Ductile bulk metallic glass by controlling structural heterogeneities.

A prerequisite to utilize the full potential of structural heterogeneities for improving the room-temperature plastic deformation of bulk metallic glasses (BMGs) is to understand their interaction with the mechanism of shear band formation and propagation. This task requires the ability to artificially create heterogeneous microstructures with controlled morphology and orientation. Here, we analyze the effect of the designed heterogeneities generated by imprinting on the tensile mechanical behavior of the Zr52.5Ti5Cu18Ni14.5Al10 BMG by using experimental and computational methods. The imprinted material is elastically heterogeneous and displays anisotropic mechanical properties: strength and ductility increase with increasing the loading angle between imprints and tensile direction. This behavior occurs through shear band branching and their progressive rotation. Molecular dynamics and finite element simulations indicate that shear band branching and rotation originates at the interface between the heterogeneities, where the characteristic atomistic mechanism responsible for shear banding in a homogeneous glass is perturbed.

Hidden Magnetic States Emergent Under Electric Field, In A Room Temperature Composite Magnetoelectric Multiferroic.

The ability to control a magnetic phase with an electric field is of great current interest for a variety of low power electronics in which the magnetic state is used either for information storage or logic operations. Over the past several years, there has been a considerable amount of research on pathways to control the direction of magnetization with an electric field. More recently, an alternative pathway involving the change of the magnetic state (ferromagnet to antiferromagnet) has been proposed. In this paper, we demonstrate electric field control of the Anomalous Hall Transport in a metamagnetic FeRh thin film, accompanying an antiferromagnet (AFM) to ferromagnet (FM) phase transition. This approach provides us with a pathway to "hide" or "reveal" a given ferromagnetic region at zero magnetic field. By converting the AFM phase into the FM phase, the stray field, and hence sensitivity to external fields, is decreased or eliminated. Using detailed structural analyses of FeRh films of varying crystalline quality and chemical order, we relate the direct nanoscale origins of this memory effect to site disorder as well as variations of the net magnetic anisotropy of FM nuclei. Our work opens pathways toward a new generation of antiferromagnetic - ferromagnetic interactions for spintronics.

Electron energy-loss spectroscopic tomography of FexCo(3-x)O4 impregnated Co3O4 mesoporous particles: unraveling the chemical information in three dimensions.

Electron energy-loss spectroscopy-spectrum image (EELS-SI) tomography is a powerful tool to investigate the three dimensional chemical configuration in nanostructures. Here, we demonstrate, for the first time, the possibility to characterize the spatial distribution of Fe and Co cations in a complex FexCo(3-x)O4/Co3O4 ordered mesoporous system. This hybrid material is relevant because of the ferrimagnetic/antiferromagnetic coupling and high surface area. We unambiguously prove that the EELS-SI tomography shows a sufficiently high resolution to simultaneously unravel the pore structure and the chemical signal.

Electrochemically synthesized amorphous and crystalline nanowires: dissimilar nanomechanical behavior in comparison with homologous flat films.

The effects of constrained sample dimensions on the mechanical behavior of crystalline materials have been extensively investigated. However, there is no clear understanding of these effects in nano-sized amorphous samples. Herein, nanoindentation together with finite element simulations are used to compare the properties of crystalline and glassy CoNi(Re)P electrodeposited nanowires (ϕ ≈ 100 nm) with films (3 µm thick) of analogous composition and structure. The results reveal that amorphous nanowires exhibit a larger hardness, lower Young's modulus and higher plasticity index than glassy films. Conversely, the very large hardness and higher Young's modulus of crystalline nanowires are accompanied by a decrease in plasticity with respect to the homologous crystalline films. Remarkably, proper interpretation of the mechanical properties of the nanowires requires taking the curved geometry of the indented surface and sink-in effects into account. These findings are of high relevance for optimizing the performance of new, mechanically-robust, nanoscale materials for increasingly complex miniaturized devices.

Nanostructured Ti-Zr-Pd-Si-(Nb) bulk metallic composites: Novel biocompatible materials with superior mechanical strength and elastic recovery.

