Honeycomb Constructs in the La-Ni Intermetallics: Controlling Dimensionality via p-Element Substitution.

The new ternary compounds La15Ni13Bi5 and La9Ni8Sn5 were obtained by arc melting under argon from appropriate amounts of the elements and subsequent annealing at 800 °C for 2 weeks. Single-crystal X-ray diffraction reveals that they represent two new structure types: La15Ni13Bi5 crystallizes in the hexagonal space group P62m [hP33, a = 14.995(3), c = 4.3421(10) Å, V = 845.5(4) Å3, Z = 1] and La9Ni8Sn5 in P63/m [hP88, a = 23.870(15), c = 4.433(3) Å, V = 2187(3) Å3, Z = 4]. The crystal structures of both compounds are characterized by hexagonal honeycomb-based motifs formed by Ni and Sn that extend along the c axis. The building motif with its three-blade wind turbine shape is reminiscent of the organic molecule triptycene and is unprecedented in extended solids. First-principles calculations have been performed in order to analyze the electronic structure and provide insight into chemical bonding. They reveal significant electron transfer from La to Ni and the respective p-element, which supports the formation of the polyanionic Ni-p-element network. DFT calculations suggest paramagnetic-like behavior for both compounds, which was confirmed by magnetic measurements.

Crystal and magnetic structures of R2Ni2In compounds (R = Tb and Ho).

Crystal and magnetic structures of R2Ni2In (R = Tb and Ho) have been studied using powder neutron diffraction at low temperatures. The compounds crystallize as orthorhombic crystal structures of the Mn2AlB2 type. At low temperatures, the magnetic moments localized solely on the rare earth atoms form antiferromagnetic structures. The Tb magnetic moments, equal to 8.8 (4) µB and parallel to the c axis, form a collinear magnetic structure described by the propagation vector k = [½ , ½ , ½]. This magnetic structure is stable up to the Néel temperature TN = 40 K. For Ho2Ni2In a complex, temperature-dependent magnetic structure is detected. In the temperature range 6.1-8.6 K, an incommensurate sinusoidal magnetic structure, described by the propagation vector k1 = [0.24, 1, 0.52] is observed, while in the temperature interval 2.2-2.5 K a square-modulated magnetic structure, related to k2 = [0.17,{{5} \over {6}},{{1} \over {2}}] (the component along the a axis slightly differs from the commensurate value) and its third harmonics 3k2 = [0.50,{{5} \over {2}},{{3} \over {2}}] is found. At 3.1-3.7 K as well as below 2 K, a coexistence of both detected magnetic structures is observed. The Ho magnetic moments remain parallel to the c axis in both the sine- and square-modulated magnetic structures. The low-temperature heat capacity data confirm a first-order transition near 3 K.

Canted antiferromagnetic order in EuZn2As2 single crystals.

Compounds containing Eu show a vast range of unique physical properties due to the interplay of electronic and magnetic properties, which can lead to a nontrivial electronic topology combined with magnetic order. We report on the growth of trigonal ([Formula: see text] space group) EuZn2As2 single crystals and on the studies of their structural, electronic and magnetic properties. A range of experimental techniques was applied including X-ray diffraction, electron microscopy, magnetic susceptibility, magnetization, heat capacity and Mössbauer spectroscopy in the study. We found that Eu has solely a 2+ valence state and its magnetic moments below TN = 19.2 K form a canted antiferromagnetic structure, tilted from the basal plane.

Structure, Morphology, Heat Capacity, and Electrical Transport Properties of Ti3(Al,Si)C2 Materials.

A study of Ti3Al1-xSixC2 (x = 0 to x = 1) MAX-phase alloys is reported. The materials were obtained from mixtures of Ti3AlC2 and Ti3SiC2 powders with hot pressing sintering technique. They were characterised with X-ray diffraction, heat capacity, electrical resistivity, and magnetoresistance measurements. The results show a good quality crystal structure and metallic properties with high residual resistivity. The resistivity weakly varies with Si doping and shows a small, positive magnetoresistance effect. The magnetoresistance exhibits a quadratic dependence on the magnetic field, which indicates a dominant contribution from open electronic orbits. The Debye temperatures and Sommerfeld coefficient values derived from specific heat data show slight variations with Si content, with decreasing tendency for the former and an increase for the latter. Experimental results were supported by band structure calculations whose results are consistent with the experiment concerning specific heat, resistivity, and magnetoresistance measurements. In particular, they reveal that of the s-electrons at the Fermi level, those of Al and Si have prevailing density of states and, thus predominantly contribute to the metallic conductivity. This also shows that the high residual resistivity of the materials studied is an intrinsic effect, not due to defects of the crystal structure.

