Fluoride doped γ-Fe2O3 nanoparticles with increased MRI relaxivity.

Iron oxide nanoparticles (IONs) are being actively researched and experimented with as contrast agents for Magnetic Resonance Imaging (MRI), as well as image-directed delivery of therapeutics. The efficiency of an MRI contrast agent can be described by its longitudinal and transverse relaxivities, r1 and r2. γ-Fe2O3 nanoparticles - doped with fluoride in a controlled manner and functionalised with citric acid - showed a 3-fold increase in r1 and a 17-fold increase in r2 in a magnetic field of 3 T and almost 6-fold increase in r1 and a 14-fold increase in r2 at 11 T. Following fluorination, PXRD shows that the crystal structure of γ-Fe2O3 is maintained, Mössbauer spectroscopy shows that the oxidation state of the Fe cation is unchanged and HREM shows that the particle size does not vary. However, magnetisation curves show a large increase in the coercive field, pointing towards a large increase in the magnetic anisotropy for the fluorinated nanoparticles compared to the un-doped γ-Fe2O3 nanoparticles. Therefore, a chemically induced increase in magnetic anisotropy appears to be the most relevant parameter responsible for the large increase in relaxivity for γ-Fe2O3 nanoparticles.

Probing magnetic coupling between LnPc2 (Ln = Tb, Er) molecules and the graphene/Ni (111) substrate with and without Au-intercalation: role of the dipolar field.

Lanthanides (Ln) bis-phthalocyanine (Pc), the so-called LnPc2double decker, are a promising class of molecules with a well-defined magnetic anisotropy. In this work, we investigate the magnetic properties of LnPc2 molecules UHV-deposited on a graphene/Ni(111) substrate and how they modify when an Au layer is intercalated between Ni and graphene. X-ray absorption spectroscopy (XAS), and linear and magnetic circular dichroism (XLD and XMCD) were used to characterize the systems and probe the magnetic coupling between LnPc2 molecules and the Ni substrate through graphene, both gold-intercalated and not. Two types of LnPc2 molecules (Ln = Tb, Er) with a different magnetic anisotropy (easy-axis for Tb, easy-plane for Er) were considered. XMCD shows an antiferromagnetic coupling between Ln and Ni(111) even in the presence of the graphene interlayer. Au intercalation causes the vanishing of the interaction between Tb and Ni(111). In contrast, in the case of ErPc2, we found that the gold intercalation does not perturb the magnetic coupling. These results, combined with the magnetic anisotropy of the systems, suggest the possible importance of the magnetic dipolar field contribution for determining the magnetic behaviour.

Mastering hysteresis in magnetocaloric materials.

Hysteresis is more than just an interesting oddity that occurs in materials with a first-order transition. It is a real obstacle on the path from existing laboratory-scale prototypes of magnetic refrigerators towards commercialization of this potentially disruptive cooling technology. Indeed, the reversibility of the magnetocaloric effect, being essential for magnetic heat pumps, strongly depends on the width of the thermal hysteresis and, therefore, it is necessary to understand the mechanisms causing hysteresis and to find solutions to minimize losses associated with thermal hysteresis in order to maximize the efficiency of magnetic cooling devices. In this work, we discuss the fundamental aspects that can contribute to thermal hysteresis and the strategies that we are developing to at least partially overcome the hysteresis problem in some selected classes of magnetocaloric materials with large application potential. In doing so, we refer to the most relevant classes of magnetic refrigerants La-Fe-Si-, Heusler- and Fe2P-type compounds.This article is part of the themed issue 'Taking the temperature of phase transitions in cool materials'.

Spin-communication channels between Ln(III) bis-phthalocyanines molecular nanomagnets and a magnetic substrate.

