On the Biomechanical Performances of Duplex Stainless Steel Graded Scaffolds Produced by Laser Powder Bed Fusion for Tissue Engineering Applications.

This experimental study aims to extend the know-how on biomechanical performances of duplex stainless steel (DSS) for tissue engineering applications to a graded lattice geometry scaffold based on the F53 DSS (UNS S32750 according to ASTM A182) produced by laser powder bed fusion (LPBF). The same dense-out graded geometry based on rhombic dodecahedral elementary unit cells investigated in previous work on 316L stainless steel (SS) was adopted here for the manufacturing of the F53 DSS scaffold (SF53). Microstructural characterization and mechanical and biological tests were carried out on the SF53 scaffold, using the in vitro behavior of the 316L stainless steel scaffold (S316L) as a control. Results show that microstructure developed as a consequence of different volume energy density (VED) values is mainly responsible for the different mechanical behaviors of SF53 and S316L, both fabricated using the same LPBF manufacturing system. Specifically, the ultimate compressive strength (σUC) and elastic moduli (E) of SF53 are three times and seven times higher than S316L, respectively. Moreover, preliminary biological tests evidenced better cell viability in SF53 than in S316L already after seven days of culture, suggesting SF53 with dense-out graded geometry as a viable alternative to 316L SS for bone tissue engineering applications.

Combined Effects of HA Concentration and Unit Cell Geometry on the Biomechanical Behavior of PCL/HA Scaffold for Tissue Engineering Applications Produced by LPBF.

This experimental study aims at filling the gap in the literature concerning the combined effects of hydroxyapatite (HA) concentration and elementary unit cell geometry on the biomechanical performances of additively manufactured polycaprolactone/hydroxyapatite (PCL/HA) scaffolds for tissue engineering applications. Scaffolds produced by laser powder bed fusion (LPBF) with diamond (DO) and rhombic dodecahedron (RD) elementary unit cells and HA concentrations of 5, 30 and 50 wt.% were subjected to structural, mechanical and biological characterization to investigate the biomechanical and degradative behavior from the perspective of bone tissue regeneration. Haralick's features describing surface pattern, correlation between micro- and macro-structural properties and human mesenchymal stem cell (hMSC) viability and proliferation have been considered. Experimental results showed that HA has negative influence on scaffold compaction under compression, while on the contrary it has a positive effect on hMSC adhesion. The unit cell geometry influences the mechanical response in the plastic regime and also has an effect on the cell proliferation. Finally, both HA concentration and elementary unit cell geometry affect the scaffold elastic deformation behavior as well as the amount of micro-porosity which, in turn, influences the scaffold degradation rate.

Colorimetric and Fluorescent Sensing of Copper Ions in Water through o-Phenylenediamine-Derived Carbon Dots.

Fluorescent nitrogen and sulfur co-doped carbon dots (NSCDs) were synthesized using a simple one-step hydrothermal method starting from o-phenylenediamine (OPD) and ammonium sulfide. The prepared NSCDs presented a selective dual optical response to Cu(II) in water through the arising of an absorption band at 660 nm and simultaneous fluorescence enhancement at 564 nm. The first effect was attributed to formation of cuprammonium complexes through coordination with amino functional groups of NSCDs. Alternatively, fluorescence enhancement can be explained by the oxidation of residual OPD bound to NSCDs. Both absorbance and fluorescence showed a linear increase with an increase of Cu(II) concentration in the range 1-100 µM, with the lowest detection limit of 100 nM and 1 µM, respectively. NSCDs were successfully incorporated in a hydrogel agarose matrix for easier handling and application to sensing. The formation of cuprammonium complexes was strongly hampered in an agarose matrix while oxidation of OPD was still effective. As a result, color variations could be perceived both under white light and UV light for concentrations as low as 10 µM. Since these color changes were similarly perceived in tap and lake water samples, the present method could be a promising candidate for simple, cost-effective visual monitoring of copper onsite.

Microstructure and Mechanical Properties of Spark Plasma Sintered CoCrFeNiNbX High-Entropy Alloys with Si Addition.

