Inorganic UV filter-based sunscreens labelled as eco-friendly threaten sea urchin populations.

Although the negative effects of inorganic UV filters have been documented on several marine organisms, sunscreen products containing such filters are available in the market and proposed as eco-friendly substitutes for harmful, and already banned, organic UV filters (e.g. octinoxate and oxybenzone). In the present study, we investigated the effects of four sunscreen products, labelled by cosmetic companies as "eco-friendly", on the early developmental stages of the sea urchin Paracentrotus lividus, a keystone species occurring in vulnerable coastal habitats. Among sunscreens tested, those containing ZnO and TiO2 or their mix caused severe impacts on sea urchin embryos. We show that inorganic UV filters were incorporated by larvae during their development and, despite the activation of defence strategies (e.g. phagocytosis by coelomocytes), generated anomalies such as skeletal malformations and tissue necrosis. Conversely, the sunscreen product containing only new-generation organic UV filters (e.g. methylene bis-benzotriazolyl tetramethyl, ethylhexyl triazone, butylphenol diethylamino hydroxybenzoyl hexyl benzoate) did not affect sea urchins, thus resulting actually eco-compatible. Our findings expand information on the impact of inorganic UV filters on marine life, corroborate the need to improve the eco-friendliness assessment of sunscreen products and warn of the risk of bioaccumulation and potential biomagnification of inorganic UV filters along the marine food chain.

Perpendicularly magnetized Co/Pd-based magneto-resistive heterostructures on flexible substrates.

Flexible magneto-resistive heterostructures have received a great deal of attention over the past few years as they allow for new product paradigms that are not possible with conventional rigid substrates. While the progress and development of systems with longitudinal magnetic anisotropy on non-planar substrates has been remarkable, flexible magneto-resistive heterostructures with perpendicular magnetic anisotropy (PMA) have never been studied despite the possibility to obtain additional functionality and improved performance. To fill this gap, flexible PMA Co/Pd-based giant magneto-resistive (GMR) spin-valve stacks were prepared by using an innovative transfer-and-bonding strategy exploiting the low adhesion of a gold underlayer to SiO x /Si(100) substrates. The approach allows overcoming the limits of the direct deposition on commonly used polymer substrates, whose high surface roughness and low melting temperature could hinder the growth of complex heterostructures with perpendicular magnetic anisotropy. The obtained PMA flexible spin-valves show a sizeable GMR ratio (∼1.5%), which is not affected by the transfer process, and a high robustness against bending as indicated by the slight change of the magneto-resistive properties upon bending, thus allowing for their integration on curved surfaces and the development of a novel class of advanced devices based on flexible magneto-resistive structures with perpendicular magnetic anisotropy. Besides endowing the family of flexible electronics with PMA magneto-resistive heterostructures, the exploitation of the results might apply to high temperature growth processes and to the fabrication of other functional and flexible multilayer materials engineered at the nanoscale.

Magnetic mesoporous silica nanostructures: investigation of magnetic properties.

Magnetic mesoporous silica (MS) nanocomposites provide the possibility of generating multi-functional objects for application in different technological areas. This paper focuses on the magnetic properties of nanocomposites constituted by spinel iron oxide nanoparticles (magnetic nanoparticles (MNPs), < D > ≈ 8-9 nm) embedded in an MS matrix. The mesoporous structure of the silica matrix and the presence of the nanoparticles inside clearly emerge from transmission electron microscopy (TEM) measurements. Low temperature (5 K) field-dependent magnetization measurements reveal saturation magnetization (MS ) close to bulk value (M S bulk ∼ 90 emu g-1) for both MNPs and MNP/MS nanocomposites, indicating that the presence of silica does not affect the magnetic features of the single MNPs. Moreover, the dependence of the remanent magnetization on field (i.e. δM plots) at low temperature has shown a small but evident decrease of interaction in an MNP/MS sample with respect to MNP samples A m2 Kg-1. Finally, a partial orientation of the easy axis is observed when the MNPs are embedded in the silica matrix.

