Balamurugan Balasubramanian

Novel Nanostructured Rare-Earth-Free Magnetic Materials with High Energy Products

Novel nanostructured Zr2 Co11 -based magnetic materials are fabricated in a single step process using cluster-deposition method. The composition, atomic ordering, and spin structure are precisely controlled to achieve a substantial magnetic remanence and coercivity, as well as the highest energy product for non-rare-earth and Pt-free permanent-magnet alloys.

Synthesis of Monodisperse TiO2−Paraffin Core−Shell Nanoparticles for Improved Dielectric Properties

Core-shell structures of oxide nanoparticles having a high dielectric constant, and organic shells with large breakdown field are attractive candidates for large electrical energy storage applications. A high growth temperature, however, is required to obtain the dielectric oxide nanoparticles, which affects the process of core-shell formation and also leads to poor control of size, shape, and size-distribution. In this communication, we report a new synthetic process to grow core-shell nanoparticles by means of an experimental method that can be easily adapted to synthesize core-shell structures from a variety of inorganic-organic or inorganic-inorganic materials. Monodisperse and spherical TiO2 nanoparticles were produced at room temperature as a collimated cluster beam in the gas phase using a cluster-deposition source and subsequently coated with uniform paraffin nanoshells using in situ thermal evaporation, prior to deposition on substrates for further characterization and device processing. The paraffin nanoshells prevent the TiO2 nanoparticles from contacting each other and also act as a matrix in which the volume fraction of TiO2 nanoparticles was varied by controlling the thickness of the nanoshells. Parallel-plate capacitors were fabricated using dielectric core-shell nanoparticles having different shell thicknesses. With respect to the bulk paraffin, the effective dielectric constant of TiO2-paraffin core-shell nanoparticles is greatly enhanced with a decrease in the shell thickness. The capacitors show a minimum dielectric dispersion and low dielectric losses in the frequency range of 100 Hz-1 MHz, which are highly desirable for exploiting these core-shell nanoparticles for potential applications.

Cluster synthesis and direct ordering of rare-earth transition-metal nanomagnets.

Rare-earth transition-metal (R-TM) alloys show superior permanent magnetic properties in the bulk, but the synthesis and application of R-TM nanoparticles remains a challenge due to the requirement of high-temperature annealing above about 800 °C for alloy formation and subsequent crystalline ordering. Here we report a single-step method to produce highly ordered R-TM nanoparticles such as YCo(5) and Y(2)Co(17), without high-temperature thermal annealing by employing a cluster-deposition system and investigate their structural and magnetic properties. The direct ordering is highly desirable to create and assemble R-TM nanoparticle building blocks for future permanent-magnet and other significant applications.

Magnetic nanostructuring and overcoming Brown's paradox to realize extraordinary high-temperature energy products

Nanoscience has been one of the outstanding driving forces in technology recently, arguably more so in magnetism than in any other branch of science and technology. Due to nanoscale bit size, a single computer hard disk is now able to store the text of 3,000,000 average-size books, and todays high-performance permanent magnets—found in hybrid cars, wind turbines, and disk drives—are nanostructured to a large degree. The nanostructures ideally are designed from Co- and Fe-rich building blocks without critical rare-earth elements, and often are required to exhibit high coercivity and magnetization at elevated temperatures of typically up to 180 °C for many important permanent-magnet applications. Here we achieve this goal in exchange-coupled hard-soft composite films by effective nanostructuring of high-anisotropy HfCo7 nanoparticles with a high-magnetization Fe65Co35 phase. An analysis based on a model structure shows that the soft-phase addition improves the performance of the hard-magnetic material by mitigating Browns paradox in magnetism, a substantial reduction of coercivity from the anisotropy field. The nanostructures exhibit a high room-temperature energy product of about 20.3 MGOe (161.5 kJ/m3), which is a record for a rare earth- or Pt-free magnetic material and retain values as high as 17.1 MGOe (136.1 kJ/m3) at 180°C.

Mn5Si3 Nanoparticles: Synthesis and Size-Induced Ferromagnetism

Mn-based silicides are fascinating due to their exotic spin textures and unique crystal structures, but the low magnetic ordering temperatures and/or small magnetic moments of bulk alloys are major impediments to their use in practical applications. In sharp contrast to bulk Mn5Si3, which is paramagnetic at room temperature and exhibits low-temperature antiferromagnetic ordering, we show ferromagnetic ordering in Mn5Si3 nanoparticles with a high Curie temperature (Tc ≈ 590 K). The Mn5Si3 nanoparticles have an average size of 8.6 nm and also exhibit large saturation magnetic polarizations (Js = 10.1 kG at 300 K and 12.4 kG at 3 K) and appreciable magnetocrystalline anisotropy constants (K1 = 6.2 Mergs/cm(3) at 300 K and at 12.8 Mergs/cm(3) at 3 K). The drastic change of the magnetic ordering and properties in the nanoparticles are attributed to low-dimensional and quantum-confinement effects, evident from first-principle density-functional-theory calculations.

