The measurements of the magnetization in high steady and pulsed fields together with neutron diffraction measurements on a powder sample and on a single crystal have been performed to study the magnetic state of the Tb 3 Co compound. It has been shown that the modulated antiferromagnetic structure which exists in Tb 3 Co below T N = 82 K transforms to the incommensurate magnetic structure with a strong ferromagnetic component along the c-axis with further cooling below the critical temperature T t ≈ 72 K. The phase transition from the high-temperature to the low-temperature magnetic state at T t is of first order. The incommensurability of the low-temperature magnetic structure of Tb 3 Co is attributed to the non-Kramers character of the Tb 3+ ion in combination with competition between the indirect exchange interaction and the low-symmetry crystal electric field.
AC- and DC-susceptibility, high-field magnetization and neutron diffraction measurements have been performed in order to study the magnetic state of R5Pd2 (R = Ho, Tb) compounds. The results show that both compounds undergo cluster-glass freezing upon cooling below Tf. According to the neutron diffraction a long-range magnetic order is absent down to 2 K and magnetic clusters with short-range incommensurate antiferromagnetic correlations exist not only below Tf but also in a wide temperature range above the freezing temperature (at least up to 2Tf). A complex cluster-glass magnetic state existing in Ho5Pd2 and Tb5Pd2 down to low temperatures results in rather complicated magnetization behavior in DC and AC magnetic fields. Such an unusual magnetic state in compounds with a high rare-earth concentration may be associated with the layered type of their crystal structure and with substantial atomic disorder, which results in frustrations in the magnetic subsystem.
Measurements of the magnetic susceptibility, magnetization, electrical resistivity and neutron diffraction have been performed for the compound Fe(0.5)TiS(2) in which Fe atoms are intercalated between S-Ti-S tri-layers. It has been shown that this compound with a monoclinic crystal structure exhibits an antiferromagnetic (AF) ground state below the Néel temperature T(N) ≈ 140 K. Small deviations from the stoichiometry and some disordering effects caused by the additional low-temperature heat treatment do not affect substantially the AF state in Fe(0.5)TiS(2). According to neutron diffraction data the magnetic structure at 2 K is described by the propagation vector k = (1/4,0,1/4). The Fe magnetic moments with a value of (2.9 ± 0.1) μ(B) are directed at an angle of (78.5 ± 1.8)° to the layers. Application of the magnetic field at T < T(N) induces a metamagnetic phase transition to the ferromagnetic (F) state, which is accompanied by the large magnetoresistance effect (|Δρ/ρ| up to 27%). Below 100 K, the field-induced AF-F transition is found to be irreversible, as evidenced by magnetoresistance and neutron diffraction measurements. The magnetization reversal in the metastable F state is accompanied at low temperatures by substantial hysteresis (ΔH ~ 100 kOe) which is associated with the Ising character of Fe ions.
Cobalt-doped
anatase Ti1–x
Co
x
O2 (0 < x ≤
0.04) nanopowders (with a particle size of 30–40 nm) were produced
by the hydrothermal synthesis method. Morphology, structure, and thermal
stability of the synthesized compounds were examined using transmission
electron microscopy, infrared spectroscopy, and X-ray diffraction
analysis. Using X-ray photoelectron spectroscopy, cobalt ions are
shown to have an oxidation state of 2+, with titanium ions having
a tetravalent state of Ti4+. In the as-prepared state,
all investigated compounds of Ti1–x
Co
x
O2 are paramagnetic, with
the value of paramagnetic susceptibility growing in proportion to
cobalt content; with the spin of cobalt ion equal to S = 3/2. Analysis of the electron paramagnetic resonance spectra reveals
that doping TiO2 with cobalt (up to 2%) is accompanied
by a significant increase in the concentration of F+ centers.
