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Synthetic antiferromagnets with perpendicular magnetic anisotropy (PMA-SAFs) have gained growing attention for both conventional and next-generation spin-based technologies. While the progress of PMA-SAF spintronic devices on rigid substrates has been remarkable, only few examples of flexible thin-film heterostructures are reported in the literature, all containing platinum group metals (PGMs). Systems based on Co/Ni may offer additional advantages with respect to devices containing PGMs, i.e., low damping and high spin polarization. Moreover, limiting the use of PGMs may relieve the demand for critical raw materials and reduce the environmental impact of related technologies, thus contributing to the transition toward a more sustainable future. Here, we discuss for the first time the realization of Co/Ni-based PMA-SAFs on polymer tapes and exploit it to obtain flexible giant magneto-resistive spin valves (GMR-SVs) with perpendicular magnetic anisotropy. Several combinations of buffer and capping layers (i.e., Pt, Pd, and Cu/Ta) are also investigated. High-quality flexible SAFs with a fully compensated antiferromagnetic region and SVs with a sizable GMR ratio (up to 4.4%), in line with the values reported in the literature for similar systems on rigid substrates, were obtained in all cases. However, we demonstrate that PGMs allows achieving the best results when used as a buffer layer, while Cu is the best choice as a capping layer to optimize the properties of the stacks. We justify the role of buffer and capping layers in terms of different interdiffusion mechanisms occurring at the interface between the metallic layers. These results, along with the high robustness of the samples' properties against bending (up to 180°), indicate that complex and bendable Co/Ni-based heterostructures with reduced content of PGMs can be obtained on flexible tapes, allowing for the development of novel flexible and sustainable spintronic devices for applications in many fields including wearable electronics, soft robotics, and biomedicine.

Silver nanoparticles are usually prepared by the reduction of silver cations through chemical and non-sustainable procedures that involve the use of reducing chemical agents. Therefore, many efforts have been made in the search for sustainable alternative methods. Among them, an ultrasound-assisted procedure could be a suitable and sustainable method to afford well-dispersed and nanometric silver particles. This paper describes a sustainable, ultrasound-assisted method using citrate as a reducing agent to prepare silver@hydroxyapatite functionalized calcium carbonate composites. For comparison, an ultrasound-assisted reduction was performed in the presence of NaBH4. The composites obtained in the presence of these two different reducing agents were compared in terms of nanoparticle nature, antimicrobial activity, and cytotoxic activity. The nanoparticle nature was investigated by several techniques, including X-ray powder diffraction, field-emission scanning electron microscopy, transmission electron microscopy, UV–Vis spectroscopic measurements, and X-ray photoemission spectroscopy. Nanoparticles with a predominance of Ag or Ag3PO4 were obtained according to the type of reducing agent used. All composites were tested for antimicrobial and antibiofilm activities against Gram-positive and Gram-negative (Staphylococcus aureus and Pseudomonas aeruginosa, respectively) bacteria and for cytotoxicity towards human skin keratinocytes and human fibroblasts. The nature of the nanoparticles, Ag or Ag3PO4, and their predominance seemed to affect the in vitro silver release and the antimicrobial and antibiofilm activities. The composites obtained by the citrate-assisted reduction gave rise to the best results.

Titanium and its alloys are widely employed in commercial dental devices. Because the surface morphology and chemical composition of Ti-based dental implants play a relevant role in osseointegration, three different commercial threaded implants have been investigated by scanning electron microscopy and X-ray photoelectron spectroscopy (XPS). The Implants A and C were made of pure Ti whereas the Implant B was made of Ti6Al4V alloy. Obtained results evidenced the common features and differences due to specific process parameters used in the treatments of mordanting and sandblasting for surface roughening. Implant A exhibits a uniform surface covered by very small dimples of about 1–2 μm. The surface of Implant B is not homogeneous: The thread tops present an irregular morphology (dimples size >10 μm) while finer dimples (about 1 μm) are observed along the thread flanks and valleys. Implant C shows an irregular morphology with dimples of different sizes and shapes distributed on thread tops, flanks, and valleys. XPS analyses revealed the presence of metal oxides: TiO2 in all the implants; Al2O3 and V2O5 only in the implant B. Moreover, these results demonstrated that Mg2SiO4 is present on the surface of Implant A, probably due to a specific preparation process. Obtained results have been discussed on the basis of the factors promoting the osseointegration.

