On the Recycling of Water Atomized Powder and the Effects on Properties of L-PBF Processed 4130 Low-Alloy Steel.

The microstructure and mechanical properties of a 4130-grade steel processed by L-PBF using a feedstock of low-cost water atomized powder have been investigated considering the effects of powder recycling. Chemical analysis of the recycled powder showed a constant amount of alloying elements with a slight reduction in oxygen content. The as-built microstructure was mainly composed of a martensitic structure separated by a high fraction of low-angle grain boundaries, suggesting the application of a direct tempering treatment starting from the as-built condition as a cost-effective post-process thermal treatment rather than the conventional quench and tempering treatment. Moreover, the degree of anisotropy generated by L-PBF in as-built specimens could be reduced after performing either the direct tempering or the quench and tempering treatments. The possible degradation of powder properties on the steel performance was also investigated. After various powder recycling events, no significant deterioration in tensile properties was measured, indicating that the water atomized powder could be a sustainable feedstock candidate for L-PBF.

Effect of silver in thermal treatments of Fe-Mn-C degradable metals: Implications for stent processing.

Twinning-induced plasticity (TWIP) steels are considered excellent materials for manufacturing products requiring extremely high mechanical properties for various applications including thin medical devices, such as biodegradable intravascular stents. It is also proven that the addition of Ag can guarantee an appropriate degradation while implanted in human body without affecting its bioactive properties. In order to develop an optimized manufacturing process for thin stents, the effect of Ag on the recrystallization behavior of TWIP steels needs to be elucidated. This is of major importance since manufacturing stents involves several intermediate recrystallization annealing treatments. In this work, the recrystallization mechanism of two Fe-Mn-C steels with and without Ag was thoroughly investigated by microstructural and mechanical analyses. It was observed that Ag promoted a finer microstructure with a different texture evolution, while the recrystallization kinetics resulted unaffected. The presence of Ag also reduced the effectiveness of the recrystallization treatment. This behavior was attributed to the presence of Ag-rich second phase particles, precipitation of carbides and to the preferential development of grains possessing a {111} orientation upon thermal treatment. The prominence of {111} grains can also give rise to premature twinning, explaining the role of Ag in reducing the ductility of TWIP steels already observed in other works. Furthermore, in vitro biological performances were unaffected by Ag. These findings could allow the design of efficient treatments for supporting the transformation of Fe-Mn-C steels alloyed with Ag into commercial products.

Six-Month Long In Vitro Degradation Tests of Biodegradable Twinning-Induced Plasticity Steels Alloyed with Ag for Stent Applications.

Twinning-induced plasticity (TWIP) Fe-Mn-C steels are biodegradable metals with far superior mechanical properties to any biodegradable metal, including Mg alloys, used in commercially available devices. For this reason, the use of Fe-Mn-C alloys to produce thinner and thinner implants can be exploited for overcoming the device size limitations that biodegradable stents still present. However, Fe-Mn steels are known to form a phosphate layer on their surface over long implantation times in animals, preventing device degradation in the required timeframe. The introduction of second phases in such alloys to promote galvanic coupling showed a short-term promise, and particularly the use of Ag looked especially effective. Nonetheless, the evolution of the corrosion mechanism of quaternary Fe-Mn-C-Ag alloys over time is still unknown. This study aims at understanding how corrosion changes over time for a TWIP steel alloyed with Ag using a simple static immersion setup. The presence of Ag promoted some galvanic coupling just in the first week of immersion; this effect was then suppressed by the formation of a mixed carbonate/hydroxide layer. This layer partly detached after 2 months and was replaced by a stable phosphate layer, over which a new carbonate/hydroxide formed after 4 months, effectively hindering the sample degradation. Attachment of phosphates to the surface matches 1-year outcomes from animal tests reported by other authors, but this phenomenon cannot be predicted using immersion up to 28 days. These results demonstrate that immersion tests of Fe-based degradable alloys can be related to animal tests only when they are carried out for a sufficiently long time and that galvanic coupling with Ag is not a viable strategy in the long term. Future works should focus more on surface modifications to control the interfacial behavior rather than alloying in the bulk.

Hydrogen Embrittlement Behavior of 18Ni 300 Maraging Steel Produced by Selective Laser Melting.

