Additively manufactured pure zinc porous scaffolds for critical-sized bone defects of rabbit femur.

Additive manufacturing has received attention for the fabrication of medical implants that have customized and complicated structures. Biodegradable Zn metals are revolutionary materials for orthopedic implants. In this study, pure Zn porous scaffolds with diamond structures were fabricated using customized laser powder bed fusion (L-PBF) technology. First, the mechanical properties, corrosion behavior, and biocompatibility of the pure Zn porous scaffolds were characterized in vitro. The scaffolds were then implanted into the rabbit femur critical-size bone defect model for 24 weeks. The results showed that the pure Zn porous scaffolds had compressive strength and rigidity comparable to those of cancellous bone, as well as relatively suitable degradation rates for bone regeneration. A benign host response was observed using hematoxylin and eosin (HE) staining of the heart, liver, spleen, lungs, and kidneys. Moreover, the pure Zn porous scaffold showed good biocompatibility and osteogenic promotion ability in vivo. This study showed that pure Zn porous scaffolds with customized structures fabricated using L-PBF represent a promising biodegradable solution for treating large bone defects.

Additive manufacturing of Zn-Mg alloy porous scaffolds with enhanced osseointegration: In vitro and in vivo studies.

Biodegradable metals (BM) and additive manufacturing (AM) are regarded revolutionary biomaterials and biofabrication technologies for bone repairing metal implants, the combination of both, namely AM of BM, is thus expected to solve the dual technical difficulties including "conventional medical metals are biologically inert and exist in the human body permanently" and "conventional manufacturing processes are inadequate to fabricate personalized implants of complicated structure". This work additively manufactured biodegradable Zn-Mg alloy porous scaffolds by laser powder bed fusion (L-PBF). By using the pre-alloyed Zn-xMg (x = 1, 2 and 5 wt.%) powder and the optimized processing conditions, high fusion quality with the relative density greater than 99.5% was confirmed for the L-PBF parts. The influence of Mg content on microstructure, mechanical properties, in vitro corrosion, cytocompatibility, in vivo degradation, biocompatibility and osteogenic effect was investigated. Fine α-Zn grains and precipitation phases including Mg2Zn11 and MgZn2 were observed in the Zn-xMg L-PBF parts. The hardness increased, and the strength increases firstly and then decreased with increasing the Mg content. The compressive strength and elastic modulus of Zn-1Mg porous scaffolds reached the highest as 40.9 ± 0.4 MPa and 1.17 ± 0.11 GPa, respectively, equivalent to those of cancellous bone. The corrosion rate and cell viability slightly rose with increasing the Mg content. Histological analysis after 6-week and 12-week implantation in rabbit femurs showed enhanced bone formation around the Zn-1Mg porous scaffolds compared with pure Zn counterparts. In summary, Zn-1Mg porous scaffolds produced by L-PBF presented promising results to fulfill customized requirements of biodegradable bone implants. STATEMENT OF SIGNIFICANCE: Additive manufacturing of biodegradable metal porous scaffolds is expected to solve the dual challenges from customized structures and bioactive function required for bone implants. It was the first to present a systematic in vitro and in vivo investigation into the compositions, microstructure, mechanical properties, biodegradation, biocompatibility and osteogenic effect of additively manufactured Zn-Mg alloy porous scaffolds. Reliable formation quality and performance evaluation was achieved by using the pre-alloyed Zn-xMg (x = 1, 2 and 5 wt.%) powder and the optimized laser powder bed fusion process. Although the Zn-1Mg scaffolds exhibited promising mechanical strength, biocompatibility, and osteogenic effect, their degradation rate needs to be further accelerated compared with the term of bone reconstruction.

Influence of Degradation Product Thickness on the Elastic Stiffness of Porous Absorbable Scaffolds Made from an Bioabsorbable Zn-Mg Alloy.

