Manipulating Stacking Fault Energy to Achieve Crack Inhibition and Superior Strength-Ductility Synergy in an Additively Manufactured High-Entropy Alloy.

Additive manufacturing (AM) is a revolutionary technology that heralds a new era in metal processing, yet the quality of AM-produced parts is inevitably compromised by cracking induced by severe residual stress. In this study, a novel approach is presented to inhibit cracks and enhance the mechanical performances of AM-produced alloys by manipulating stacking fault energy (SFE). A high-entropy alloy (HEA) based on an equimolar FeCoCrNi composition is selected as the prototype material due to the presence of microcracks during laser powder bed fusion (LPBF) AM process. Introducing a small amount (≈2.4 at%) of Al doping can effectively lower SFE and yield the formation of multiscale microstructures that efficiently dissipate thermal stress during LPBF processing. Distinct from the Al-free HEA containing visible microcracks, the Al-doped HEA (Al0.1CoCrFeNi) is crack free and demonstrates ≈55% improvement in elongation without compromising tensile strength. Additionally, the lowered SFE enhances the resistance to crack propagation, thereby improving the durability of AM-printed products. By manipulating SFE, the thermal cycle-induced stress during the printing process can be effectively consumed via stacking faults formation, and the proposed strategy offers novel insights into the development of crack-free alloys with superior strength-ductility synergy for intricate structural applications.

The Printability, Microstructure, and Mechanical Properties of Fe80-xMnxCo10Cr10 High-Entropy Alloys Fabricated by Laser Powder Bed Fusion Additive Manufacturing.

This work investigated the effect of Fe/Mn ratio on the microstructure and mechanical properties of non-equimolar Fe80-xMnxCo10Cr10 (x = 30% and 50%) high-entropy alloys (HEAs) fabricated by laser powder bed fusion (LPBF) additive manufacturing. Process optimization was conducted to achieve fully dense Fe30Mn50Co10Cr10 and Fe50Mn30Co10Cr10 HEAs using a volumetric energy density of 105.82 J·mm-3. The LPBF-printed Fe30Mn50Co10Cr10 HEA exhibited a single face-centered cubic (FCC) phase, while the Fe50Mn30Co10Cr10 HEA featured a hexagonal close-packed (HCP) phase within the FCC matrix. Notably, the fraction of HCP phase in the Fe50Mn30Co10Cr10 HEAs increased from 0.94 to 28.10%, with the deformation strain ranging from 0 to 20%. The single-phase Fe30Mn50Co10Cr10 HEA demonstrated a remarkable combination of high yield strength (580.65 MPa) and elongation (32.5%), which surpassed those achieved in the FeMnCoCr HEA system. Comparatively, the dual-phase Fe50Mn30Co10Cr10 HEA exhibited inferior yield strength (487.60 MPa) and elongation (22.3%). However, it displayed superior ultimate tensile strength (744.90 MPa) compared to that in the Fe30Mn50Co10Cr10 HEA (687.70 MPa). The presence of FCC/HCP interfaces obtained in the Fe50Mn30Co10Cr10 HEA resulted in stress concentration and crack expansion, thereby leading to reduced ductility but enhanced resistance against grain slip deformation. Consequently, these interfaces facilitated an earlier attainment of yield limit point and contributed to increased ultimate tensile strength in the Fe50Mn30Co10Cr10 HEA. These findings provide valuable insights into the microstructure evolution and mechanical behavior of LPBF-printed metastable FeMnCoCr HEAs.

Process Optimization and Tailored Mechanical Properties of a Nuclear Zr-4 Alloy Fabricated via Laser Powder Bed Fusion.

A nuclear Zr-4 alloy with a near full density was fabricated via laser powder bed fusion (LPBF). The influences of process parameters on the printability, surface roughness, and mechanical properties of the LPBF-printed Zr-4 alloy were investigated. The results showed that the relative density of the Zr-4 alloy samples was greater than 99.3% with the laser power range of 120-160 W and the scanning speed range of 600-1000 mm/s. Under a moderate laser power in the range of 120-140 W, the printed Zr-4 alloy possessed excellent surface molding quality with a surface roughness less than 10 µm. The microstructure of the printed Zr-4 alloy was an acicular α phase with an average grain size of about 1 µm. The Zr-4 alloy printed with a laser power of 130 W and a scanning speed of 400 mm/s exhibited the highest compression strength of 1980 MPa and the highest compression strain of 28%. The findings demonstrate the potential in the fabrication of complex Zr-4 alloy parts by LPBF for industrial applications.

