Superparamagnetic iron oxide nanoparticles (SPIONs) are nanoparticles used in a lot of applications such as batteries, and biomedical, horizontal ellipsis To obtain these nanoparticles, several techniques exist such as coprecipitation, thermal decomposition, sol-gel process but they have some advantages (synthesis in a water media, high crystallinity, high monodispersity) and disadvantages (using an organic solvent, large distribution of size, poor crystallinity). The goal of this work is to synthesize SPIONs for biomedical applications (for example as a contrast agent for the MRI): SPIONs should be stable in an aqueous media, monodisperse, and have good crystallinity and magnetic properties. To achieve this result, a microwave process is carried out. However, any study describes the microwave parameter on the synthesis of the nanoparticles. This work offers to determine the best conditions of the microwave to obtain ideal SPIONs for MRI. For this, an experimental design is carried out to determine these parameters thanks to different techniques of characterization (Transmission Electronic Microscopy, Dynamic Light Scattering, X-ray diffraction, Thermogravimetric Analysis, magnetic characterizations). With the different results of these characterizations, the best conditions of the microwave are determined, and a simulation of all experiments is realized with a surface response. The goal is to determine the best microwave parameters of iron oxide nanoparticles synthesis for a better control of properties. An experimental design is performed to reduce the number of experiments from 1024 to 16 and a statistical approach is carried out to check the reproducibility and the repeatability. A simulation of these 1024 experiments is compared with random experiments. image

We have investigated the laser induced ultrafast dynamics of Gd 4f spins at the surface of CoxGd100-x alloys by means of surface-sensitive and time-resolved dichroic resonant Auger spectroscopy. We have observed that the laser induced quenching of Gd 4f magnetic order at the surface of the CoxGd100-x alloys occur on a much longer time scale than that previously reported in bulk sensitive time-resolved experiments. In parallel, we have characterized the static structural and magnetic properties at the surface and in the bulk of these alloys by combining Physical Property Measurement System (PPMS) magnetometry with X-ray Magnetic Circular Dichroism in absorption spectroscopy (XMCD) and X-Ray Photoelectron spectroscopy (XPS). The PPMS and XMCD measurements give information regarding the composition in the bulk of the alloys. The XPS measurements show non-homogeneous composition at the surface of the alloys with a strongly increased Gd content within the first layers compared to the nominal bulk values. Such larger Gd concentration results in a reduced indirect Gd 4f spin-lattice coupling. It explains the slower Gd 4f demagnetization we have observed in our surface-sensitive and time-resolved measurements compared to that previously reported by bulk-sensitive measurements.

The study examines the impact of microstructure and polymethyl methacrylate (PMMA) grafting on the degradability of Zn-Mg alloys. The mechanical properties of a Zn alloy containing 0.68 wt% Mg and extruded at 200 °C are enhanced for degradable load-bearing applications, addressing a crucial need in the field. The material exhibits a bimodal grain size distribution that is random texture, consisting of secondary phases, grains, and sub-grains. With an elongation to failure of 16 %, the yield and ultimate tensile strengths are 325.9 and 414.5 MPa, respectively, and the compressive yield strength is 450.5 MPa. The "grafting-from" method was used to coat a few micrometers thick of PMMA on both bulk and scaffold Zn alloys to mitigate the corrosion rate. The last one is a porous structure, with a porosity of 65.8 %, considered as in the first approach of an orthopedic implant. After being immersed for 720 h, the PMMA-grafted bulk alloy's corrosion rate decreased from 0.43 to 0.25 mm/y. Similarly, the scaffold alloy's corrosion rate reduced from 1.24 to 0.49 mm/y. These results indicate that the method employed could be used for future orthopedic applications.

Surface-initiated atom transfer radical polymerization created hybrid Ti sheet systems grafted with the poly(methyl methacrylate) (PMMA) family for biomedical application. This metal/polymer hybrid material exhibits strong bonding at the interface. While the first research concentrated on PMMA on millimeter-sized Ti samples, the technique was expanded to large-sized (100 × 200mm²) using methyl methacrylate (MMA) and also a blend of MMA and butyl methacrylate instead of the MMA during the polymerization step.