For orthopaedic applications, additive manufactured (AM) porous scaffolds made of absorbable metals such as magnesium, zinc or iron are of particular interest. They do not only offer the potential to design and fabricate bio-mimetic or rather bone-equivalent mechanical properties, they also do not need to be removed in further surgery. Located in a physiological environment, scaffolds made of absorbable metals show a decreasing Young's modulus over time, due to product dissolution. For magnesium-based scaffolds during the first days an increase of the smeared Young's modulus can be observed, which is mainly attributed to a forming substrate layer of degradation products on the strut surfaces. In this study, the influence of degradation products on the stiffness properties of metallic scaffolds is investigated. For this, analytical calculations and finite-element simulations are performed to study the influence of the substrate layer thickness and Young's modulus for single struts and for a new scaffold geometry with adapted polar cubic face-centered unit cells with vertical struts (f2cc,z). The finite-element model is further validated by compression tests on AM scaffolds made from Zn1Mg (1 wt% Mg). The results show that even low thicknesses and Young's moduli of the substrate layer significantly increases the smeared Young's modulus under axial compression.

Influence of Laser Energy Input and Shielding Gas Flow on Evaporation Fume during Laser Powder Bed Fusion of Zn Metal.

Laser powder bed fusion (LPBF) of Zn-based metals exhibits prominent advantages to produce customized biodegradable implants. However, massive evaporation occurs during laser melting of Zn so that it becomes a critical issue to modulate laser energy input and gas shielding conditions to eliminate the negative effect of evaporation fume during the LPBF process. In this research, two numerical models were established to simulate the interaction between the scanning laser and Zn metal as well as the interaction between the shielding gas flow and the evaporation fume, respectively. The first model predicted the evaporation rate under different laser energy input by taking the effect of evaporation on the conservation of energy, momentum, and mass into consideration. With the evaporation rate as the input, the second model predicted the elimination effect of evaporation fume under different conditions of shielding gas flow by taking the effect of the gas circulation system including geometrical design and flow rate. In the case involving an adequate laser energy input and an optimized shielding gas flow, the evaporation fume was efficiently removed from the processing chamber during the LPBF process. Furthermore, the influence of evaporation on surface quality densification was discussed by comparing LPBF of pure Zn and a Titanium alloy. The established numerical analysis not only helps to find the adequate laser energy input and the optimized shielding gas flow for the LPBF of Zn based metal, but is also beneficial to understand the influence of evaporation on the LPBF process.

Rapid Alloy Development of Extremely High-Alloyed Metals Using Powder Blends in Laser Powder Bed Fusion.

The design of new alloys by and for metal additive manufacturing (AM) is an emerging field of research. Currently, pre-alloyed powders are used in metal AM, which are expensive and inflexible in terms of varying chemical composition. The present study describes the adaption of rapid alloy development in laser powder bed fusion (LPBF) by using elemental powder blends. This enables an agile and resource-efficient approach to designing and screening new alloys through fast generation of alloys with varying chemical compositions. This method was evaluated on the new and chemically complex materials group of multi-principal element alloys (MPEAs), also known as high-entropy alloys (HEAs). MPEAs constitute ideal candidates for the introduced methodology due to the large space for possible alloys. First, process parameters for LPBF with powder blends containing at least five different elemental powders were developed. Secondly, the influence of processing parameters and the resulting energy density input on the homogeneity of the manufactured parts were investigated. Microstructural characterization was carried out by optical microscopy, electron backscatter diffraction (EBSD), and energy-dispersive X-ray spectroscopy (EDS), while mechanical properties were evaluated using tensile testing. Finally, the applicability of powder blends in LPBF was demonstrated through the manufacture of geometrically complex lattice structures with energy absorption functionality.

Influence of design and postprocessing parameters on the degradation behavior and mechanical properties of additively manufactured magnesium scaffolds.