Corrosion fatigue behavior and anti-fatigue mechanisms of an additively manufactured biodegradable zinc-magnesium gyroid scaffold.

Additively manufactured biodegradable zinc (Zn) alloy scaffolds constitute an important branch in orthopedic implants because of their moderate degradation behavior and bone-mimicking mechanical properties. This work investigated the corrosion fatigue response of a zinc-magnesium (Zn-Mg) alloy gyroid scaffold fabricated via laser-powder-bed-fusion additive manufacturing at the first time. The high-cycle compression-compression fatigue testing of the printed Zn-Mg scaffold was conducted in simulated body fluid, showing its favorable fatigue strength, structural reliability, and anti-fatigue capability. The printed Zn-Mg scaffold obtained a 227% higher fatigue strength than that of the printed Zn scaffold but 17% lower strain accumulation at 106 cycles. The accumulative strain of the Zn-Mg scaffold at its fatigue strength was dominant by fatigue ratcheting, since the fatigue damage strain of the scaffold was approximately zero. The corrosion products (ZnO and Zn(OH)2) were conducive to the inhibition of fatigue ratcheting and fatigue damage. Dislocation pile-up and solid solution phases at the grain boundaries of the Zn-Mg scaffold could retard the spreading of the crack tip and impede excessive grain coarsening, improving its fatigue endurance limit. Notably, the printed Zn-Mg scaffold could dissipate the fatigue energy through moderate grain boundary migration, thus reducing its plastic deformation. These findings illuminated the anti-fatigue mechanisms related to microstructural features and corrosive environments and highlighted the promising prospects of additively manufactured Zn-Mg scaffolds in orthopedic applications. STATEMENT OF SIGNIFICANCE: Additive manufacturing (AM) of biodegradable metals shows unprecedented prospects for bone tissue regeneration medicine. The corrosion fatigue property is one of the key determinants in the performance of AM biodegradable scaffolds. In this study, a Zn-Mg gyroid scaffold was additively manufactured with admirable fatigue endurance limit and anti-fatigue capability. We reported that the corrosion fatigue performance was highly relevant to the microstructural features, validating that the grain boundary engineering strategy improved fatigue strength and inhibited crack penetration. Notably, moderate grain boundary migration could dissipate fatigue energy and reduce plastic deformation. Furthermore, corrosion products were conducive to impeding fatigue ratcheting and fatigue damage, indicating the promising potential of AM Zn-Mg scaffolds in treating load-bearing bone defects.

Microstructure and Superior Corrosion Resistance of an In-Situ Synthesized NiTi-Based Intermetallic Coating via Laser Melting Deposition.

A nickel-titanium (NiTi)-based intermetallic coating was in-situ synthesized on a Ti-6Al-4V (TC4) substrate via laser melting deposition (LMD) using Ni-20Cr and TC4 powders. Scanning electron microscopy, X-ray diffraction, a digital microhardness tester and an electrochemical analyzer were used to evaluate the microstructure, Vicker's microhardness and electrochemical corrosion resistance of the intermetallic coating. Results indicate that the microstructure of the intermetallic coating is composed of NiTi2, NiTi and Ni3Ti. The measured microhardness achieved is as high as ~850 HV0.2, ~2.5 times larger than that of the TC4 alloy, which can be attributed to the solid solution strengthening of Al and Cr, dispersion strengthening of the intermetallic compounds, and grain refinement strengthening from the rapid cooling of LMD. During the electrochemical corrosion of 3.5% NaCl solution, a large amount of Ti ions were released from the intermetallic coating surface and reacted with Cl- ions to form [TiCl6]2 with an increase in corrosion voltage. In further hydrolysis reactions, TiO2 formation occurred when the ratio of [TiCl6]2- reached a critical value. The in-situ synthesized intermetallic coating can achieve a superior corrosion resistance compared to that of the TC4 alloy.

Densification, Tailored Microstructure, and Mechanical Properties of Selective Laser Melted Ti-6Al-4V Alloy via Annealing Heat Treatment.

