Production of Composite Zinc Oxide-Polylactic Acid Radiopaque Filaments for Fused Deposition Modeling: First Stage of a Feasibility Study.

Three-dimensional printing technologies are becoming increasingly attractive for their versatility; the geometrical customizability and manageability of the final product properties are the key points. This work aims to assess the feasibility of producing radiopaque filaments for fused deposition modeling (FDM), a 3D printing technology, starting with zinc oxide (ZnO) and polylactic acid (PLA) as the raw materials. Indeed, ZnO and PLA are promising materials due to their non-toxic and biocompatible nature. Pellets of PLA and ZnO in the form of nanoparticles were mixed together using ethanol; this homogenous mixture was processed by a commercial extruder, optimizing the process parameters for obtaining mechanically stable samples. Scanning electron microscopy analyses were used to assess, in the extruded samples, the homogenous distribution of the ZnO in the PLA matrix. Moreover, X-ray microtomography revealed a certain homogenous radiopacity; this imaging technique also confirmed the correct distribution of the ZnO in the PLA matrix. Thus, our tests showed that mechanically stable radiopaque filaments, ready for FDM systems, were obtained by homogenously loading the PLA with a maximum ZnO content of 6.5% wt. (nominal). This study produced multiple outcomes. We demonstrated the feasibility of producing radiopaque filaments for additive manufacturing using safe materials. Moreover, each phase of the process is cost-effective and green-oriented; in fact, the homogenous mixture of PLA and ZnO requires only a small amount of ethanol, which evaporates in minutes without any temperature adjustment. Finally, both the extruding and the FDM technologies are the most accessible systems for the additive manufacturing commercial apparatuses.

Chemical engineering of cationic distribution in spinel ferrite nanoparticles: the effect on the magnetic properties.

A set of ∼9 nm CoFe2O4 nanoparticles substituted with Zn2+ and Ni2+ was prepared by thermal decomposition of metallic acetylacetonate precursors to correlate the effects of replacement of Co2+ with the resulting magnetic properties. Due to the distinct selectivity of these cations for the spinel ferrite crystal sites, we show that it is possible to tailor the magnetic anisotropy, saturation magnetization, and interparticle interactions of the nanoparticles during the synthesis stage. This approach unlocks new possibilities for enhancing the performance of spinel ferrite nanoparticles in specific applications. Particularly, our study shows that the replacement of Co2+ by 48% of Zn2+ ions led to an increase in saturation magnetization of approximately 40% from ∼103 A m2 kg-1 to ∼143 A m2 kg-1, whereas the addition of Ni2+ at a similar percentage led to an ∼30% decrease in saturation magnetization to 68-72 A m2 kg-1. The results of calculations based on the two-sublattice Néel model of magnetization match the experimental findings, demonstrating the model's effectiveness in the strategic design of spinel ferrite nanoparticles with targeted magnetic properties through doping/inversion degree engineering.

Unraveling Exchange Coupling in Ferrites Nano-Heterostructures.

The magnetic coupling of a set of SrFe12 O19 /CoFe2 O4 nanocomposites is investigated. Advanced electron microscopy evidences the structural coherence and texture at the interfaces of the nanostructures. The fraction of the lower anisotropy phase (CoFe2 O4 ) is tuned to assess the limits that define magnetically exchange-coupled interfaces by performing magnetic remanence, first-order reversal curves (FORCs), and relaxation measurements. By combining these magnetometry techniques and the structural and morphological information from X-ray diffraction, electron microscopy, and Mössbauer spectrometry, the exchange intergranular interaction is evidenced, and the critical thickness within which coupled interfaces have a uniform reversal unraveled.

Tunable particle-agglomeration and magnetic coupling in bi-magnetic nanocomposites.

A set of non-stoichiometric Zn-Co-ferrite nanoparticles (NPs) was prepared by thermal decomposition of metallic complexes, in the presence of oleic acid, and, after a ligand-exchange process, was coated by a hydrophilic surfactant: these NPs were used as seeds in a sol-gel self-combustion synthesis to prepare nanocomposites (NCs) with a fixed weight ratio. Our focus here is the development of an efficient synthetic approach to control the magnetic coupling between a hard-magnetic matrix (Sr-ferrite) and NPs. The physico-chemical synthetic conditions (temperature, pH, colloidal stability) were optimized in order to tune their effect on the final particles' agglomeration in the matrix. We demonstrate that our synthetic approach is a novel way to produce strongly magnetically coupled NCs, where the final extrinsic properties could be tuned by controlling (i) the agglomeration of seeds in the matrix and (ii) their elemental doping.

