Magnetic Properties of a High-Pressure Torsion Deformed Co-Zr Alloy.

Co-Zr amorphous alloys exhibit soft magnetic properties, whereas the Co-rich crystalline magnetic phases in this alloy system displayed a hard magnetic behavior. In this study, an initial two-phase Co-Zr composite with an overall composition of 75 at.% Co and 25 at.% Zr was processed by high-pressure torsion (HPT), and the effects of severe plastic deformation and subsequent thermal treatment on the composite's structural evolution and its magnetic properties were investigated. HPT processing allowed us to achieve an amorphous microstructure with low coercivity in its as-deformed state. To further tune the alloy's magnetic properties and study its crystallization behavior, various annealed states were investigated. The microstructural properties were correlated with the magnetic properties, and a decreasing coercivity with increasing annealing temperatures was observed despite the onset of crystallization in the amorphous alloy. At higher annealing temperatures, coercivity increased again. The results appear promising for obtaining tuneable rare-earth free magnetic materials by severe plastic deformation.

Exchange Bias Demonstrated in Bulk Nanocomposites Processed by High-Pressure Torsion.

Ferromagnetic (Fe or Fe20Ni80) and antiferromagnetic (NiO) phases were deformed by high-pressure torsion, a severe plastic deformation technique, to manufacture bulk-sized nanocomposites and demonstrate an exchange bias, which has been reported predominantly for bilayer thin films. High-pressure torsion deformation at elevated temperatures proved to be the key to obtaining homogeneous bulk nanocomposites. X-ray diffraction investigations detected nanocrystallinity of the ferromagnetic and antiferromagnetic phases. Furthermore, an additional phase was identified by X-ray diffraction, which formed during deformation at elevated temperatures through the reduction of NiO by Fe. Depending on the initial powder composition of Fe50NiO50 or Fe10Ni40NiO50 the new phase was magnetite or maghemite, respectively. Magnetometry measurements demonstrated an exchange bias in high-pressure torsion-processed bulk nanocomposites. Additionally, the tailoring of magnetic parameters was demonstrated by the application of different strains or post-process annealing. A correlation between the amount of applied strain and exchange bias was found. The increase of exchange bias through applied strain was related to the microstructural refinement of the nanocomposite. The nanocrystalline maghemite was considered to have a crucial impact on the observed changes of exchange bias through applied strain.

Manufacturing of Textured Bulk Fe-SmCo5 Magnets by Severe Plastic Deformation.

Exchange-coupling between soft- and hard-magnetic phases plays an important role in the engineering of novel magnetic materials. To achieve exchange coupling, a two-phase microstructure is necessary. This interface effect is further enhanced if both phase dimensions are reduced to the nanometer scale. At the same time, it is challenging to obtain large sample dimensions. In this study, powder blends and ball-milled powder blends of Fe-SmCo5 are consolidated and are deformed by high-pressure torsion (HPT), as this technique allows us to produce bulk magnetic materials of reasonable sizes. Additionally, the effect of severe deformation by ball-milling and severe plastic deformation by HPT on exchange coupling in Fe-SmCo5 composites is investigated. Due to the applied shear deformation, it is possible to obtain a texture in both phases, resulting in an anisotropic magnetic behavior and an improved magnetic performance.

Vapochromism and Magnetochemical Switching of a Nickel(II) Paddlewheel Complex by Reversible NH3 Uptake and Release.

Reaction of [NiCl2 (PnH)4 ] (1) (PnH=6-tert-butyl-pyridazine-3-thione) with NiCl2 affords the binuclear paddlewheel (PW) complex [Ni2 (Pn)4 ] (2). Diamagnetic complex 2 is the first example of a PW complex capable of reversibly binding and releasing NH3 . The NH3 ligand in [Ni2 (Pn)4 (NH3 )] (2⋅NH3 ) enforces major spectroscopic and magnetic susceptibility changes, thus displaying vapochromic properties (λmax (2)=532 nm, λmax (2⋅NH3 )=518 nm) and magnetochemical switching (2: S=0; 2⋅NH3 : S=1). Upon repeated adsorption/desorption cycles of NH3 the PW core remains intact. Compound 2 can be embedded into thin polyurethane films (2P ) under retention of its sensing abilities. Therefore, 2 qualifies as reversible optical probe for ammonia. The magnetochemical switching of 2 and 2⋅NH3 was studied in detail by SQUID measurements showing that in 2⋅NH3 , solely the Ni atom coordinated the NH3 molecule is responsible for the paramagnetic behavior.