Effect of Grinding and the Mill Type on Magnetic Properties of Carboxylated Multiwall Carbon Nanotubes.

The influence of the grinding process on the magnetic properties of as prepared and functionalized multiwall carbon nanotubes (MWCNTs) is presented. We have observed that 3 h mechanical grinding at 400 rpm in contrast to functionalization does not remove the iron contamination from MWCNTs. However, it changes the Fe chemical states. The magnetic properties of iron nanoparticles (Fe-NPs) embedded in the carbon matrix of MWCNTs have been analyzed in detail. We have proven that single-domain non-interacting Fe(C,O)-NPs enriched in the Fe3C phase (~10 nm) enclosed inside these nanotubes are responsible for their magnetic properties. Mechanical grinding revealed a unique impact of -COOH groups (compared to -COONH4 groups) on the magnetism of functionalized MWCNTs. In MWCNT-COOH ground in a steel mill, the contribution of the Fe2O3 and α-Fe phases increased while the content of the magnetically harder Fe3C phase decreased. This resulted in a 2-fold coercivity (Hc) decrease and saturation magnetization (MS) increase. A 2-fold remanence (Mr) decrease in MWCNT-COOH ground in an agate mill is related to the modified Fe(C,O)-NP magnetization dynamics. Comparison of the magnetostatic exchange and effective anisotropy length estimated for Fe(C,O)-NPs allows concluding that the anisotropy energy barrier is higher than the magnetostatic energy barrier. The enhanced contribution of surface anisotropy to the effective anisotropy constant and the unique effect of the -COOH groups on the magnetic properties of MWCNTs are discussed. The procedure for grinding carboxylated MWCNTs with embedded iron nanoparticles using a steel mill has a potential application for producing Fe-C nanocomposites with desired magnetic properties.

Correlation of magnetic and magnetoresistive properties of nanoporous Co/Pd thin multilayers fabricated on anodized TiO2 templates.

In this study, we consider a technological approach to obtain a high perpendicular magnetic anisotropy of the Co/Pd multilayers deposited on nanoporous TiO2 templates of different types of surface morphology. It is found that the use of templates with homogeneous and smoothed surface relief, formed on silicon wafers, ensures conservation of perpendicular anisotropy of the deposited films inherent in the continuous multilayers. Also, their magnetic hardening with doubling of the coercive field is observed. However, inhomogeneous magnetic ordering is revealed in the porous films due to the occurrence of magnetically soft regions near the pore edges and/or inside the pores. Modeling of the field dependences of magnetization and electrical resistance indicates that coherent rotation is the dominant mechanism of magnetization reversal in the porous system instead of the domain-wall motion typical of the continuous multilayers, while their magnetoresistance is determined by electron-magnon scattering, similarly to the continuous counterpart. The preservation of spin waves in the porous films indicates a high uniformity of the magnetic ordering in the fabricated porous systems due to a sufficiently regular pores array introduced into the films, despite the existence of soft-magnetic regions. The results are promising for the design and fabrication of future spintronic devices.

Complex magnetic ordering in nanoporous [Co/Pd]5-IrMn multilayers with perpendicular magnetic anisotropy and its impact on magnetization reversal and magnetoresistance.