Atmospheric Pressure Plasma Deposition of Hybrid Nanocomposite Coatings Containing TiO2 and Carbon-Based Nanomaterials.

Among the different applications of TiO2, its use for the photocatalytic abatement of organic pollutants has been demonstrated particularly relevant. However, the wide band gap (3.2 eV), which requires UV irradiation for activation, and the fast electron-hole recombination rate of this n-type semiconductor limit its photocatalytic performance. A strategy to overcome these limitations relies on the realization of a nanocomposite that combines TiO2 nanoparticles with carbon-based nanomaterials, such as rGO (reduced graphene oxide) and fullerene (C60). On the other hand, the design and realization of coatings formed of such TiO2-based nanocomposite coatings are essential to make them suitable for their technological applications, including those in the environmental field. In this work, aerosol-assisted atmospheric pressure plasma deposition of nanocomposite coatings containing both TiO2 nanoparticles and carbon-based nanomaterials, as rGO or C60, in a siloxane matrix is reported. The chemical composition and morphology of the deposited films were investigated for the different types of prepared nanocomposites by means of FT-IR, FEG-SEM, and TEM analyses. The photocatalytic activity of the nanocomposite coatings was evaluated through monitoring the photodegradation of methylene blue (MB) as a model organic pollutant. Results demonstrate that the nanocomposite coatings embedding rGO or C60 show enhanced photocatalytic performance with respect to the TiO2 counterpart. In particular, TiO2/C60 nanocomposites allow to achieve 85% MB degradation upon 180 min of UV irradiation.

Thin-Film Heterostructures Based on Co/Ni Synthetic Antiferromagnets on Polymer Tapes: Toward Sustainable Flexible Spintronics.

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.

Silk fibroin films with embedded magnetic nanoparticles: evaluation of the magneto-mechanical stimulation effect on osteogenic differentiation of stem cells.

We report about a biomaterial in the form of film ∼10 µm thick, consisting of a silk fibroin matrix with embedded iron oxide superparamagnetic nanoparticles, for prospective applications as bioactive coating in regenerative medicine. Films with different load of magnetic nanoparticles are produced (nanoparticles/silk fibroin nominal ratio = 5, 0.5 and 0 wt%) and the structural, mechanical and magnetic properties are studied. The nanoparticles form aggregates in the silk fibroin matrix and the film stiffness, as tested by nanoindentation, is spatially inhomogeneous, but the protein structure is not altered. In vitro biological tests are carried out on human bone marrow-derived mesenchymal stem cells cultured on the films up to 21 days, with and without an applied static uniform magnetic field. The sample with the highest nanoparticles/silk fibroin ratio shows the best performance in terms of cell proliferation and adhesion. Moreover, it promotes a faster and better osteogenic differentiation, particularly under magnetic field, as indicated by the gene expression level of typical osteogenic markers. These findings are explained in light of the results of the physical characterization, combined with numerical calculations. It is established that the applied magnetic field triggers a virtuous magneto-mechanical mechanism in which dipolar magnetic forces between the nanoparticle aggregates give rise to a spatial distribution of mechanical stresses in the silk fibroin matrix. The film with the largest nanoparticle load, under cell culture conditions (i.e. in aqueous environment), undergoes matrix deformations large enough to be sensed by the seeded cells as mechanical stimuli favoring the osteogenic differentiation.

Disclosing the Nature of Asymmetric Interface Magnetism in Co/Pt Multilayers.

Nowadays, a wide number of applications based on magnetic materials rely on the properties arising at the interface between different layers in complex heterostructures engineered at the nanoscale. In ferromagnetic/heavy metal multilayers, such as the [Co/Pt]N and [Co/Pd]N systems, the magnetic proximity effect was demonstrated to be asymmetric, thus inducing a magnetic moment on the Pt (Pd) layer that is typically higher at the top Co/Pt(Pd) interface. In this work, advanced spectroscopic and imaging techniques were combined with theoretical approaches to clarify the origin of this asymmetry both in Co/Pt trilayers and, for the first time, in multilayer systems that are more relevant for practical applications. The different magnetic moment induced at the Co/Pt interfaces was correlated to the microstructural features that are in turn affected by the growth processes that induce a different intermixing during the film deposition, thus influencing the interface magnetic profile.

Improving the radiopacity of Fe-Mn biodegradable metals by magnetron-sputtered W-Fe-Mn-C coatings: Application for thinner stents.