Learning the art of exploiting the interplay between different units at the atomic scale is a fundamental step in the realization of functional nano-architectures and interfaces. In this context, understanding and controlling the magnetic coupling between molecular centers and their environment is still a challenging task. Here we present a combined experimental-theoretical work on the prototypical case of the bis(phthalocyaninato)-lanthanide(III) (LnPc2) molecular nanomagnets magnetically coupled to a Ni substrate. By means of X-ray magnetic circular dichroism we show how the coupling strength can be tuned by changing the Ln ion. The microscopic parameters of the system are determined by ab-initio calculations and then used in a spin Hamiltonian approach to interpret the experimental data. By this combined approach we identify the features of the spin communication channel: the spin path is first realized by the mediation of the external (5d) electrons of the Ln ion, keeping the characteristic features of the inner 4 f orbitals unaffected, then through the organic ligand, acting as a bridge to the external world.

Simultaneous Study of Brownian and Néel Relaxation Phenomena in Ferrofluids by Mössbauer Spectroscopy.

We demonstrate the ability of Mössbauer spectroscopy to simultaneously investigate Brownian motion and Néel relaxation in ferrofluidic samples. For this purpose, Mössbauer spectra of coated iron oxide nanoparticles with core diameters of 6.0-26.4 nm dissolved in 70 vol % glycerol solution were recorded in the temperature range of 234-287 K and compared to low-temperature spectra without Brownian motion. By comparison to theory, we were able to determine the particle coating thickness and the dynamic viscosity of the fluid from the broadening of the absorption lines (Brownian motion), as well as the state of Néel relaxation. Results from Mössbauer spectroscopy were crosschecked by AC-susceptometry at several temperatures for Brownian motion and in the high-frequency regime (100 Hz-1 MHz) for Néel relaxation.

Doping of inorganic materials in microreactors - preparation of Zn doped Fe3O4 nanoparticles.

Microreactor systems are now used more and more for the continuous production of metal nanoparticles and metal oxide nanoparticles owing to the controllability of the particle size, an important property in many applications. Here, for the first time, we used microreactors to prepare metal oxide nanoparticles with controlled and varying metal stoichiometry. We prepared and characterised Zn-substituted Fe3O4 nanoparticles with linear increase of Zn content (ZnxFe3-xO4 with 0 ≤ x ≤ 0.48), which causes linear increases in properties such as the saturation magnetization, relative to pure Fe3O4. The methodology is simple and low cost and has great potential to be adapted to the targeted doping of a vast array of other inorganic materials, allowing greater control on the chemical stoichiometry for nanoparticles prepared in microreactors.

Element-resolved thermodynamics of magnetocaloric LaFe(13-x)Si(x).

By combination of two independent approaches, nuclear resonant inelastic x-ray scattering and first-principles calculations in the framework of density functional theory, we demonstrate significant changes in the element-resolved vibrational density of states across the first-order transition from the ferromagnetic low temperature to the paramagnetic high temperature phase of LaFe(13-x)Si(x). These changes originate from the itinerant electron metamagnetism associated with Fe and lead to a pronounced magneto-elastic softening despite the large volume decrease at the transition. The increase in lattice entropy associated with the Fe subsystem is significant and contributes cooperatively with the magnetic and electronic entropy changes to the excellent magneto- and barocaloric properties.

Correlation of superparamagnetic relaxation with magnetic dipole interaction in capped iron-oxide nanoparticles.

Six nanometer sized iron-oxide nanoparticles capped with an organic surfactant and/or silica shell of various thicknesses have been synthesized by a microemulsion method to enable controllable contributions of interparticle magnetic dipole interaction via tunable interparticle distances. Bare particles with direct surface contact were used as a reference to distinguish between interparticle interaction and surface effects by use of Mössbauer spectroscopy. Superparamagnetic relaxation behaviour was analyzed by SQUID-magnetometry techniques, showing a decrease of the blocking temperature with decreasing interparticle interaction energies kBT0 obtained by AC susceptibility. A many-state relaxation model enabled us to describe experimental Mössbauer spectra, leading to an effective anisotropy constant Keff ≈ 45 kJm(-3) in case of weakly interacting particles, consistent with results from ferromagnetic resonance. Our unique multi-technique approach, spanning a huge regime of characteristic time windows from about 10 s to 5 ns, provides a concise picture of the correlation of superparamagnetic relaxation with interparticle magnetic dipole interaction.

