x)Al₁₅Nb_x (x = 5–20 at.%) metallic glasses with a mixture structure of amorphous and nanocrystal phases exhibited superconductivity of T_c,on = 1.8–2.6 K. The maximum T_c,on = 2.6 K was obtained for the Zr₅₅Co₁₀Al₁₅Nb₂₀ metallic glass. This was attributable to the superconducting property of nanocrystalline particles contained in the Zr₅₅Co₁₀Al₁₅Nb₂₀ alloy. The increase of Nb element in the Zr₅₅Co_(30–x)Al₁₅Nb_x alloy led to the increase of T_c,on and the decrease of glass transition temperature. The glass transition temperature was between 704 and 749 K for the Zr₅₅Co_(30–x)Al₁₅Nb_x (x = 0–20 at.%) alloys. The temperature interval of supercooled liquid state was between 51 and 68 K for the Zr₅₅Co_(30–x)Al₁₅Nb_x (x = 0–20 at.%) alloys.     

Current controlled negative differential resistance behavior in Co2FeO2BO3 and Fe3O2BO3 single crystals

I–V curves showing negative differential resistance (NDR) are reported for single crystals of Co₂FeO₂BO₃ at 315 K and 290 K and for Fe₃O₂BO₃ at 300 K, 260 K and 220 K. Resistivity measurements are presented for both systems, parallel and perpendicular to the c axis, in the range 315–120 K. The high hysteretic behavior of the I–V curves in Co₂FeO₂BO₃ around room temperature is discussed and the heat dissipated is estimated, suggesting an increase in the sample temperature of almost 22 K for the I–V curve at 315 K and a dominant contribution of Joule self-heating for the observed NDR. In contrast, insignificant hysteresis is observed on the I–V curves of Fe₃O₂BO₃ around room temperature. The depinning of charge order domains is suggested as the main contribution to the NDR phenomenon for Fe₃O₂BO₃. The high reproducibility of the NDR in the Fe₃O₂BO₃ single crystal allows its use as a low frequency oscillator, as it is demonstrated.     

Magnetic characterisation and hydrogen absorption characteristics of Pr3(Fe,Ti)29Hx

An interstitial Pr₃(Fe,Ti)₂₉ hydride was synthesised by gas-phase hydrogenation on Pr₃(Fe,Ti)₂₉ powder using H₂. The reaction kinetics between Pr₃(Fe,Ti)₂₉ and H₂ gases was studied in a constant-volume reactor. The sample starts to rapidly absorb hydrogen, interstitially, at about 533 K. Absorption passes through a maximum at about 598 K (1.6 H/f.u) and then interstitial hydrogen desorption takes place up to the temperature of 673 K. By cooling to room temperature, the sample absorbs more hydrogen, interstitially, reaching the value of 3.6 H/f.u. By remaining at room temperature, the sample absorbs even more hydrogen reaching the value of 5.2 H/f.u. The lattice expansion observed is 2.1% and the Curie temperature, T_C, increased from 392 to 518 K. The hydride exhibits saturation magnetisation, M_S, of 145.4 and 157.5 Am²/kg at room temperature (RT) and at 5 K, respectively, anisotropy field, H_A, of 2.1 T (RT) and 4.5 T (5 K) and average hyperfine field, H_eff, of 23.3 T (RT). The magnetic anisotropy of Pr₃(Fe,Ti)₂₉ hydride is the same as that of the parent compounds, easy-cone-like, changing only in the cone angle (from 34° to 26°).     

High coercivity Nd2(Fe,Co)14C-type ribbons prepared by melt spinning

Melt-spun Nd₁₃Dy₂Fe_77−xCo_xC₆B₂ (x=0, 5, 10, 15, 20) ribbons with a high coercivity more than 2 T have been obtained. It was found that the ribbons quenched at the optimum wheel speed 15 m/s (as-spun ribbons) mainly consist of ferromagnetic 2 : 14 : 1 phase and paramagnetic NdC₂ phase, and the ribbons spun at 25 m/s and subsequently annealed at 973 K for 15 min (as-annealed ribbons) are primarily composed of the magnetic 2 : 14 : 1 and 2 : 17 phases. The magnetization process of as-spun ribbons controlled by a pinning of the domain wall is different from that of as-annealed ribbons determined by a nucleation of the reverse domain. This significant difference originates possibly from the existence of paramagnetic NdC₂ phase acting as a pinning center in as-spun ribbons. In the as-annealed ribbons, the substitution of Co for Fe leads to increase of remanence (μ₀M_r), maximum energy product ((BH)_max) from 0.67 T, 9.7 MGOe for x=0 to 0.84 T, 14.4 MGOe for x=10, respectively. A coercivity of 2.74 T is obtained for as-quenched Nd₁₃Dy₂Fe_77−xCo_xC₆B₂ (x=0) ribbons.     

