S. Z. Nazarova

In situ study of atomic-vacancy ordering in stoichiometric titanium monoxide by the magnetic susceptibility

An in situ temperature study of a variation in the degree of long-range order in stoichiometric titanium monoxide has been performed by the magnetic susceptibility method. The measurements have been performed on annealed and quenched titanium monoxide in the temperature range from 300 to 1200 K. It has been found that the degree of long-range order depends on the regime and temperature of annealing of the initial samples. The degree of long-range order in the process of measurement of the magnetic susceptibility varies from 0.21 to 1.00; the larger the degree of long-range order, the smaller the magnetic susceptibility. Furthermore, the long-range order parameter decreases with an increase in the temperature above 1200 K and vanishes sharply at the order-disorder transition temperature. According to the results of this work, the critical long-range order parameter is 0.21 and the temperature of the nonequilibrium disorder-order transition is about 1073 K.

Magnetic properties of a monocrystalline quasicrystal in the Al-Pd-Mn system

Magnetic susceptibility of a monocrystalline icosahedral Al70.2Pd21.3Mn8.5 quasicrystal was measured over the temperature range from 4 to 1100 K. The susceptibility was found to include the temperature-independent diamagnetic contribution, the temperature-dependent Curie’s contribution, and the contribution from the Pauli paramagnetism of an electron system with energy gap. An analysis of the low-temperature susceptibility revealed the presence of about 0.008% of ions with magnetic moment 4µB in the quasicrystal at 4 K. It is assumed that the ions with uncompensated magnetic moments appear near the structural vacancies in the quasicrystal lattice. The energy gap between the valence and conduction bands is estimated at Δ=0.64 eV, and the effective mass of charge carriers is equal to approximately 70 electron masses.

Effect of the size and structure factors on the magnetic susceptibility of nanoparticles of cadmium sulfide

The dependence of the Van Vleck component of the magnetic susceptibility of nanostructured cadmium sulfide CdS on the geometry and structure of CdS nanoparticles has been established by analyzing the data obtained from diffraction and magnetic measurements. It has been found that a decrease in the size of wurtzite CdS nanoparticles leads to an increase in the degree of distortion of the sp3 orbitals (i.e., the degree of covalence), which reaches a limiting value for elongated particles with an average size of 9 nm. In particles with smaller sizes, the character of the orbital distortion sharply changes, and the Van Vleck contribution returns to the value typical of coarse-grained CdS. Nanoparticles less than 9 nm in size have a specific disordered close-packed structure and a centrosymmetric shape. The data obtained have made it possible to understand the reason of the dimensional phase transition from the crystalline state to a specific nanostate of cadmium sulfide.

Influence of particle size, stoichiometry, and degree of long-range order on magnetic susceptibility of titanium monoxide

In situ measurements of the magnetic susceptibility of ordered and disordered titanium monoxides TiOy in the temperature range from 300 to 1200 K have revealed that it depends on the size of crystals, their stoichiometry, and long-range order parameters. Analysis of the data for both the ordered and disordered TiOy has demonstrated that the dependence of the Van Vleck paramagnetism on the nanocrystal size is inversely proportional due to the breaking of symmetry of the local environment of titanium and oxygen atoms near the surface of nanocrystals. It has been found that the Van Vleck contribution from the atomic vacancy disorder in monoxide nanocrystals of superstoichiometric composition, as well as in the crystalline stoichiometric monoxide, is proportional to the deviation of the degree of long-range order from the maximum value.

Planar defects in the icosahedral phase in quasicrystal-forming AlCuFe alloys

Electron microscopy has revealed that, upon the formation of a stable icosahedral (i) AlCuFe phase, there arise a large number of planar defects. The revealed defects are nanometer-sized coherent intergrowths of the P1-pentagonal approximant. It has been found that the formation of these defects is the result of a nonequilibrium intermediate transformation. The intergrowths are located in the planes with the fivefold symmetry axis and give rise to an elastic-strain state of the i-phase. Analysis of the diffraction contrast has revealed the presence of phason and phonon atomic displacements due to the mismatch between the quasiperiodic (i-phase) and periodic (P1-phase) lattices. The formed structure exhibits a higher electrical resistance as compared to the i-phase and has been considered as a model state of the imperfect icosahedral phase with preferred phonon displacements.