Unusual spin correlations in a nanomagnet

We show how atomic-scale exchange phenomena can be controlled and exploited in nanoscale itinerant magnets to substantially improve magnetic properties. Cluster-deposition experiments, first-principle simulations, and analytical calculations are used to demonstrate the effect in Co2Si nanoclusters, which have average sizes varying from about 0.6 to 29.5 nm. The cluster-deposited nanoparticles exhibit average magnetic moments of up to 0.70 μB/Co at 10 K and 0.49 μB/Co at 300 K with appreciable magnetocrystalline anisotropies, in sharp contrast to the nearly vanishing bulk magnetization. The underlying spin correlations and associated cluster-size dependence of the magnetization are explained by a surface induced ferromagnetic spin polarization with a decay length of the order of 1 nm, much larger than the nearest-neighbor interatomic distance in the alloy.

High-coercivity magnetism in nanostructures with strong easy-plane anisotropy

We report the fabrication of a rare-earth-free permanent-magnet material Co3Si in the form of nanoparticles and investigate its magnetic properties by experiments and density-functional theory (DFT). The DFT calculations show that bulk Co3Si has an easy-plane anisotropy with a high K1 ≈ −64 Merg/cm3 (−6.4 MJ/m3) and magnetic polarization of 9.2 kG (0.92 T). In spite of having a negative anisotropy that generally leads to negligibly low coercivities in bulk crystals, Co3Si nanoparticles exhibit high coercivities (17.4 kOe at 10 K and 4.3 kOe at 300 K). This result is a consequence of the unique nanostructure made possible by an effective easy-axis alignment in the cluster-deposition method and explained using micromagnetic analysis as a nanoscale phenomenon involving quantum-mechanical exchange interactions.

Crystal structure and magnetic properties of new Fe3Co3X2(X = Ti, Nb) intermetallic compounds

The structure and magnetic properties of new magnetic Fe3Co3 X 2 (X = Ti, Nb) compounds are studied by genetic algorithm, first-principles density functional theory (DFT) calculations, and experiments. The atomic structure of a hexagonal structure with P-6m2 symmetry is determined. The simulated x-ray diffraction (XRD) spectra of the P-6m2 structures agree well with experimental XRD data for both Fe3Co3Ti2 and Fe3Co3Nb2. The magnetic properties of these structures as well as the effect of the disorder of Fe and Co on their magnetic properties are also investigated. The magnetocrystalline anisotropy energy is found to be very sensitive to the occupancy disorder between Fe and Co.

Anti-site mixing and magnetic properties of Fe3Co3Nb2 studied via neutron powder diffraction

We studied the crystal structure and magnetic properties of the rare-earth-free intermetallic compound Fe3Co3Nb2, which has recently been demonstrated to have potentially high magnetic anisotropy, using temperature-dependent neutron powder diffraction. The temperature dependence of the diffraction spectra reveals a magnetic transition between 300 and 400 K, in agreement with the magnetometry measurements. According to the structural refinement of the paramagnetic state and the substantial magnetic contribution to the diffuse scattering in the ferromagnetic state, the Fe/Co anti-site mixing is so strong that the site occupation for Fe and Co is almost random. The projection of the magnetic moments turned out to be non-zero along the c axis and in the a–b plane of Fe3Co3Nb2, most likely because of the exchange interactions between the randomly orientated nanograins in the samples. These findings suggest that future studies on the magnetism of Fe3Co3Nb2 need to take the Fe/Co anti-site mixing into account, and the exchange interactions need to be suppressed to obtain large remanence and coercivity.

Effect of size confinement on skyrmionic properties of MnSi nanomagnets

Bulk magnetic materials with the noncentrosymmetric cubic B20 structure are fascinating due to skyrmion spin structures associated with Dzyaloshinskii-Moriya interactions, but the size of skyrmions are generally larger than 50 nm. The control of such spin structures in the 10 nm size ranges is essential to explore them for spintronics, ultra-high-density magnetic recording, and other applications. In this study, we have fabricated MnSi nanoparticles with average sizes of 9.7, 13.1 and 17.7 nm and investigated their structural and magnetic properties. X-ray diffraction and transmission electron microscope studies show that the MnSi nanoparticles crystallize in the cubic B20 structure. Field-dependent dc susceptibility data of the MnSi samples with average particle sizes of 17.7 and 13.1 nm show anomalies in limited field (about 25-400 Oe) and temperature (25 K-43 K) ranges. These features are similar to the signature of the skyrmion-like spin structures observed below the Curie temperature of MnSi. Our results also show that this anomalous behavior is size-dependent and suppressed in the smallest nanoparticles (9.7 nm), and this suppression is interpreted as a confinement effect that leads to a truncation of the skyrmion structure.