Symbiotic, low-temperature, and scalable synthesis of bi-magnetic complex oxide nanocomposites.

Functional oxide nanocomposites, where the individual components belong to the family of strongly correlated electron oxides, are an important class of materials, with potential applications in several areas such as spintronics and energy devices. For these materials to be technologically relevant, it is essential to design low-cost and scalable synthesis techniques. In this work, we report a low-temperature and scalable synthesis of prototypical bi-magnetic LaFeO3-CoFe2O4 nanocomposites using a unique sol-based synthesis route, where both the phases of the nanocomposite are formed during the same time. In this bottom-up approach, the heat of formation of one phase (CoFe2O4) allows the crystallization of the second phase (LaFeO3), and completely eliminates the need for conventional high-temperature annealing. A symbiotic effect is observed, as the second phase reduces grain growth of the first phase, thus yielding samples with lower particle sizes. Through thermogravimetric, structural, and morphological studies, we have confirmed the reaction mechanism. The magnetic properties of the bi-magnetic nanocomposites are studied, and reveal a distinct effect of the synthesis conditions on the coercivity of the particles. Our work presents a basic concept of significantly reducing the synthesis temperature of bi-phasic nanocomposites (and thus also the synthesis cost) by using one phase as nucleation sites for the second one, as well as using the heat of formation of one phase to crystallize the other.

Glassy Magnetic Behavior and Correlation Length in Nanogranular Fe-Oxide and Au/Fe-Oxide Samples.

In nanoscale magnetic systems, the possible coexistence of structural disorder and competing magnetic interactions may determine the appearance of a glassy magnetic behavior, implying the onset of a low-temperature disordered collective state of frozen magnetic moments. This phenomenology is the object of an intense research activity, stimulated by a fundamental scientific interest and by the need to clarify how disordered magnetism effects may affect the performance of magnetic devices (e.g., sensors and data storage media). We report the results of a magnetic study that aims to broaden the basic knowledge of glassy magnetic systems and concerns the comparison between two samples, prepared by a polyol method. The first can be described as a nanogranular spinel Fe-oxide phase composed of ultrafine nanocrystallites (size of the order of 1 nm); in the second, the Fe-oxide phase incorporated non-magnetic Au nanoparticles (10-20 nm in size). In both samples, the Fe-oxide phase exhibits a glassy magnetic behavior and the nanocrystallite moments undergo a very similar freezing process. However, in the frozen regime, the Au/Fe-oxide composite sample is magnetically softer. This effect is explained by considering that the Au nanoparticles constitute physical constraints that limit the length of magnetic correlation between the frozen Fe-oxide moments.

Co/Pd-Based synthetic antiferromagnetic thin films on Au/resist underlayers: towards biomedical applications.

Thin film stacks consisting of multiple repeats M of synthetic antiferromagnetic (SAF) [Co/Pd]N/Ru/[Co/Pd]N units with perpendicular magnetic anisotropy were explored as potential starting materials to fabricate free-standing micro/nanodisks, which represent a promising candidate system for theranostic applications. The films were directly grown on a sacrificial resist layer spin-coated on SiOx/Si(100) substrates, required for the preparation of free-standing disks after its dissolution. Furthermore, the film stack was sandwiched between two Au layers to allow further bio-functionalization. For M ≤ 5, the samples fulfill all the key criteria mandatory for biomedical applications, i.e., zero remanence, zero field susceptibility at small fields and sharp switching to saturation, together with the ability to vary the total magnetic moment at saturation by changing the number of repetitions of the multi-stack. Moreover, the samples show strong perpendicular magnetic anisotropy, which is required for applications relying on the transduction of a mechanical force through the micro/nano-disks under a magnetic field, such as the mechanical cell disruption, which is nowadays considered a promising alternative to the more investigated magnetic hyperthermia approach for cancer treatment. In a further step, SAF microdisks were prepared from the continuous multi-stacks by combining electron beam lithography and Ar ion milling, revealing similar magnetic properties as compared to the continuous films.