A study was performed to investigate the hydrogen embrittlement behavior of 18-Ni 300 maraging steel produced by selective laser melting and subjected to different heat treatment strategies. Hydrogen was pre-charged into the tensile samples by an electro-chemical method at the constant current density of 1 A m-2 and 50 A m-2 for 48 h at room temperature. Charged and uncharged specimens were subjected to tensile tests and the hydrogen concentration was eventually analysed using quadrupole mass spectroscopy. After tensile tests, uncharged maraging samples showed fracture surfaces with dimples. Conversely, in H-charged alloys, quasi-cleavage mode fractures occurred. A lower concentration of trapped hydrogen atoms and higher elongation at fracture were measured in the H-charged samples that were subjected to solution treatment prior to hydrogen charging, compared to the as-built counterparts. Isothermal aging treatment performed at 460 °C for 8 h before hydrogen charging increased the concentration of trapped hydrogen, giving rise to higher hydrogen embrittlement susceptibility.

The addition of silver affects the deformation mechanism of a twinning-induced plasticity steel: Potential for thinner degradable stents.

While Fe-based alloys have already been reported to possess all mechanical properties required for vascular stenting, their relatively low degradation rate in vivo still constitutes their main bottleneck. The inflammatory reaction generated by a stent is inversely proportional to its mass. Therefore, the tendency in stenting is to lower the section so to reduce the inflammatory reaction. Twinning-induced plasticity steels (TWIP) possess excellent mechanical properties for envisaging the next generation of thinner degradable cardiovascular stents. To accelerate the degradation, the addition of noble elements was proposed, aimed at promoting corrosion by galvanic coupling. In this context, silver was reported to generally increase the degradation rate. However, its impact on the deformation mechanism of TWIP steels has not been reported yet. Results show that the use of Ag significantly reduces the ductility without altering the strength of the material. Furthermore, the presence of Ag was found to promote a different deformation texture, thus stimulating the formation of mechanical martensite. Since a stent works in the deformed state, understanding the microstructure and texture resulting from plastic deformation can effectively help to forecast the degradation mechanisms taking place during implantation and the expected degradation time. Moreover, knowing the deformed microstructure allows to understand the formability of very small tubes, as precursors of the next generation of thin section degradable stents. STATEMENT OF SIGNIFICANCE: Commercial degradable magnesium stents are limited from their relatively big structure size. Twinning-induced plasticity steels possess outstanding mechanical properties, but their degradation time goes beyond the timeframe expected from clinics. The inclusion of noble Ag particles, which favor galvanic coupling, is known to promote corrosion and solve this limitation. However, it is necessary to understand the impact that Ag has on the deformation microstructure and on the mechanical properties. The addition of Ag reduces the ductility of a twinning-induced plasticity steel because of a different deformation microstructure. Since a stent works in a deformed state inside an artery, understanding the microstructural evolution after plastic deformation allows to better predict the device performances during service life.

In Vitro Degradation of Absorbable Zinc Alloys in Artificial Urine.

Absorbable metals have potential for making in-demand rigid temporary stents for the treatment of urinary tract obstruction, where polymers have reached their limits. In this work, in vitro degradation behavior of absorbable zinc alloys in artificial urine was studied using electrochemical methods and advanced surface characterization techniques with a comparison to a magnesium alloy. The results showed that pure zinc and its alloys (Zn⁻0.5Mg, Zn⁻1Mg, Zn⁻0.5Al) exhibited slower corrosion than pure magnesium and an Mg⁻2Zn⁻1Mn alloy. The corrosion layer was composed mostly of hydroxide, carbonate, and phosphate, without calcium content for the zinc group. Among all tested metals, the Zn⁻0.5Al alloy exhibited a uniform corrosion layer with low affinity with the ions in artificial urine.

Zinc-based alloys for degradable vascular stent applications.

The search for biodegradable metals with mechanical properties equal or higher to those of currently used permanent biomaterials, such as stainless steels, cobalt chromium and titanium alloys, desirable in vivo degradation rate and uniform corrosion is still an open challenge. Magnesium (Mg), iron (Fe) and zinc (Zn)-based alloys have been proposed as biodegradable metals for medical applications. Over the last two decades, extensive research has been done on Mg and Fe. Fe-based alloys show appropriate mechanical properties, but their degradation rate is an order of magnitude below the benchmark value. In comparison, alongside the insufficient mechanical performance of most of its alloys, Mg degradation rate has proven to be too high in a physiological environment and corrosion is rarely uniform. During the last few years, Zn alloys have been explored by the biomedical community as potential materials for bioabsorbable vascular stents due to their tolerable corrosion rates and tunable mechanical properties. This review summarizes recent progress made in developing Zn alloys for vascular stenting application. Novel Zn alloys are discussed regarding their microstructural characteristics, mechanical properties, corrosion behavior and in vivo performance. STATEMENT OF SIGNIFICANCE: Numerous studies on magnesium and iron materials have been reported to date, in an effort to formulate bioabsorbable stents with tailorable mechanical characteristics and corrosion behavior. Crucial concerns regarding poor ductility and remarkably rapid corrosion of magnesium, and very slow degradation of iron, seem to be still not desirably fulfilled. Zinc was introduced as a potential implant material in 2013 due to its promising biodegradability and biocompatibility. Since then, extensive investigations have been made toward development of zinc alloys that meet clinical benchmarks for vascular scaffolding. This review critically surveys the zinc alloys developed since 2013 from metallurgical and biodegradation points of view. Microstructural features, mechanical, corrosion and in vivo performances of these new alloys are thoroughly reviewed and evaluated.

