Synchrotron Fe‐K X‐ray absorption spectroscopy and transmission electron microscopy have been used to investigate the mineralogy and Fe‐redox variations in the space‐weathered (SW) rims of asteroidal samples. This study focuses on the FIB lift‐out sections from five Itokawa grains, returned by the Hayabusa spacecraft, including samples RB‐QD04‐0063, RB‐QD04‐0080, RB‐CV‐0011, RB‐CV‐0089, and RB‐CV‐0148. Each of the samples featured partially amorphized SW rims, caused by irradiation damage from implanted low mass solar wind ions, and the impacting of micrometeorites. Using bright‐field and HAADF‐STEM imaging, vesicular blistering and nanophase Fe metal (npFe 0 ) particles were observed within grain rims, and solar flare tracks were observed in the substrate host grain, confirming the presence of SW zones. We use Fe‐K XANES mapping to investigate Fe‐redox changes between the host mineral and the SW zones. All SW zones measured show some increases in the ferric‐ferrous ratio (Fe 3+ /ΣFe) relative to their respective host grains, likely the result of the implanted solar wind H + ions reacting with the segregated ferrous Fe in the surface material.

We describe magnetometry measurements performed on nanocomposite films formed of Fe nanoparticles embedded in Al matrix. The samples were prepared using a flexible co-deposition technique under Ultra-High Vacuum (UHV) environments. Fe nanoparticles, made by using a gas aggregation source, were co-deposited with an atomic Al beam, made by an MBE source. The Volume Filling Fraction (VFF) of nanoparticles was varied controllably between 4% and 45%, while the mean diameter of Fe nanoparticles produced by the source was similar to 2 nm. Fe K edge extended x-ray absorption fine structure (EXAFS) experiments show that there is a high degree of alloying between Fe nanoparticles and Al atoms. Magnetism in the embedded Fe nanoparticle samples was investigated using a SQUID magnetometer. Atomic moment of Fe in the Fe/Al nanocomposite films increases slightly when the proportion of Fe nanoparticles is increased, but is still significantly lower than the bulk Fe value. In a more detailed analysis, the magnetisation curves were fitted using the Random Anisotropy Model (RAM) which allowed the exchange field and random anisotropy field to be evaluated. The findings and issues raised by this approach are discussed. (C) 2019 Elsevier B.V. All rights reserved.

The mineralogy of comet 81P/Wild 2 particles, collected in aerogel by the Stardust mission, has been determined using synchrotron Fe-K X-ray absorption spectroscopy with insitu transmission XRD and X-ray fluorescence, plus complementary microRaman analyses. Our investigation focuses on the terminal grains of eight Stardust tracks: C2112,4,170,0,0; C2045,2,176,0,0; C2045,3,177,0,0; C2045,4,178,0,0; C2065,4,187,0,0; C2098,4,188,0,0; C2119,4,189,0,0; and C2119,5,190,0,0. Three terminal grains have been identified as near pure magnetite Fe3O4. The presence of magnetite shows affinities between the Wild 2 mineral assemblage and carbonaceous chondrites, and probably resulted from hydrothermal alteration of the coexisting FeNi and ferromagnesian silicates in the cometary parent body. In order to further explore this hypothesis, powdered material from a CR2 meteorite (NWA 10256) was shot into the aerogel at 6.1kms(-1), using a light-gas gun, and keystones were then prepared in the same way as the Stardust keystones. Using similar analysis techniques to the eight Stardust tracks, a CR2 magnetite terminal grain establishes the likelihood of preserving magnetite during capture in silica aerogel.