Controlling magnetic coupling in bi-magnetic nanocomposites.

Magnetic nanocomposites constitute a vital class of technologically relevant materials, in particular for next-generation applications ranging from biomedicine, catalysis, and energy devices. Key to designing such materials is determining and controlling the extent of magnetic coupling in them. In this work, we show how the magnetic coupling in bi-magnetic nanocomposites can be controlled by the growth technique. Using four different synthesis strategies to prepare prototypical LaFeO3-CoFe2O4 and LaFeO3-Co0.5Zn0.5Fe2O4 nanocomposite systems, and by performing comprehensive magnetic measurements, we demonstrate that the final material exhibits striking differences in their magnetic coupling that is distinct to the growth method. Through structural and morphological studies, we confirm the link between the magnetic coupling and growth methods due to distinct levels of particle agglomeration at the very microscopic scale. Our studies reveal an inverse relationship between the strength of magnetic coupling and the degree of particle agglomeration in the nanocomposites. Our work presents a basic concept of controlling the particle agglomeration to tune magnetic coupling, relevant for designing advanced bi-magnetic nanocomposites for novel applications.

Mechanism of magnetic heating in Mn-doped magnetite nanoparticles and the role of intertwined structural and magnetic properties.

We study the mechanism of heat generation, induced by an alternating magnetic field, in magnetite nanoparticles doped with manganese, produced by thermal decomposition from organometallic precursors. We investigate a set of four samples obtained by varying the duration of the reflux treatment carried out at a temperature of 300 °C during the synthetic procedure. On increasing this parameter from 60 to 180 minutes, the mean size of the nanoparticles increases, though remaining below 10 nm, as well as the saturation magnetization, which in all the samples, thanks to the Mn doping, is higher than that in magnetite nanoparticles taken as a reference. The combination of these two events has two main consequences. First, it determines the intensity of dipolar interactions between the nanoparticles, thus influencing their magnetic relaxing behavior, which, in turn, is closely related to the heating efficiency. Secondly, in a heating test, it is possible to operate in the regime of non-linear magnetic response of the nanoparticles at values of amplitude and frequency of the alternating field usually employed for biomedical applications. We show that, in this regime, the Specific Absorption Rate (SAR) in each sample depends linearly on the fraction of nanoparticles that are not superparamagnetic. This opens the possibility of modulating the heating capacity of the produced nanoparticles, so as to match specific needs, changing only a single synthesis parameter and opportunely exploiting the strict connection between structural features, magnetic properties and measurement conditions.

Tunable single-phase magnetic behavior in chemically synthesized AFeO3-MFe2O4 (A = Bi or La, M = Co or Ni) nanocomposites.

The properties of magnetic nanocomposites rely strongly on the interplay between those of the constituent components. When the individual components themselves are complex systems belonging to the family of correlated electron oxide systems which typically exhibit exotic physical properties, it becomes nontrivial to customize the properties of the nanocomposite. In this paper, we demonstrate an easy, but effective method to synthesize and tune the magnetic properties of nanocomposites consisting of correlated electron oxide systems as the individual components. Our method is based on a novel synthesis technique by which the two components of the nanocomposite can be directly integrated with each other, yielding homogeneous samples on the nanoscale with magnetic behavior reminiscent of a single phase. We illustrate our method using multiferroic BiFeO3 (BFO) and LaFeO3 (LFO) as the major phase (i.e., matrix), and MFe2O4 (M = Co2+ or Ni2+) as the embedded magnetic phase. Furthermore, we show that by a proper selection of the second phase in the nanocomposite, it is possible to customize the magnetic properties of the matrix. We illustrate this by choosing CoFe2O4 and NiFe2O4, two oxides with widely differing magnetic anisotropies, as the embedded phase, and demonstrate that the coercivity of BFO and LFO can be increased or decreased depending on the choice of the embedded phase in the nanocomposite.

