Study on Material Design and Corrosion Resistance Based on Multi-Principal Component Alloying Theory
Abstract
:1. Introduction
2. Materials and Methods
2.1. Design Philosophy
2.2. Alloy Fabrication
2.3. Corrosion Tests
2.4. Phase Identification and Microstructure
2.5. Theoretical Calculation of Alloy Properties
3. Discussion
3.1. Corrosion and Degradation Mechanism of Mg and Mg Alloys
3.2. Morphological Analysis of Mg30Zn30Sn30Sr5Bi5 Alloy before Corrosion
3.3. Phase Analysis of Mg30Zn30Sn30Sr5Bi5 Alloy
3.4. Electrochemical Corrosion Performance of Mg30Zn30Sn30Sr5Bi5 Alloy
3.4.1. Potentiodynamic Polarization Result Analysis
3.4.2. EIS Result Analysis
3.5. Morphological Analysis of Mg30Zn30Sn30Sr5Bi5 Alloy after Corrosion
4. Conclusions
- Based on the theory of biomaterials and the high entropy alloy theory, the elements of the alloy were determined to be Mg, Zn, Sn, Sr, Bi, and the atomic percentage of the element was 30: 30: 30: 5: 5. High-purity metal elements was used for smelting to produce the alloy through the magnetic levitation smelting technology. The initial purpose of this study was to find ways to improve the corrosion resistance of Mg alloy biomaterials. Therefore, this study mainly demonstrated its feasibility by comparing the electrochemical corrosion resistance of alloys and pure Mg.
- The corrosion rate of Mg30Zn30Sn30Sr5Bi5 alloy is 0.066 mm/y, which is much lower than that of pure magnesium (0.32 mm/y) under the same test conditions. Combined with the existing research results, the corrosion rate of common magnesium alloys is higher than that of the Mg30Zn30Sn30Sr5Bi5 alloys prepared in this study. Such as, the corrosion rate of ZK60 is 2.6791 mm/y, AM60 is 1.9573 mm/y, AZ31 is 3.1404 mm/y, etc. [52,53].The electrochemical corrosion experiment demonstrates that the self-corrosion current density of Mg30Zn30Sn30Sr5Bi5 alloy was 2.52 μA/cm−2, and that of pure magnesium was 12.39 μA/cm−2. The self-corrosion potential of the alloy is −634.7 mV, while that of pure magnesium was −845.6 mV. The corrosion degradation rate is 0.066 mm/y, and that of pure magnesium is 0.32 mm/y.
- Based on analysis of the SEM, EDS, and XRD test results of Mg30Zn30Sn30Sr5Bi5 alloy before and after the corrosion, it could be inferred that there were many different phases in the alloy, and various elements had a certain impact on the corrosion resistance of the material. As the important elements, Sn and Zn exist in the alloy in the form of the Sn phase, Mg2Sn phase, MgZn2, etc., which hinder the diffusion of Cl− ions in m-SBF and protect the Mg (OH) phase generated by Mg2+ ions. Meanwhile, the formation of Mg4O4, NaO3, MgO, Bi7.38Na0.62O11.38, SrSnO3, and other oxides also served as a protective layer on the alloy surface to prevent further corrosion. The presence of hydroxyapatite also played a role in protecting the surface of the alloy by slowing down the occurrence of galvanic corrosion, and thus met the design requirements for a low corrosion rate. After corrosion, the alloy surface displayed two main states. One is the presence of a mixture of hydroxide, oxide, hydroxyapatite, and other substances in dense granular form on the material surface. The other is cracks on the alloy surface due to the intensification of corrosion, because the protective layer was damaged by the increase in Cl− and higher secondary phases and later the formation of MgCl and other phases.
- The research results proved that the alloy prepared in this study displayed good corrosion resistance at low self-corrosion current density in the electrochemical corrosion test in the m-SBF. Anodic corrosion always shows good corrosion resistance, but cathodic corrosion shows poor corrosion resistance due to the increase in self-corrosion current density.