Three mechanically alloyed (MA) and spark plasma sintered (SPS) CoCrFeNiNbX (X = 5, 20, and 35 at.%) alloys with an addition of 5 at.% of SiC were investigated. The face-centered cubic (FCC) high-entropy solid solution, NbC carbides, and hexagonal Laves phase already developed during MA. In addition, the SPS compacting led to the formation of oxide particles in all alloys, and the Cr7C3 carbides in the Nb5 alloy. The fraction of the FCC solid solution decreased with increasing Nb concentration at the expense of the NbC carbide and the Laves phase. Long-term annealing at 800 °C led to the disappearance of the Cr7C3 carbide in the Nb5 alloy, and new oxides-Ni6Nb6O, Cr2O3, and CrNbO4-were formed. At laboratory temperature, the Nb5 alloy, containing only the FCC matrix and carbide particles, was relatively strong and very ductile. At a higher Nb content (Nb20 and Nb35), the alloys became brittle. After annealing for 100 h at 800 °C, the Nb5 alloy conserved its plasticity and the Nb20 and Nb35 alloys maintained or even increased their brittleness. When tested at 800 °C, the Nb5 and Nb20 alloys deformed almost identically (CYS ~450 MPa, UTS ~500 MPa, plasticity ~18%), whereas the Nb35 alloy was much stronger (CYS of 1695 MPa, UCS of 1817 MPa) and preserved comparable plasticity.

Instrumented Nanoindentation Tests Applied to Bulk Metallic Materials: From Calibration Issue to Pile-Up Phenomena.

Instrumented nanoindentation tests have reached an effective level of theoretical and practical knowledge to become an interesting and useful tool for determining hardness, H, and local elasticity (reduced Young's modulus), Er, of a variety of materials, from coatings and thin films to bulk metallic materials. Nanoindentation instruments are equipped with analysis software for raw data for hardness and reduced Young's modulus evaluation, generally based on the Oliver and Pharr analysis method. On the other hand, it is widely known and recognized that prior data acquisition, a tip-dependent calibration procedure of compliance, and area function are needed. With this in view, an accurate and sound calibration protocol is here reported. Hardness and local elastic modulus is measured on different bulk metallic materials, showing the distinctive strengths of using nanoindentation. Finally, a local elastic-plastic phenomenon mostly induced by the nanoindentation tip on ductile metallic material (i.e., pile-up) is also reported and modelled. This manuscript is thus intended to favor and account for the importance of using the instrumented nanoindentation tests for H and Er measurements of metallic materials.

Phase Composition of Al-Si Coating from the Initial State to the Hot-Stamped Condition.

The chemical and phase composition of the coating and the coating/substrate interface of an Al-Si-coated 22MnB5 hot stamped steel was investigated by means of SEM-EDS, XRD, micro-XRD and electron diffraction. Moreover, the surface profile was analyzed by XPS and roughness measurements. The XPS measurements showed that the thickness of the Si and Al oxide layers increased from 14 to 76 nm after die-quenching, and that the surface roughness increased as well as a result of volume changes caused by phase transformations. In addition to the FeAl(Si) and Fe2Al5 phases and the interdiffusion layer forming complex structures in the coating, electron diffraction confirmed the presence of an Fe2Al5 phase, and also revealed very thin layers of Fe3(Al,Si)C, Fe2(Al,Si)5 and Al-bearing rod-shaped particles in the immediate vicinity of the steel interface. Moreover, the scattered nonuniform layer of the Fe2Al8Si phase was identified in the outermost layer of the coating. Despite numerous studies devoted to researching the phase composition of the Al-Si coating applied to hot stamped steel, electron diffraction revealed very thin layers and particles on the coating/substrate interface and outermost layer, which have not been analyzed in detail.

Solutions of Critical Raw Materials Issues Regarding Iron-Based Alloys.

The Critical Raw Materials (CRMs) list has been defined based on economic importance and supply risk by the European Commission. This review paper describes two issues regarding critical raw materials: the possibilities of their substitution in iron-based alloys and the use of iron-based alloys instead of other materials in order to save CRMs. This review covers strategies for saving chromium in stainless steel, substitution or lowering the amounts of carbide-forming elements (especially tungsten and vanadium) in tool steel and alternative iron-based CRM-free and low-CRM materials: austempered ductile cast iron, high-temperature alloys based on intermetallics of iron and sintered diamond tools with an iron-containing low-cobalt binder.

Development of TiAl-Si Alloys-A Review.

This paper describes the effect of silicon on the manufacturing process, structure, phase composition, and selected properties of titanium aluminide alloys. The experimental generation of TiAl-Si alloys is composed of titanium aluminide (TiAl, Ti3Al or TiAl3) matrix reinforced by hard and heat-resistant titanium silicides (especially Ti5Si3). The alloys are characterized by wear resistance comparable with tool steels, high hardness, and very good resistance to oxidation at high temperatures (up to 1000 °C), but also low room-temperature ductility, as is typical also for other intermetallic materials. These alloys had been successfully prepared by the means of powder metallurgical routes and melting metallurgy methods.