Recent progress in the research of n -type materials for organic thermoelectrics has drawn the attention to the metal coordination polymer poly(nickel-ethylenetetrathiolate) (poly(Ni-ett)). These polymers have excellent stability in air because their backbone structure is composed of air -stable ligands and exhibit good electronic properties when pressed into pellets or grown into crystals. However, due to their brittle nature and limited solubility, they are often blended with solution processable but electrically insulating polymers to produce composite films. Herein, we demonstrate the possibility of exploiting the 3D structuring ability of a polymer scaffolding matrix (based on polyvinylidene fluoride (PVDF)) to fabricate porous bulk structures. Porosity is introduced to reduce the lattice contribution to the thermal conductivity and used as a lever to increase the thermoelectric efficiency of the composite aerogel poly(Ni-ett): PVDF. For practical applications, these materials have great potential for vertical thermoelectric generators, as the low thermal conductivity and millimetre -thick samples would allow a thermal gradient to be maintained across it (without actively cooling one side, as in the case of certain thin-film technologies). In this manuscript, we present an original approach for the fabrication of novel n -type polymer aerogels resulting in lightweight and bulk size thermoelectric materials. The composite aerogels exhibit a low thermal conductivity of 52 mW m-1 K-1, and their figure of merit zT is comparable to the dense neat pellet with reasonable stability over six months.

The thorough characterization of polymer chains grafted through a “grafting-from” process onto substrates based on the determination of number (Mn) and weight (Mw) average molar masses, as well as dispersity (Ɖ), is quite challenging. It requires the cleavage of grafted chains selectively at the polymer–substrate bond without polymer degradation to allow their analysis in solution with steric exclusion chromatography, in particular. The study herein describes a technique for the selective cleavage of PMMA grafted onto titanium substrate (Ti-PMMA) using an anchoring molecule that combines an atom transfer radical polymerization (ATRP) initiator and a UV-cleavable moiety. This technique allows the demonstration of the efficiency of the ATRP of PMMA on titanium substrates and verification that the chains were grown homogeneously.

We have studied the laser induced ultrafast quenching of Gd 4f magnetic order in ferrimagnetic Co 100-x Gd x alloys to highlight the role of the Co 3d–Gd 5d inter-atomic exchange coupling. We have taken advantage of the ultrashort soft X-ray pulses deliver by the femtoslicing beamline at the BESSY II synchrotron radiation source at the Helmholtz–Zentrum Berlin to perform element- and time-resolved X-ray Magnetic Circular Dichroism spectroscopy. Our results show that the laser induced quenching of Gd 4f magnetic order occurs on very different time-scales for the Co 72 Gd 28 , the Co 77 Gd 23 and the Co 79 Gd 21 alloys. Most of the magnetic moment losses occur within the first picosecond (ps) while the electron distribution is strongly out of equilibrium. After the equilibration of the electrons and lattice temperatures ( t > 1 ps), the magnetic losses occur on slower rates that depend on the alloy composition: increasing the Co composition speeds up the demagnetization of Gd 4f sublattice. The strength of the Co 3d–Gd 5d inter-atomic exchange coupling which depends on composition, determines the efficiency of the angular momentum flow from the Gd 4f spin towards the lattice. Our results are in qualitative agreements with the predictions of the microscopic three temperatures model for ferrimagnetic alloys.