5. Patents
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Criteria and Principles | Content |
---|---|
High entropy alloy theory | The material contains five or more major elements [20]; |
The atomic percentage of each element is between 5% and 35% [21]; | |
In order to easily form solid solution phase, the difference in atomic size of each element should be less than or equal to 7% [22]; | |
The elements that are easier to form high entropy alloy with, summarized by Scholars in the field of high entropy alloy research, are shown in Figure 1 [23]. | |
Element implantability requirements [24,25] | Metal elements must have good biological characteristics and are safe for organisms without any toxic side effects; |
One of the main goals of medical Mg and Mg alloy design is to improve the method, which can realize solution strengthening, fine grain strengthening, and aging strengthening by adding different elements; | |
The metal elements should be the ones that appear with high frequency currently in the research of Mg alloy biomaterials. |
No. | Element Types | Atomic Radius nm | Biological Characteristics |
---|---|---|---|
1 | Mg | 136 | Mg and Mg alloys have good biocompatibility. Mg is an important element involved in human metabolism and maintenance of the normal operation of human tissues. According to the new RDA standard of the United States, the mass of Mg in normal adults is 21–28 g, and the daily intake of adults is 180–350 mg. A total of 53% of Mg exists in bones, and the rest is usually in muscle tissues and organs, such as liver, brain, and kidney. In addition, Mg is an activator of many enzymes, a common regulator of protein synthesis and muscle contraction, and a stabilizer of DNA and RNA [26,27]. |
2 | Zn | 125 | Zn is one of the essential trace elements for human body, and plays an extremely important role in human growth, immunity, endocrine, and other physiological processes. Therefore, it is called “the flower of life” and “the source of intelligence”. Zn can contribute to the normal function of many enzymes; promote wound healing; improve nerve transmission and synapse formation; support protein and DNA synthesis as well as the sense of taste and smell; enhance immunological activity. Zn deficiency leads to delayed responses to T cell-dependent and T cell-independent antigens [28,29,30]. |
3 | Sn | 140 | Sn is a trace element in the human body, which is relatively non-toxic within a certain range. In the human body, Sn can not only improve the activity of a variety of enzymes, but also interfere with the metabolism of Zn, Cu, and Ca, changing their concentrations in human tissues. In the existing Mg-Sn alloy studies, researchers have confirmed that an appropriate amount of Sn in the human body has good biocompatibility and blood compatibility, and will not cause cytotoxicity [31,32,33]. |
4 | Sr | 191 | Sr is a natural bone-seeking element that accumulates in bones due to its close physical and chemical properties to Ca. It can reduce bone absorption; stimulate the growth of osteoblasts; and enhance bone strength and bone mineral density. In addition, the degradation of Mg-Sr alloy is conducive to the deposition of hydroxyapatite and bone mineralization [34,35,36,37]. |
5 | Bi | 146 | Bi is not an essential element for animals and plants, and the trace amount is harmless to human body. It is often used in medicine in the form of compounds, such as contrast agents, bismuth potassium tartrate, etc. Although Bi is similar to Pb, it is harmless to human body and is a “green metal” because there has been a trend for Bi to replace Pb as a green, environmentally friendly material. Adding Bi to Mg alloys can promote bone formation without generating gas, and has great potential clinical application value [24]. |
No. | Name | Purity | Size | Shape |
---|---|---|---|---|
1 | High-purity Mg | 99.99 wt.% | Ø4 × 4 mm | Particles |
2 | High-purity Zn | 99.999 wt.% | 1–3 mm | Particles |
3 | High-purity Sn | 99.999 wt.% | 1–6 mm | Particles |
4 | High-purity Sr | 99.9 wt.% | 1–3 cm | Particles |
5 | High-purity Bi | 99.999 wt.% | 1–3 mm | Particles (spherical approximately) |
Formulation | Na+ | K+ | Mg2+ | Ca2+ | Cl− | HCO−3 | HPO2−4 | SO2−4 | pH |
---|---|---|---|---|---|---|---|---|---|
Blood Plasma | 142.0 | 5.0 | 1.5 | 2.5 | 103.0 | 27.0 | 1.0 | 0.5 | 7.4–7.5 |
m-SBF | 142.0 | 5.0 | 1.5 | 2.5 | 103.0 | 10.0 | 1.0 | 0.5 | 7.4 |
SBF | 142.0 | 5.0 | 1.5 | 2.5 | 147.8 | 4.2 | 1.0 | 0.5 | 7.4 |
Material | Ecorr | icorr | Rp | Corrosion Rate |
---|---|---|---|---|
Mg30Zn30Sn30Sr5Bi5 alloy | −634.7 | 5.669 | 4.708 × 103 | 2.591 |
Pure Mg | −845.6 | 27.28 | 3.093 × 102 | 12.7 |
Samples | Rs (Ω cm2) | CPE-T | CPE-P | Rct (Ω cm2) |
---|---|---|---|---|
Mg30Zn30Sn30Sr5Bi5 | 3.666 | 9.7436 × 10−5 | 0.89675 | 4454 |
Pure Mg | 3.348 | 0.011928 | 0.75321 | 420.9 |
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Ma, B.; Zhao, H.; Ju, D.; Yang, Z.; Chen, M.; Liu, Q. Study on Material Design and Corrosion Resistance Based on Multi-Principal Component Alloying Theory. Materials 2023, 16, 1939. https://doi.org/10.3390/ma16051939
Ma B, Zhao H, Ju D, Yang Z, Chen M, Liu Q. Study on Material Design and Corrosion Resistance Based on Multi-Principal Component Alloying Theory. Materials. 2023; 16(5):1939. https://doi.org/10.3390/ma16051939
Chicago/Turabian StyleMa, Beiyi, Hongyang Zhao, Dongying Ju, Zhibo Yang, Ming Chen, and Qian Liu. 2023. "Study on Material Design and Corrosion Resistance Based on Multi-Principal Component Alloying Theory" Materials 16, no. 5: 1939. https://doi.org/10.3390/ma16051939