High fatigue resistance in a titanium alloy via near-void-free 3D printing.

The advantage of 3D printing-that is, additive manufacturing (AM) of structural materials-has been severely compromised by their disappointing fatigue properties1,2. Commonly, poor fatigue properties appear to result from the presence of microvoids induced by current printing process procedures3,4. Accordingly, the question that we pose is whether the elimination of such microvoids can provide a feasible solution for marked enhancement of the fatigue resistance of void-free AM (Net-AM) alloys. Here we successfully rebuild an approximate void-free AM microstructure in Ti-6Al-4V titanium alloy by development of a Net-AM processing technique through an understanding of the asynchronism of phase transformation and grain growth. We identify the fatigue resistance of such AM microstructures and show that they lead to a high fatigue limit of around 1 GPa, exceeding the fatigue resistance of all AM and forged titanium alloys as well as that of other metallic materials. We confirm the high fatigue resistance of Net-AM microstructures and the potential advantages of AM processing in the production of structural components with maximum fatigue strength, which is beneficial for further application of AM technologies in engineering fields.

Hierarchical Surface Pattern on Ni-Free Ti-Based Bulk Metallic Glass to Control Cell Interactions.

Ni-free Ti-based bulk metallic glasses (BMGs) are exciting materials for biomedical applications because of their outstanding biocompatibility and advantageous mechanical properties. The glassy nature of BMGs allows them to be shaped and patterned via thermoplastic forming (TPF). This work demonstrates the versatility of the TPF technique to create micro- and nano-patterns and hierarchical structures on Ti40Zr10Cu34Pd14Sn2 BMG. Particularly, a hierarchical structure fabricated by a two-step TPF process integrates 400 nm hexagonal close-packed protrusions on 2.5 µm square protuberances while preserving the advantageous mechanical properties from the as-cast material state. The correlations between thermal history, structure, and mechanical properties are explored. Regarding biocompatibility, Ti40Zr10Cu34Pd14Sn2 BMGs with four surface topographies (flat, micro-patterned, nano-patterned, and hierarchical-structured surfaces) are investigated using Saos-2 cell lines. Alamar Blue assay and live/dead analysis show that all tested surfaces have good cell proliferation and viability. Patterned surfaces are observed to promote the formation of longer filopodia on the edge of the cytoskeleton, leading to star-shaped and dendritic cell morphologies compared with the flat surface. In addition to potential implant applications, TPF-patterned Ti-BMGs enable a high level of order and design flexibility on the surface topography, expanding the available toolbox for studying cell behavior on rigid and ordered surfaces.

Mapping Shear Bands in Metallic Glasses: From Atomic Structure to Bulk Dynamics.

A deep understanding of the mechanisms controlling shear banding is of fundamental importance for improving the mechanical properties of metallic glasses. Atomistic simulations highlight the importance of nanoscale stresses and strains for shear banding, but corresponding experimental proofs are scarce due to limited characterization techniques. Here, by using precession nanodiffraction mapping in the transmission electron microscope, the atomic density and strain distribution of an individual shear band is quantitatively mapped at 2 nm resolution. We demonstrate that shear bands exhibit density alternation from the atomic scale to the submicron scale and complex strain fields exist, causing shear band segmentation and deflection. The atomic scale density alternation reveals the autocatalytic generation of shear transformation zones, while the density alternation at submicron scale results from the progressive propagation of shear band front and extends to the surrounding matrix, forming oval highly strained regions with density consistently higher (∼0.2%) than the encapsulated shear band segments. Through combination with molecular dynamic simulations, a complete picture for shear band formation and propagation is established.

Metallic Glass Films with Nanostructured Periodic Density Fluctuations Supported on Si/SiO2 as an Efficient Hydrogen Sorber.

Nanostructured metallic glass films (NMGF) can exhibit surface and intrinsic effects that give rise to unique physical and chemical properties. Here, a facile synthesis and electrochemical, structural, and morphologic characterization of Pd-Au-Si based MGs of approximately 50 nm thickness supported on Si/SiO2 is reported. Impressively, the maximum total hydrogen charge stored in the Pd-Au-Si nanofilm is equal to that in polycrystalline Pd films with 1 µm thickness in 0.1 m H2 SO4 electrolyte. The same NMGF has a volumetric desorption charge that is more than eight times and 25 % higher than that of polycrystalline PdNF and Pd-Cu-Si NMGF with the same thickness supported on Si/SiO2 , respectively. A significant number of nanovoids originating from PdHx crystals, and an increase in the average interatomic spacing is detected in Pd-Au-Si NMGF by high-resolution TEM. Such a high amount of hydrogen sorption is linked to the unique density fluctuations without any chemical segregation exclusively observed for this NMGF.