The microstructure, mechanical behaviour, and biocompatibility (cell culture, morphology, and cell adhesion) of nanostructured Ti45 Zr15 Pd35- x Si5 Nbx with x = 0, 5 (at. %) alloys, synthesized by arc melting and subsequent Cu mould suction casting, in the form of rods with 3 mm in diameter, are investigated. Both Ti-Zr-Pd-Si-(Nb) materials show a multi-phase (composite-like) microstructure. The main phase is cubic ß-Ti phase (Im3m) but hexagonal α-Ti (P63/mmc), cubic TiPd (Pm3m), cubic PdZr (Fm3m), and hexagonal (Ti, Zr)5 Si3 (P63/mmc) phases are also present. Nanoindentation experiments show that the Ti45 Zr15 Pd30 Si5 Nb5 sample exhibits lower Young's modulus than Ti45 Zr15 Pd35 Si5 . Conversely, Ti45 Zr15 Pd35 Si5 is mechanically harder. Actually, both alloys exhibit larger values of hardness when compared with commercial Ti-40Nb, (HTi-Zr-Pd-Si ≈ 14 GPa, HTi-Zr-Pd-Si-Nb ≈ 10 GPa and HTi-40Nb ≈ 2.7 GPa). Concerning the biological behaviour, preliminary results of cell viability performed on several Ti-Zr-Pd-Si-(Nb) discs indicate that the number of live cells is superior to 94% in both cases. The studied Ti-Zr-Pd-Si-(Nb) bulk metallic system is thus interesting for biomedical applications because of the outstanding mechanical properties (relatively low Young's modulus combined with large hardness), together with the excellent biocompatibility.

Electrodeposition of magnetic, superhydrophobic, non-stick, two-phase Cu-Ni foam films and their enhanced performance for hydrogen evolution reaction in alkaline water media.

Two-phase Cu-Ni magnetic metallic foams (MMFs) with tunable composition have been prepared by electrodeposition taking advantage of hydrogen co-evolution as a source of porosity. It is observed that Ni tends to deposit inside the porous network defined by the Cu building blocks. Contact angle measurements reveal that the prepared porous films show a remarkable superhydrophobicity (contact angle values larger than 150°) and a non-sticking property to aqueous droplets. This behavior is predominately ascribed to the morphology of the films - hierarchical micro/nanoporosity, wall thickness, and spatial arrangement. The electrochemical activity and stability towards hydrogen evolution reaction of the Cu-Ni MMFs has been investigated by cyclic voltammetry in 1 M KOH at 298 K, and the optimal Ni content is found to be 15 at%. Furthermore, all the foam-like films exhibit ferromagnetic behaviour due to the presence of the Ni-rich phase, with coercivity values ranging from 114 Oe to 300 Oe. From the technological point of view, the Cu-Ni MMFs are promising candidates for magnetically-actuated micro/nano-electromechanical systems (MEMS/NEMS) and micro/nanorobotic platforms with a large surface-area to volume ratio or in magnetic sensors or separators.

One-pot electrosynthesis of multi-layered magnetic metallopolymer nanocomposites.

Researchers have been investigating various methodologies for fabricating well-defined, homogenous composites consisting of nanoparticles (NPs) dispersed in a matrix. The main challenges are to prevent particle agglomerations during fabrication and to obtain nanoparticles whose size distribution could be tuned on demand. One of the methods that can provide these features is electrodeposition. We report for the first time the fabrication of a thin magnetic multilayer nanocomposite film by electrodeposition from one bath containing both a monomer and metal salts. Cobalt and cobalt-nickel NPs were deposited on conductive polymer polypyrrole thin films using different electrodeposition potentials and times. Multilayer nanocomposite films were fabricated by subsequent electrodeposition of polymer and nanoparticle layers. Scanning electron microscopy analysis showed that a wide range of NPs (70-230 nm) could be synthesized by manipulating growth potentials and times. The cobalt-nickel NPs were found to contain hexagonal close-packed (hcp) and face-centered cubic (fcc) phases based on X-ray diffraction and selected area electron diffraction. Magnetic measurements proved that both the single and the multi-layered nanocomposites were magnetic at room temperature.

In vitro biocompatibility assessment of Ti40Cu38Zr10Pd12 bulk metallic glass.