Soft Magnetic Properties of Ultra-Strong and Nanocrystalline Pearlitic Wires.

The paper describes the capability of magnetic softening of a coarse-grained bulk material by a severe deformation technique. Connecting the microstructure with magnetic properties, the coercive field decreases dramatically for grains smaller than the magnetic exchange length. This makes the investigation of soft magnetic properties of severely drawn pearlitic wires very interesting. With the help of the starting two-phase microstructure, it is possible to substantially refine the material, which allows the investigation of magnetic properties for nanocrystalline bulk material. Compared to the coarse-grained initial, pearlitic state, the coercivities of the highly deformed wires decrease while the saturation magnetization values increase-even beyond the value expectable from the individual constituents. The lowest coercivity in the drawn state is found to be 520 A m-1 for a wire of 24-µm thickness and an annealing treatment has a further positive effect on it. The decreasing coercivity is discussed in the framework of two opposing models: grain refinement on the one hand and dissolution of cementite on the other hand. Auxiliary measurements give a clear indication for the latter model, delivering a sufficient description of the observed evolution of magnetic properties.

Magneto-Ionic Switching of Superparamagnetism.

Electrochemical reactions represent a promising approach to control magnetization via electric fields. Favorable reaction kinetics have made nanoporous materials particularly interesting for magnetic tuning experiments. A fully reversible ON and OFF switching of magnetism in nanoporous Pd(Co) at room temperature is demonstrated, triggered by electrochemical hydrogen sorption. Comprehensive magnetic characterization in combination with high-resolution scanning transmission electron microscopy reveals the presence of Co-rich, nanometer-sized clusters in the nanoporous Pd matrix with distinct superparamagnetic behavior. The strong magneto-ionic effect arises from coupling of the magnetic clusters via a Ruderman-Kittel-Kasuya-Yoshida-type interaction in the Pd matrix which is strengthened upon hydrogen sorption. This approach offers a new pathway for the voltage control of magnetism, for application in spintronic or microelectromagnetic devices.

Redox processes in sodium vanadium phosphate cathodes - insights from operando magnetometry.

Operando magnetic susceptibility measurements of sodium ion cathode materials during repetitive electrochemical cycling enable a continuous and bulk sensitive monitoring of the transition metal oxidation states. Such measurements on NaxV2(PO4)3 identified vanadium to be the only ion undergoing oxidation/reduction processes upon battery operation. For the initial battery charging-discharging cycle as well as for the first cycle after prolonged room temperature storage, however, peculiarities within the magnetic susceptibility measurements indicate parasitic side reactions, likely on the cathode surface.

Magnetic Binary Supersaturated Solid Solutions Processed by Severe Plastic Deformation.

Samples consisting of one ferromagnetic and one diamagnetic component which are immiscible at the thermodynamic equilibrium (Co-Cu, Fe-Cu, Fe-Ag) are processed by high-pressure torsion at various compositions. The received microstructures are investigated by electron microscopy and synchrotron X-ray diffraction, showing a microstructural saturation. Results gained from microstructural investigations are correlated to magnetometry data. The Co-Cu samples show mainly ferromagnetic behavior and a decrease in coercivity with increasing Co-content. The saturation microstructure of Fe-Cu samples is found to be dual phase. Results of magnetic measurements also revealed the occurrence of two different magnetic phases in this system. For Fe-Ag, the microstructural and magnetic results indicate that no intermixing between the elemental phases takes place.

Effects of concentration and vendor specific composition of formalin on postmortem MRI of the human brain.

