Size effects in the magnetic behaviour of TbAl_2 milled alloys

The study of the magnetic properties depending upon mechanical milling of the ferromagnetic polycrystalline TbAl_2 material is reported. The Rietveld analysis of the X-ray diffraction data reveals a decrease of the grain size down to 14 nm and -0.15 % of variation of the lattice parameter, after 300 hours of milling time. Irreversibility in the zero field cooled - field cooled (ZFC-FC) DC-susceptibility and clear peaks in the AC susceptibility between 5 and 300 K show that the long-range ferromagnetic structure is inhibited in favour of a disordered spin arrangement below 45 K. This glassy behaviour is also deduced from the variation of the irreversibility transition with the field (H^{2/3}) and frequency. The magnetization process of the bulk TbAl_2 is governed by domain wall thermal activation processes. By contrast, in the milled samples, cluster-glass properties arise as a result of cooperative interactions due to the substitutional disorder. The interactions are also influenced by the nanograin structure of the milled alloys, showing a variation of coercivity with the grain size, below the crossover between the multi- and single-domain behaviours.Comment: 23 pages, 11 figures, to appear in J. Phys.: Condens. Ma

Development of an in-line magnetometer for flow chemistry and its demonstration for magnetic nanoparticle synthesis

Despite the wide usage of magnetic nanoparticles, it remains challenging to synthesise particles with properties that exploit each application's full potential. Time consuming experimental procedures and particle analysis hinder process development, which is commonly constrained to a handful of experiments without considering particle formation kinetics, reproducibility and scalability. Flow reactors are known for their potential of large-scale production and high-throughput screening of process parameters. These advantages, however, have not been utilised for magnetic nanoparticle synthesis where particle characterisation is performed, with a few exceptions, post-synthesis. To overcome this bottleneck, we developed a highly sensitive magnetometer for flow reactors to characterise magnetic nanoparticles in solution in-line and in real-time using alternating current susceptometry. This flow magnetometer enriches the flow-chemistry toolbox by facilitating continuous quality control and high-throughput screening of magnetic nanoparticle syntheses. The sensitivity required to monitor magnetic nanoparticle syntheses at the typically low concentrations (<100 mM of Fe) was achieved by comparing the signals induced in the sample and reference cell, each of which contained near-identical pairs of induction and pick-up coils. The reference cell was filled only with air, whereas the sample cell was a flow cell allowing sample solution to pass through. Balancing the flow and reference cell impedance with a newly developed electronic circuit was pivotal for the magnetometer's sensitivity. To showcase its potential, the flow magnetometer was used to monitor two iron oxide nanoparticle syntheses with well-known particle formation kinetics, i.e., co-precipitation syntheses with sodium carbonate and sodium hydroxide as base, which have been previously studied via synchrotron X-ray diffraction. The flow magnetometer facilitated batch (on-line) and flow (in-line) synthesis monitoring, providing new insights into the particle formation kinetics as well as, effect of temperature and pH. The compact lab-scale flow device presented here, opens up new possibilities for magnetic nanoparticle synthesis and manufacturing, including 1) early stage reaction characterisation 2) process monitoring and control and 3) high-throughput screening in combination with flow reactors

Systematic first-principles study of impurity hybridization in NiAl

We have performed a systematic first-principles computational study of the effects of impurity atoms (boron, carbon, nitrogen, oxygen, silicon, phosporus, and sulfur) on the orbital hybridization and bonding properties in the intermetallic alloy NiAl using a full-potential linear muffin-tin orbital method. The matrix elements in momentum space were used to calculate real-space properties: onsite parameters, partial densities of states, and local charges. In impurity atoms that are empirically known to be embrittler (N and O) we found that the 2s orbital is bound to the impurity and therefore does not participate in the covalent bonding. In contrast, the corresponding 2s orbital is found to be delocalized in the cohesion enhancers (B and C). Each of these impurity atoms is found to acquire a net negative local charge in NiAl irrespective of whether they sit in the Ni or Al site. The embrittler therefore reduces the total number of electrons available for covalent bonding by removing some of the electrons from the neighboring Ni or Al atoms and localizing them at the impurity site. We show that these correlations also hold for silicon, phosporus, and sulfur.Comment: Revtex, 8 pages, 7 eps figures, to appear in Phys. Rev.