Introduction: Terminal grains in Stardust keystones provide the most pristine cometary material for study collected from Comet Wild2. Investigation of these particles has revealed increasing evidence of similarities between the Wild2 constituents and carbonaceous chondrites. Such evidence includes Al-rich, and FeMg chondrule fragments and particles similar to late-forming chondrules in CR chondrites [1,2], as well as Al-rich and Ti-bearing clinopyroxenes with Mg-Al spinel consistent with CAI’s [3,4]. Another feature of the Wild2 particles is the iron oxides identified in Stardust keystones, suggesting further similarities with carbonaceous chondrites [5-7]. Magnetite and magnetitehematite mixtures [6,8] have been found along track walls and magnetite has been found in terminal grains [5,9,10], which are consistent with carbonaceous chondrite matrix material. The magnetite is assumed to be the result of the hydrous alteration of co-existing ferromagnesian minerals, also abundant in the Wild2 grains [10]. In order to identify the closest chondrite analogues for Wild2 we are studying mineralogically characterised CR2 and CV3 powders shot into aerogel, and then prepared as keystones, analogous to the way Wild2 samples were captured by Stardust and subsequently analysed. Methods: Polished sections were made from NWA 4502 (CV3) and NWA 10256 (CR2). Interior parts of each sample, away from the crust, were ground into a powder with grain size 25 200 μm. Half of the powders were fired into aerogel of density gradient 25-55 mg/cm at speeds of 6.1-6.3 kms using the University of Kent light gas gun [11] while the other half were made into polished blocks for further analysis. The sections and blocks were characterised using a Phillips XL30 ESEM with Oxford INCA 350 EDX system at the University of Leicester. Raman analyses were made at the University of Kent [6] and keystones at the University of Berkeley [12]. Results: Image analysis of NWA 4502 showed 38% matrix, 14% CAI’s and 48% chondrules. Pyroxene is En5098Wo0-34Fs0-2 and olivine Fo66-100 within chondrules; with olivine Fo36-50, Fe-Ni-metals, Fe oxide and sulfides present in the matrix. NWA 10256 was found to have 42% matrix including sulfides, metal and Fe oxide. Chondrule pyroxene and olivine are En89-98Wo0-1Fs1-10, Fo91-99, with more fayalitic olivine Fo34-40 present in the matrix. Raman Analyses of the Tracks. Hematite, enstatite and forsterite have been identified in three of the aerogel tracks of the CR2 powdered sample.

We present the results of an investigation into the atomic structure and magnetism of 2 nm diameter Co nanoparticles embedded in an antiferromagnetic Cr matrix. The nanocomposite films used in this study were prepared by co-deposition directly from the gas phase, using a gas aggregation source for the Co nanoparticles and a molecular beam epitaxy (MBE) source for the Cr matrix material. Co K and Cr K edge extended x-ray absorption fine structure (EXAFS) experiments were performed in order to investigate atomic structure in the embedded nanoparticles and matrix respectively, while magnetism was investigated by means of a vibrating sample magnetometer. The atomic structure type of the Co nanoparticles is the same as that of the Cr matrix (bcc) although with a degree of disorder. The net Co moment per atom in the Co/Cr nanocomposite films is significantly reduced from the value for bulk Co, and decreases as the proportion of Co nanoparticles in the film is decreased; for the sample with the most dilute concentration of Co nanoparticles (4.9% by volume), the net Co moment was 0.25 μB/atom. After field cooling to below 30 K all samples showed an exchange bias, which was largest for the most dilute sample. Both the structural and magnetic results point towards a degree of alloying at the nanoparticle/matrix interface, leading to a core/shell structure in the embedded nanoparticles consisting of an antiferromagnetic CoCr alloy shell surrounding a reduced ferromagnetic Co core.

Static and dynamical magnetic properties of Fe nanoparticles (NPs) embedded in non-magnetic (Ag) and antiferromagnetic (Cr) matrices with a volume filling fraction (VFF) of 10% have been investigated. In both Fe@Ag and Fe@Cr nanocomposites, the Fe NPs have a narrow size distribution, with a mean particle diameter around 2nm. In both samples, the saturation magnetization reaches that of Fe bulk bcc, suggesting the absence of alloying with the matrices. The coercivity at 5K is much larger in Fe@Cr than in Fe@Ag as a result of the strong interaction between the Fe NPs and the Cr matrix. Temperature-dependent magnetization and ac-susceptibility measurements point out further evidence of the enhanced interparticle interaction in the Fe@Cr system. While the behaviour of Fe@Ag indicates the presence of weakly interacting magnetic monodomain particles with a wide distribution of blocking temperatures, Fe@Cr behaves like a superspin glass produced by the magnetic interactions between NPs.