The use of biocompatible materials has attained an increasing importance for tissue regeneration and transplantation. The excellent mechanical and corrosion properties of Ti40Cu38Zr10Pd12 bulk metallic glass (BMG) turn it into a potential candidate for its use in orthopaedic implants. Before being considered as a biomaterial, some biological parameters must be taken into account. In this study,mouse preosteoblasts were cultured in the presence or absence of the alloy at different times (24 h, 7 and 21 days) and no differences in cell viability were detected.Moreover, cells were able to adhere to the alloy surface by establishing focal contacts, and displayed a flattened polygonal morphology. After 14 days in culture, differentiation into osteoblasts was observed. Besides, the amount of Cu ions released and their potential toxic effects were analyzed, showing that the amount of Cu released did not increase cell death. Finally, the low levels of inflammatory cytokines secreted by THP-1 differentiated macrophages exposed to the alloy suggest the absence of an immunogenic response to the alloy. In conclusion, in vitro studies indicate that the Ti40Cu38Zr10Pd12 BMG could be considered as a biomaterial to be used in orthopaedic implants.

White-light photoluminescence and photoactivation in cadmium sulfide embedded in mesoporous silicon dioxide templates studied by confocal laser scanning microscopy.

SBA-15 and SBA-16 silica templates have been infiltrated with CdS by means of nanocasting using a hybrid precursor. The morphology and structure of both the SiO2@CdS nanocomposites and the silica-free CdS replicas have been characterized. The three-dimensional nanocrystalline CdS networks embedded in SBA-15 and SBA-16 silica templates exhibit broad photoluminescence (PL) spectra over the entire visible range, together with enhanced PL intensity compared to silica-free CdS replicas. These effects result from the role silica plays in passivating the surface of the CdS mesostructures. Furthermore, photoactivation is eventually observed during continuous illumination because of both structural and chemical surface modifications. Owing to this combination of properties, these materials could be appealing for solid-state lighting, where ultra-bright near-white PL emission is indispensable.

On the biodegradability, mechanical behavior, and cytocompatibility of amorphous Mg72 Zn23 Ca5 and crystalline Mg70 Zn23 Ca5 Pd2 alloys as temporary implant materials.

The evolution of microstructure and mechanical properties of almost fully amorphous Mg(72) Zn(23) Ca(5) and crystalline Mg(70) Zn(23) Ca(5) Pd(2) alloys during immersion in Hank's balanced salt solution (HBSS), as well as their cytocompatibility, are investigated in order to assess the feasibility of both materials as biodegradable implants. Though the crystalline Mg(70) Zn(23) Ca(5) Pd(2) sample shows lower wettability and more positive corrosion potential, this sample degrades much faster upon incubation in HBSS as a consequence of the formation of micro-galvanic couples between the nobler Pd-rich dendrites and the surrounding phases. After 22-h immersion, the concentration of Mg ions in the HBSS medium containing the Mg(70) Zn(23) Ca(5) Pd(2) sample is six times larger than for Mg(72) Zn(23) Ca(5) . Due to the Zn enrichment and the incipient porosity, the mechanical properties of the Mg(72) Zn(23) Ca(5) sample improve within the first stages of biodegradation (i.e., hardness increases while the Young's modulus decreases, thus rendering an enhanced wear resistance). Cytocompatibility studies reveal that neither Mg(72) Zn(23) Ca(5) nor Mg(70) Zn(23) Ca(5) Pd(2) are cytotoxic, although preosteoblast cell adhesion is to some extent precluded, particularly onto the surface of Mg(70) Zn(23) Ca(5) Pd(2) , because of the relatively high hydrophobicity. Because of their outstanding properties and their time-evolution, the use of the Pd-free alloy in temporary implants such as screws, stents, and sutures is envisioned.

Strongly exchange coupled inverse ferrimagnetic soft/hard, Mn(x)Fe(3-x)O4/Fe(x)Mn(3-x)O4, core/shell heterostructured nanoparticles.