Finite-Size and surface effects in maghemite nanoparticles: Monte Carlo simulations

Finite-size and surface effects in fine particle systems are investigated by Monte Carlo simulation of a model of a $\gamma$-Fe$_2$O$_3$ (maghemite) single particle. Periodic boundary conditions have been used to simulate the bulk properties and the results compared with those for a spherical shaped particle with free boundaries to evidence the role played by the surface on the anomalous magnetic properties displayed by these systems at low temperatures. Several outcomes of the model are in qualitative agreement with the experimental findings. A reduction of the magnetic ordering temperature, spontaneous magnetization, and coercive field is observed as the particle size is decreased. Moreover, the hysteresis loops become elongated with high values of the differential susceptibility, resembling those from frustrated or disordered systems. These facts are consequence of the formation of a surface layer with higher degree of magnetic disorder than the core, which, for small sizes, dominates the magnetization processes of the particle. However, in contradiction with the assumptions of some authors, our model does not predict the freezing of the surface layer into a spin-glass-like state. The results indicate that magnetic disorder at the surface simply facilitates the thermal demagnetization of the particle at zero field, while the magnetization is increased at moderate fields, since surface disorder diminishes ferrimagnetic correlations within the particle. The change in shape of the hysteresis loops with the particle size demonstrates that the reversal mode is strongly influenced by the reduced atomic coordination and disorder at the surface.Comment: Twocolumn RevTex format. 19 pages, 15 Figures included. Submitted to Phys. Rev.

Equilibrium susceptibilities of superparamagnets: longitudinal & transverse, quantum & classical

The equilibrium susceptibility of uniaxial paramagnets is studied in a unified framework which permits to connect traditional results of the theory of quantum paramagnets, \Sm=1/2, 1, 3/2, ..., with molecular magnetic clusters, \Sm\sim5, 10, 20, all the way up, \Sm=30, 50, 100,... to the theory of classical superparamagnets. This is done using standard tools of quantum statistical mechanics and linear response theory (the Kubo correlator formalism). Several features of the temperature dependence of the susceptibility curves (crossovers, peaks, deviations from Curie law) are studied and their scalings with \Sm identified and characterized. Both the longitudinal and transverse susceptibilities are discussed, as well as the response of the ensemble with anisotropy axes oriented at random. For the latter case a simple approximate formula is derived too, and its range of validity assessed, so it could be used in modelization of experiments.Comment: 32 pages, 5 figures. Submitted to J.Phys.Condens.Matte

Combustion Reactions of Some “Metal-Oxide” Systems under Conditions of Zero and Applied Magnetic Fields: Thermal Imaging Experiments

The effect of an external magnetic field of 0.2 T on the self-propagating high temperature syntheses (SHS) of a mixture of first row transition metals and their oxides was studied by using a very sensitive thermal imaging method involving an IR-camera and software developed by MIKRON Instrument Co., Inc. (M9100 Pyrovision Series – Imaging Pyrometer). For the basic conversion of first row transition metals to their corresponding oxide, there was no observable difference in propagation behavior between applied and zero field reactions. However the average wave velocity for the iron system showed a significantly greater value when the SHS was conducted under conditions of an applied field. This enabled accurate monitoring of the combustion process in particular propagation velocity, maximum temperature, cooling rates, synthesis wave width and pathway. Several interesting phenomena, such as hole formation in the pellet and combustion wave segmentation were detected in some systems

Thermosensitive polymer-grafted iron oxide nanoparticles studied by in situ dynamic light backscattering under magnetic hyperthermia