The structure of 2nm diameter (340 atoms) Fe nanoparticles embedded in a Cr matrix was determined using X-ray Absorption Fine Structure (EXAFS) and the magnetic properties studied by Superconducting Quantum Interference Device (SQUID) magnetometry. The thin films were produced by the co-deposition of pre-formed gas-phase Fe clusters synthesised by a gas aggregation source with an atomic vapour of Cr produced by an MBE source. The behaviour was studied as a function of Fe nanoparticle volume fraction in the range 5–20% and was compared to previous results on ferromagnetic nanoparticles in antiferromagnetic matrices. EXAFS showed that the atomic structure in the Cr-embedded Fe nanoparticles is the same as the bulk bcc structure. Whereas alloying between the nanoparticles and matrix material has previously been shown to be very pronounced for Co nanoparticles in antiferromagnetic Mn, it was found that any alloying between Fe nanoparticles and Cr matrix material is limited. For dilute samples of Fe nanoparticles in Cr the measured saturation magnetisation (MS) was 1µB/Fe atom, which is significantly less than the bulk MS value of 2.22µB/Fe atom indicating that the surface of Fe nanoparticles is either antiferromagnetic or non-magnetic. An increase in the volume fraction produces an increase in the value of MS and at a volume fraction of 20%, MS exceeds the value of bulk Fe showing that some Cr spins provide a ferromagnetic contribution. After field cooling below 30K, all films show Exchange Bias (EB) and an increase of coercivity, which are both much larger for the most concentrated sample. The Cr spins at the surface of the Fe particles play a key role in determining the overall magnetic behaviour.

Static and dynamical magnetic properties of Fe nanoparticles (NPs) embedded in non-magnetic (Ag) and antiferromagnetic (Cr) matrices with a volume filling fraction (VFF) of 10% have been investigated. In both Fe@Ag and Fe@Cr nanocomposites, the Fe nanoparticles have a narrow size distribution, with a mean particle diameter around 2 nm. In both samples, the saturation magnetization reaches that of Fe bulk bcc, suggesting the absence of alloying with the matrices. The coercivity at 5 K is much larger in Fe@Cr than in Fe@Ag as a result of the strong interaction between the Fe NPs and the Cr matrix. Temperature-dependent magnetization and ac-susceptibility measurements point out further evidence of the enhanced inter-particle interaction in the Fe@Cr system. While the behavior of Fe@Ag indicates the presence of weakly interacting magnetic monodomain particles with a wide distribution of blocking temperatures, Fe@Cr behaves like a superspin glass produced by the magnetic interaction between nanoparticles.

"Magnetic nanoparticles and nanocomposite materials have attracted much interest due to their novel magnetic behaviour, and their potential use in a range of applications. One of the main reasons for their novel magnetism, appreciated for some time, is the high proportion of under-coordinated atoms at the surface of nanoparticles. In the case of magnetic transition metals this leads to a narrowing of the 3d bands that are responsible for magnetism in these materials, leading to size-dependent nanoparticle properties. The atomic structure adopted by nanoparticles is also a key factor in determining their magnetism. Unlike in bulk materials atomic structure in nanoparticles can be changed more readily by, for example, embedding them in suitable matrix materials. Here we describe how a high level of control over crystal structure in nanoparticles can be achieved, using EXAFS to ""fingerprint"" their crystal structure, and show how this in turn leads to a high degree of control over nanoparticle magnetism. We describe a flexible co-deposition process based around a gas aggregation source, which enables a high degree of control over structure in transition metal nanoparticles embedded in various matrices. EXAFS experiments and analysis used to probe atomic structure in embedded Fe and Co nanoparticles are described [1]. Examples presented include the system of Fe nanoparticles embedded in a CuAu alloy matrix where we show that is not only the ability to change the atomic structure of embedded nanoparticles that is important but the ability to fine-tune their structure once changed [2]. In this case, this enables the atomic magnetic Fe moment to be fine-tuned to a value higher than in the bulk Fe structure, in agreement with theory. In some systems alloying at the particle/interface can be significant. We describe how this is the case for Fe nanoparticles in Pd [3], and how such alloying could be useful in forming magnetic nanocomposites with superior properties."