PURPOSE: Formalin fixation prevents tissue autolysis by crosslinking proteins and changes tissue microstructure and MRI signal characteristics. Previous studies showed high variations in MR relaxation time constants of formalin fixed brain tissue, which has been attributed to the use of different formalin concentrations. Our investigations confirmed the influence of formalin concentration on relaxation times and unexpectedly revealed an influence of vendor specific formalin composition, which has not been investigated so far. METHODS: We systematically analyzed relaxation times of human brain tissue fixed with 4% and 10% formalin compared with unfixed condition at 3 Tesla MRI. Furthermore, we assessed relaxation times of nine formalin solutions from different vendors and performed comparisons of their magnetic susceptibility by SQUID (superconducting quantum interference device) magnetometry. RESULTS: Tissue relaxation times decreased approximately twice as fast using 10% than in 4% formalin fixation. The vendor specific composition of the formalin solutions and concentration dependent paramagnetic effects showed a substantial contribution to differences in relaxation times of formalin. CONCLUSION: Our study demonstrates that differences of the formalin composition have substantial effects on MRI signal characteristics after fixation, which can explain the divergence of reported relaxation times beyond the effect of differences in formalin concentration. Magn Reson Med 79:1111-1115, 2018. © 2017 International Society for Magnetic Resonance in Medicine.

Using Functionalized Silyl Ligands To Suppress Solvent Coordination to Silyl Lanthanide(II) Complexes.

The reaction of the potassium 1,3-trisilanediide Me2Si[Si(Me3Si)2K]2 with SmI2 and YbI2 was found to give the respective disilylated complexes Me2Si[Si(Me3Si)2]2Sm·2THF and Me2Si[Si(Me3Si)2]2Yb·2THF. Desolvation of coordinated solvent molecules in these complexes made their handling difficult. However, using a number of functionalized silanide ligands, complexes with a diminished number or even no coordinated solvent molecules were obtained ((R3Si)2Ln(THF)x (x = 0-3)). The structures of all new lanthanide compounds were determined by X-ray single-crystal structure analysis. NMR spectroscopic analysis of some Yb-silyl complexes pointed at highly ionic interactions between the silyl ligands and the lanthanides. This bonding picture was supported by DFT calculations at the B3PW91/Basis1 level of theory. Detailed theoretical analysis of a disilylated Eu(II) complex suggests that its singly occupied molecular orbitals (SOMOs) are very close in energy to the ligand silicon lone pairs (HOMO), and SQUID magnetometry measurements of the complex showed a deviation from the expected behavior for a free Eu(II) ion, which might be due to a ligand-metal interaction.

Electrochemical cell for in situ electrodeposition of magnetic thin films in a superconducting quantum interference device magnetometer.

An electrochemical cell is designed and applied for in situ electrodeposition of magnetic thin films in a commercial SQUID magnetometer system. The cell is constructed in such a way that any parasitic contribution of the cell and of the substrate for electrodeposition to the magnetic moment of the deposited film is reduced to a minimum. A remanent minor contribution is readily taken into account by a proper analysis of the detected signal. Thus, a precise determination of the absolute magnetic moment of the electrodeposited magnetic film during its growth and dissolution is achieved. The feasibility of the cell design is demonstrated by performing Co electrodeposition using cyclic voltammetry. For an average Co film thickness of (35.6 ± 3.0) atomic layers, a magnetic moment per Co atom of (1.75 ± 0.11) µ(B) was estimated, in good agreement with the literature bulk value.

Iron mapping using the temperature dependency of the magnetic susceptibility.

PURPOSE: The assessment of iron content in brain white matter (WM) is of high importance for studying neurodegenerative diseases. While R2 * mapping and quantitative susceptibility mapping is suitable for iron mapping in gray matter, iron mapping in WM still remains an unsolved problem. We propose a new approach for iron mapping, independent of diamagnetic contributions of myelin by assessing the temperature dependency of the paramagnetic susceptibility. THEORY AND METHODS: We used unfixed human brain slices for relaxometry and calculated R2 ' as a measure for microscopic susceptibility variations at several temperatures (4°C-37°C) at 3 Tesla. The temperature coefficient of R2 ' (TcR2p) was calculated by linear regression and related to the iron concentration found by subsequent superconducting quantum interference device (SQUID) magnetometry and by inductively coupled plasma mass spectrometry. RESULTS: In line with SQUID measurements, R2 ' mapping showed a linear temperature dependency of the bulk susceptibility with the highest slope in gray matter. Even in WM, TcR2p yielded a high linear correlation with the absolute iron concentration. CONCLUSION: According to Curie's law, only paramagnetic matter exhibits a temperature dependency while the diamagnetism shows no effect. We have demonstrated that the temperature coefficient (TcR2p) can be used as a measure of the paramagnetic susceptibility despite of an unknown diamagnetic background.