Thin films of barium fluorides with different thicknesses were deposited on GaAs substrate by electron beam evaporation. The aim of the work was to identify the best growth conditions for the production of coatings with a low work function suitable for the anode of hybrid thermionic-photovoltaic (TIPV) devices. The chemical composition and work function ? of the films with different thicknesses were investigated by X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS). The lowest value of ? = 2.1 eV was obtained for the film with a thickness of ~2 nm. In the valence band spectra of the films at low kinetic energy, near the cutoff, a characteristic peak of negative electron affinity was present. This effect contributed to a further reduction of the film's work function.

The outstanding mechanical strength of as-deposited DC-electrodeposited nanocrystalline (nc) Ni-Fe alloys has been the subject of numerous researches in view of their scientific and practical interest. However, recent studies have reported a dramatic drop in ductility upon annealing above 350 degrees C, associated with a concomitant abnormal rapid grain growth. The inherent cause has been ascribed to the presence of a detrimental product or by product in the bath, which affects either the microstructure or causes defects in the concentration and/or distribution of the as-deposited films. The present work has been inspired by the observed abnormal behaviour of annealed electrodeposited nc Ni-Fe alloy, which has here been addressed by considering the relationship between the composition of the bath (iron-chloride, nickel-sulphate solution, saccharin and ascorbic acid) and deposition defects (e.g. grain boundary pores) in the case of an nc Ni-Fe (Fe 48 wt%) alloy. The current investigations have included X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) in both as-deposited and post-annealed conditions (300 degrees C-400 degrees C). XPS depth profiling with Ar ion sputtering showed a significant amount of C and O impurities entrapped in the foils during deposition. As such impurities are often overlooked in common analytical techniques, new scenarios may need to be rationalised to explain the observed drop in tensile ductility of the as-deposited Ni-Fe alloys.

The main purpose of the present work is to analyze a series of Ag nanoparticles (NPs) with different size or ligand functionalization by using X-ray photoelectron spectroscopy (XPS) and to identify the differences in the band-shape and energy peak position of photoemission spectra due to the particle dimension. A transmission electron microscopy characterization was performed, to verify the consistency of the results. Three types of samples were prepared starting from AgNO3 water solution and adding different capping agents. In the first two cases, the formation of NPs was promoted by the reduction of silver ions Ag+1 to metallic Ag-0 through the addition of sodium borohydride, whereas in the last case, it was triggered by the exposure to UV light. Depending on the size of the NPs, a different physical behavior can be recognized. NPs with diameter of about 5 nm are characterized by the phenomenon of localized surface plasmon resonance (LSPR). The other type of samples having a diameter of about 1.5 nm presents discrete energy levels instead of electronic bands, and in this case, a typical fluorescence phenomenon can be observed. In the latter case, we can refer to such systems as nanoclusters. The XPS analyses were focused on the Ag 3D spectra looking for the possible shifts of the Ag doublet as a function of the particles size. The ultraviolet photoelectron spectroscopy with He II source was used for the investigation of possible changes in the valence band.

Silver@Hydroxyapatite functionalized calcium carbonate composites have been prepared through different sustainable methods, without involving the use of organic solvents and additional reagents. The composites were characterized by X-ray powder diffraction, field emission scanning electron microscopy, transmission electron microscopy, spectrophotometric measurements and X-ray photoemission spectroscopy. From the characterization techniques, the obtained nanoparticles resulted constituted essentially by Ag3PO4 nanostructures, whose size varied from 70 to 100 nm and were uniformly distributed on the calcium carbonate surface. Upon VIS irradiation, the formation of plasmonic nanostructures with a more defined dimensional distribution and reduced size could be obtained, as a prove of a partial silver reduction. All composites exhibited good antimicrobial and antibiofilm activities against Staphylococcus aureus and Pseudomonas aeruginosa whereas they showed low cytotoxicity effects towards human skin keratinocytes and human fibroblasts. These results enable these composites to be promising candidates for biomedical and pharmaceutical applications.