Anthropogenic activities have led to a significant accumulation of Pb in the environment, posing a threat to ecosystems. Iron oxides that display magnetic properties are ubiquitous in the environment and Pb partitioning onto these minerals is considered one of the most critical geochemical processes controlling its environmental fate. In anoxic environments, iron oxides undergo redox cycling due to biotic and abiotic routes, resulting in their transformation/dissolution and evolution of their magnetic characteristics. However, there is still a lack of knowledge on the impact of Pb on the dynamic of iron oxides bioreduction. Furthermore, there is little information available regarding the nature of biogenic minerals and their magnetic signatures. Here we incubated Pb-bearing ferrihydrites (Fh_Pb) with various Pb/(Fe + Pb) molar ratios (i.e., 0, 2 and 5%) with the iron-reducing bacterium Shewanella oneidensis MR-1, for 21 days. XRD analyses of the initial Fh_Pb displayed characteristic features of Fh and a decrease of magnetization in the presence of Pb. During the bio-reduction process, Pb doping led to a drop in the rate and extent of reduction. At the end of the incubation period, the analysis of the aqueous solutions revealed a minor proportion of Pb in solution, indicating that a significant proportion of the Pb is sorbed onto the biogenic minerals. Magnetite (95%) and siderite (5%) formed during the bioreduction of Fh, while magnetite (-80%) and goethite (-20%) precipitated in the presence of Pb as revealed by transmission Mo??ssbauer spectroscopy. Furthermore, the size of the magnetite particles decreased from about 11 nm in absence of Pb to 6 nm with 2% of Pb-bearing, while 5% of Pb led to particles too small to be quantified with our TEM measurements. The combined effect of the decrease in particle size of magnetite, substitution of Pb and the precipitation of goethite in the Pb-dopped assay led to a significant decrease of magnetization at room temperature. Overall, this study highlights the effect of Pb on iron oxides bio-reduction and transformation processes and the sensitivity of magnetism to serve as a monitoring method.

Recent theory and experiments have showcased how to harness quantum mechanics to assemble heat/information engines with efficiencies that surpass the classical Carnot limit. So far, this has required atomic engines that are driven by cumbersome external electromagnetic sources. Here, using molecular spintronics, an implementation that is both electronic and autonomous is proposed. The spintronic quantum engine heuristically deploys several known quantum assets by having a chain of spin qubits formed by the paramagnetic Co center of phthalocyanine (Pc) molecules electronically interact with electron-spin-selecting Fe/C60 interfaces. Density functional calculations reveal that transport fluctuations across the interface can stabilize spin coherence on the Co paramagnetic centers, which host spin flip processes. Across vertical molecular nanodevices, enduring dc current generation, output power above room temperature, two quantum thermodynamical signatures of the engine's processes, and a record 89% spin polarization of current across the Fe/C60 interface are measured. It is crucially this electron spin selection that forces, through demonic feedback and control, charge current to flow against the built-in potential barrier. Further research into spintronic quantum engines, insight into the quantum information processes within spintronic technologies, and retooling the spintronic-based information technology chain, can help accelerate the transition to clean energy.

We report on an element- and time-resolved investigation of femtosecond laser induced ultrafast dynamics of 3d and 4f spins in a ferrimagnetic Co80Dy20 alloy as a function of temperature. We observe an increase of the Co3d characteristic demagnetization time and a decrease of the Dy4f demagnetization time when the temperature is approaching the Curie temperature. It suggests that the critical slowing down regime, which affects the laser induced ultrafast dynamics in pure 3d transition metals and 4f rare-earth ferromagnetic layers, vanishes for the Dy sublattice in the CoDy alloy, in line with the theoretical predictions of the Landau-Lifshitz-Bloch model.