© 2015 IOP Publishing Ltd. Thermometry at the nanoscale is an emerging area fostered by intensive research on nanoparticles (NPs) that are capable of converting electromagnetic waves into heat. Recent results suggest that stationary gradients can be maintained between the surface of NPs and the bulk solvent, a phenomenon sometimes referred to as \u27cold hyperthermia\u27. However, the measurement of such highly localized temperatures is particularly challenging. We describe here a new approach to probing the temperature at the surface of iron oxide NPs and enhancing the understanding of this phenomenon. This approach involves the grafting of thermosensitive polymer chains to the NP surface followed by the measurement of macroscopic properties of the resulting NP suspension and comparison to a calibration curve built up by macroscopic heating. Superparamagnetic iron oxide NPs were prepared by the coprecipitation of ferrous and ferric salts and functionalized with amines, then azides using a sol-gel route followed by a dehydrative coupling reaction. Thermosensitive poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA) with an alkyne end-group was synthesized by controlled radical polymerization and was grafted using a copper assisted azide-alkyne cycloaddition reaction. Measurement of the colloidal properties by dynamic light scattering (DLS) indicated that the thermosensitive NPs exhibited changes in their Zeta potential and hydrodynamic diameter as a function of pH and temperature due to the grafted PDMAEMA chains. These changes were accompanied by changes in the relaxivities of the NPs, suggesting application as thermosensitive contrast agents for magnetic resonance imaging (MRI). In addition, a new fibre-based backscattering setup enabled positioning of the DLS remote-head as close as possible to the coil of a magnetic heating inductor to afford in situ probing of the backscattered light intensity, hydrodynamic diameter, and temperature. This approach provides a promising platform for estimating the response of magnetic NPs to application of a radiofrequency magnetic field or for understanding the behaviour of other thermogenic NPs

How is rape a weapon of war?: feminist international relations, modes of critical explanation and the study of wartime sexual violence

Rape is a weapon of war. Establishing this now common claim has been an achievement of feminist scholarship and activism and reveals wartime sexual violence as a social act marked by gendered power. But the consensus that rape is a weapon of war obscures important, and frequently unacknowledged, differences in ways of understanding and explaining it. This article opens these differences to analysis. Drawing on recent debates regarding the philosophy of social science in IR and social theory, it interprets feminist accounts of wartime sexual violence in terms of modes of critical explanation – expansive styles of reasoning that foreground particular actors, mechanisms, reasons and stories in the formulation of research. The idea of a mode of critical explanation is expanded upon through a discussion of the role of three elements (analytical wagers, narrative scripts and normative orientations) which accomplish the theoretical work of modes. Substantive feminist accounts of wartime sexual violence are then differentiated in terms of three modes – of instrumentality, unreason and mythology – which implicitly structure different understandings of how rape might be a weapon of war. These modes shape political and ethical projects and so impact not only on questions of scholarly content but also on the ways in which we attempt to mitigate and abolish war rape. Thinking in terms of feminist modes of critical explanation consequently encourages further work in an unfolding research agenda. It clarifes the ways in which an apparently commonality of position can conceal meaningful disagreements about human action. Exposing these disagreements opens up new possibilities for the analysis of war rape

Electron energy loss spectra of C 60 and C 70 fullerenes

Abstract The electron energy loss spectra of C 60 and C 70 fullerenes are investigated using spectroscopy measurements and theoretical calculations. An additional peak has been identified for C 70 above the carbon K-edge onset from our high-resolution electron energy loss spectra and analysed by density functional theory. Good agreement between theory and experiment is obtained, and the additional peak is found to be due to the electronic states associated with the 10 equatorial atoms in C 70

Magnetically assisted delivery of cells using a magnetic resonance imaging system

A simple analytical model is presented which enables rapid interactive prediction and control of magnetically labelled cells in an arterial bifurcation using magnetic field gradients produced by a magnetic resonance imaging (MRI) system. This model is compared against experimental results for human mononuclear cells labelled with micrometre sized superparamagnetic iron oxide particles. Experimental and theoretical results highlight the importance of cell aggregation for magnetic targeting in a strong magnetic field. These predicted aggregates are confirmed via confocal endoscopy which allows the visualization of cell aggregates and their movement inside a vascular flow model in a 9.4 T preclinical MRI scanner. © 2011 IOP Publishing Ltd