Inverted soft/hard, in contrast to conventional hard/soft, bi-magnetic core/shell nanoparticles of Mn(x)Fe(3-x)O(4)/Fe(x)Mn(3-x)O(4) with two different core sizes (7.5 and 11.5 nm) and fixed shell thickness (∼0.6 nm) have been synthesized. The structural characterization suggests that the particles have an interface with a graded composition. The magnetic characterization confirms the inverted soft/hard structure and evidences a strong exchange coupling between the core and the shell. Moreover, larger soft core sizes exhibit smaller coercivities and loop shifts, but larger blocking temperatures, as expected from spring-magnet or graded anisotropy structures. The results indicate that, similar to thin film systems, the magnetic properties of soft/hard core/shell nanoparticles can be fine tuned to match specific applications.

Improved mechanical performance and delayed corrosion phenomena in biodegradable Mg-Zn-Ca alloys through Pd-alloying.

The influence of partial substitution of Mg by Pd on the microstructure, mechanical properties and corrosion behaviour of Mg(72-x)Zn(23)Ca(5)Pd(x) (x=0, 2 and 6 at.%) alloys, synthesized by copper mould casting, is investigated. While the Mg(72)Zn(23)Ca(5) alloy is mainly amorphous, the addition of Pd decreases the glass-forming ability, thus favouring the formation of crystalline phases. From a mechanical viewpoint, the hardness increases with the addition of Pd, from 2.71 GPa for x=0 to 3.9 GPa for x=6, mainly due to the formation of high-strength phases. In turn, the wear resistance is maximized for an intermediate Pd content (i.e., Mg(70)Zn(23)Ca(5)Pd(2)). Corrosion tests in a simulated body fluid (Hank's solution) indicate that Pd causes a shift in the corrosion potential towards more positive values, thus delaying the biodegradability of this alloy. Moreover, since the cytotoxic studies with mouse preosteoblasts do not show dead cells after culturing for 27 h, these alloys are potential candidates to be used as biomaterials.

Enhanced mechanical properties and in vitro corrosion behavior of amorphous and devitrified Ti40Zr10Cu38Pd12 metallic glass.

The effects of annealing treatments on the microstructure, elastic/mechanical properties, wear resistance and corrosion behavior of rod-shaped Ti40Zr10Cu38Pd12 bulk glassy alloys, synthesized by copper mold casting, are investigated. Formation of ultrafine crystals embedded in an amorphous matrix is observed for intermediate annealing temperatures, whereas a fully crystalline microstructure develops after heating to sufficiently high temperatures. The glassy alloy exhibits large hardness, relatively low Young's modulus, good wear resistance and excellent corrosion behavior. Nanoindentation measurements reveal that the sample annealed in the supercooled liquid region exhibits a hardness value of 9.4 GPa, which is 20% larger than in the completely amorphous state and much larger than the hardness of commercial Ti-6Al-4V alloy. The Young's modulus of the as-cast alloy (around 100 GPa, as determined from acoustic measurements) increases only slightly during partial devitrification. Finally, the anticorrosion performance of the Ti40Zr10Cu38Pd12 alloy in Hank's solution has been shown to ameliorate as crystallization proceeds and is roughly as good as in the commercial Ti-6Al-4V alloy. The outstanding mechanical and corrosion properties of the Ti40Zr10Cu38Pd12 alloy, both in amorphous and crystalline states, are appealing for its use in biomedical applications.

Structural and magnetic characterization of batch-fabricated nickel encapsulated multi-walled carbon nanotubes.

We report on the growth and fabrication of Ni-filled multi-walled carbon nanotubes (Ni-MWNTs) with an average diameter of 115 nm and variable length of 400 nm-1 µm. The Ni-MWNTs were grown using template-assisted electrodeposition and low pressure chemical vapor deposition (LPCVD) techniques. Anodized alumina oxide (AAO) templates were fabricated on Si using a current controlled process. This was followed by the electrodeposition of Ni nanowires (NWs) using galvanostatic pulsed current (PC) electrodeposition. Ni NWs served as the catalyst to grow Ni-MWNTs in an atmosphere of H2/C2H2 at a temperature of 700 °C. Time dependent depositions were carried out to understand the diffusion and growth mechanism of Ni-MWNTs. Characterization was carried out using scanning electron microscopy (SEM), focused ion beam (FIB) milling, transmission electron microscopy (TEM), Raman spectroscopy and energy dispersive x-ray spectroscopy (EDX). TEM analysis revealed that the Ni nanowires possess a fcc structure. To understand the effects of the electrodeposition parameters, and also the effects of the high temperatures encountered during MWNT growth on the magnetic properties of the Ni-MWNTs, vibrating sample magnetometer (VSM) measurements were performed. The template-based fabrication method is repeatable, efficient, enables batch fabrication and provides good control on the dimensions of the Ni-MWNTs.

