Degradation Behaviour of Mg0.6Ca and Mg0.6Ca2Ag Alloys with Bioactive Plasma Electrolytic Oxidation Coatings
<p>Backscattered electron micrographs of the studied alloys: (<b>a</b>,<b>b</b>) Mg0.6Ca and (<b>c</b>,<b>d</b>) Mg0.6Ca2Ag.</p> "> Figure 2
<p>Transmission electron micrographs of the Mg0.6Ca alloy with locations of EDS analysis: (<b>a</b>) Mg0.6Ca 0.5 μm and (<b>b</b>) Mg0.6Ca 0.5 nm.</p> "> Figure 3
<p>Transmission electron micrographs of the Mg0.6Ca2Ag alloy with locations of EDS analysis. (<b>a</b>) Mg0.6Ca2Ag 0.5 μm and (<b>b</b>) Mg0.6Ca2Ag 50 nm.</p> "> Figure 4
<p>SEM backscattered images (<b>a</b>,<b>d</b>), surface potential maps (<b>b</b>,<b>e</b>) and potential profile (<b>c</b>,<b>f</b>) in selected areas of the Mg0.6Ca alloy.</p> "> Figure 5
<p>SEM backscattered image (<b>a</b>), surface potential maps (<b>b</b>) and potential profile (<b>c</b>) in selected areas of the Mg0.6Ca2Ag alloy.</p> "> Figure 6
<p>Backscattered electron micrographs of coating surface morphologies and cross-sections after corrosion of Mg0.6Ca/PEO (<b>a</b>,<b>c</b>,<b>e</b>) and PEO-Mg0.6Ca2Ag (<b>b</b>,<b>d</b>,<b>f</b>).</p> "> Figure 7
<p>XDR patterns from bulk material and PEO coatings.</p> "> Figure 8
<p>(<b>a</b>) Hydrogen volume and (<b>b</b>) hydrogen evolution rate of Mg0.6Ca and Mg0.6Ca/PEO after 60 days of immersion in m-SBF.</p> "> Figure 9
<p>Hydrogen volume for Mg0.6Ca2Ag and Mg0.6Ca2Ag/PEO after 4 days of immersion in m-SBF.</p> "> Figure 10
<p>3D macrograph of (<b>a</b>) Mg0.6Ca, (<b>b</b>) Mg0.6Ca/PEO after 60 days, (<b>c</b>) Mg0.6Ca2Ag and (<b>d</b>) Mg0.6Ca2Ag/PEO after 4 days of immersion in m-SBF.</p> "> Figure 11
<p>Cross-section before corrosion (<b>a</b>) Mg0.6Ca, (<b>b</b>) Mg0.6Ca/PEO after 60 days and (<b>c</b>) Mg0.6Ca2Ag and (<b>d</b>) Mg0.6Ca2Ag/PEO after 4 days of immersion in SBF.</p> "> Figure 12
<p>Schematic diagram of corrosion attack at the grain boundary and loss of grains (labeled with letters).</p> "> Figure 13
<p>Fluoride ions released of PEO coating for 120 min.</p> ">
Abstract
:1. Introduction
2. Materials and Methods
3. Results
3.1. Characterisation
3.2. Hydrogen Evolution Measurement
3.3. Fluoride Release
4. Conclusions
- PEO coatings of 32–35 μm thickness, containing bioactive calcium fluoride, magnesium fluoride and fluorapatite phases, were generated on Mg0.6Ca and Mg0.6Ca2Ag alloys for biomedical implant applications.
- The hydrogen evolution rate of PEO-coated Mg0.6Ca 3D prototypes evaluated during long-term immersion tests (up to 60 days), was 3.86 mL/cm2 week during the first month of immersion in SBF and 1.75 mL/cm2 week during the second month of immersion. The uncoated alloy generated two times more hydrogen in the first month of the test.
- The degradation mechanism during immersion of the studied materials corresponds to a generalized corrosion in both alloys. The Mg0.6Ca2Ag alloys degrade much faster than Mg0.6Ca due to the varied content of Ag and impurities in Mg–Ca–Ag intermetallic particles, which are mainly distributed along the grain boundaries; some of them acting as local anodes and causing the loss of the whole grain or clusters of grains. This also happens in Mg0.6Ca but to a much lesser extent, which leads to a slower corrosion process.
- The PEO coatings liberate fluoride ions during immersion in 0.9 M NaCl. The fluoride release is increased throughout 24 h of immersion time for Mg0.6Ca/PEO. The fluoride reserves of the coating have not been completely depleted in the course of the 24 h immersion.