In situ monitoring magnetism and resistance of nanophase platinum upon electrochemical oxidation.

Controlled tuning of material properties by external stimuli represents one of the major topics of current research in the field of functional materials. Electrochemically induced property tuning has recently emerged as a promising pathway in this direction making use of nanophase materials with a high fraction of electrode-electrolyte interfaces. The present letter reports on electrochemical property tuning of porous nanocrystalline Pt. Deeper insight into the underlying processes could be gained by means of a direct comparison of the charge-induced response of two different properties, namely electrical resistance and magnetic moment. For this purpose, four-point resistance measurements and SQUID magnetometry were performed under identical in situ electrochemical control focussing on the regime of electrooxidation. Fully reversible variations of the electrical resistance and the magnetic moment of 6% and 1% were observed upon the formation or dissolution of a subatomic chemisorbed oxygen surface layer, respectively. The increase of the resistance, which is directly correlated to the amount of deposited oxygen, is considered to be primarily caused by charge-carrier scattering processes at the metal-electrolyte interfaces. In comparison, the decrease of the magnetic moment upon positive charging appears to be governed by the electric field at the nanocrystallite-electrolyte interfaces due to spin-orbit coupling.

SQUID magnetometry combined with in situ cyclic voltammetry: A case study of tunable magnetism of [Formula: see text]-Fe2O3 nanoparticles.

SQUID magnetometry combined with in situ cyclic voltammetry by means of a three-electrode chemical cell opens up novel potentials for studying correlations between electrochemical processes and magnetic behaviour. The combination of these methods shows that the charge-induced variation of the magnetic moment of nanocrystalline maghemite ([Formula: see text]-Fe2O3) of about 4% strongly depends on the voltage regime of charging. Upon positive charging, the charge-induced variation of the magnetic moment is suppressed due to adsorption layers. The pronounced charge-sensitivity of the magnetic moment in the regime of negative charging may either be associated with a redox reaction or with charge-induced variations of the magnetic anisotropy or magnetoelastic coupling.

Detection of laser-induced nanosecond ultrasonic pulses in metals using a pancake coil and a piezoelectric sensor.

A piezoelectric sensor and a pancake coil sensor were used for broadband detection of laser-induced ultrasound in single-crystal aluminum and polycrystalline nickel. Pressure pulses with pronounced compression phases were induced by laser pulses of 5 ns duration from one side of the specimens and detected from the opposite side. A coupling layer of water was required for the piezoelectric method, whereas the pancake coil placed in the biasing permanent field of a cylindrical magnet ~0.25 T allowed noncontact detection. The signals detected by a piezoelectric transducer showed bipolar form and their spectra covered the range from 5 to 90 MHz. The signal measured in aluminum by a pancake coil was assigned to the eddy current sources and had single polarity. The peak-to-peak value of the signal in nickel was higher and had bipolar form because of the inverse magnetostrictive effect. The high-frequency limit detected by the pancake coil approached 200 MHz.

Attenuation of ultrasound in severely plastically deformed nickel.

Ultrasound attenuation was measured in nickel specimens of about 30 mm diameter prepared using the high pressure torsion technique. The cold working process produced an equivalent shear strain increasing from zero at the center up to 1000% at the edge of the specimen. The fragmentation of the grains due to multiple dislocations led to an ultrafine microstructure with large angle grain boundaries. The mean value of the grain size distribution gradually decreased from ∼50 µm at the center to 0.2 µm at the edge. Laser pulses of 5 ns were employed for the excitation of broadband ultrasound pulses covering the spectral range of 0.1-150 MHz. The ultrasound pulses were measured from the opposite side of the specimen by means of an optical interferometer and a piezoelectric foil transducer in two experimental setups. The features of the detected signal forms are discussed. The absolute value of the attenuation decreases from the center to the edge of the specimen showing nearly linear frequency dependence. The variation of the phase velocity was measured in a 6 mm-thick high pressure torsion nickel sample, revealing a velocity increase from the center to the edge.