L10-FeNi films on Au-Cu-Ni buffer-layer: a high-throughput combinatorial study.

The fct L10-FeNi alloy is a promising candidate for the development of high performance critical-elements-free magnetic materials. Among the different materials, the Au-Cu-Ni alloy has resulted very promising; however, a detailed investigation of the effect of the buffer-layer composition on the formation of the hard FeNi phase is still missing. To accelerate the search of the best Au-Cu-Ni composition, a combinatorial approach based on High-Throughput (HT) experimental methods has been exploited in this paper. HT magnetic characterization methods revealed the presence of a hard magnetic phase with an out-of-plane easy-axis, whose coercivity increases from 0.49 kOe up to 1.30 kOe as the Au content of the Cu-Au-Ni buffer-layer decreases. Similarly, the out-of-plane magneto-crystalline anisotropy energy density increases from 0.12 to 0.35 MJ/m3. This anisotropy is attributed to the partial formation of the L10 FeNi phase induced by the buffer-layer. In the range of compositions we investigated, the buffer-layer structure does not change significantly and the modulation of the magnetic properties with the Au content in the combinatorial layer is mainly related to the different nature and extent of interlayer diffusion processes, which have a great impact on the formation and order degree of the L10 FeNi phase.

Effects of build orientation and element partitioning on microstructure and mechanical properties of biomedical Ti-6Al-4V alloy produced by laser sintering.

Direct Metal Laser Sintering (DMLS) technology was used to produce tensile and flexural samples based on the Ti-6Al-4V biomedical composition. Tensile samples were produced in three different orientations in order to investigate the effect of building direction on the mechanical behavior. On the other hand, flexural samples were submitted to thermal treatments to simulate the firing cycle commonly used to veneer metallic devices with ceramics in dental applications. Roughness and hardness measurements as well as tensile and flexural mechanical tests were performed to study the mechanical response of the alloy while X-ray diffraction (XRD), electron microscopy (SEM, TEM, STEM) techniques and microanalysis (EDX) were used to investigate sample microstructure. Results evidenced a difference in the mechanical response of tensile samples built in orthogonal directions. In terms of microstructure, samples not submitted to the firing cycle show a single phase acicular α' (hcp) structure typical of metal parts subject to high cooling rates. After the firing cycle, samples show a reduction of hardness and strength due to the formation of laths of the ß (bcc) phase at the boundaries of the primary formed α' plates as well as to lattice parameters variation of the hcp phase. Element partitioning during the firing cycle gives rise to high concentration of V atoms (up to 20wt%) at the plate boundaries where the ß phase preferentially forms.

A new micromechanical approach for the preparation of graphene nanoplatelets deposited on polyethylene.

An advantageous micromechanical technique to deposit large area graphene nanoplatelet (GNP) thin films on a low-density polyethylene substrate is proposed. This method is based on the application of shear-stress and friction forces to a graphite platelets/ethanol paste on the surface of a polymeric substrate; it allows us to obtain a continuous film of superimposed nanoplatelets mainly made of 13-30 graphene layers. X-ray diffraction (XRD), atomic force and transmission electron microscopy (TEM) measurements support the occurrence of a partial exfoliation of the graphite platelets due to shear-stress and friction forces applied during film formation. Scanning electron microscopy (SEM) observations point out that the surface of the polymer is uniformly coated by the overlap of GNPs, and TEM analysis reveals the tendency of the nanoplatelets to align parallel to the interface plane. It has been found that the deposited samples, under white light illumination, exhibit a negative photoconductivity and a linear photoresponse as a function of the applied voltage and the optical power density in the -120 ÷ 120 mV and 20.9 ÷ 286.2 mW cm-2 ranges, respectively.