The optoelectronic features of 3-hydroxyflavone (3HF) self-assembled on the surface of an n-type semiconducting metal oxide (TiO2) and an insulator (Al2O3) are herein investigated. 3HF molecules use the coordinatively unsaturated metal ions present on the oxide surface to form metal complexes, which exhibit different behaviors upon light irradiation, depending on the nature of the metal ion. Specifically, we show that the photoluminescence of the surface species can be modulated according to the chemical properties of the complex (i.e. the binding metal ion), resulting in solid-state emitters in a high quantum yield (about 15%). Furthermore, photoinduced charge injection can be promoted or inhibited, providing a multifunctional hybrid system. Validerad;2023;Nivå 2;2023-02-10 (joosat);Licens fulltext: CC BY License

Fluoride excess in water represents an environmental issue and a risk for human health since it can cause several diseases, such as fluorosis, osteoporosis, and damage of the nervous system. Layered double hydroxides (LDHs) can be exploited to remove this contaminant from water by taking advantage of their high ion-exchange capability. LDHs are generally mixed with polluted water in the form of powders, which then cause the problem of uneasy separation of the contaminated LDH sludge from the purified liquid. In this work, Zn–Al LDH films were directly grown in situ on aluminum foams that acted both as the reactant and substrate. This method enabled the removal of fluoride ions by simple immersion, with ensuing withdrawal of the foam from the de-contaminated water. Different LDH synthesis methods and aluminum foam types were investigated to improve the adsorption process. The contact time, initial fluoride concentration, adsorbent dosage, and pH were studied as the parameters that affect the fluoride adsorption capacity and efficiency. The highest absorption efficiency of approximately 70% was obtained by using two separate growth methods after four hours, and it effectively reduced the fluoride concentration from 3 mg/L to 1.1 mg/L, which is below the threshold value set by WHO for drinking water.

Surfaces of commercial molybdenum (Mo) plates have been textured by fs-laser treatments with the aim to form low-cost and efficient solar absorbers and substrates for thermionic cathodes in Concentrated Solar Power conversion devices. Morphological (SEM and AFM), optical (spectrophotometry), and structural (Raman spectroscopy) properties of the samples treated at different laser fluences (from 1.8 to 14 J/cm2) have been characterized after the laser treatments and also following long thermal annealing for simulating the operating conditions of thermionic converters. A significant improvement of the solar absorptance and selectivity, with a maximum value of about four times higher than the pristine sample at a temperature of 800 K, has been detected for sample surfaces treated at intermediate fluences. The effects observed have been related to the light trapping capability of the laser-induced nanotexturing, whereas a low selectivity, together with a high absorptance, could be revealed when the highest laser fluence was employed due to a significant presence of oxide species. The ageing process confirms the performance improvement shown when treated samples are used as solar absorbers, even though, due to chemical modification occurring at the surface, a decrease of the solar absorptance takes place. Interestingly, the sample showing the highest quantity of oxides preserves more efficiently the laser texturing. The observation of this behaviour allows to extend the applicability of the laser treatments since, by further nanostructuring of the Mo oxides, it could be beneficial also for sensing applications.

Carbon quantum dots (CQD) were prepared from three different precursors and by three bottom-up synthesis methods: classical pyrolysis of citric acid (CAP), microwave irradiation of glucose (GM), and hydrothermal treatment of glucosamine hydrochloride (GAH). CQD were further functionalized using various nitrogen-containing compounds: 6-aminohexanoic acid, 1,6-diaminohexane, N-octylamine, dimethylamine, and tryptophan. Special attention was dedicated to investigate how the combination of synthetic method and starting material affected the nature and properties of CQD. The analysis indicated that CAP were good candidates for covalent post-functionalization, GM allowed an easy passivation, and GAH permitted the direct introduction of nitrogen into the core. The size distribution showed a core–shell structure for CQD functionalized with an aminoacid by microwave irradiation, whereas the thermal decomposition evidenced the degradation of functionalizing molecules and the presence of pyridinic and pyrrolic nitrogen after hydrothermal synthesis. Photoluminescence spectra revealed important differences between the synthesis techniques, related to the occurrence of surface states, and the highest fluorescence quantum yield for hydrothermally prepared CQD. These approaches led to CQD with properties that can be exploited in many fields from energy conversion to sensing.