Mechanochemical reaction of Al and melamine: a potential approach towards the in situ synthesis of aluminum nitride-carbon nanotube nanocomposites.

In the current study, an inexpensive solid-state mechanochemical technique is proposed for the in situ synthesis of nanostructured aluminum nitride (AlN) and carbon nanotubes (CNTs). The CNTs and nitrogen-doped CNTs are synthesized through a novel bottom-up milling approach in which melamine as the solid source of both carbon and nitrogen is milled with aluminum. However, the efficiency of CNT formation remarkably enhances when the milled powder is exposed to a subsequent heat treatment. The effect of various parameters such as milling media, aluminum-to-melamine molar ratio (Al/M), milling time and subsequent heating temperature on the yield and formation mechanism of the produced CNTs are assessed. A detailed characterization of the final products reveals that small amorphous carbon nitride domains resulting from polymerization of melamine molecules at the intermediate stages of milling are responsible for the synthesis of CNTs either during the milling or subsequent heat treatment processes.

Mechanochemical synthesis of nanostructured metal nitrides, carbonitrides and carbon nitride: a combined theoretical and experimental study.

Nowadays, the development of highly efficient routes for the low cost synthesis of nitrides is greatly growing. Mechanochemical synthesis is one of those promising techniques which is conventionally employed for the synthesis of nitrides by long term milling of metallic elements under a pressurized N2 or NH3 atmosphere (A. Calka and J. I. Nikolov, Nanostruct. Mater., 1995, 6, 409-412). In the present study, we describe a versatile, room-temperature and low-cost mechanochemical process for the synthesis of nanostructured metal nitrides (MNs), carbonitrides (MCNs) and carbon nitride (CNx). Based on this technique, melamine as a solid nitrogen-containing organic compound (SNCOC) is ball milled with four different metal powders (Al, Ti, Cr and V) to produce nanostructured AlN, TiCxN1-x, CrCxN1-x, and VCxN1-x (x ∼ 0.05). Both theoretical and experimental techniques are implemented to determine the reaction intermediates, products, by-products and finally, the mechanism underling this synthetic route. According to the results, melamine is polymerized in the presence of metallic elements at intermediate stages of the milling process, leading to the formation of a carbon nitride network. The CNx phase subsequently reacts with the metallic precursors to form MN, MCN or even MCN-CNx nano-composites depending on the defect formation energy and thermodynamic stability of the corresponding metal nitride, carbide and C/N co-doped structures.

Direct in situ observations of single Fe atom catalytic processes and anomalous diffusion at graphene edges.

Single-atom catalysts are of great interest because of their high efficiency. In the case of chemically deposited sp(2) carbon, the implementation of a single transition metal atom for growth can provide crucial insight into the formation mechanisms of graphene and carbon nanotubes. This knowledge is particularly important if we are to overcome fabrication difficulties in these materials and fully take advantage of their distinct band structures and physical properties. In this work, we present atomically resolved transmission EM in situ investigations of single Fe atoms at graphene edges. Our in situ observations show individual iron atoms diffusing along an edge either removing or adding carbon atoms (viz., catalytic action). The experimental observations of the catalytic behavior of a single Fe atom are in excellent agreement with supporting theoretical studies. In addition, the kinetics of Fe atoms at graphene edges are shown to exhibit anomalous diffusion, which again, is in agreement with our theoretical investigations.

Alloying Behavior of Self-Assembled Noble Metal Nanoparticles.

The atomic redistribution processes occurring in multiparticle nanostructures are hardly understood. To obtain a more detailed insight, we applied high-resolution microscopic, diffraction and spectroscopic characterization techniques to investigate the fine structure and elemental distribution of various bimetallic aerogels with 1:1 compositions, prepared by self-assembly of single monometallic nanoparticles. The system Au-Ag exhibited a complete alloy formation, whereas Pt-Pd aerogels formed a Pd-based network with embedded Pt particles. The assembly of Au and Pd nanoparticles resulted in a Pd-shell formation around the Au particles. This work confirms that bimetallic aerogels are subject to reorganization processes during their gel formation.

Layered-to-Tunnel Structure Transformation and Oxygen Redox Chemistry in LiRhO2 upon Li Extraction and Insertion.