This work investigated the influence of process parameters on the densification, microstructure, and mechanical properties of a Ti-6Al-4V alloy printed by selective laser melting (SLM), followed by annealing heat treatment. In particular, the evolution mechanisms of the microstructure and mechanical properties of the printed alloy with respect to the annealing temperature near the ß phase transition temperature were investigated. The process parameter optimization of SLM can lead to the densification of the printed Ti-6Al-4V alloy with a relative density of 99.51%, accompanied by an ultimate tensile strength of 1204 MPa and elongation of 7.8%. The results show that the microstructure can be tailored by altering the scanning speed and annealing temperature. The SLM-printed Ti-6Al-4V alloy contains epitaxial growth ß columnar grains and internal acicular martensitic α' grains, and the width of the ß columnar grain decreases with an increase in the scanning speed. Comparatively, the printed alloy after annealing in the range of 750-1050 °C obtains the microstructure consisting of α + ß dual phases. In particular, network and Widmanstätten structures are formed at the annealing temperatures of 850 °C and 1050 °C, respectively. The maximum elongation of 14% can be achieved at the annealing temperature of 950 °C, which was 79% higher than that of as-printed samples. Meanwhile, an ultimate tensile strength larger than 1000 MPa can be maintained, which still meets the application requirements of the forged Ti-6Al-4V alloy.

Insights into unit cell size effect on mechanical responses and energy absorption capability of titanium graded porous structures manufactured by laser powder bed fusion.

Schwartz diamond graded porous structures (SDGPSs), constructed by a triply-periodic-minimal-surface diamond unit cell topology, were developed with various unit cell sizes and printed by laser powder bed fusion (LPBF) from a commercially pure titanium powder for bone implant applications. The effect of unit cell size on the printability, strut dimensions, stress and strain distributions, mechanical properties and energy absorption capability of SDGPSs was investigated. The results indicate the good printability of SDGPSs via LPBF with multiple unit cell sizes from 3.5 mm to 5.5 mm through the three-dimensional reconstruction from micro-computed tomography. The unit cell size plays a critical role in both strut diameters and specific surface areas of SDGPSs. An increase in the unit cell size leads to a reduction in the experimental Young's modulus from 673.08 MPa to 518.71 MPa and compressive yield strength from 11.43 MPa to 7.73 MPa. The mechanical properties of LPBF-printed SDGPSs are higher than those predicted by the finite element method, which is attributed to the higher volume fractions of the printed SDGPSs than the designed values. Furthermore, a rise in unit cell size leads to the decrease of energy absorption capability from 6.06 MJ/mm3 to 4.32 MJ/mm3 and exhibits little influence on the absorption efficiency. These findings provide a good understanding and guidance to the optimization on the unit cell size of functionally graded porous structures for desirable properties.

Recent Advances on High-Entropy Alloys for 3D Printing.

Boosted by the success of high-entropy alloys (HEAs) manufactured by conventional processes in various applications, the development of HEAs for 3D printing has been advancing rapidly in recent years. 3D printing of HEAs gives rise to a great potential for manufacturing geometrically complex HEA products with desirable performances, thereby inspiring their increased appearance in industrial applications. Herein, a comprehensive review of the recent achievements of 3D printing of HEAs is provided, in the aspects of their powder development, printing processes, microstructures, properties, and potential applications. It begins with the introduction of the fundamentals of 3D printing and HEAs, as well as the unique properties of 3D-printed HEA products. The processes for the development of HEA powders, including atomization and mechanical alloying, and the powder properties, are then presented. Thereafter, typical processes for printing HEA products from powders, namely, directed energy deposition, selective laser melting, and electron beam melting, are discussed with regard to the phases, crystal features, mechanical properties, functionalities, and potential applications of these products (particularly in the aerospace, energy, molding, and tooling industries). Finally, perspectives are outlined to provide guidance for future research.

In situ fabrication of a titanium-niobium alloy with tailored microstructures, enhanced mechanical properties and biocompatibility by using selective laser melting.

A titanium-niobium (Ti-Nb) alloy with tailored microstructures, enhanced mechanical properties and biocompatibility was in situ fabricated by selective laser melting (SLM) using a blended powder with 25 wt.% Nb content. The effect of laser energy density from 70 J/mm3 to 110 J/mm3 on the phase transformation, microstructure, and mechanical properties of the SLM-printed Ti-25Nb alloy was investigated. The results indicate that the energy density of 110 J/mm3 results in the highest relative density and homogeneous element distributions in the alloy. The α' and ß phases with an orientation relationship of [023]ß//[-12-16]α' were identified through X-ray diffraction and transmission electron microscopy, and their proportions are crucially determined by the laser energy density. With an increase in the energy density, the microstructure of the Ti-25Nb alloy varies from acicular-shaped grains to coarsened lath-shaped grains and to lath-shaped grain + cellular-shaped subgrains, due to the decrease in cooling rate and the rise in temperature gradient. The yield strength and microhardness of the printed Ti-25Nb alloy decrease with the increase in energy density from 70 J/mm3 to 100 J/mm3, and then increase to the highest values of 645 MPa and 264 HV at 110 J/mm3, respectively. This variation of mechanical properties is dependent on both the coarsening of α' phase and the formation of ß (Ti, Nb) solid solution. Besides, the SLM-printed Ti-25Nb alloy exhibits both the excellent in vitro apatite-forming capability and better cell spread and proliferation compared to pure Ti.

