The Joining of Alumina to Hastelloy by a TiZrCuNi Filler Metal: Wettability and Interfacial Reactivity.

A systematic microstructural characterization of alumina joined to Hastelloy C22® by means of a commercial active TiZrCuNi alloy, named BTi-5, as a filler metal is reviewed and discussed. The contact angles of the liquid BTi-5 alloy measured at 900°C for the two materials to be joined are 12° and 47° for alumina and Hastelloy C22® after 5 min, respectively, thus demonstrating good wetting and adhesion at 900 °C with very little interfacial reactivity or interdiffusion. The thermomechanical stresses caused by the difference in the coefficient of thermal expansion (CTE) between the Hastelloy C22® superalloy (≈15.3 × 10-6 K-1) and its alumina counterpart (≈8 × 10-6 K-1) were the key issues that had to be resolved to avoid failure in this joint. In this work, a circular configuration of the Hastelloy C22®/alumina joint was specifically designed to produce a feedthrough for sodium-based liquid metal batteries operating at high temperatures (up to 600 °C). In this configuration, adhesion between the metal and ceramic components was enhanced after cooling by compressive forces created on the joined area due to the difference in CTE between the two materials.

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.

Surface processing for iron-based degradable alloys: A preliminary study on the importance of acid pickling.

The formation of a heterogeneous oxidized layer, also called scale, on metallic surfaces is widely recognized as a rapid manufacturing event for metals and their alloys. Partial or total removal of the scale represents a mandatory integrated step for the industrial fabrication processes of medical devices. For biodegradable metals, acid pickling has already been reported as a preliminary surface preparation given further processes, such as electropolishing. Unfortunately, biodegradable medical prototypes presented discrepancies concerning acid pickling studies based on samples with less complex geometry (e.g., non-uniform scale removal and rougher surface). Indeed, this translational knowledge lacks a detailed investigation on this process, deep characterization of treated surfaces properties, as well as a comprehensive discussion of the involved mechanisms. In this study, the effects of different acidic media (HCl, HNO3, H3PO4, CH3COOH, H2SO4 and HF), maintained at different temperatures (21 and 60 °C) for various exposition time (15-240 s), on the chemical composition and surface properties of a Fe-13Mn-1.2C biodegradable alloy were investigated. Changes in mass loss, morphology and wettability evidenced the combined effect of temperature and time for all conditions. Pickling in HCl and HF solutions favor mass loss (0.03-0.1 g/cm2) and effectively remove the initial scale.

Characterization of a Magnesium Fluoride Conversion Coating on Mg-2Y-1Mn-1Zn Screws for Biomedical Applications.

MgF2-coated screws made of a Mg-2Y-1Mn-1Zn alloy, called NOVAMag® fixation screws (biotrics bioimplants AG), were tested in vitro for potential applications as biodegradable implants, and showed a controlled corrosion rate compared to non-coated screws. While previous studies regarding coated Mg-alloys have been carried out on flat sample surfaces, the present work focused on functional materials and final biomedical products. The substrates under study had a complex 3D geometry and a nearly cylindrical-shaped shaft. The corrosion rate of the samples was investigated using an electrochemical setup, especially adjusted to evaluate these types of samples, and thus, helped to improve an already patented coating process. A MgF2/MgO coating in the µm-range was characterized for the first time using complementary techniques. The coated screws revealed a smoother surface than the non-coated ones. Although the cross-section analysis revealed some fissures in the coating structure, the electrochemical studies using Hanks' salt solution demonstrated the effective role of MgF2 in retarding the alloy degradation during the initial stages of corrosion up to 24 h. The values of polarization resistance (Rp) of the coated samples extrapolated from the Nyquist plots were significantly higher than those of the non-coated samples, and impedance increased significantly over time. After 1200 s exposure, the Rp values were 1323 ± 144 Ω.cm2 for the coated samples and 1036 ± 198 Ω.cm2 for the non-coated samples, thus confirming a significant decrease in the degradation rate due to the MgF2 layer. The corrosion rates varied from 0.49 mm/y, at the beginning of the experiment, to 0.26 mm/y after 1200 s, and decreased further to 0.01 mm/y after 24 h. These results demonstrated the effectiveness of the applied MgF2 film in slowing down the corrosion of the bulk material, allowing the magnesium-alloy screws to be competitive as dental and orthopedic solutions for the biodegradable implants market.

Improving the radiopacity of Fe-Mn biodegradable metals by magnetron-sputtered W-Fe-Mn-C coatings: Application for thinner stents.

In this exploratory work, micrometric radiopaque W-Fe-Mn-C coatings were produced by magnetron sputtering plasma deposition, for the first time, with the aim to make very thin Fe-Mn stents trackable by fluoroscopy. The power of Fe-13Mn-1.2C target was kept constant at 400 W while that of W target varied from 100 to 400 W producing three different coatings referred to as P100, P200, P400. The effect of the increased W power on coatings thickness, roughness, structure, corrosion behavior and radiopacity was investigated. The coatings showed a power-dependent thickness and W concentration, different roughness values while a similar and uniform columnar structure. An amorphous phase was detected for both P100 and P200 coatings while γ-Fe, bcc-W and W3C phases found for P400. Moreover, P200 and P400 showed a significantly higher corrosion rate (CR) compared to P100. The presence of W, W3C as well as the Fe amount variation determined two different micro-galvanic corrosion mechanisms significantly changing the CR of coatings, 0.26 ± 0.02, 59.68 ± 1.21 and 59.06 ± 1.16 µm/year for P100, P200 and P400, respectively. Sample P200 with its most uniform morphology, lowest roughness (RMS = 3.9 ± 0.4 nm) and good radiopacity (∼6%) appeared the most suitable radiopaque biodegradable coating investigated in this study.

Interface Design in Lightweight SiC/TiSi2 Composites Fabricated by Reactive Infiltration Process: Interaction Phenomena between Liquid Si-Rich Si-Ti Alloys and Glassy Carbon.

To properly design and optimize liquid-assisted processes, such as reactive infiltration for fabricating lightweight and corrosion resistant SiC/TiSi2 composites, the extensive knowledge about the interfacial phenomena taking place when liquid Si-rich Si-Ti alloys are in contact with glassy carbon (GC) is of primary importance. To this end, the wettability of GC by two different Si-rich Si-Ti alloys was investigated for the first time by both the sessile and pendant drop methods at T = 1450 °C. The results obtained, in terms of contact angle values, spreading kinetics, reactivity, and developed interface microstructures, were compared with experimental observations previously obtained for the liquid Si-rich Si-Ti eutectics processed under the same operating conditions. As the main outcome, a different Si content did not seem to affect the final contact angle values. Contrarily, the final developed microstructure at the interface and the spreading kinetics were observed as weakly dependent on the composition. From a practical point of view, Si-Ti alloy compositions with a Si content falling in the simple eutectic region of the Si-Ti phase diagram might be potentially used as infiltrating materials of C- and SiC-based composites.

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.