Giant magnetic refrigerant capacity in Ho3Al2 compound

Magnetic properties and magnetocaloric effects (MCEs) of the intermetallic Ho₃Al₂ compound are investigated by magnetization and heat capacity measurements. Two successive magnetic transitions, a spin-reorientation (SR) transition at T_SR=31 K followed by a ferromagnetic (FM) to paramagnetic (PM) transition at T_C=40 K, are observed. Both magnetic transitions contribute to the MCE and result in a large magnetic entropy change (ΔS_M) in a wide temperature range. The maximum values of ?ΔS_M and adiabatic temperature change (ΔT_ad) reach 18.7 J/kg K and 4.8 K for the field changes of 0–5 T, respectively. In particular, a giant value of refrigerant capacity (RC) is estimated to be 704 J/kg for a field change of 5 T, which is much higher than those of many potential refrigerant materials with similar transition temperatures.     

Magnetic structure of the ternary germanide Ce3Ni2Ge7

The ternary germanide Ce₃Ni₂Ge₇ has been studied by means of neutron powder diffraction and Ce L_III X-ray absorption (XAS). This compound which orders antiferromagnetically below T_N=7.2(2) K, crystallizes in the orthorhombic (Cmmm space group) La₃Co₂Sn₇-type structure where Ce atoms occupying two inequivalent crystallographic sites: Ce1 at 2d site and Ce2 at 4i site. Below T_N, the antiferromagnetic structure of Ce₃Ni₂Ge₇ is collinear but only the Ce2 atoms carry a magnetic moment (1.98(2) μ_B at 1.4 K). The absence of ordered magnetic moment on Ce1 atoms can be correlated to the average valence v=3.03(1), determined by X-ray absorption spectroscopy, suggesting an intermediate valence state of cerium in the 2d site.     

Synthesis and characterization of layered Li1−x(Ni0.5Co0.5)1−yFeyO2(0 ≤ (1 − x) ≤ 1 and 0 ≤ y ≤ 0.2) cathodes

Layered Li(Ni_0.5Co_0.5)_1−yFe_yO₂ cathodes with 0 ≤ y ≤ 0.2 have been synthesized by firing the coprecipitated hydroxides of the transition metals and lithium hydroxide at 700 °C and characterized as cathode materials for lithium ion batteries to various cutoff charge voltages (up to 4.5 V). While the y = 0.05 sample shows an improvement in capacity, cyclability, and rate capability, those with y = 0.1 and 0.2 exhibit a decline in electrochemical performance compared to the y = 0 sample. Structural characterization of the chemically delithiated Li_1−x(Ni_0.5Co_0.5)_1−yFe_yO₂ samples indicates that the initial O3 structure is maintained down to a lithium content (1 − x) ≈ 0.3. For (1 − x) < 0.3, while a P3 type phase is formed for the y = 0 sample, an O1 type phase is formed for the y = 0.05, 0.1 and 0.2 samples. Monitoring the average oxidation state of the transition metal ions with lithium contents (1 − x) reveals that the system is chemically more stable down to a lower lithium content (1 − x) ≈ 0.3 compared to the Li_1−xCoO₂ system. The improved structural and chemical stabilities appear to lead to better cyclability to higher cutoff charge voltages compared to that found before with the LiCoO₂ system.     

Oxygen nonstoichiometry,mixed valency and mixed conduction in (La,Sr)(Co,Fe)O3−δ

Defect chemistry for a mixed conductor, La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ was studied. Samples were treated under controlled oxygen partial pressure, P(O₂), conditions at 1273 K [10^− 11.1 ≤ P(O₂)/atm ≤ 1], and cooled to room temperature. Oxygen nonstoichiometry and valences of transition metal ions for the treated samples were evaluated by iodometry and X-ray absorption spectroscopy, respectively. With decreasing P(O₂), preferential reduction of Co³⁺ to Co²⁺ was observed, while iron preserved its higher valence above 3 under conditions studied. A dependency of its electrical conductivity on P(O₂) was discussed along with a change in concentration of oxygen vacancies and mixed valences.     