Effect of pore geometry on the fatigue properties and cell affinity of porous titanium scaffolds fabricated by selective laser melting.

Porous titanium scaffolds with different unit cell type (tetrahedron and octahedron) and pore size (500 µm and 1000 µm) were fabricated by selective laser melting (SLM), and the effects of unit cell type and pore size on their fatigue properties and cell affinity were studied. The fatigue properties were performed by static and dynamic mechanical testing, while the cell affinity was evaluated in vitro with mouse osteoblast cells. It was found that octahedron scaffolds exhibited superior static mechanical properties, longer fatigue lives and higher fatigue strength in comparison to those of tetrahedron ones. As expected, scaffolds with 1000 µm pore resulted in lower compressive properties and shorter fatigue lives compared to those with 500 µm pore. The differences were analyzed based on the unit cell structure, porosity, and manufacturing imperfections. Scanning electron microscopy (SEM) and immunofluorescence showed that cells spread better on octahedron scaffolds than those on tetrahedron ones. Meanwhile, the scaffolds with 1000 µm pore were more suitable for cell attachment and growth within the same unit cell owing to higher porosity. The comparison of different pore geometry on the mechanical and biological property provided further insight into designing an optimal porous scaffold.

Continuous functionally graded porous titanium scaffolds manufactured by selective laser melting for bone implants.

A significant requirement for a bone implant is to replicate the functional gradient across the bone to mimic the localization change in stiffness. In this work, continuous functionally graded porous scaffolds (FGPSs) based on the Schwartz diamond unit cell with a wide range of graded volume fraction were manufactured by selective laser melting (SLM). The micro-topology, strut dimension characterization and effect of graded volume fraction on the mechanical properties of SLM-processed FGPSs were systematically investigated. The micro-topology observations indicate that diamond FGPSs with a wide range of graded volume fraction from 7.97% to 19.99% were fabricated without any defects, showing a good geometric reproduction of the original designs. The dimensional characterization demonstrates the capability of SLM in manufacturing titanium diamond FGPSs with the strut size of 483-905µm. The elastic modulus and yield strength of the titanium diamond FGPSs can be tailored in the range of 0.28-0.59GPa and 3.79-17.75MPa respectively by adjusting the graded volume fraction, which are comparable to those of the cancellous bone. The mathematical relationship between the graded porosity and compression properties of a FGPS was revealed. Furthermore, two equations based on the Gibson and Ashby model have been established to predict the modulus and yield strength of SLM-processed diamond FGPSs. Compared to homogeneous diamond porous scaffolds, FGPSs provide a wide range of mutative pore size and porosity, which are potential to be tailored to optimize the pore space for bone tissue growth. The findings provide a basis of new methodologies to design and manufacture superior graded scaffolds for bone implant applications.

Electrophoretic Deposition of Gentamicin-Loaded Silk Fibroin Coatings on 3D-Printed Porous Cobalt-Chromium-Molybdenum Bone Substitutes to Prevent Orthopedic Implant Infections.

In addition to customizing shapes of metal bone substitutes for patients, the 3D printing technique can reduce the modulus of the substitutes through the design and manufacture of interconnected porous structures, achieving the modulus match between substitute and surrounding bone to improve implant longevity. However, the porous bone substitutes take more risks of postoperative infection due to its much larger surface area compared with the traditional casting solid bone substitute. Here, we prepared of gentamicin-loaded silk fibroin coatings on 3D-printed porous cobalt-chromium-molybdenum (CoCrMo) bone substitutes via electrophoretic deposition technique. Through optimization, relatively intact, continuous, homogeneous, and conformal coatings with a thickness of 2.30 ± 0.58 µm were deposited around the struts with few pore blocked. The porous metal structures exhibited no loss in mechanical properties after the anode galvanic corrosion in EPD process. The initial osteoblastic response on coatings was better than that on metal surface, including cell spreading, proliferation and cytotoxicity. Antibacterial efficacy experiments showed that the coatings had an antibacterial effect on both adherent and planktonic bacteria within 1 week. These results suggested that the beneficial properties of anode electrophoretic deposited silk fibroin coatings could be exploited to improve the biological functionality of porous structures made of medical metals.