Further growth of the cobalt content results in a relatively wide
line (nearly 600 Oe) in the spectrum, with a g-factor
of about 2.005, demonstrating exchange-coupled regions being formed,
the fraction of which increases with cobalt content, while the intensity
of F+-center signals is reduced appreciably. Annealing
of Ti0.96Co0.04O2 in vacuum at 1000
K is shown to have resulted in the substantial localization of cobalt
atoms in the subsurface layers, resulting in an approximately 3-fold
increase in the Co atoms content on the surface of nanoparticles as
compared with that in the bulk. This is shown to be accompanied by
appearance of spontaneous magnetization at room temperature, the value
of which depends on the cobalt content in TiO2 nanopowders.
The value of magnetic moment per Co atom decreases monotonically down
to a value of ≃1 μB with cobalt content increasing.
A core–shell model proposed to be the most adequate for describing
the magnetic properties of TiO2:Co after the reducing annealing.
A hypothesis is put forward suggesting that the defect surface enriched
with Co atoms and vacancies is described with itinerant type magnetism,
allowing for the delocalized nature of electrons near vacancies.
A comparative study of four series of pyrrhotite-type chalcogenide compounds Fe(7-y)M(y)X(8) (X = S, Se) with substitution of Ti or Co for iron has been performed by means of x-ray and neutron powder diffraction, and by magnetization measurements. In Fe(7-y)M(y)X(8) compounds having a ferrimagnetic order at y = 0, the substitution of either Ti or Co for iron is observed to result in a monotonous decrease of the magnetic ordering temperature, while the resultant magnetization shows a non-monotonous behavior with a minimum around y = 1.0-1.5 in all the Fe(7-y)M(y)X(8) families except Fe(7-y)Co(y)Se(8). Suppression of a magnetically ordered state with substitutions in Fe(7-y)M(y)X(8) is ascribed to nearly zero values of Ti and Co magnetic moments, while the non-monotonous changes of the resultant magnetization are explained by the compensation of the sublattice magnetizations due to the non-random substitutions in alternating metallic layers. The difference in the cation partitioning observed in Fe(7-y)Ti(y)X(8) and Fe(7-y)Co(y)X(8) is attributed to the difference in the spatial extension of Ti and Co 3d orbitals. High coercive field values (20-24 kOe) observed at low temperatures in the Ti-containing compounds Fe(7-y)Ti(y)X(8) with y ⩾ 3 are suggested to result from the enhancement of Fe orbital moment due to the Ti for Fe substitution.
Co-doped
TiO2 is one of the most extensively studied
oxides for applying as dilute magnetic semiconductors due to its room
temperature magnetism. Here we present results of the studies of Ti0.97Co0.03O2 nanopowders synthesized
by microwave-assisted hydrothermal method by means of X-ray diffraction,
soft X-ray absorption spectroscopy (Ti L2,3 and Co L2,3 spectra), hard X-ray absorption spectroscopy (Co K spectra),
and 1s3p resonant inelastic X-ray scattering at the Co K edge. According
to X-ray diffraction data and Ti L2,3 X-ray absorption
spectra, all the samples before the thermal treatment exhibit anatase
structure with substantial amount of amorphous phase. After annealing
the Ti0.97Co0.03O2 samples in vacuum
or hydrogen at 700 °C, the anatase structure persists while amorphous
phase contribution is eliminated. Surface-sensitive soft X-ray absorption
Co L2,3 spectroscopy revealed only Co2+ ions
tetrahedrally coordinated by oxygen ions and no sign of metallic Co.
Co2+ tetrahedral sites (instead of typical octahedral ones)
are an additional evidence for Co2+ localization at the
distorted TiO2 particle surface. Bulk-sensitive X-ray diffraction,
Co K X-ray absorption spectroscopy, and 1s3p resonant inelastic X-ray
scattering at the Co K edge revealed clustering of metallic cobalt
inside of the large agglomerates formed by TiO2 nanoparticles
in annealed TiO2:Co nanopowders.
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