In this exploratory work, micrometric radiopaque W-Fe-Mn-C coatings were produced by magnetron sputtering plasma deposition, for the first time, with the aim to make very thin Fe-Mn stents trackable by fluoroscopy. The power of Fe-13Mn-1.2C target was kept constant at 400 W while that of W target varied from 100 to 400 W producing three different coatings referred to as P100, P200, P400. The effect of the increased W power on coatings thickness, roughness, structure, corrosion behavior and radiopacity was investigated. The coatings showed a power-dependent thickness and W concentration, different roughness values while a similar and uniform columnar structure. An amorphous phase was detected for both P100 and P200 coatings while γ-Fe, bcc-W and W3C phases found for P400. Moreover, P200 and P400 showed a significantly higher corrosion rate (CR) compared to P100. The presence of W, W3C as well as the Fe amount variation determined two different micro-galvanic corrosion mechanisms significantly changing the CR of coatings, 0.26 ± 0.02, 59.68 ± 1.21 and 59.06 ± 1.16 µm/year for P100, P200 and P400, respectively. Sample P200 with its most uniform morphology, lowest roughness (RMS = 3.9 ± 0.4 nm) and good radiopacity (∼6%) appeared the most suitable radiopaque biodegradable coating investigated in this study.

Transformation of industrial and organic waste into titanium doped activated carbon - cellulose nanocomposite for rapid removal of organic pollutants.

Production of cost-efficient composite materials with desired physicochemical properties from low-cost waste material is much needed to meet the growing needs of the industrial sector. As a step forward, the current study reports for the first time an effective utilization of industrial metal (inorganic) waste as well as fall leaves (organic waste), to produce three types of nanomaterials at the same time; "Titanium Doped Activated Carbon Nanostructures (Ti-ACNs)", "Nanocellulose (NCel)", and combination of both "Titanium Doped Activated Carbon Cellulose Nanocomposite (Ti-AC-Cel-NC)". X-ray diffraction (XRD), transmission electron microscopy (TEM) and microanalysis (EDXS) measurements reveal that the Ti-ACNs material is formed by Ti-nanostructures, generally poorly crystalized but in some cases forming hexagonal Ti-crystallites of 15 nm, embedded in mutated graphene clouds. Micro- Fourier transform infrared spectroscopy (micro-FTIR) confirms that the chemical structure of NCel with bond vibrations between 1035 to 2917 cm-1 remained preserved during Ti-AC-Cel-NC formation. The prepared materials (Ti-ACNs, Ti-AC-Cel-NC) have demonstrated rapid removal of organic pollutants (Crystal Violet, Methyl Violet) from wastewater through surface adsorption and photocatalysis. In the first 20 min, Ti-ACNs have adsorbed ≈87% of the organic pollutants and further photocatalyzed them up to ≈96%. When Ti-ACNs are combined with NCel, their efficiency is increased of about four times. This performance originates from the adsorption by mutated graphene-like carbon and assisted photocatalysis by Ti nanostructures as well as the good supporting capacity of NCel for the homogenous Ti-ACNs distribution.

Complex correlations between microstructure and magnetic behavior in SrFe12O19 hexaferrite nanoparticles.

The magnetic properties of SrFe12O19 (SFO) hard hexaferrites are governed by the complex relation to its microstructure, determining their relevance for permanent magnets´ applications. A set of SFO nanoparticles obtained by sol-gel self-combustion synthesis was selected for an in-depth structural X-Rays powder diffraction (XRPD) characterization by means of G(L) line-profile analysis. The obtained crystallites´ size distribution reveal a clear dependence of the size along the [001] direction on the synthesis approach, resulting in the formation of platelet-like crystallites. In addition, the size of the SFO nanoparticles was determined by transmission electron microscopy (TEM) analysis and the average number of crystallites within a particle was estimated. These results have been evaluated to illustrate the formation of single-domain state below a critical value, and the activation volume was derived from time dependent magnetization measurements, aiming to clarify the reversal magnetization process of hard magnetic materials.

Wavy graphene sheets from electrochemical sewing of corannulene.

The presence of non-hexagonal rings in the honeycomb carbon arrangement of graphene produces rippled graphene layers with valuable chemical and physical properties. In principle, a bottom-up approach to introducing distortion from planarity of a graphene sheet can be achieved by careful insertion of curved polyaromatic hydrocarbons during the growth of the lattice. Corannulene, the archetype of such non-planar polyaromatic hydrocarbons, can act as an ideal wrinkling motif in 2D carbon nanostructures. Herein we report an electrochemical bottom-up method to obtain egg-box shaped nanographene structures through a polycondensation of corannulene that produces a new conducting layered material. Characterization of this new polymeric material by electrochemistry, spectroscopy, electron microscopy (SEM and TEM), scanning probe microscopy, and laser desorption-ionization time of flight mass spectrometry provides strong evidence that the anodic polymerization of corannulene, combined with electrochemically induced oxidative cyclodehydrogenations (Scholl reactions), leads to polycorannulene with a wavy graphene-like structure.