Antimony (Sb) is a naturally occurring element; it is enriched in the environment by anthropogenic activities. Like other metalloid species, Sb partitions to mineral phases such as oxyhydroxides. In reducing environments, Fe(III) may serve as a terminal electron acceptor during dissimilatory iron reduction leading to its transformation. Relatively little is known concerning the effect of Sb(V) on the precipitation of biogenic minerals in relation to microbiologically mediated redox reactions. To further our understanding, Sb-bearing ferrihydrites (0.5 g) with variable Sb/(Fe + Sb) molar ratios of 0.04, 0.06 and 0.1, were incubated in the presence of Shewanella oneindensis MR-1 (1 x 10(8) cell mL(-1)) under N-2 atmosphere. Additionally, we synthesized abiotic GR1(CO32-) in the presence of Sb(V) to examine the effect of Sb(V) on this mineral formation and stabilization. A combination of wet chemistry and solid analysis techniques (XRD, Mossbauer and Raman spectroscopies) was used to characterize the reactions. The Sb loading affected the rate and the extent of bio-reduction compared with pure ferrihydrite. Only a minor fraction of the total Sb, less than 0.5%, was released into the solution by the end of the incubation period, suggesting that the metalloid partitioned mainly in a newly formed phase. Furthermore, XPS analyses showed the presence of Sb(V) and Sb(III) species on the biogenic minerals. Magnetite was the main biogenic precipitate (91%) in the absence of Sb(V). Increasing of the molar ratios [Sb/(Fe + Sb)] to 0.1 resulted mainly in the precipitation of carbonated green (47%) rust and goethite (37%). Abiotic green rust synthesis carried out in the presence of Sb(V) indicated the latter's stabilizing effect on the green rust structure, as for phosphate species. Thus, it is likely that Sb(V) preserve biogenic green rust, hindering its transformation to more thermodynamically stable phases. (C) 2021 Published by Elsevier Ltd.

The evolution of chiral spin structures is studied in ferrimagnet Ta/Ir/Fe/GdFeCo/Pt multilayers as a function of temperature using scanning electron microscopy with polarization analysis (SEMPA). The GdFeCo ferrimagnet exhibits pure right-hand Néel-type domain wall (DW) spin textures over a large temperature range. This indicates the presence of a negative Dzyaloshinskii-Moriya interaction (DMI) that can originate from both the top Fe/Pt and the Co/Pt interfaces. From measurements of the DW width, as well as complementary magnetic characterization, the exchange stiffness as a function of temperature is ascertained. The exchange stiffness is surprisingly mostly constant, which is explained by theoretical predictions. Beyond single skyrmions, we find by direct imaging a pure Néel-type skyrmionium, which due to the absence of a skyrmion Hall angle is a promising topological spin structure to enable high impact potential applications in the next generation of spintronic devices.

The generation of ultrashort hot-electron pulses in metallic heterostructures offers attractive perspectives for the ultrafast spin manipulation on the picosecond time scale. In such approach, the hot-electron pulses are produced by exciting a non-magnetic capping layer with femtosecond infrared laser pulses. These hot-electron pulses propagate towards a buried magnetic layer to trigger ultrafast demagnetization. Lately, it was shown that the demagnetization onset and characteristic demagnetization times are both affected by the transport regime (ballistic or diffusive) of the photo-excited hot-electrons. In this work, we show that the hot-electron pulses produced by photo-exciting a Al(3)/Ta(3)/Cu(60) capping layer undergo a temporal stretching and delays when they go across a [Co(0.1)/Ni(0.6)](x5) multilayer. These information were extracted from a study of hot-electron induced demagnetization in CoDy alloys by means of Time-Resolved X-Ray Magnetic Circular Dichroism.

The investigation of ultrafast dynamics, taking place on the few to sub-picosecond time scale, is today a very active research area pursued in a variety of scientific domains. With the recent advent of X-ray free-electron lasers (XFELs), providing very intense X-ray pulses of duration as short as a few femtoseconds, this research field has gained further momentum. As a consequence, the demand for access strongly exceeds the capacity of the very few XFEL facilities existing worldwide. This situation motivates the development of alternative sub-picosecond pulsed X-ray sources among which femtoslicing facilities at synchrotron radiation storage rings are standing out due to their tunability over an extended photon energy range and their high stability. Following the success of the femtoslicing installations at ALS, BESSY-II, SLS and UVSOR, SOLEIL decided to implement a femtoslicing facility. Several challenges were faced, including operation at the highest electron beam energy ever, and achievement of slice separation exclusively with the natural dispersion function of the storage ring. SOLEIL's setup also enables, for the first time, delivering sub-picosecond pulses simultaneously to several beamlines. This last feature enlarges the experimental capabilities of the facility, which covers the soft and hard X-ray photon energy range. In this paper, the commissioning of this original femtoslicing facility is reported. Furthermore, it is shown that the slicing-induced THz signal can be used to derive a quantitative estimate for the degree of energy exchange between the femtosecond infrared laser pulse and the circulating electron bunch.