The fracture surfaces of a 10.5 wt.% Cr martensitic stainless steel broken in Charpy tests have been investigated through X-ray photoelectron spectroscopy (XPS). The specimens have been examined in two different conditions: as-quenched and heat treated for 10 h at 700 &deg, C. The trends of Fe/Cr ratio vs. test temperature are similar to the sigmoidal curves of absorbed energy and, after both ductile and quasi-cleavage brittle fractures, such ratio is always significantly lower than the nominal value of the steel chemical composition. Cr segregation does not occur on a macroscopic scale but takes place in microscopic zones which represent weaker spots in the steel matrix and a preferred path for moving cracks. Small area (diameter 300 &micro, m) XPS measurements evidenced a higher density of such microscopic zones in the inner part of probes, this is explained by the different diffusion length of Cr atoms in the external and inner parts during quenching from austenitic field which has been calculated through FEM simulations. No significant differences of Cr concentration were observed in fracture surfaces of probes with and without heat treatment. The results highlight how Cr segregation plays a role not only in the intergranular mode of fracture but also in the quasi-cleavage and ductile ones.

Metal nanoparticles have attracted more and more attention in the last years due to their unique chemical and physical properties which are very different from the metal bulk material. In particular, when the size of nanoparticles decreases below two nm, nanoparticles can be described as nanoclusters (NCs), and they present peculiar optical properties. The excited electrons in addition to specific absorption bands show also a bright luminescence related to the quantum size effect which produce discrete energy levels. Optical properties (absorption and fluorescence) of these NCs are widely used in many different applications in science and engineering, such as chemical sensors, fluorescent probes for bio imaging or in environmental issues. In the present study, we report on the synthesis of silver nanoclusters (AgNCs) in aqueous phase using silver nitrate as precursor salt and L-Glutathione (GSH) as stabilizer. AgNCs were characterized using absorption and fluorescence spectroscopy, and transmission electron microscopy (TEM). The strong absorption and luminescence shown by these NCs are very promising for a possible exploitation both as label for bioimaging and for optical sensors for heavy metal ions.

We investigated the adsorption of heavy metal ions on a nanostructured coating of zinc-aluminum layered double hydroxides (Zn-Al LDHs) grown on aluminum foam by one-step hydrothermal process. This approach aimed to increase the interactive surface and provide a more practical medium for removal of toxic heavy metals from aqueous media. The foam coated with LDH was characterized by using scanning electron microscopy and X-ray diffraction. After immersion in a copper-rich water solution, X-ray photoelectron spectroscopy demonstrated the occurrence of adsorbed copper on the LDH-coated foam with two oxidation states: particles of metallic copper Cu(0)with oxidized surface Cu+1. X-ray diffraction showed the presence of Cu(+2)in the LDH structure.

Cr martensitic steels are promising materials for structural applications in future nuclear fusion reactors. Because the embrittlement after tempering treatments can be a serious problem, the fracture mode of a steel with 10.5 wt% of Cr treated at 700 degrees C for 18 h has been investigated through Charpy tests in the temperature range from -100 degrees C to +150 degrees C. X-ray photoelectron spectroscopy (XPS) analyses carried out on the fracture surfaces evidenced the segregation of Cr in both ductile and brittle (quasicleavage) fields. The unexpected result indicates that Cr segregation weakens the atomic bonds; thus, the fracture path in both the cases corresponds to the zones with higher Cr content.