Ordering of structural vacancies in vanadium monoxide of substoichiometric composition

The order-disorder phase transition in vanadium monoxide of substoichiometric compositions VOy has been studied for the first time in situ by the Faraday method with a pendulum magnetic balance of the Domenically type. A minimum is found on the temperature dependence of the magnetic susceptibility of vanadium monoxide of different compositions at a temperature of about 700 K. X-ray diffraction analysis performed before and after measuring the magnetic susceptibility confirmed the change in the structure of vanadium monoxide and the possibility of atom-vacancy processes upon cooling and heating of the samples.

Magnetic Susceptibility of Tungsten Carbide: Relaxation and Impurity Effects

The magnetic susceptibility χ of coarse-grained WC and nanocrystalline n-WC tungsten carbides has been studied in a temperature range of 300–1250 K. The dependence χ (T) for coarse-grained WC carbide has no singularities. A stable particle size of about 55 nm remains in the n-WC nanopowder after annealing at 300–1200 K, whereas the relaxation of microstrains occurs at 550–920 K. The dependence χ(T) for nanocrystalline n-WC carbide in a range of 550–920 K exhibits features associated with the annealing of microstrains, which reduces the contribution of orbital paramagnetism to the susceptibility of n-WC carbide and initiates the precipitation of small iron and cobalt impurities in the form of superparamagnetic particles.

Dependence of Van-Vleck paramagnetism on the size of nanocrystals in superstoichiometric TiO y

In situ measurements of the magnetic susceptibility of titanium monoxide nanocrystals with superstoichiometric composition TiOy (y > 1) in the 300–1200 K temperature range showed that this value depends not only on the structural state of a sample, but also on the size of crystals. Analysis of data obtained for both ordered and disordered TiOy showed that the Van-Vleck paramagnetism is inversely proportional to the nanocrystal size because of breakage of the symmetry of local environment of the near-surface atoms of titanium and oxygen. The Van-Vleck paramagnetism contribution due to atomic-vacancy disorder in superstoichiometric titanium monoxide nanocrystals, as well as in the stoichiometric composition, is proportional to a deviation of the degree of long-range order from its maximum value.

Magnetic Susceptibility and Thermal Stability of Particle Size of Nanocrystalline Tungsten Carbide WC

The magnetic susceptibility χ of coarse-grained and nanocrystalline tungsten carbides was studied in the temperature range 300–1250 K. The temperature dependence of the susceptibility χ(T) of coarse-grained carbide WC is typical of weak Pauli paramagnets and has no specific features. The χ(T) dependence of nanocrystalline carbide (n-WC) in the range 550–920 K exhibits features associated with annealing of microstrains, which leads to a decrease in the contribution of orbital paramagnetism to the magnetic susceptibility of n-WC and initiates precipitation of minor impurities of iron and cobalt as superparamagnetic particles. A nanocrystalline n-WC powder retains a stable particle size of ∼55 nm after long annealing at temperatures of 300 to 1200 K, whereas microstrains relax at 550–920 K.

Iron Nanoparticles in Severe-plastic-deformed Copper

Superparamagnetic iron nanoparticles with a size of a few nanometers were produced in copper by severe plastic deformation. In a isochronal annealing experiment near a temperature of 450 K, which corresponds to the temperature of structural relaxation and the first step of grain growth (from 128 to 150 nm) of submicrocrystalline copper, an abrupt increase in the magnetic susceptibility is detected. This increase is shown to be due to iron nanoparticles increasing in size from 2.8 to 3.3 nm. The vanishing of the ferromagnetic contribution by iron nanoparticles observed at 850 K, well below the Curie temperature of iron, is due to the dissolution of nanoparticles in plastically deformed copper.