Layered Li(M,Li)O2 (where M is a transition metal) ordered rock-salt-type structures are used in advanced metal-ion batteries as one of the best hosts for the reversible intercalation of Li ions. Besides the conventional redox reaction involving oxidation/reduction of the M cation upon Li extraction/insertion, creating oxygen-located holes because of the partial oxygen oxidation increases capacity while maintaining the oxidized oxygen species in the lattice through high covalency of the M-O bonding. Typical degradation mechanism of the Li(M,Li)O2 electrodes involves partially irreversible M cation migration toward the Li positions, resulting in gradual capacity/voltage fade. Here, using LiRhO2 as a model system (isostructural and isoelectronic to LiCoO2), for the first time, we demonstrate an intimate coupling between the oxygen redox and M cation migration. A formation of the oxidized oxygen species upon electrochemical Li extraction coincides with transformation of the layered Li1-xRhO2 structure into the γ-MnO2-type rutile-ramsdellite intergrowth LiyRh3O6 structure with rutile-like [1 × 1] channels along with bigger ramsdellite-like [2 × 1] tunnels through massive and concerted Rh migration toward the empty positions in the Li layers. The oxidized oxygen dimers with the O-O distances as short as 2.26 Å are stabilized in this structure via the local Rh-O configuration reminiscent to that in the µ-peroxo-µ-hydroxo Rh complexes. The LiyRh3O6 structure is remarkably stable upon electrochemical cycling illustrating that proper structural implementation of the oxidized oxygen species can open a pathway toward deliberate employment of the anion redox chemistry in high-capacity/high-voltage positive electrodes for metal-ion batteries.

Direct growth of ultrafast transparent single-layer graphene defoggers.

The idea flat surface, superb thermal conductivity and excellent optical transmittance of single-layer graphene promise tremendous potential for graphene as a material for transparent defoggers. However, the resistance of defoggers made from conventional transferred graphene increases sharply once both sides of the film are covered by water molecules which, in turn, leads to a temperature drop that is inefficient for fog removal. Here, the direct growth of large-area and continuous graphene films on quartz is reported, and the first practical single-layer graphene defogger is fabricated. The advantages of this single-layer graphene defogger lie in its ultrafast defogging time for relatively low input voltages and excellent defogging robustness. It can completely remove fog within 6 s when supplied a safe voltage of 32 V. No visible changes in the full defogging time after 50 defogging cycles are observed. This outstanding performance is attributed to the strong interaction forces between the graphene films and the substrates, which prevents the permeation of water molecules. These directly grown transparent graphene defoggers are expected to have excellent prospects in various applications such as anti-fog glasses, auto window and mirror defogging.

SEI-component formation on sub 5 nm sized silicon nanoparticles in Li-ion batteries: the role of electrode preparation, FEC addition and binders.

Silicon is a promising negative electrode for secondary lithium-based batteries, but the electrochemical reversibility of particularly nanostructured silicon electrodes drastically depends on their interfacial characteristics, commonly known as the solid electrolyte interface (SEI). The beneficial origin of certain electrolyte additives or different binders is still discussed controversially owing to the challenging peculiarities of interfacial post-mortem investigations of electrodes. In this work, we address the common difficulties of SEI investigations of porous silicon/carbon nanostructures and study the addition of a fluoroethylene carbonate (FEC) as a stabilizing additive as well as the use of two different binders, carboxymethyl cellulose/styrene-butadiene rubber (CMC/SBR) and polyacrylic acid (PAA), for the SEI formation. The electrode is composed of silicon nanocrystallites below 5 nm diameter allowing a detailed investigation of interfacial characteristics of silicon owing to the high surface area. We first performed galvanostatic long-term cycling (400 times) and carried out comprehensive ex situ characterization of the cycled nanocrystalline silicon electrodes with XRD, EDXS, TEM and XPS. We modified the preparation of the electrode for post-mortem characterization to distinguish between electrolyte components and the actual SEI. The impact of the FEC additive and two different binders on the interfacial layer is studied and the occurrence of diverse compounds, in particular LiF, Li2O and phosphates, is discussed. These results help to understand general issues in SEI formation and to pave the way for the development of advanced electrolytes allowing for a long-term performance of nanostructured Si-based electrodes.

A growth mechanism for free-standing vertical graphene.