A precise surface decoration technique, ion implantation, was examined for tuning the p-type gas sensing properties of CuO nanowires. To understand the effects of ion size, ion beam energy and ion beam fluence, heavy Fe and light N ions were implanted with two different ion beam energies (60, 100 keV) and fluences (1 × 1013, 2.5 × 1016 ions/cm2). The morphological changes after ion bombardments have been tracked by a scanning electron microscope (SEM), revealing massive destruction of the nanowires on Fe ion-implanted samples with high energy and fluence values. Transmission electron microscopy (TEM) provided a closer look on single ion-implanted nanowires, highlighting the different size and mass effects of Fe and N ions. The reduction of CuO peaks intensities registered in GI-XRD profiles and the shifts of Cu 2p peaks in X-ray photoemission spectra (XPS) suggest that the monoclinic crystal structure of the CuO nanowires was transformed to amorphous Cu2O and Cu(OH)2 after ion implantations. All ion-implanted sensors improved their sensing abilities compared to pristine CuO nanowires towards various concentrations of target gases (hydrogen, ethanol, and acetone) at 400 °C in dry air flows. In the presence of humid air, sensors showed different characteristics related to outcomes of surface-ion beam interactions.

Metal nanoclusters (MNCs) are small aggregates of metal atoms with a mean diameter up to 2 nm, that when excited by electromagnetic radiation of suitable energy present an intense florescence. This optical property can be exploited in many fields such as bioimaging, drug delivery and optical sensing in environmental monitoring. In the present work, we synthesized silver nanoclusters (AgNCs) in water starting from AgNO3 and exploiting poly (methacrylic acid) (PMAA) as capping agent. The reduction of the silver ions Ag(I) to Ag(0) was promoted by the exposition of the solution to UV light radiation for 6 minutes. We studied the UV-Vis absorption and the fluorescence spectra for different pH values. The morphological characterization of the solution was accomplished by Transmission Electron Microscopy (TEM) and the statistical analysis showed that the mean diameter of the AgNCs was around 2 nm for the solution at pH = 4 which presented also the strongest fluorescence. Moreover, we studied the time stability of the absorption and fluorescence spectra. AgNCs stored in the dark at 4 °C were stable for more than 60 days. A possible application of the synthesized AgNCs deals with water monitoring by optical sensing based on the change of the fluorescence property in presence of heavy metal ions. Preliminary investigations show a high sensitivity to Pb(II) ions.Metal nanoclusters (MNCs) are small aggregates of metal atoms with a mean diameter up to 2 nm, that when excited by electromagnetic radiation of suitable energy present an intense florescence. This optical property can be exploited in many fields such as bioimaging, drug delivery and optical sensing in environmental monitoring. In the present work, we synthesized silver nanoclusters (AgNCs) in water starting from AgNO3 and exploiting poly (methacrylic acid) (PMAA) as capping agent. The reduction of the silver ions Ag(I) to Ag(0) was promoted by the exposition of the solution to UV light radiation for 6 minutes. We studied the UV-Vis absorption and the fluorescence spectra for different pH values. The morphological characterization of the solution was accomplished by Transmission Electron Microscopy (TEM) and the statistical analysis showed that the mean diameter of the AgNCs was around 2 nm for the solution at pH = 4 which presented also the strongest fluorescence. Moreover, we studied the time stability ...

Materials possessing long-term antibacterial behavior and high cytotoxicity are of extreme interest in several applications, from biomedical devices to food packaging. Furthermore, for the safeguard of the human health and the environment, it is also stringent keeping in mind the need to gather good functional performances with the development of ecofriendly materials and processes. In this study, we propose a green fabrication method for the synthesis of silver nanoparticles supported on oxidized nanocellulose (ONCs), acting as both template and reducing agent. The complete structural and morphological characterization shows that well-dispersed and crystalline Ag nanoparticles of about 10–20 nm were obtained in the cellulose matrix. The antibacterial properties of Ag-nanocomposites (Ag–ONCs) were evaluated through specific Agar diffusion tests against E. coli bacteria, and the results clearly demonstrate that Ag–ONCs possess high long-lasting antibacterial behavior, retained up to 85% growth bacteria inhibition, even after 30 days of incubation. Finally, cell viability assays reveal that Ag-ONCs show a significant cytotoxicity in mouse embryonic fibroblasts.