Influence of ECAP process on mechanical and corrosion properties of pure Mg and ZK60 magnesium alloy for biodegradable stent applications.

Equal channel angular pressing (ECAP) was performed on ZK60 alloy and pure Mg in the temperature range 150-250 °C. A significant grain refinement was detected after ECAP, leading to an ultrafine grain size (UFG) and enhanced formability during extrusion process. Comparing to conventional coarse grained samples, fracture elongation of pure Mg and ZK60 alloy were significantly improved by 130% and 100%, respectively, while the tensile strength remained at high level. Extrusion was performed on ECAP processed billets to produce small tubes (with outer/inner diameter of 4/2.5 mm) as precursors for biodegradable stents. Studies on extruded tubes revealed that even after extrusion the microstructure and microhardness of the UFG ZK60 alloy were almost stable. Furthermore, pure Mg tubes showed an additional improvement in terms of grain refining and mechanical properties after extrusion. Electrochemical analyses and microstructural assessments after corrosion tests demonstrated two major influential factors in corrosion behavior of the investigated materials. The presence of Zn and Zr as alloying elements simultaneously increases the nobility by formation of a protective film and increase the local corrosion damage by amplifying the pitting development. ECAP treatment decreases the size of the second phase particles thus improving microstructure homogeneity, thereby decreasing the localized corrosion effects.

Microstructure, texture evolution, mechanical properties and corrosion behavior of ECAP processed ZK60 magnesium alloy for biodegradable applications.

Ultra-fine grained ZK60 Mg alloy was obtained by multi-pass equal-channel angular pressing at different temperatures of 250°C, 200°C and 150°C. Microstructural observations showed a significant grain refinement after ECAP, leading to an equiaxed and ultrafine grain (UFG) structure with average size of 600nm. The original extrusion fiber texture with planes oriented parallel to extrusion direction was gradually undermined during ECAP process and eventually it was substituted by a newly stronger texture component with considerably higher intensity, coinciding with ECAP shear plane. A combination of texture modification and grain refinement in UFG samples led to a marked reduction in mechanical asymmetric behavior compared to the as-received alloy, as well as adequate mechanical properties with about 100% improvement in elongation to failure while keeping relatively high tensile strength. Open circuit potential, potentiodynamic and weight loss measurements in a phosphate buffer solution electrolyte revealed an improved corrosion resistance of UFG alloy compared to the extruded one, stemming from a shift of corrosion regime from localized pitting in the as-received sample to a more uniform corrosion mode with reduced localized attack in ECAP processed alloy. Compression tests on immersed samples showed that the rate of loss of mechanical integrity in the UFG sample was lower than that in the as-received sample.

The processing of ultrafine-grained Mg tubes for biodegradable stents.

An investigation was carried out on equal-channel angular pressing (ECAP) and extrusion processing of a ZM21 Mg alloy to obtain an improved candidate material for the manufacturing of biodegradable Mg stents. Ultrafine-grain size billets of the ZM21 alloy were obtained by two-stage ECAP aimed at achieving an initial refining of the structure at 200°C and then reaching the submicrometer grain size range by lowering the processing temperature down to 150°C. The investigation revealed a significant improvement in the properties of the ECAP-treated samples compared with the starting coarse-grained ZM21 alloy. The 0.2% yield strength rose from 180 to 340 MPa after 150°C ECAP processing, while maintaining a fairly high tensile ductility. The ultrafine ZM21 alloy billets were then used for the extrusion of stent precursors having the form of small-size tubes. The grain size after extrusion remained in the submicrometer range while the hardness was revealed to be significantly higher than that of the coarse-grained ZM21 Mg alloy. It was demonstrated that processing of biodegradable Mg stent having an ultrafine-grained microstructure by ECAP and low-temperature extrusion is feasible and that the obtained products feature promising properties.