We propose a detailed mechanism for the growth of vertical graphene by plasma-enhanced vapor deposition. Different steps during growth including nucleation, growth, and completion of the free-standing two-dimensional structures are characterized and analyzed by transmission electron microscopy. The nucleation of vertical graphene growth is either from the buffer layer or from the surface of carbon onions. A continuum model based on the surface diffusion and moving boundary (mass flow) is developed to describe the intermediate states of the steps and the edges of graphene. The experimentally observed convergence tendency of the steps near the top edge can be explained by this model. We also observed the closure of the top edges that can possibly stop the growth. This two-dimensional vertical growth follows a self-nucleated, step-flow mode, explained for the first time.

Room temperature in situ growth of B/BOx nanowires and BOx nanotubes.

Despite significant advances in the synthesis of nanostructures, our understanding of the growth mechanisms of nanowires and nanotubes grown from catalyst particles remains limited. In this study we demonstrate a straightforward route to grow coaxial amorphous B/BOx nanowires and BOx nanotubes using gold catalyst particles inside a transmission electron microscope at room temperature without the need of any specialized or expensive accessories. Exceedingly high growth rates (over 7 µm/min) are found for the coaxial nanowires, and this is attributed to the highly efficient diffusion of B species along the surface of a nanowire by electrostatic repulsion. On the other hand the O species are shown to be relevant to activate the gold catalysts, and this can occur through volatile O species. The technique could be further developed to study the growth of other nanostructures and holds promise for the room temperature growth of nanostructures as a whole.

Deformation at ambient and high temperature of in situ Laves phases-ferrite composites.

The mechanical behavior of a Fe80Zr10Cr10 alloy has been studied at ambient and high temperature. This Fe80Zr10Cr10 alloy, whoose microstructure is formed by alternate lamellae of Laves phase and ferrite, constitutes a very simple example of an in situ CMA phase composite. The role of the Laves phase type was investigated in a previous study while the present work focuses on the influence of the microstructure length scale owing to a series of alloys cast at different cooling rates that display microstructures with Laves phase lamellae width ranging from ∼50 nm to ∼150 nm. Room temperature compression tests have revealed a very high strength (up to 2 GPa) combined with a very high ductility (up to 35%). Both strength and ductility increase with reduction of the lamella width. High temperature compression tests have shown that a high strength (900 MPa) is maintained up to 873 K. Microstructural study of the deformed samples suggests that the confinement of dislocations in the ferrite lamellae is responsible for strengthening at both ambient and high temperature. The microstructure scale in addition to CMA phase structural features stands then as a key parameter for optimization of mechanical properties of CMA in situ composites.

How to catch a shear band and explain plasticity of metallic glasses with continuum mechanics.

Capturing a shear band in a metallic glass during its propagation experimentally is very challenging. Shear bands are very narrow but extend rapidly over macroscopic distances, therefore, characterization of large areas at high magnification and high speed is required. Here we show how to control the shear bands in a pre-structured thin film metallic glass in order to directly measure local strains during initiation, propagation, or arrest events. Based on the experimental observations, a model describing the shear banding phenomenon purely within the frameworks of continuum mechanics is formulated. We claim that metallic glasses exhibit an elastic limit of about 5% which must be exceeded locally either at a stress concentrator to initiate a shear banding event, or at the tip of a shear band during its propagation. The model can successfully connect micro- and macroscopic plasticity of metallic glasses and suggests an alternative interpretation of controversial experimental observations.

Energy Absorption and Beam Damage during Microfocus Synchrotron X-ray Diffraction.

In this study, we combine in situ fast differential scanning calorimetry (FDSC) with synchrotron X-ray measurements to study simultaneously the structure and thermophysical properties of materials. Using the example of the organic compound BCH-52, we show that the X-ray beam can heat the sample and induce a shift of the heat-flow signal. The aim of this paper is to investigate the influence of radiation on sample behavior. The calorimetric data is used to quantify the absorbed beam energy and, together with the diffraction data, reveal an irreversible damage of the sample. The results are especially important for materials with high absorption coefficients and for high-energy X-ray and electron beams. Our findings illustrate that FDSC combined with X-ray diffraction is a suitable characterization method when beam damage must be minimized.

Circumventing Solidification Cracking Susceptibility in Al-Cu Alloys Prepared by Laser Powder Bed Fusion.

