In situ production of low-modulus Ti-Nb alloys by selective laser melting and their functional assessment toward orthopedic applications.

This work aimed to manufacture Ti-28.5Nb and Ti-40.0Nb (wt%) alloys in situ via selective laser melting (SLM) from Ti and Nb elemental powders. X-ray diffraction analysis revealed complete ß-phase (cubic) in Ti-40.0Nb and a mixture of (α'' orthorhombic + ß cubic) phases in Ti-28.5Nb were formed, whereas few of the Nb particles remained only partially fused during manufacturing. The fraction of partially melted Nb particles was determined as ∼2 and ∼18% in Ti-28.5Nb and Ti-40Nb, respectively. Mechanical characterization revealed higher hardness and more strength in Ti-28.5Nb than in Ti-40.0Nb due to the presence of the α'' phase in the former. Tribocorrosion tests reveal a significantly better wear-corrosion resistance for Ti-40.0Nb, as determined from a lower total volume loss in Ti-40.0Nb (∼2 × 10-4 mm-3) than in Ti-28.5Nb (∼13 × 10-2 mm-3). The lower volume loss and better corrosion resistance behavior are attributed to the ß phase, which was dominant in Ti-40.0Nb. Cell studies reveal no toxicity for up to 7 days. Both the alloys were better at supporting cell proliferation than wrought Ti6Al4V. This study presents a route to preparing Ti-Nb alloys in situ by SLM that are promising candidates for biomedical applications.

Surface nanocrystallization enhances the biomedical performance of additively manufactured stainless steel.

Additive manufacturing enables the fabrication of patient-specific implants of complex geometries. Although selective laser melting (SLM) of 316L stainless steel (SS) is well established, post-processing is essential to preparing high-performance biomedical implants. The goal of this study was to investigate surface mechanical attrition treatment (SMAT) as a means to enhance the electrochemical, biomechanical, and biological performances of 316L SS fabricated by SLM in devices for the repair of bone tissues. The SMAT conditions were optimized to induce surface nanocrystallization on the additively manufactured samples. SMAT resulted in a thicker oxide layer, which provided corrosion resistance by forming a passive layer. The fretting wear results showed that the rate of wear decreased after SMAT owing to the formation of a harder nanostructured layer. Surface modification of the alloy by SMAT enhanced its ability to support the attachment and proliferation of pre-osteoblasts in vitro. The study of the response in vivo to the additively manufactured alloy in a critical-sized cranial defect murine model revealed enhanced interactions with the cellular components after the alloy was subjected to SMAT without inducing any adverse immune response. Taken together, the results of this work establish SMAT of additively manufactured metallic implants as an effective strategy for engineering next-generation, high-performance medical devices for orthopedics and craniomaxillofacial applications.

Anisotropy of Additively Manufactured Co-28Cr-6Mo Influences Mechanical Properties and Biomedical Performance.

Additive manufacturing (AM) of biomedical alloys such as Co-Cr-Mo alloys holds immense potential for fabricating implants with complex geometry and tailored to meet patient-specific needs. However, layer-by-layer fabrication in AM processes results in undesired anisotropy due to the solidification texture and grain morphology. The present study aimed to investigate the effect of build orientation on the mechanical properties and functional performance, including tribocorrosion behavior and cytocompatibility of an orthopedic Co-28Cr-6Mo alloy manufactured by selective laser melting. Although the fabricated alloy showed weak crystallographic texture due to the rotational scanning strategy, significant anisotropy was found in the tensile properties due to the grain size and morphology. The presence of larger, elongated grains along the build direction as compared to smaller, equiaxed grains perpendicular to the build direction imparted the observed tensile anisotropy. Quantitative analysis based on current models for strengthening mechanisms is insufficient to explain the observed anisotropy, which is ascribed to the possible role of the cellular dendrites and stacking fault strengthening in Co-Cr alloys. Unlike the electrochemical behavior, which was largely independent of the build orientation, the bio-tribocorrosion studies revealed an anisotropic wear rate under fretting conditions. Osteoblast attachment and proliferation were found to be higher on the plane perpendicular to the build direction, owing to the differences in grain size. This work provides novel insights into the role of the manufacturing parameters in a selective-laser-melted Co-Cr alloy and its potential application in engineering load-bearing orthopedic implants.