The main principles and development of electron spectroscopy for chemical analysis (ESCA) are briefly reviewed. The role of ESCA techniques (X-ray photoelectron spectroscopy and Auger electron spectroscopy) in the investigation of metallic surfaces is discussed, evidencing their importance and analytical potentiality. An overview is given of a series of recent experimental cases of ESCA application for the characterization of different metals and metallic alloys, illustrating the main results and various phenomena, such as the formation of impurity defects, corrosion, migration of constituent elements in various alloys, clustering in liquid alloy, etc., that can occur on the surface and the interface of investigated materials. These materials comprise the collection coins of noble metals, some metal alloys and Ni-based superalloys, nitride coatings on stainless steel, composite material with TiAlV alloy, treated austenitic steels, and graphene interface with polycrystalline metal foils. The present review could be particularly recommended for the newcomers to the research field of surface analysis and its application for various metals, their treatments, and possible modifications in operating conditions.

The demand to increase the sensitivity to magnetic field in a broad magnetic field ranges has led to the research of novel materials for sensor applications. Therefore, the hybrid system consisting of two different magnetoresistive materials – nanostructured Co-doped manganite La1−xSrx(Mn1−yCoy)zO3 and single- and few-layer graphene – were combined and investigated as potential system for magnetic field sensing. The negative colossal magnetoresistance (CMR) of manganite-cobaltite and positive one of graphene gives the possibility to increase the sensitivity to magnetic field of the hybrid sensor. The performed magnetoresistance (MR) measurements of individual few layer (n = 1–5) graphene structures revealed the highest MR values for three-layer graphene (3LG), whereas additional Co-doping increased the MR values of nanostructured manganite films. The connection of 3LG graphene and Co-doped magnanite film in a voltage divider configuration significantly increased the sensitivity of the hybrid sensor at low and intermediate magnetic fields (1–2 T): 70 mV/VT of hybrid sensor in comparison with 56 mV/VT for 3LG and 12 mV/VT for Co-doped magnanite film, respectively, and broadened the magnetic field operation range (0.1–20) T of the produced sensor prototype.

We have synthesized fluorescent and stable silver nanoclusters (AgNCs) capped with poly (methacrylic acid), PMAA, by UV irradiation process. The NCs are well dispersed in aqueous solution and present a uniform distribution with an average dimension of 1.45 ± 0.26 nm. The fluorescence excited at 340 nm was found to be sensitive to the presence of heavy metal ions in solution. In particular, a peculiar fluorescence enhancement was detected upon interaction with lead(II) ions. A linear behavior of the fluorescence intensity as a function of the Pb2+ concentration was measured and a detection limit of 60 nM was estimated. A possible mechanism of the interaction between AgNCs and metal ions is discussed.

In the last years, a hybrid thermionic-photovoltaic (TIPV) direct converter has been proposed and developed for the conversion of concentrated solar energy in the frame of European H2020 project AMADEUS. In order to improve the device performance, the active materials must be characterized by a low work function. Not only, for the thermionic anode must be selected a material with specific characteristics: 1) work function lower than that of the cathode; 2) optical transparency to the blackbody radiation emitted by the emitter. A good strategy is represented by the deposition of a functional coating on the TPV surface. For this reason, BaF2 thin films have been deposited on GaAs substrates by electron-beam thermal evaporation. The thickness of the BaF2 coating has been varied from hundreds of nm down to 1 Å, in order to select the sample with the best performance. The influence of the thickness on the chemical composition and on the work function has been investigated by XPS and UPS, respectively. In particular, the work function values have been calculated from the signal cut-off in acquired He I valence band spectra. In order to avoid the low kinetic energy cut-off caused by the spectrometer, a negative bias V has been applied to the samples. The obtained results revealed that a low work function of 2.1 eV can be reached, when the thickness of the film is of ≈ 1 nm, which is a promising value for a practical application in hybrid TIPV devices. A very interesting effect appeared in the ultra-thin layers of BaF2 with a thickness of only few Å:a new peak positioned at low kinetic energy, near the signal cut-off, appeared in the valence band spectra. This result could be interpreted by considering that conductive band maximum moves above the vacuum level, resulting in negative electron affinity.