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Element | Mg0.6Ca | Mg0.6Ca2Ag | Element | Mg0.6Ca | Mg0.6Ca2Ag |
---|---|---|---|---|---|
Mg | 99.4 | 97 | Nd | 0.00107 | 0.0009 |
Ca | >0.504 | >0.504 | Si | <0.0010 | <0.0010 |
Ag | 0.0005 | 2.417 | Sr | 0.0006 | 0.0007 |
Pr | 0.02844 | 0.02579 | Sn | <0.0005 | <0.0005 |
Al | 0.01985 | <0.00020 | Ni | 0.0004 | 0.0005 |
Th | 0.01547 | 0.01437 | P | <0.0003 | <0.0003 |
Mn | 0.015 | 0.03715 | Zr | <0.0003 | <0.0003 |
Cu | 0.00156 | 0.0004 | Fe | <0.0002 | <0.0002 |
Alloy | Location | Mg | Ca | Al | Si | Ag |
---|---|---|---|---|---|---|
Mg0.6Ca | 1 | 96.77 | 2.3 | 0.73 | 0.2 | – |
2 | 90.2 | 9.42 | 0.38 | – | – | |
3 | 92.66 | 7.11 | 0.27 | – | – | |
Mg0.6Ca2Ag | 4 | 99.4 | 0.15 | – | – | 0.4 |
5 | 98.13 | 0.3 | – | – | 1.57 | |
6 | 76.03 | 7.47 | – | – | 15.57 |
Alloy | Location | Mg | Ca | Ag | Fe | Al | Ni | Co | Cr | Si |
---|---|---|---|---|---|---|---|---|---|---|
Mg0.6Ca | 1 | 92.59 | 7.08 | – | – | 0.33 | – | – | – | – |
2 | 85.04 | 12.7 | – | 0.05 | 1.29 | 0.86 | – | – | – | |
Mg0.6Ca2Ag | 3 | 74.6 | 7.27 | 16.52 | 0.59 | – | 0.15 | 0.51 | 0.62 | 0.15 |
4 | 99.08 | 0.15 | 0.31 | 0.15 | – | – | 0.12 | 0.18 | – |
Alloy | Location | Mg | Ca | Si | O | Al |
---|---|---|---|---|---|---|
Mg0.6Ca | 1 | 91.31 | 6.15 | – | 2.23 | 0.3 |
2 | 80.42 | 7.38 | 10.87 | 1.33 | – | |
3 | 95.67 | 4.33 | – | – | – |
Alloy | Location | Mg | Ca | O | Ag |
---|---|---|---|---|---|
Mg0.6Ca2Ag | 1 | 91.44 | 5.04 | 1.42 | 2.11 |
2 | 81.67 | 8.32 | 0.71 | 9.31 |
Alloy | Location | Mg | O | F | Na | P | Ca | Ag | Ca/P |
---|---|---|---|---|---|---|---|---|---|
Mg0.6Ca | Surface | 22.1 | 44.9 | 16.3 | 4.2 | 5.2 | 7.3 | – | 1.42 |
Inner layer | 39.7 | 24.5 | 32.5 | 0.3 | 2.9 | 0.1 | – | 0.63 | |
Intermediate layer | 35.2 | 21.2 | 36.7 | 1.9 | 4.4 | 0.6 | – | 0.14 | |
Outer layer | 36.5 | 34.9 | 18.6 | 4.2 | 3.6 | 2.3 | – | 0.05 | |
Mg0.6Ca2Ag | Surface | 27 | 42.5 | 16.2 | 3.7 | 4.2 | 6.4 | – | 1.53 |
Inner layer | 37.6 | 22.3 | 34.7 | 1 | 3.8 | 0.5 | 0.2 | 0.4 | |
Intermediate layer | 32.4 | 26.3 | 30.1 | 4.3 | 5.1 | 1.5 | 0.2 | 0.3 | |
Outer layer | 36.2 | 37.3 | 13 | 4.6 | 6.3 | 2.5 | – | 0.12 |
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Moreno, L.; Mohedano, M.; Mingo, B.; Arrabal, R.; Matykina, E. Degradation Behaviour of Mg0.6Ca and Mg0.6Ca2Ag Alloys with Bioactive Plasma Electrolytic Oxidation Coatings. Coatings 2019, 9, 383. https://doi.org/10.3390/coatings9060383
Moreno L, Mohedano M, Mingo B, Arrabal R, Matykina E. Degradation Behaviour of Mg0.6Ca and Mg0.6Ca2Ag Alloys with Bioactive Plasma Electrolytic Oxidation Coatings. Coatings. 2019; 9(6):383. https://doi.org/10.3390/coatings9060383
Chicago/Turabian StyleMoreno, Lara, Marta Mohedano, Beatriz Mingo, Raul Arrabal, and Endzhe Matykina. 2019. "Degradation Behaviour of Mg0.6Ca and Mg0.6Ca2Ag Alloys with Bioactive Plasma Electrolytic Oxidation Coatings" Coatings 9, no. 6: 383. https://doi.org/10.3390/coatings9060383