Mössbauer study of temperature-dependent cycloidal ordering in BiFeO3 nanoparticles.

To study the effects of different temperatures and particle sizes on the anharmonic cycloidal spin structure in BiFeO3 nanoparticles, Mössbauer spectroscopy was applied to three sets of particles with different mean diameters in the range of 54 nm to 1.6 µm at temperatures between 4.2 and 800 K. The paramagnetic transition showed a distinct broadening upon decreasing particle size with Néel temperatures decreasing from 652 to 631 K. The anharmonicity of the long-range cycloidal structure, calculated from experimental Mössbauer spectra, is revealed to decrease upon rising temperature, starting at 150-200 K and reaching the harmonic state at about 400 K.

The dipole moment of the spin density as a local indicator for phase transitions.

The intra-atomic magnetic dipole moment - frequently called ⟨Tz⟩ term - plays an important role in the determination of spin magnetic moments by x-ray absorption spectroscopy for systems with nonspherical spin density distributions. In this work, we present the dipole moment as a sensitive monitor to changes in the electronic structure in the vicinity of a phase transiton. In particular, we studied the dipole moment at the Fe(2+) and Fe(3+) sites of magnetite as an indicator for the Verwey transition by a combination of x-ray magnetic circular dichroism and density functional theory. Our experimental results prove that there exists a local change in the electronic structure at temperatures above the Verwey transition correlated to the known spin reorientation. Furthermore, it is shown that measurement of the dipole moment is a powerful tool to observe this transition in small magnetite nanoparticles for which it is usually screened by blocking effects in classical magnetometry.

Effect of particle size on ferroelectric and magnetic properties of BiFeO3 nanopowders.

The ferroelectric and magnetic behaviour of multiferroic BiFeO3 nanoparticles has been studied using piezoresponse force microscopy (PFM), Mössbauer spectroscopy and SQUID magnetometry. The results of the PFM studies indicate a decay of the spontaneous polarization with decreasing particle size. Nevertheless, particles with diameter ∼50 nm still manifest ferroelectric behaviour. At the same time these particles are weakly ferromagnetic. The Mössbauer spectroscopy studies prove that the weak ferromagnetic state is due to non-compensated surface spins rather than distortions of the cycloidal spin structure characteristic for bulk BiFeO3.

Tailoring the nature of magnetic coupling of Fe-porphyrin molecules to ferromagnetic substrates.

We demonstrate that an antiferromagnetic coupling between paramagnetic Fe-porphyrin molecules and ultrathin Co and Ni magnetic films on Cu(100) substrates can be established by an intermediate layer of atomic oxygen. The coupling energies have been determined from the temperature dependence of x-ray magnetic circular dichroism measurements. By density functional theory+U calculations the coupling mechanism is shown to be superexchange between the Fe center of the molecules and Co surface-atoms, mediated by oxygen.

Inhomogeneous alloying in FePt nanoparticles as a reason for reduced magnetic moments.

The reduced magnetic moments of oxide-free FePt nanoparticles are discussed in terms of lattice expansion and local deviation from the averaged composition. By analyses of the extended x-ray absorption fine structure of FePt nanoparticles and bulk material measured both at the Fe K and Pt L(3) absorption edge, the composition within the single nanoparticles is found to be inhomogeneous, i.e. Pt is in a Pt-rich environment and, consequently, Fe is in an Fe-rich environment. The standard Fourier transformation-based analysis is complemented by a wavelet transformation method clearly visualizing the difference in the local composition. The dependence of the magnetic properties, i.e. the element-specific magnetic moments on the composition in chemically disordered Fe(x)Pt(1-x) alloys, is studied by fully relativistic SPR-KKR band structure calculations supported by experimental results determined from the x-ray magnetic circular dichroism of 50 nm thick films and bulk material.

Substrate-induced magnetic ordering and switching of iron porphyrin molecules.