We have used X-ray magnetic circular dichroism and magnetometry to study isolated Fe@Cr core-shell nanoparticles with an Fe core diameter of 2.7 nm (850 atoms) and a Cr shell thickness varying between 1 and 2 monolayers. The addition of Cr shells significantly reduces the spin moment but does not change the orbital moment. At least two Cr atomic layers are required to stabilize a ferromagnetic/antiferromagnetic interface and generate the associated exchange bias and increase in coercivity.

Monte Carlo simulations of the dynamic magnetic behavior of an assembly of ferromagnetic core/antiferromagnetic shell nanoparticles are reported and compared with the experimental results on a system of Co nanoparticles in Mn matrix. Memory effects on low-field zero-field-cooled magnetization curves have been investigated. Our simulations show that the memory effects increase with the concentration and that both the interface exchange coupling and the dipolar interparticle interactions contribute to the observed dynamic behavior. In particular the interface exchange interaction provides an additive source for the frustration of the system resulting in an enhancement of the memory effect. The numerical data reproduce well the experimental results confirming the glassy behavior of the investigated nanoparticle systems.

We have investigated atomic structure and magnetism in Fe nanoparticles with a diameter of 2 nm embedded in a Pd matrix. The samples for these studies were prepared directly from the gas phase by co-deposition, using a gas aggregation source and an MBE-type source for the Fe nanoparticles and Pd matrix respectively. Extended absorption fine structure (EXAFS) measurements indicate that there is an appreciable degree of alloying at the nanoparticle/matrix interface; at dilute nanoparticle concentrations, more than half of the Fe atoms are alloyed with Pd. This leads to a core/shell structure in the embedded nanoparticles, with an FexPd1-x shell surrounding a reduced pure Fe core. Magnetism in the nanocomposite samples was probed by means of magnetometry measurements, which were interpreted in the light of their atomic structure. These point to a magnetized cloud of Pd atoms surrounding the embedded nanoparticles which is significantly larger than around single Fe atoms in Pd. The coercivities in the Fe/Pd nanocomposite samples are larger than in FexPd1-x atomic alloys of corresponding composition, which is consistent with exchange coupling between the magnetically harder and softer regions in the nanocomposite samples.

We have studied the Exchange Bias (EB) effect in nanocomposite films consisting of Fe nanoparticles (mean size ∼1.9nm) embedded in an antiferromagnetic Mn matrix. They were produced by co-deposition through a gas aggregation cluster source and molecular beam epitaxy and have different Fe volume filling fractions (2.2% and 24.8%). The exchange field, higher in the sample with higher Fe concentration (at T=5K, Hex∼460Oe for 24.8% and ∼310Oe for 2.2% ), in both the samples decreases with increasing T, finally disappearing at T∼40K. The EB properties have been studied in conjunction with results on the thermal dependence of the magnetic coercivity, zero-field-cooled and field-cooled magnetization and thermoremanence. The different Fe content strongly affects the magnetothermal properties, featuring superparamagnetic relaxation in the diluted sample and a reentrant ferromagnet-type transition in the concentrated one. Hence, the EB properties of the two samples have been discussed in consideration of such peculiarities of the magnetic behavior and highlighting the role of the Mn matrix.

We report a new method to produce liquid suspensions of nanoparticles by co-deposition with water vapour from the gas-phase in ultra-high vacuum (UHV) conditions. The water is injected from outside the vacuum as a molecular beam onto a substrate maintained at 77 K and forms an ice layer with a UHV vapour pressure. Molecular dynamics simulations confirm that the nanoparticles are soft-landed close to the surface of the growing ice layer. We show that the un-agglomerated size distribution within the liquid is similar to the gas-phase size distribution and demonstrate that the inclusion of surfactants in the injected water prevents agglomeration. The method allows the flexibility and tight size control available with gas-phase production methods to be applied to making nanoparticle suspensions with any desired properties. This is important for practical applications, especially in medicine. We have extended the method to include core–shell nanoparticles, in which there is flexible control over the core size and shell thickness and free choice of the material in either. Here, we report the production of suspensions of Cu, Ag and Au elemental nanoparticles and Fe@Au and Fe@Fe-oxide core–shell nanoparticles with diameters in the range 5–15 nm. We demonstrate the power of the method in practical applications in the case of Fe@Fe-oxide nanoparticles, which have a specific absorption rate of an applied oscillating magnetic field that is significantly higher than available Fe-oxide nanoparticle suspensions and the highest yet reported. These will thus have a very high-performance in the treatment of tumours by magnetic nanoparticle hyperthermia.