Laser powder bed fusion (LPBF) of Al-Cu alloys shows high susceptibility to cracking due to a wide solidification temperature range. In this work, 2024 alloys were manufactured by LPBF at different laser processing parameters. The effect of processing parameters on the densification behavior and mechanical properties of the LPBF-processed 2024 alloys was investigated. The results show that the porosity increases significantly with increasing laser power, while the number of cracks and lack-of-fusion defects increase distinctly with increasing scan speed. The solidification cracking susceptibility of the LPBF-processed 2024 alloys prepared at different processing parameters was analyzed based on a finite element model, which was accurately predicted by theoretical calculations. Dense and crack-free 2024 samples with a high densification of over 98.1% were manufactured at a low laser power of 200 W combined with a low laser scan speed of 100 mm/s. The LPBF-processed 2024 alloys show a high hardness of 110 ± 4 HV0.2, an ultimate tensile strength of 300 ± 15 MPa, and an elongation of ∼3%. This work can serve as reference for obtaining crack-free and high-performance Al-Cu alloys by LPBF.

Anticorrosion and Antimicrobial Tannic Acid-Functionalized Ti-Metallic Glass Ribbons for Dental Abutment.

In this study, a recently reported Ti-based metallic glass (MG), without any toxic element, but with a significant amount of metalloid (Si-Ge-B, 18 atom %) and minor soft element (Sn, 2 atom %), was produced in ribbon form using conventional single-roller melt-spinning. The produced Ti60Zr20Si8Ge7B3Sn2 ribbons were investigated by differential scanning calorimetry and X-ray diffraction to confirm their amorphous structure, and their corrosion properties were further investigated by open-circuit potential and cyclic polarization tests. The ribbon's surface was functionalized by tannic acid, a natural plant-based polyphenol, to enhance its performance in terms of corrosion prevention and antimicrobial efficacy. These properties can potentially be exploited in the premucosal parts of dental implants (abutments). The Folin and Ciocalteu test was used for the quantification of tannic acid (TA) grafted on the ribbon surface and of its redox activity. Fluorescent microscopy and ζ-potential measurements were used to confirm the presence of TA on the surfaces of the ribbons. The cytocompatibility evaluation (indirect and direct) of TA-functionalized Ti60Zr20Si8Ge7B3Sn2 MG ribbons toward primary human gingival fibroblast demonstrated that no significant differences in cell viability were detected between the functionalized and as-produced (control) MG ribbons. Finally, the antibacterial investigation of TA-functionalized samples against Staphylococcus aureus demonstrated the specimens' antimicrobial properties, shown by scanning electron microscopy images after 24 h, presenting a few single colonies remaining on their surfaces. The thickness of bacterial aggregations (biofilm-like) that were formed on the surface of the as-produced samples reduced from 3.5 to 1.5 µm.

Hydrothermal carbon-based nanostructured hollow spheres as electrode materials for high-power lithium-sulfur batteries.

Carbon hollow spheres were produced using a sustainable approach, i.e. hydrothermal carbonization, using monosaccharides as carbon precursors and silica nanoparticles as hard-templates. Hydrothermal carbonization is an eco-efficient and cost-effective route to synthesize nanostructured carbonaceous materials from abundant biomass-derived molecules. After further thermal treatment under an inert atmosphere and removal of the silica-based core by chemical etching, porous hollow spheres depicting 5-8 nm thin shells were obtained. Subsequently, carbon-sulfur composites were synthesized via a melt diffusion method and used as nanostructured composites for cathodes in lithium-sulfur (Li-S) cells. The morphology of the hollow spheres was controlled and optimized to achieve improved electrochemical properties. Both high specific energies and high specific powers were obtained, due to the unique nanostructure of the hollow spheres. These results revealed that using optimized carbonaceous materials, it is possible to design sustainable Li-S cells showing promising electrochemical properties.

Thermal stability and phase transformations of martensitic Ti-Nb alloys.

Aiming at understanding the governing microstructural phenomena during heat treatments of Ni-free Ti-based shape memory materials for biomedical applications, a series of Ti-Nb alloys with Nb concentrations up to 29 wt% was produced by cold-crucible casting, followed by homogenization treatment and water quenching. Despite the large amount of literature available concerning the thermal stability and ageing behavior of Ti-Nb alloys, only few studies were performed dealing with the isochronal transformation behavior of initially martensitic Ti-Nb alloys. In this work, the formation of martensites (α' and α″) and their stability under different thermal processing conditions were investigated by a combination of x-ray diffraction, differential scanning calorimetry, dilatometry and electron microscopy. The effect of Nb additions on the structural competition in correlation with stable and metastable phase diagrams was also studied. Alloys with 24 wt% Nb or less undergo a [Formula: see text] transformation sequence on heating from room temperature to 1155 K. In alloys containing >24 wt% Nb α″ martensitically reverts back to ß0, which is highly unstable against chemical demixing by formation of isothermal ωiso. During slow cooling from the single phase ß domain α precipitates and only very limited amounts of α″ martensite form.