To realize molecular spintronic devices, it is important to externally control the magnetization of a molecular magnet. One class of materials particularly promising as building blocks for molecular electronic devices is the paramagnetic porphyrin molecule in contact with a metallic substrate. Here, we study the structural orientation and the magnetic coupling of in-situ-sublimated Fe porphyrin molecules on ferromagnetic Ni and Co films on Cu(100). Our studies involve X-ray absorption spectroscopy and X-ray magnetic circular dichroism experiments. In a combined experimental and computational study we demonstrate that owing to an indirect, superexchange interaction between Fe atoms in the molecules and atoms in the substrate (Co or Ni) the paramagnetic molecules can be made to order ferromagnetically. The Fe magnetic moment can be rotated along directions in plane as well as out of plane by a magnetization reversal of the substrate, thereby opening up an avenue for spin-dependent molecular electronics.

Measuring the kernel of time-dependent density functional theory with x-ray absorption spectroscopy of transition metals.

The 2p-3d core-hole interaction in the L2.3 absorption spectra of the transition metals is treated within time-dependent density functional theory. A simple three-level model explains the origin of the strong deviations from the one-particle branching ratio and yields matrix elements of the unknown exchange-correlation kernel directly from experiment.

Direct observation of orbital magnetism in cubic solids.

We present x-ray magnetic circular dichroism determinations of the orbital/spin magnetic moment ratios of dilute 3d-series impurities in Au (and Cu) host matrices. This is the first direct measurement of considerable orbital moments in cubic symmetry for a localized impurity in a bulk metal host. It is shown that the unquenching of orbital magnetism depends on a delicate balance of hybridization effects between the local impurity with the host and the filling of the 3d states of the impurity. The results are accompanied by ab initio calculations that support our experimental findings.

Requirements for the protection against aircraft noise.

In preparation of the revised edition of the Air Traffic Noise Act the Federal Environmental Agency formulated targets for aircraft noise control. They were prepared oriented to the Federal Immission Control Act. The assessment periods were chosen analogously to the regulations on other traffic noise sources (rail traffic, road traffic). The control targets cover the following affected areas * aural, extra-aural health * night's sleep * annoyance * communication * recreation Considerable nuisance can be avoided by limiting the exposure to aircraft noise(outside) to equivalent levels below 55 dB(A) by day and 45 dB(A) at night, and impairment of health can be avoided by limiting the exposure to aircraft noise (outside) to equivalent levels below 60 dB(A) by day and 50 dB(A) at night.

Systematics of the induced magnetic moments in 5d layers and the violation of the third Hund's rule.

X-ray magnetic circular dichroism measurements are reported at the beginning (W) and at the end (Ir, Pt) of the 5d series of the periodic table. Considerable induced magnetic moments of about 0.2 mu(B)/atom were probed for the nonmagnetic W and Ir and compared to previous data for the Pt induced moments in multilayers. W was found to couple antiferromagnetically and Ir ferromagnetically to the 3d layers. Finally, the W spin and orbital magnetic moment couple in parallel, contrary to what is expected from the third Hund's rule. This remarkable finding shows that the induced magnetic behavior of 5d layers may be radically different than that of impurities and alloys.

Magnetic EXAFS at Gd L-edges: the spin-pair-distribution function of Gd neighbors.

The purpose of the experiment is to study the normal and the Magnetic EXAFS (MEXAFS) since EXAFS is the method of choice to investigate the local pair- and spin-pair-distribution function. We present MEXAFS and EXAFS measurements at the L-edges of a Gd single crystal in the temperature range of 10 K to 250 K. Therefore we are able to investigate the MEXAFS in a wide range of the reduced temperature t=T/Tc of 0.04 < or = t < or = 0.85 with Tc=293 K. We find a strong decrease of the nearest neighbor EXAFS which retains only about 35% of its 10 K value already at 250 K. This highlights the importance of lattice vibrations. To analyze the individual scattering contributions to the MEXAFS and the EXAFS, ab initio calculations (FEFF code) have been carried out. The comparison of the temperature-dependent damping of the normal EXAFS with the spin-dependent MEXAFS allows us to separate the influence of lattice vibrations (Debye temperature 160 K) from the magnetic ordering (Curie temperature) on the MEXAFS.