Combined Bottom-Up and Top-Down Approach for Highly Ordered One-Dimensional Composite Nanostructures for Spin Insulatronics.

Engineering magnetic proximity effects-based devices requires developing efficient magnetic insulators. In particular, insulators, where magnetic phases show dramatic changes in texture on the nanometric level, could allow us to tune the proximity-induced exchange splitting at such distances. In this paper, we report the fabrication and characterization of highly ordered two-dimensional arrays of LaFeO3 (LFO)-CoFe2O4 (CFO) biphasic magnetic nanowires, grown on silicon substrates using a unique combination of bottom-up and top-down synthesis approaches. The regularity of the patterns was confirmed using atomic force microscopy and scanning electron microscopy techniques, whereas magnetic force microscopy images established the magnetic homogeneity of the patterned nanowires and absence of any magnetic debris between the wires. Transmission electron microscopy shows a close spatial correlation between the LFO and CFO phases, indicating strong grain-to-grain interfacial coupling, intrinsically different from the usual core-shell structures. Magnetic hysteresis loops reveal the ferrimagnetic nature of the composites up to room temperature and the presence of a strong magnetic coupling between the two phases, and electrical transport measurements demonstrate the strong insulating behavior of the LFO-CFO composite, which is found to be governed by Mott-variable range hopping conduction mechanisms. A shift in the Raman modes in the composite sample compared to those of pure CFO suggests the existence of strain-mediated elastic coupling between the two phases in the composite sample. Our work offers ordered composite nanowires with strong interfacial coupling between the two phases that can be directly integrated for developing multiphase spin insulatronic devices and emergent magnetic interfaces.

Magnetic Nanoparticles Coated with (R)-9-Acetoxystearic Acid for Biomedical Applications.

The well-known ability to selectively drive nanomagnetic materials coated with anticancer drugs into tumor cells suggested the synthesis and the characterization of magnetic nanoparticles (MNPs) functionalized with (R)-9-acetoxystearic acid, the acetic ester of (R)-9-hydroxystearic acid (9-HSA), an antiproliferative agent active against different cancer cells. The acyl chloride of (R)-9-acetoxystearic acid, synthesized in two steps from 9-HSA, was reacted with (3-aminopropyl)triethoxysilane, chosen as a linker between MNPs and the stearyl moiety. In the last step, the novel amide was bound to magnetite NPs by reaction with silyl groups. A detailed structural, chemical, and magnetic characterization of the obtained material proved that it possesses properties in agreement with the requirements for drug delivery, opening the possibility to further insights focused on the 9-HSA biomedical applications.

Encapsulation of a Neutral Molecule into a Cationic Clay Material: Structural Insight and Cytotoxicity of Resveratrol/Layered Double Hydroxide/BSA Nanocomposites.

Resveratrol (RES) is a stilbenoid polyphenol with interesting antitumor activity compromised by its poor solubility and bioavailability; thus, new approaches are necessary to improve its therapeutic effectiveness. In the present study, bovine serum albumin coated layered double hydroxide (LDH-BSA) was employed to encapsulate RES in order to overcome the above-mentioned usage limits. To evaluate the feasibility of neutral RES complexation with cationic LDH, we carried out molecular dynamics simulation in order to predict its structure and stability. In the supramolecular complex formed with LDH, RES disposes itself in the interlamellar region of LDH where it is stabilized by intermolecular interactions. The physico-chemical characteristics of the resulting nanocomplexes were studied by X-ray powder diffraction, transmission electron microscopy, and attenuated total reflection Fourier transform infrared spectroscopy. The encapsulation efficiency and drug release studies were also performed. The combined experimental and computational approach were highly effective in giving insight into the interaction mode of the neutral RES with the charged LDH. Finally, the nanohybrid's anticancer ability was evaluated in human lung cancer cell line (A549) resulting in higher activity with respect to bare RES. Overall, the results showed that the nanocomposites are suitable for biomedical applications as delivery agents of RES.

Thermoresistive Properties of Graphite Platelet Films Supported by Different Substrates.