We describe the realization of a high moment state in fcc Fe nanoparticles through a controlled change in their atomic structure. Embedding Fe nanoparticles in a Cu(1-x)Au(x) matrix causes their atomic structure to switch from bcc to fcc. Extended x-ray absorption fine structure (EXAFS) measurements show that the structure in both the matrix and the Fe nanoparticles expands as the amount of Au in the matrix is increased, with the data indicating a tetragonal stretch in the Fe nanoparticles. The samples were prepared directly from the gas phase by co-deposition, using a gas aggregation source and MBE-type sources respectively for the nanoparticle and matrix materials. The structure change in the Fe nanoparticles is accompanied by a sharp increase in atomic magnetic moment, ultimately to values of ~2.5 ± 0.3 μ(B)/atom .

Core/shell Fe/Cu and Fe/Au nanoparticles were prepared directly by deposition from the gas phase. A detailed study of the atomic structure in both the cores and shells of the nanoparticles was undertaken by means of extended absorption fine structure (EXAFS) measurements. For Fe/Cu nanoparticles, a Cu shell ∼ 20 monolayers thick appears similar in structure to bulk Cu and is sufficient to cause the structure in the Fe core to switch from body centred cubic (bcc; as in bulk Fe) to face centred cubic. This is not the case for thinner Cu shells, 1-2 monolayers in thickness, in which there is a considerable contraction in nearest-neighbour interatomic distance as the shell structure changes to bcc. In Fe/Au nanoparticles, the crystal structure in the Fe core remains bcc for all Au thicknesses although there is some stretching of the lattice. In thin Au shells ∼ 2 monolayers thick, there is strong contraction in interatomic distances. There does not appear to be significant alloying at the Fe/Au interface.

The structural and magnetic properties of 1.8 nm Co particles dispersed in a Mn matrix by co-depositing pre-formed mass-selected Co clusters with an atomic vapour of Mn onto a common substrate have been studied by using EXAFS (extended x-ray absorption fine structure), XMCD (x-ray magnetic circular dichroism), magnetometry, and theoretical modelling. At low Co volume fraction (5%) Co@Mn shows a significant degree of alloying and the well-defined particles originally deposited become centres of high Co concentration CoMn alloy that evolves from pure Co at the nanoparticle centre to the pure Mn matrix within a few nm. Each inhomogeneity is a core-shell particle with a Co-rich ferromagnetic core in contact with a Co-depleted antiferromagnetic shell. The XMCD reveals that the Co moment localized on the Co atoms within the Co-rich cores is much smaller than the ferromagnetic moment of the Co nanoparticles deposited at the same volume fraction in Ag. Electronic structure calculations indicate that the small magnitude of the core Co moment can be understood only if significant alloying occurs. Monte Carlo modelling replicates the exchange bias (EB) behaviour observed at low temperature from magnetometry measurements. We ascribe EB to the interaction between the ferromagnetic Co-rich cores and the antiferromagnetic Mn-rich shells.

We have studied the magnetic behaviour of polycrystalline dysprosium films grown in their pure state and containing Fe impurity. The films were grown by MBE in ultra-high vacuum and Fe impurity was introduced either as Fe atoms from a conventional MBE source or as 1.8nm diameter Fe nanoparticles from a gas aggregation source. We show that with a suitable magnetothermal history it is possible to produce a large thermal hysteresis up to room temperature in all samples. In the Dy ferromagnetic state both types of Fe impurity cause a reduction in the observed magnetisation but the reduction of average moment observed in the case of the Fe nanoparticles is much greater than that for atoms for a similar quantity of Fe. Despite the low solubility of Fe in Dy EXAFS data clearly indicates alloying in the case of embedded Fe nanoparticles. We attribute the low moment in the Dy films containing nanoparticles to alloying within the particles producing a significant proportion of high-Fe-concentration Dy–Fe alloy.