Effects of thermal treatments on microstructure and mechanical properties of a Co-Cr-Mo-W biomedical alloy produced by laser sintering.

Direct Metal Laser Sintering (DMLS) technology based on a layer by layer production process was used to produce a Co-Cr-Mo-W alloy specifically developed for biomedical applications. The alloy mechanical response and microstructure were investigated in the as-sintered state and after post-production thermal treatments. Roughness and hardness measurements, and tensile and flexural tests were performed to study the mechanical response of the alloy while X-ray diffraction (XRD), electron microscopy (SEM, TEM, STEM) techniques and microanalysis (EDX) were used to investigate the microstructure in different conditions. Results showed an intricate network of ε-Co (hcp) lamellae in the γ-Co (fcc) matrix responsible of the high UTS and hardness values in the as-sintered state. Thermal treatments increase volume fraction of the ε-Co (hcp) martensite but slightly modify the average size of the lamellar structure. Nevertheless, thermal treatments are capable of producing a sensible increase in UTS and hardness and a strong reduction in ductility. These latter effects were mainly attributed to the massive precipitation of an hcp Co3(Mo,W)2Si phase and the contemporary formation of Si-rich inclusions.

Designing new ferrite/manganite nanocomposites.

Two kinds of nanocomposites of transition metal oxides were synthesized and investigated. Each nanocomposite comprises nanoparticles of La0.67Ca0.33MnO3 and CoFe2O4 in similar volume fractions, however arranged with different morphologies. The temperature-dependent magnetic and electrical properties of the two systems are found to greatly differ, suggesting different degrees of interaction and coupling of their constituents. This is confirmed by magnetic field-dependent experiments, which reveal contrasted magnetization reversal and magnetoresistance in the systems. We discuss this morphology-physical property relationship, and the possibility to further tune the magnetism and magneto-transport in such nanocomposites.

Structural characterization of biomedical Co-Cr-Mo components produced by direct metal laser sintering.

Direct metal laser sintering (DMLS) is a technique to manufacture complex functional mechanical parts from a computer-aided design (CAD) model. Usually, the mechanical components produced by this procedure show higher residual porosity and poorer mechanical properties than those obtained by conventional manufacturing techniques. In this work, a Co-Cr-Mo alloy produced by DMLS with a composition suitable for biomedical applications was submitted to hardness measurements and structural characterization. The alloy showed a hardness value remarkably higher than those commonly obtained for the same cast or wrought alloys. In order to clarify the origin of this unexpected result, the sample microstructure was investigated by X-ray diffraction (XRD), electron microscopy (SEM and TEM) and energy dispersive microanalysis (EDX). For the first time, a homogeneous microstructure comprised of an intricate network of thin ε (hcp)-lamellae distributed inside a γ (fcc) phase was observed. The ε-lamellae grown on the {111}γ planes limit the dislocation slip inside the γ (fcc) phase, causing the measured hardness increase. The results suggest possible innovative applications of the DMLS technique to the production of mechanical parts in the medical and dental fields.

Strain-driven morphology of Si1-xGex islands grown on Si(100)

A study has been carried out on the morphology and structure of three-dimensional (3D) SiGe islands grown by molecular beam epitaxy (MBE) on Si(100) substrates. Samples of Si1-xGex alloys have been prepared to investigate the effects either of the alloy composition or of the growth temperature. Atomic force microscopy (AFM) evidenced the growth of 3D islands and transmission electron microscopy (TEM) demonstrated wetting layer growth on Si(100), independently on the deposition conditions. Energy dispersive spectroscopy (EDS) micro-analyses carried out on cross-sections of large Si1-xGex islands with defects allowed a measurement of the Ge distribution in the islands. To the best of our knowledge, these have been the first experimental evidences of a composition change inside SiGe islands. The interpretation of the experimental results has been done in terms of strain-enhanced diffusion mechanisms both of the growing species (Si and Ge) and of small islands.