We have systematically investigated the magnetization reversal characteristics and magnetoresistance of continuous and nanoporous [Co/Pd]5-IrMn multilayered thin films with perpendicular magnetic anisotropy at different temperatures (4-300 K). For their nanostructuring, porosity was induced by means of deposition onto templates of anodized titania with small (∼30 nm in diameter) homogeneously distributed pores. The magnetization reversal and magnetoresistance of the porous films were found to be closely related to the splitting of the ferromagnetic material into regions with different magnetic properties, in correlation with the complex morphology of the porous system. Independent magnetization reversal is detected for these regions, and is accompanied by its strong impact on the magnetic order in the capping IrMn layer. Electron-magnon scattering is found to be a dominant mechanism of magnetoresistance, determining its almost linear field dependence in a high magnetic field and contributing to its magnetoresistance behavior, similar to magnetization reversal, in a low magnetic field. Partial rotation of IrMn magnetic moments, consistent with the magnetization reversal of the ferromagnet, is proposed as an explanation for the two-state resistance behavior observed in switching between high-resistive and low-resistive values at the magnetization reversal of the porous system studied.

Dynamics of Superparamagnetic Iron Oxide Nanoparticles with Various Polymeric Coatings.

In this article, the results of a study of the magnetic dynamics of superparamagnetic iron oxide nanoparticles (SPIONs) with chitosan and polyethylene glycol (PEG) coatings are reported. The materials were prepared by the co-precipitation method and characterized by X-ray diffraction, dynamic light scattering and scanning transmission electron microscopy. It was shown that the cores contain maghemite, and their hydrodynamic diameters vary from 49 nm for PEG-coated to 200 nm for chitosan-coated particles. The magnetic dynamics of the nanoparticles in terms of the function of temperature was studied with magnetic susceptometry and Mössbauer spectroscopy. Their superparamagnetic fluctuations frequencies, determined from the fits of Mössbauer spectra, range from tens to hundreds of megahertz at room temperature and mostly decrease in the applied magnetic field. For water suspensions of nanoparticles, maxima are observed in the absorption part of magnetic susceptibility and they shift to higher temperatures with increasing excitation frequency. A step-like decrease of the susceptibility occurs at freezing, and from that, the Brown's and Néel's contributions are extracted and compared for nanoparticles differing in core sizes and types of coating. The results are analyzed and discussed with respect to the tailoring of the dynamic properties of these nanoparticle materials for requirements related to the characteristic frequency ranges of MRI and electromagnetic field hyperthermia.

Fabrication of Functional Carbon/Magnetic Nanocomposites as A Promising Model of Utilization of Used Crosslinked Polymers.

The utilization of used crosslinked functional polymers (CFP) applied as sorbents or ion-exchangers is a great challenge arising from the need to protect the environment. In this paper we report a very promising way of obtaining carbon/magnetic composites based on metal (Co2+; Ni2+; Fe3+) derivatives of butadiene rubber-based phosphorus-containing polymer, which were treated as the model used CFP. We proposed a facile one-step thermal degradation approach to transform used CFP into carbon/magnetic composites (CMC). The obtained CMCs contained a mixture of metal phosphates and metal phosphides that exhibited strong magnetic properties due to the presence of nanosized metal derivatives with diameters of 100⁻140 nm. Structural and morphological changes of CFP and CMC after thermal degradation were investigated by the FTIR technique, X-ray Diffraction analysis, Scanning Electron Microscope, and Atomic Force Microscope⁻Magnetic Force Microscope. Moreover, thermal degradation kinetics parameters were determined to optimize the efficiency of the process.

Electrochemical synthesis of magnetic iron oxide nanoparticles with controlled size.

We present a novel and facile method enabling synthesis of iron oxide nanoparticles, which are composed mainly of maghemite according to X-ray diffraction (XRD) and Mössbauer spectroscopy studies. The proposed process is realized by anodic iron polarization in deaerated LiCl solutions containing both water and ethanol. Water seems to play an important role in the synthesis. Morphology of the product was studied by means of transmission electron microscopy and XRD. In the solution containing almost 100% of water a black suspension of round shaped maghemite nanoparticles of 20-40 nm size is obtained. Regulating water concentration allows to control nanoparticle size, which is reduced to 4-6 nm for 5% of water with a possibility to reach intermediate sizes. For 3% or lower water concentration nanoparticles are of a needle-like shape and form a reddish suspension. In this case phase determination is problematic due to a small particle size with the thickness of roughly 3 nm. However, XRD studies indicate the presence of ferrihydrite. Coercivities of the materials are similar to those reported for nanoparticle magnetite powders, whereas the saturation magnetization values are considerably smaller.