Electrophoretic Deposition of Nanocrystalline Calcium Phosphate Coating for Augmenting Bioactivity of Additively Manufactured Ti-6Al-4V.

Additive manufacturing (AM) is being widely explored for engineering biomedical implants. The microstructure and surface finish of additively manufactured parts are typically different from wrought parts and exhibit limited bioactivity despite the other advantages of using AM for fabrication. The aim of this study was to enhance the bioactivity of selective laser melted Ti-6Al-4V alloy by electrophoretic deposition of nanohydroxyapatite (nanoHAp) coatings. The deposition parameters were systematically investigated after the coatings were deposited on the as-manufactured surface or after polishing the surface of the additively-manufactured sample. The surfaces were coated with nanoHAp suspended in either ethanol or butanol using different voltages (10, 30, or 50 V) for varied deposition times. The formation of the nanoHAp coating was confirmed by Fourier-transform infrared spectroscopy and X-ray diffraction. Microstructural analysis revealed that several conditions of the coating led to crack formation. The coated samples were subsequently heat-treated to improve the integrity of the coating. Heat treatment led to crack formation in several conditions due to thermal shrinkages. Coatings prepared using butanol were more uniform and had minimal cracks compared with the use of ethanol. Nanoindentation confirmed good stability and integrity of the nanoHAP coatings on the as-manufactured and polished surfaces. The coating on the as-manufactured sample exhibited higher hardness and lower elastic modulus as compared with the coating on the polished sample. In vitro study revealed that the nanoHAp coating markedly enhanced the attachment, proliferation, and differentiation of preosteoblasts on the alloy. These results provide a viable route to enhancing the bioactivity through deposition of nanoHAp with important implications for engineering additively manufactured orthopedic and dental implants suitable for better clinical performance.

Review of recent developments in surface nanocrystallization of metallic biomaterials.

Metallic materials are widely used to prepare implants for both short-term and long-term use in the human body. The performance of these implants is greatly influenced by their surface characteristics, which has motivated the development of several surface modification techniques. Surface severe plastic deformation (S2PD) techniques have emerged as promising strategies to enhance the performance of metallic biomaterials. They do not involve chemical modification of the surface and impart minimal changes to the surface topography. S2PD processes are based on the principle of generating nanocrystals at the surface, which can improve performance metrics, such as fatigue, wear, corrosion resistance, and biocompatibility through various mechanisms, such as surface hardening and alterations to the surface oxide layer. This review presents the state of the art on the development of different S2PD processes and their applications on metallic biomaterials. Brief descriptions of the different processes have been provided, followed by a discussion on the microstructural changes induced by these processes for different generations of biomaterials. The effect of S2PD on surface and bulk characteristics of the biomaterials and their performance is critically reviewed. As an emerging class of surface engineering techniques in biomaterials science, more work is needed to fully leverage their potential in this field, and these opportunities are discussed in this review.

Zinc and cerium synergistically enhance the mechanical properties, corrosion resistance, and osteogenic activity of magnesium as resorbable biomaterials.

Magnesium and its alloys have the potential to serve as a revolutionary class of biodegradable materials, specifically in the field of degradable implants for orthopedics. However, the corrosion rate of commercially pure magnesium is high and does not match the rate of regeneration of bone tissues. In this work, magnesium alloys containing zinc and cerium, either alone or in combination, were investigated and compared with commercially-pure magnesium as biomaterials. The microstructure, mechanical properties, corrosion resistance, and response of osteoblastsin vitrowere systematically assessed. Results reveal that alloying with Ce results in grain refinement and weakening of texture. The tensile test revealed that the ternary alloy offered the best combination of elastic modulus (41.1 ± 0.5 GPa), tensile strength (234.5 ± 4.5 MPa), and elongation to break (17.1 ± 0.4%). The ternary alloy was also the most resistant to corrosion (current of 0.85 ± 0.05 × 10-4A cm-2) in simulated body fluid than the other alloys. The response of MC3T3-E1 cellsin vitrorevealed that the ternary alloy imparts minimal cytotoxicity. Interestingly, the ternary alloy was highly efficient in supporting osteogenic differentiation, as revealed by the expression of alkaline phosphatase and calcium deposition. In summary, the extruded Mg alloy containing both Zn and Ce exhibits a combination of mechanical properties, corrosion resistance, and cell response that is highly attractive for engineering biodegradable orthopedic implants.