Influence on magnetic properties of substitution of Co for Fe in TbFe11.3Nb0.7

The magnetic properties of Tb(Fe_1−xCo_x)_11.3Nb_0.7 compounds with x=0, 0.05, 0.1, 0.15, 0.2 and 0.3 have been investigated. All compounds studied crystallize in the ThMn₁₂-type of structure. Substitution of Co for Fe leads to a contraction of the unit-cell volume. The Curie temperature clearly increases with increasing Co content from 551 K for x=0 to 831 K for x=0.3. The magnetic moment of the transition-metal sublattice increases with increasing Co content from 22.2 μ_B/f.u. for x=0 to 23.1 μ_B/f.u. for x=0.3. As the temperature increases, a spin reorientation from easy-plane to easy-cone is found in all compounds investigated. The spin-reorientation temperatures T_sr have been derived from the temperature dependence of the magnetization in a low field and decrease monotonously with increasing Co content. The easy magnetization direction at room temperature has been determined by X-ray diffraction on magnetically-aligned powder samples. The influence of the substitution of Co for Fe on the magnetic anisotropy is discussed in terms of crystal-field theory.     

The studies on structural and thermal properties of delithiated LixNi1/3Co1/3Mn1/3O2 (0 < x ≤ 1) as a cathode material in lithium ion batteries

The structural and thermal properties of the delithiated Li_xNi_1/3Co_1/3Mn_1/3O₂ (0 < x ≤ 1) material have been investigated by using diffraction and thermoanalytical techniques such as XRD and TG-DSC methods. XRD result shows that the delithiated materials maintain the O3-type structure with defined stoichiometric number at the range of 0.24 < x ≤ 1, exhibiting good crystal structural stability. The cobalt and nickel ions in the delithiated materials change their valence state (i.e. Co³⁺ to Co⁴⁺ and Ni³⁺ to Ni⁴⁺) when x < 0.49; the irreversible changes of the transformation may affect the first cycle of charge–discharge efficiency of the materials. A comparison of the results of TG-DSC with TPD-MS shows that the irreversible change of oxygen species during the delithiation process of Li_xNi_1/3Co_1/3Mn_1/3O₂ have great influence on the structural and thermal stability and reversibility of the materials.     

A comparative study of the Ruddlesden-Popper series,Lan+1NinO3n+1 (n = 1, 2 and 3), for solid-oxide fuel-cell cathode applications

A comparative investigation of the much-studied La₂NiO_4+δ (n = 1) phase and the higher-order Ruddlesden-Popper phases, La_n+1Ni_nO_3n+1 (n = 2 and 3), has been undertaken to determine their suitability as cathodes for intermediate-temperature solid-oxide fuel cells. As n is increased, a structural phase transition is observed from tetragonal I4/mmm in the hyperstoichiometric La₂NiO_4.15 (n = 1) to orthorhombic Fmmm in the oxygen-deficient phases, La₃Ni₂O_6.95 (n = 2) and La₄Ni₃O_9.78 (n = 3). High temperature d.c. electrical conductivity measurements reveal a dramatic increase in overall values from n = 1, 2 to 3 with metallic behavior observed for La₄Ni₃O_9.78. Impedance spectroscopy measurements on symmetrical cells with La_0.9Sr_0.10Ga_0.80Mg_0.20O_3−δ (LSGM-9182) as the electrolyte show a systematic improvement in the electrode performance from La₂NiO_4.15 to La₄Ni₃O_9.78 with ∼ 1 Ω cm² observed at 1073 K for the latter. Long-term thermal stability tests show no impurity formation when La₃Ni₂O_6.95 and La₄Ni₃O_9.78 are heated at 1123 K for 2 weeks in air, in contrast to previously reported data for La₂NiO_4.15. The relative thermal expansion coefficients of La₃Ni₂O_6.95 and La₄Ni₃O_9.78 were found to be similar at ∼ 13.2 × 10^− 6 K^− 1 from 348 K to 1173 K in air compared to 13.8 × 10^− 6 K^− 1 for La₂NiO_4.15. Taken together, these observations suggest favourable use for the n = 2 and 3 phases as cathodes in intermediate-temperature solid-oxide fuel cells when compared to the much-studied La₂NiO_4+δ (n = 1) phase.