Magnetic proximity effect features in antiferromagnetic/ferrimagnetic core-shell nanoparticles.

A study of "inverted" core-shell, MnO/gamma-Mn(2)O(3), nanoparticles is presented. Crystal and magnetic structures and characteristic sizes have been determined by neutron diffraction for the antiferromagnetic core (MnO) and the ferrimagnetic shell (gamma-Mn(2)O(3)). Remarkably, while the MnO core is found to have a T_{N} not far from its bulk value, the magnetic order of the gamma-Mn(2)O(3) shell is stable far above T_{C}, exhibiting two characteristic temperatures, at T approximately 40 K [T_{C}(gamma-Mn(2)O(3))] and at T approximately 120 K [ approximately T_{N}(MnO)]. Magnetization measurements are consistent with these results. The stabilization of the shell moment up to T_{N} of the core can be tentatively attributed to core-shell exchange interactions, hinting at a possible magnetic proximity effect.

Magnetic properties of Ni-NiO (ferromagnetic-antiferromagnetic) nanocomposites obtained from a partial mechanochemical reduction of NiO.

The magnetic properties of ferromagnetic (FM)-antiferromagnetic (AFM), Ni-NiO, nanocomposites obtained from a reactive ball milling reduction of NiO in H2 atmosphere have been studied. The formation of ferromagnetic Ni from antiferromagnetic NiO can be accurately followed by the increase of the saturation magnetization. The microstructure of the nanocomposite, consisting of FM Ni nanoparticles embedded in an AFM NiO matrix leads to exchange bias effects, i.e., loop shifts and coercivity enhancement, after field cooling from above the Néel temperature of NiO.

Magnetic instability regions in patterned structures: influence of element shape on magnetization reversal dynamics.

We report a time-resolved imaging study of the influence of shape on magnetic instabilities in patterned magnetic structures. We find that in rectangular structures magnetization reversal initiates at the ends and interior simultaneously, while in structures with tapered ends the reversal begins in the middle of the structures and spreads out to the ends. The degree of tapering is important for both the switching field and the time required for full reversal. A model based on the concept of local instability regions yields good agreement with the observed location of the reversal onsets.

Shell-driven magnetic stability in core-shell nanoparticles.

The magnetic properties of ferromagnetic-antiferromagnetic Co-CoO core-shell nanoparticles are investigated as a function of the in-plane coverage density from 3.5% to 15%. The superparamagnetic blocking temperature, the coercivity, and the bias field radically increase with increasing coverage. This behavior cannot be attributed to the overall interactions between cores. Rather, it can be semiquantitatively understood by assuming that the shells of isolated core-shell nanoparticles have strongly degraded magnetic properties, which are rapidly recovered as nanoparticles come into contact.

Imprinting vortices into antiferromagnets.

The effect of imprinting symmetric and displaced vortex structures into an antiferromagnetic material is investigated in micron-sized disks consisting of exchange coupled ferromagnetic-antiferromagnetic bilayers. The imprint of displaced vortices manifests itself by the occurrence of a new type of asymmetric hysteresis loops characterized by curved, reversible, central sections with nonzero remanent magnetization. Such an imprint is achieved by cooling the disks through the blocking temperature of the system in small fields. Micromagnetic simulations reveal that asymmetric vortexlike loops naturally result from the competition between the different energies involved in the system.

Magnetization reversal in submicron disks: exchange biased vortices.

Submicron, circular, ferromagnetic-antiferromagnetic dots exhibit different magnetization reversal mechanisms depending on the direction of the magnetic applied field. Shifted, constricted hysteresis loops, typical for vortex formation, are observed for fields along the exchange bias direction. However, for fields applied close to perpendicular to the exchange bias direction, magnetization reversal occurs via coherent rotation. Magnetic force microscopy imaging together with micromagnetic simulations are used to further clarify the different magnetic switching behaviors.