Enhanced biomechanical performance of additively manufactured Ti-6Al-4V bone plates.

As the global trauma fixation devices market expands rapidly, it is imperative to improve the production of fixation devices through enhanced design accuracy and fit for best performance and maximum patient comfort. Selective laser melting (SLM) is one of the mature additive manufacturing methods, which provides a viable route for the rapid production of such devices. In this work, the ability of SLM to produce near-net-shape parts, as desired for medical implants, was utilized for the fabrication of bone plates from Ti-6Al-4V alloy powder. Martensitic microstructure obtained after the printing of alloy resulted in poor ductility, limiting its application in the field of orthopedics. A specially designed repeated cyclic heating and cooling close to but below the ß-transus was used to transform from acicular to a bimodal microstructure without the need for plastic deformation prior to heat treatment for improving the ductility. Bone plates subjected to this heat treatment were mechanically tested by means of tensile and 3-point bend tests and demonstrated large improvement in ductility, and the values were comparable to those similar plates prepared from wrought alloy. Other important properties required for implants were assessed, such as corrosion resistance in simulated body fluid and cytocompatibility in vitro using MC3T3-E1 cells. These results for the bone plate after heat treatment were excellent and similar to those of the additively manufactured and wrought plates. Taken together, the performance of the additively manufactured bone plates after subjecting to heat treatment was similar to those of bone plate manufactured using wrought alloy. These results have important implications for the fabrication of patient-specific metallic orthopedic devices using SLM without compromising their biomechanical performance by subjecting them to a tailored heat treatment.

Surface mechanical attrition treatment of low modulus Ti-Nb-Ta-O alloy for orthopedic applications.

Surface mechanical attrition treatment (SMAT) is recognized as a surface severe plastic deformation (SPD) method that is effective in improving the surface-dependent mechanical and functional properties of conventional metallic biomaterials. In this study, we aimed to systemically investigate the effect of SMAT on the physical, electrochemical, tribological and biological performances of a newly developed low modulus ß Ti-Nb-Ta-O alloy with two different microstructures, namely, single phase ß-treated and dual phase ß + α aged. The microhardness results showed considerable hardening for the ß-treated condition due to formation of deformation substructures; that was associated with increased corrosion resistance resulting from a stronger and denser passive layer on the surface, as revealed by Tafel polarization, impedance studies and Mott-Scottky plots. The wear volume loss during fretting in serum solution was found to decrease by 46% while friction coefficient decreased only marginally, due to presence of a harder and more brittle surface. In the ß + α condition of the alloy, minimal hardening was observed due to coarsening of the precipitates during SMAT. However, this also reduced the number of α-ß interfaces, which in turn minimized the tendency for galvanic corrosion resulting in lower corrosion rate after SMAT. Wear resistance was enhanced after SMAT, with 32% decrease in wear volume loss and 21% decrease in friction coefficient resulted due to improved ductility on the surface. The attachment and growth of osteoblasts on the alloys in vitro were not affected by SMAT and was comparable to that on commercially pure Ti. Taken together, these results provide new insights into the effects of surface SPD of low modulus ß- Ti alloys for orthopedic applications and underscore the importance of the initial microstructure in determining the performance of the alloy.

Role of aging induced α precipitation on the mechanical and tribocorrosive performance of a ß Ti-Nb-Ta-O orthopedic alloy.