The SOLEIL synchrotron radiation source is regularly operated in special filling modes dedicated to pump-probe experiments. Among others, the low-α mode operation is characterized by shorter pulse duration and represents the natural bridge between 50 ps synchrotron pulses and femtosecond experiments. Here, the capabilities in low-α mode of the experimental set-ups developed at the TEMPO beamline to perform pump-probe experiments with soft X-rays based on photoelectron or photon detection are presented. A 282 kHz repetition-rate femtosecond laser is synchronized with the synchrotron radiation time structure to induce fast electronic and/or magnetic excitations. Detection is performed using a two-dimensional space resolution plus time resolution detector based on microchannel plates equipped with a delay line. Results of time-resolved photoelectron spectroscopy, circular dichroism and magnetic scattering experiments are reported, and their respective advantages and limitations in the framework of high-time-resolution pump-probe experiments compared and discussed.

The mechanism underlying femtosecond laser-pulse-induced ultrafast magnetization dynamics remains elusive, despite two decades of intense research on this phenomenon. Most experiments focused so far on characterizing magnetization and charge carrier dynamics, while the first direct measurements of structural dynamics during ultrafast demagnetization were reported only very recently. We here present our investigation of the infrared laser-pulse-induced ultrafast demagnetization process in a thin Ni film, which characterizes simultaneously magnetization and structural dynamics. This is achieved by employing femtosecond time-resolved x-ray resonant magnetic reflectivity (tr-XRMR) as the probe technique. The experimental results reveal unambiguously that the subpicosecond magnetization quenching is accompanied by strong changes in nonmagnetic x-ray reflectivity. These changes vary with reflection angle, and changes up to 30% have been observed. By modeling the x-ray reflectivity of the investigated thin film, we can reproduce these changes by a variation of the apparent Ni layer thickness of up to 1%. Extending these simulations to larger incidence angles, we show that tr-XRMR can be employed to discriminate experimentally between currently discussed models describing the ultrafast demagnetization phenomenon.

We have investigated ultrafast quenching of the Tb 4f magnetic order in Co74Tb26 alloys, induced by femtosecond hot-electron pulses. The hot-electron pulses were produced in specific nonmagnetic capping layers by infrared femtosecond laser pulses. Our experimental results show that subpicosecond dynamics of Tb 4f magnetic moments can be induced by nonthermal and thermal hot-electron. We further demonstrate that the demagnetization efficiencies of nonthermal and thermal hot-electron are similar. However, the characteristic demagnetization times show values of 0.35 ps for nonthermal hot-electron excitations and 1.2 ps for thermal hot-electron excitations. We explain this temporal elongation by the propagation time of thermal hot-electron through the 15-nm-thick CoTb film.

Femtosecond laser induced ultrafast magnetization dynamics have been studied in multisublattice CoxDy1-x alloys. By performing element and time-resolved X-ray spectroscopy, we distinguish the ultrafast quenching of Co3d and Dy4f magnetic order when the initial temperatures are below (T=150K) or above (T=270K) the temperature of magnetic compensation (Tcomp). In accordance with former element-resolved investigations and theoretical calculations, we observe different dynamics for Co3d and Dy4f spins. In addition we observe that, for a given laser fluence, the demagnetization amplitudes and demagnetization times are not affected by the existence of a temperature of magnetic compensation. However, our experiment reveals a twofold increase of the ultrafast demagnetization rates for the Dy sublattice at low temperature. In parallel, we measure a constant demagnetization rate of the Co3d sublattice above and below Tcomp. This intriguing difference between the Dy4f and Co3d sublattices calls for further theoretical and experimental investigations.