Surface Modification of an Absorbable Bimodal Fe-Mn-Ag Alloy by Nitrogen Plasma Immersion Ion Implantation.

Recently, Fe-Mn-based alloys have been increasingly catching the attention of the scientific community, because of their tunable and outstanding mechanical properties, and suitable degradation behavior for biomedical applications. In spite of these assets, their corrosion rate (CR) is, in general, too low to satisfy the requirements that need to be met for cardiovascular device applications, such as stents. In fact, the CR is not always the same for all of the degradation stages of the material, and in addition, a finely tuned release rate, especially during the first steps of the corrosion pattern, is often demanded. In this work, a resorbable bimodal multi-phase alloy Fe-3Mn-1Ag was designed by mechanical alloying and spark plasma sintering (SPS) to accelerate the corrosion rate. The presence of several phases, for example α-Fe, α-Mn, γ-FeMn and Ag, provided the material with excellent mechanical properties (tensile strength UTS = 722 MPa, tensile strain A = 38%) and a higher corrosion rate (CR = 3.2 ± 0.2 mm/year). However, higher corrosion rates, associated with an increased release of degradation elements, could also raise toxicity concerns, especially at the beginning of the corrosion pattern. In this study, The focus of the present work was the control of the CR by surface modification, with nitrogen plasma immersion ion implantation (N-PIII) treatment that was applied to mechanically polished (MP) samples. This plasma treatment (PT) improved the corrosion resistance of the material, assessed by static degradation immersion tests (SDITs), especially during the first degradation stages. Twenty-eight days later, the degradation rate reached the same value of the MP condition. Nitrogen compounds on the surface of the substrate played an important role in the corrosion mechanism and corrosion product formation. The degradation analysis was carried out also by potentiodynamic tests in modified Hanks' balanced salt solution (MHBSS), and Dulbecco's phosphate buffered saline solution (DPBSS). The corrosion rate was higher in MHBSS for both conditions. However, there was no significant difference between the corrosion rate of the PT in DPBSS (CR = 1.9 ± 0.6 mm/year) and in MHBSS (CR = 2 ± 1.4 mm/year). The cell viability was assessed with human vein endothelial cells (HUVECs) via an indirect metabolic activity test (MTT assay). Due to the lower ion release of the PT condition, the cell viability increased significantly. Thus, nitrogen implantation can control the in vitro corrosion rate starting from the very first stage of the implantation, improving cell viability.

Purification of the leaching solution of recycling zinc from the hazardous electric arc furnace dust through an as-bearing jarosite.

Leaching of the hazardous electric arc furnace (EAF) dust containing mainly zinc ferrite and zinc oxide, accompanied by minor concentrations of arsenic compounds, was investigated using sulfuric acid. In order to reach the maximum recovery of zinc, the leaching solution was adjusted to recover both iron and zinc at their maximum possible values. To obtain a high recovery value of zinc and iron, analyzed by AAS, the optimum leaching condition was found to be the temperature of 90 °C, the sulfuric acid concentration of 3 M, the particle size of 75 µm, the S/L ratio of 1:10 g/mL and the leaching time of 2 h. The percentages of the zinc and iron recovery under the optimum condition were ca. 98.6% and 99.1% respectively, which were verified by a confirmation test and were very close to the predicted values of 100% based on the optimized model, obtained through the software. From the thermodynamics' point of view, it has been found that Zn2+ is the predominant species (90%) under the leaching condition applied. Moreover, the predominant species of iron are FeSO4+, FeHSO42+, Fe(SO4)2- and Fe3+ in the magnitudes of 65.8%, 25.6%, 4.4% and 4.0%, respectively. According to the kinetic results, the controlling step in the leaching was the chemical reaction at the most of the operating temperatures and times. In order to purify the zinc solution for electrowinning, iron and arsenic were removed through the jarosite formation process as confirmed by the XRD results. The speciation of arsenic in the precipitated jarosite was explored by XPS. Finally, the low concentrations of arsenic (less than 0.1 ppm) and iron (less than 50 ppm) were determined by the ICP analysis.

In Vitro Degradation, Hemocompatibility, and Cytocompatibility of Nanostructured Absorbable Fe-Mn-Ag Alloys for Biomedical Application.

The addition of noble elements such as Ag was shown as a successful method to accelerate the corrosion rate of absorbable Fe-based alloys. One major concern of Ag addition is its effect on hemocompatibility and biocompatibility. In this study, in vitro degradation and surface analysis of Fe-30Mn-xAg (x = 0, 1, and 3 wt %) alloys as well as their effects on hemocompatibility and cell viability of human umbilical vein endothelial cells (HUVECs) were investigated. The static degradation rate of the alloys was 4.97, 4.69, and 4.49 mg/cm2 for Fe-30Mn, Fe-30Mn-1Ag, and Fe-30Mn-3Ag, respectively. The surface analysis after degradation showed that γ-FeOOH was formed on Fe-30Mn-3Ag, while α-FeOOH was more dominant on Fe-30Mn and Fe-30Mn-1Ag. As γ-FeOOH is more soluble than α-FeOOH, it assists further degradation of Fe-30Mn-3Ag alloy. The high amount of Ag, which induced the hemolysis ratio, however, inhibited coagulation by decreasing the platelet adhesion. Fe-30Mn-1Ag and Fe-30Mn-3Ag alloys show an improved cell viability as compared to that of Fe-Mn alloy. Shear yield strength and shear elastic modulus of the samples after immersion tests were increased, while the ultimate shear strength was not affected. On the basis of the acceptable hemolysis rate, low platelet adhesion, acceptable cell viability, and appropriate mechanical properties after degradation, Fe-30Mn-1Ag can be considered as a suitable blood-contacting Fe-based absorbable alloy.

Novel antibacterial biodegradable Fe-Mn-Ag alloys produced by mechanical alloying.

Various compositions and synthesis methods of biodegradable iron-based alloys have been studied aiming for the use of temporary medical implants. However, none is focused on nano-structured alloy and on adding antibacterial property to the alloy. In this study, new Fe-30Mn-(1-3)Ag alloys were synthesized by means of mechanical alloying and assessed for their microstructure, mechanical properties, corrosion rate, antibacterial activity and cytotoxicity. Results showed that the alloy with 3 wt% Ag content displayed the highest relative density, shear strength, micro hardness and corrosion rate. However, optimum cytotoxicity and the antibacterial activity were reached by the alloy with 1 wt% Ag content. The compositional and processing effects of the alloys' properties are further discussed in this work.