Magnesium shows promising properties concerning its use in absorbable implant applications such as biodegradability, improved mechanical strength and plastic deformability. Following extensive research, the first fixation and compression screws composed of magnesium rare earth alloys were commercialised, notably in the field of orthopaedic surgery. Preclinical and clinical follow-up studies showed that the rapid degradation of unprotected metallic Magnesium surfaces and concomitant hydrogen gas bursts still raise concern regarding certain surgical indications and need to be further improved. In order to enlarge the scope of further applications, the development of future magnesium implants must aim at freedom of design and reduction of volume, hereby enabling higher functionalised implants, as e.g. plate systems or scaffold grafts for bone replacement therapy. In order to overcome the boundaries of conventional manufacturing methods such as turning or milling, the process of Laser Powder Bed Fusion (LPBF) for magnesium alloys was recently introduced. It enables the production of lattice structures, therefore allowing for reduction of implant material volume. Nevertheless, the concomitant increase of free surface of such magnesium scaffolds further stresses the aforementioned disadvantages of vast degradation and early loss of mechanical stability if not prevented by suitable postprocessing methods. Magnesium scaffold structures with different pore sizes were therefore manufactured by LPBF and consequently further modified either by thermal heat treatment or Plasma Electrolytic Oxidation (PEO). Implant performance was assessed by conducting degradation studies and mechanical testing. PEO modified scaffolds with small pore sizes exhibited improved long-term stability, while heat treated specimens showed impaired performance regarding degradation and mechanical stability. STATEMENT OF SIGNIFICANCE: Magnesium based scaffold structures offer wide possibilities for advanced functionalized bioabsorbable implants. By implementing lattice structures, big implant sizes and mechanically optimized implant geometries can be achieved enabling full bone replacement or large-scale plate systems, e.g. for orthopedic applications. As shape optimization and lattice structuring of such scaffolds consequently lead to enlarged surface, suitable design and postprocessing routines come into focus. The presented study addresses these new and relevant topics for the first time by evaluating geometry as well as heat and surface treatment options as input parameters for improved chemical and mechanical stability. The outcome of these variations is measured by degradation tests and mechanical analysis. Evaluating these methods, a significant contribution to the development of absorbable magnesium scaffolds is made. The findings can help to better understand the interdependence of high surface to volume ratio Magnesium implants and to deliver methods to incorporate such lattice structures into future large-scale implant applications manufactured from bioabsorbable Magnesium alloys.

Additive manufacturing of biodegradable metals: Current research status and future perspectives.

The combination of biodegradable metals and additive manufacturing (AM) leads to a revolutionary change of metal implants in many aspects including materials, design, manufacturing, and clinical applications. The AM of nondegradable metals such as titanium and CoCr alloys has proven to be a tremendous success in clinical applications. The AM of biodegradable metals including magnesium (Mg), iron (Fe), and zinc (Zn) is still in its infancy, although much progress has been made in the research field. Element loss and porosity are common processing problems for AM of biodegradable metals like Zn and Mg, which are mainly caused by evaporation during melting under a high-energy beam. The resulting formation quality and properties are closely related to material, design, and processing, making AM of biodegradable metals a typical interdisciplinary subject involving biomaterials, mechanical engineering, and medicine. This work reviews the state of research and future perspective on AM of biodegradable metals from extensive viewpoints such as material, processing, formation quality, design, microstructure, and properties. Effects of powder properties and processing parameters on formation quality are characterized in detail. The microstructure and metallurgical defects encountered in the AM parts are described. Mechanical and biodegradable properties of AM samples are introduced. Design principles and potential applications of biodegradable metal implants produced by AM are discussed. Finally, current research status is summarized together with some proposed future perspectives for advancing knowledge about AM of biodegradable metals. STATEMENT OF SIGNIFICANCE: Rapid development of research and applications on biodegradable metals and additive manufacturing (AM) has been made in recent years. Customized geometric shapes of medical metals with porous structure can be realized accurately and efficiently by laser powder bed fusion (L-PBF), which is beneficial to achieve reliable stress conduction and balanced properties. This review introduces the development history and current status of AM of biodegradable metals and then critically surveys L-PBF of Mg-, Fe-, and Zn-based metals from multiple viewpoints including materials, processing, formation quality, structural design, microstructure, and mechanical and biological properties. The present findings are summarized together with some proposed future challenges for advancing AM of biodegradable metals into real clinical applications.