A low modulus ß Ti-Nb-Ta-O alloy was subjected to heat treatment to investigate its phase stability upon aging. The resultant effect on the mechanical and functional properties was systematically evaluated. The aging of the ß-only microstructure, obtained by solutionizing and quenching, resulted in the formation of ultrafine α-precipitates with increasing order of size as the aging temperature increased from 400 °C to 600 °C. The variation in the size of α-precipitates effected the mechanical properties at the three different aging temperature. The highest hardening observed at 400 °C was associated with macroscopic embrittlement, whereas age softening was observed in samples aged at 600 °C due to coarsening of precipitates and softening of the ß-matrix. In contrast, aging at 500 °C resulted in about 32% increase in tensile strength from the ß-solutionized condition. As the samples aged at 500 °C showed optimum combination of mechanical properties among the aged samples, these were further characterized for their electrochemical, tribological and biological responses. The fretting wear studies showed that the wear rate of the solution-treated samples increased after aging due to the higher corrosion rate leading to a higher rate of tribocorrosive dissolution and formation of a transfer layer harder than that of solution treated sample. The Ti-Nb-Ta-O alloy supported the attachment and proliferation of osteoblasts similar to that on commercially pure Ti. Taken together, this work provides new insights into the preparation of next-generation Ti alloys for biomedical applications with high strength and low modulus through microstructural control induced by heat treatment.

Engineering the next-generation tin containing ß titanium alloys with high strength and low modulus for orthopedic applications.

Metastable ß Ti alloys are the new emerging class of biomaterial for load bearing orthopedic applications. However, these alloys in the single ß phase microstructure have insufficient strength for use in load bearing applications. It is imperative to strengthen these alloys by carefully designed thermo-mechanical processing routes that typically involve aging treatment. In this investigation two newly designed Sn based ß Ti alloys of composition Ti-32Nb-(2, 4) Sn are evaluated. The effects of Sn content on the mechanical properties and biological performance of these alloys processed through designed thermo-mechanical processing route are investigated. The increase in the Sn content led to a reduction in the elastic modulus of the alloy. An increase in the Sn content increased the aspect ratio of the α precipitates, which led to a significant strengthening in the alloy while keeping the elastic modulus low. In addition, the corrosion behavior of the alloy was evaluated in simulated body fluid. The Sn containing ß alloys have an excellent corrosion resistance as desired for an implant material. The corrosion resistance improved with an increase in Sn content. These alloys were also observed to have excellent cytocompatibility as they not only supported the attachment and proliferation of human mesenchymal stem cells but also their osteogenic differentiation in vitro. The combination of high strength, low elastic modulus, superior corrosion resistance and biocompatibility underscores the promise of Sn containing ß Ti alloys for use in orthopedic applications.

Enhancing the mechanical and biological performance of a metallic biomaterial for orthopedic applications through changes in the surface oxide layer by nanocrystalline surface modification.

Nanostructured metals are a promising class of biomaterials for application in orthopedics to improve the mechanical performance and biological response for increasing the life of biomedical implants. Surface mechanical attrition treatment (SMAT) is an efficient way of engineering nanocrystalline surfaces on metal substrates. In this work, 316L stainless steel (SS), a widely used orthopedic biomaterial, was subjected to SMAT to generate a nanocrystalline surface. Surface nanocrystallization modified the nature of the oxide layer present on the surface. It increased the corrosion-fatigue strength in saline by 50%. This increase in strength is attributed to a thicker oxide layer, residual compressive stresses, high strength of the surface layer, and lower propensity for intergranular corrosion in the nanocrystalline layer. Nanocrystallization also enhanced osteoblast attachment and proliferation. Intriguingly, wettability and surface roughness, the key parameters widely acknowledged for controlling the cellular response remained unchanged after nanocrystallization. The observed cellular behavior is explained in terms of the changes in electronic properties of the semiconducting passive oxide film present on the surface of 316L SS. Nanocrystallization increased the charge carrier density of the n-type oxide film likely preventing denaturation of the adsorbed cell-adhesive proteins such as fibronectin. In addition, a net positive charge developed on the otherwise neutral oxide layer, which is known to facilitate cellular adhesion. The role of changes in the electronic properties of the oxide films on metal substrates is thus highlighted in this work. This study demonstrates the advantages of nanocrystalline surface modification by SMAT for processing metallic biomaterials used in orthopedic implants.