Plasma-immersion ion implantation surface oxidation on a cobalt-chromium alloy for biomedical applications.

Co-Cr alloys such as L605 are widely applied for the manufacture of medical devices, including tiny cardiovascular stents. The presence of potentially toxic and allergenic release of Ni, Co, and Cr ions from these devices remains an unsolved concern. Surface modification by oxygen plasma immersion implantation (PIII) could be an excellent technique to create a dense and thin passive oxide layer on a relatively complex shape of a tiny device, such as a stent, thus reducing the potential release of metallic ions. The effect of oxygen PIII was investigated on L605 alloy specimens, from 5 to 50 mTorr gas pressures, and under pulsed bias voltages from -0.1 to -10 kV. The surface chemistry was investigated by x-ray photoelectron spectroscopy, while its morphology and surface energy were evaluated, respectively, by atomic force microscopy and scanning electron microscopy and by a sessile drop static contact angle. Electrochemical characterization was performed by potentiodynamic tests in the saline solution. Mechanical properties of the modified surface layer, specifically film adhesion and hardness (H), were assessed by scratch and nanoindentation tests. Results shown that the oxidized layers were composed of a mixture of Co and Cr oxides and hydroxides and were rich in Co. The corrosion rate was considerably reduced after O PIII, even for treatments using low bias voltage (-0.1 kV) and with consequent low oxygen implantation depth. Moreover, O PIII also improved surface hardness. The oxidized layers were found to have good adhesion and to be scratch resistant.

Post-FSW Cold-Rolling Simulation of ECAP Shear Deformation and Its Microstructure Role Combined to Annealing in a FSWed AA5754 Plate Joint.

Friction stir welds are considered reliable joints for their lack of voids, cracks and distortions. When compared to the base material, friction stir welding (FSW) joints typically exhibit finer grain structured (especially at the nugget zone, NZ). Similarly, refined grain structure can also be obtained by severe plastic deformation (SPD) techniques, such as equal channel angular pressing (ECAP). In fact, the fine grain structures produced within the NZ of FSW or friction stir processed (FSP) materials are usually coarser than the ones achieved by ECAP. The former is characterized by lower dislocation density, higher high-angle boundary fraction and different mechanical strength, compared to what can be obtained by ECAP. In this study, a dedicated cold-rolling (CR) set-up, specifically designed to simulate an ECAP-equivalent shear deformation, was used to further refine the grain structure of FSW AA5754 sheets. The effect of ECAP-equivalent deformation induced by CR in a 2 mm-thick AA5754-H111 FSW joint was investigated. FSW was carried out at two different rotational (ω) and translational (v) welding speeds, 600 rpm, 200 mm/min and 1800 rpm, 75 mm/min, respectively. FSW sheets were then CR to obtain an equivalent shear strain of ε ~ 1.08, that is equivalent to 1-ECAP pass carried out with an internal die channels intersecting at an angle φ = 90° with a curvature extending over an angle Ψ = 20°. By CR, the sheet thickness reduced only by ~20%. The role of annealing on the FSW and CR plastically deformed AA5754 was also investigated. This was applied either prior or after FSW, and it resulted that whenever it follows the FSW, the mean volume fraction of dispersoids and Mg-rich particles is higher than the case of annealing preceding the FSW process. On the contrary, it was found that the annealing treatment had a minimal role on the dispersoids and particles mean size. The here reported post-FSW ECAP-simulated deformation, obtained by a customized CR process, showed sheet integrity and a significant concurrent grain size refinement.

High-Pressure Spark Plasma Sintering (HP SPS): A Promising and Reliable Method for Preparing Ti-Al-Si Alloys.

Ti-Al-Si alloys are prospective material for high-temperature applications. Due to low density, good mechanical properties, and oxidation resistance, these intermetallic alloys can be used in the aerospace and automobile industries. Ti-Al-Si alloys were prepared by powder metallurgy using reactive sintering, milling, and spark plasma sintering. One of the novel SPS techniques is high-pressure spark plasma sintering (HP SPS), which was tested in this work and applied to a Ti-10Al-20Si intermetallic alloy using a pressure of 6 GPa and temperatures ranging from 1318 K (1045 °C) to 1597 K (1324 °C). The low-porosity consolidated samples consist of Ti5Si3 silicides in an aluminide (TiAl) matrix. The hardness varied between 720 and 892 HV 5.