Large-area graphitic films, produced by an advantageous technique based on spraying a graphite lacquer on glass and low-density polyethylene (LDPE) substrates were studied for their thermoresistive applications. The spray technique uniformly covered the surface of the substrate by graphite platelet (GP) unities, which have a tendency to align parallel to the interfacial plane. Transmission electron microscopy analysis showed that the deposited films were composed of overlapped graphite platelets of different thickness, ranging from a few tens to hundreds of graphene layers, and Raman measurements provided evidence for a good graphitic quality of the material. The GP films deposited on glass and LDPE substrates exhibited different thermoresistive properties during cooling-heating cycles in the -40 to +40 °C range. Indeed, negative values of the temperature coefficient of resistance, ranging from -4 × 10-4 to -7 × 10-4 °C-1 have been observed on glass substrates, while positive values varying between 4 × 10-3 and 8 × 10-3 °C-1 were measured when the films were supported by LDPE. These behaviors were attributed to the different thermal expansion coefficients of the substrates. The appreciable thermoresistive properties of the graphite platelet films on LDPE could be useful for plastic electronic applications.

Solid-State Phase Transformations in Thermally Treated Ti-6Al-4V Alloy Fabricated via Laser Powder Bed Fusion.

Laser Powder Bed Fusion (LPBF) technology was used to produce samples based on the Ti-6Al-4V alloy for biomedical applications. Solid-state phase transformations induced by thermal treatments were studied by neutron diffraction (ND), X-ray diffraction (XRD), scanning transmission electron microscopy (STEM) and energy-dispersive spectroscopy (EDS). Although, ND analysis is rather uncommon in such studies, this technique allowed evidencing the presence of retained ß in α' martensite of the as-produced (#AP) sample. The retained ß was not detectable by XRD analysis, nor by STEM observations. Martensite contains a high number of defects, mainly dislocations, that anneal during the thermal treatment. Element diffusion and partitioning are the main mechanisms in the α ↔ ß transformation that causes lattice expansion during heating and determines the final shape and size of phases. The retained ß phase plays a key role in the α' → ß transformation kinetics.

Encapsulation of vitamin B12 into nanoengineered capsules and soft matter nanosystems for targeted delivery.

Targeted delivery of vitamins to a desirable area is an active branch in a modern pharmacology. The most important and difficult delivery of vitamin B12 is that to bone marrow and nerve cells. Herein we present a first step towards the development of two types of smart carriers, polymer capsules and lyotropic liquid-crystalline nanosystems, for vitamin B12 targeted delivery and induced release. A vitamin B12 encapsulation technique into nanoengineered polymeric capsules produced by layer-by-layer assembling of polymeric shells on CaCO3 templates has been developed. The effectiveness of the process was demonstrated by optical absorption spectroscopy, transmission electron microscopy (TEM), atomic force microscopy (AFM) and small-angle X-ray diffraction. TEM and AFM analyses performed on capsules after their drying, confirmed the presence of the vitamin B12 inside the capsules in the form of crystalline nanoaggregates, 50-300 nm in diameter. Soft lipid nanovectors consisting of amphiphilic phytantriol molecules, which in water excess spontaneously self-assembly in 3D well-ordered inverse bicontinuous cubic bulk phase, were used as alternative carriers for vitamin B12. It was shown that about 30% of the vitamin added in the preparation of the soft lipid system was actually encapsulated in cubosomes and that no structural changes occurred upon loading. The Vitamin stabilizes the lipid system playing the role of its structure-forming element. The biocompatible nature, the stability and the feasibility of these systems make them good candidates as carriers for hydrophilic vitamins.

Cross-Contamination Quantification in Powders for Additive Manufacturing: A Study on Ti-6Al-4V and Maraging Steel.

Metal additive manufacturing is now taking the lead over traditional manufacturing techniques in applications such as aerospace and biomedicine, which are characterized by low production volumes and high levels of customization. While fulfilling these requirements is the strength of metal additive manufacturing, respecting the tight tolerances typical of the mentioned applications is a harder task to accomplish. Powder bed fusion (PBF) is a class of additive manufacturing in which layers of metal powder are fused on top of each other by a high-energy beam (laser or electron beam) according to a computer-aided design (CAD) model. The quality of raw powders for PBF affects the mechanical properties of additively manufactured parts strongly, and therefore it is crucial to avoid the presence of any source of contamination, particularly cross-contamination. In this study, the identification and quantification of cross-contamination in powders of Ti-6Al-4V and maraging steel was performed using scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS) techniques. Experimental results showed an overall good reliability of the developed method, opening the way for applications in machine learning environments.