Microstructure and property evolutions of titanium/nano-hydroxyapatite composites in-situ prepared by selective laser melting.

Titanium (Ti)-hydroxyapatite (HA) composites have the potential for orthopedic applications due to their favorable mechanical properties, excellent biocompatibility and bioactivity. In this work, the pure Ti and nano-scale HA (Ti-nHA) composites were in-situ prepared by selective laser melting (SLM) for the first time. The phase, microstructure, surface characteristic and mechanical properties of the SLM-processed Ti-nHA composites were studied by X-ray diffraction, transmission electron microscope, atomic force microscope and tensile tests, respectively. Results show that SLM is a suitable method for fabricating the Ti-nHA composites with refined microstructure, low modulus and high strength. A novel microstructure evolution can be illustrated as: Relatively long lath-shaped grains of pure Ti evolved into short acicular-shaped and quasi-continuous circle-shaped grains with the varying contents of nHA. The elastic modulus of the Ti-nHA composites is 3.7% higher than that of pure Ti due to the effect of grain refinement. With the addition of 2% nHA, the ultimate tensile strength significantly reduces to 289MPa but still meets the application requirement of bone implants. The Ti-nHA composites exhibit a remarkable improvement of microhardness from 336.2 to 600.8 HV and nanohardness from 5.6 to 8.3GPa, compared to those of pure Ti. Moreover, the microstructure and property evolution mechanisms of the composites with the addition of HA were discussed and analyzed. It provides some new knowledge to the design and fabrication of biomedical material composites for bone implant applications.

Electrophoretic deposition of chitosan/gelatin coatings with controlled porous surface topography to enhance initial osteoblast adhesive responses.

Electrophoretically deposited (EPD) coatings have often been employed recently for the addition of different new chemical compositions to classic chitosan coatings to improve the biocompatibility and therapeutic potential of coated implants. However, little attention has been paid to enhance the cell response to EPD coatings via integrating the effects of chemical components and surface topography. Here, we fabricated EPD chitosan/gelatin (CS/G) coatings with controlled porous surface topography by controlling bubble generation in the EPD process via changing the gelatin content in solution from 0, 0.01, 0.1, and 1 to 10 mg ml-1. The pure chitosan coating surface was characterized by homogeneous large pores of 500 µm. After 0.01 mg ml-1 gelatin was added, 180 µm small pores appeared on the walls of large pores. As the gelatin content increased to 0.1 mg ml-1, a number of small pores increased noticeably. When the gelatin content reached 1 mg ml-1, large pores disappeared, and the coating displayed homogeneous small pores. 10 mg ml-1 gelatin concentration led to coatings consisting of small pores with not integral and continuous structures. The initial osteoblastic responses, including cell adherence progress, spreading area, proliferation rate, and focal adhesion-related gene expression, gradually improved from 0 to 0.01, 0.1, and 1 mg ml-1 gelatin content, but decreased from 1 to 10 mg ml-1. All these results indicated that the initial cell responses to coatings reached a peak when it was 1 mg ml-1 gelatin and they had homogeneous small pores, which might contribute to the synergistic effects of the porous surface structure and components. This work would be beneficial for expanding the potential application of EPD coatings.

Porous niobium coatings fabricated with selective laser melting on titanium substrates: Preparation, characterization, and cell behavior.

Nb, an expensive and refractory element with good wear resistance and biocompatibility, is gaining more attention as a new metallic biomaterial. However, the high price of the raw material, as well as the high manufacturing costs because of Nb's strong oxygen affinity and high melting point have limited the widespread use of Nb and its compounds. To overcome these disadvantages, porous Nb coatings of various thicknesses were fabricated on Ti substrate via selective laser melting (SLM), which is a 3D printing technique that uses computer-controlled high-power laser to melt the metal. The morphology and microstructure of the porous Nb coatings, which had pores ranging from 15 to 50 µm in size, were characterized with scanning electron microscopy (SEM). The average hardness of the coating, which was measured with the linear intercept method, was 392±37 HV. In vitro tests of the porous Nb coating which was monitored with SEM, immunofluorescence, and CCK-8 counts of cells, exhibited excellent cell morphology, attachment, and growth. The simulated body fluid test also proved the bioactivity of the Nb coating. Therefore, these new porous Nb coatings could potentially be used for enhanced early biological fixation to bone tissue. In addition, this study has shown that SLM technique could be used to fabricate coatings with individually tailored shapes and/or porosities from group IVB and VB biomedical metals and their alloys on stainless steel, Co-Cr, and other traditional biomedical materials without wasting raw materials.