Abstract
Degradable zinc alloys are a new type of medical material that has great potentials to be used in bone implants. In this work, a series of degradable Zn-3Al-xCu (x = 0, 0.5, 1.0, and 1.5 wt.%) alloys were designed, and the effects of copper content on the mechanical, degradable and antibacterial properties were systematically investigated. These include microstructural observation, tensile, electrochemical, immersion, and antibacterial tests. The results showed that Cu addition contributed to the grain refinement effect, and the grain size of Zn-3Al-1.5Cu alloy could reach a minimum of 5 μm. A tensile test showed that Cu addition improved the mechanical properties of the Zn-3Al-Cu alloys with ultimate tensile strength (UTS) reaching up to 209.30 ± 1.91 MPa and elongation up to 9.11 ± 0.48%. The in vitro immersion examination showed that the degradation rate of the Zn-3Al-xCu alloys accelerated with increasing Cu content, and the fastest corrosion rate of 0.025 ± 0.0005 mm/y was achieved for the Zn-3Al-1.5Cu alloy. Moreover, the antibacterial tests also displayed that the Zn-3Al-xCu alloys exhibited a significant antibacterial effect against S. aureus, and their inhibition zone diameters improved from 0.2 ± 0.1 to 4.9 ± 0.4 mm.
Similar content being viewed by others
References
C. Liu, Y. Li, Q. Ge, Z. Liu, A. Qiao, and Y. Mu, Mechanical Characteristics and In Vitro Degradation of Biodegradable Zn-Al alloy, Mater. Lett., 2021 https://doi.org/10.1016/j.matlet.2021.130181
M.P. Staiger, A.M. Pietak, J. Huadmai, and G. Dias, Magnesium and Its Alloys as Orthopedic Biomaterials: A Review, Biomaterials, 2006, 27(9), p 1728–1734. https://doi.org/10.1016/j.biomaterials.2005.10.003
F. Witte, The History of Biodegradable Magnesium Implants: A Review, Acta Biomater., 2010, 6(5), p 1680–1692. https://doi.org/10.1016/j.actbio.2010.02.028
M. Peuster, P. Wohlsein, M. Brügmann, M. Ehlerding, K. Seidler, C. Fink, H. Brauer, A. Fischer, and G. Hausdorf, A Novel Approach to Temporary Stenting: Degradable Cardiovascular Stents Produced from Corrodible Metal—Results 6-18 Months After Implantation into New Zealand White Rabbits, Heart, 2001, 86(5), p 563–569. https://doi.org/10.1136/heart.86.5.563
C.J. Frederickson, J.Y. Koh, and A.I. Bush, The Neurobiology of Zinc in Health and Disease, Nat. Rev. Neurosci., 2005, 6(6), p 449–462. https://doi.org/10.1038/nrn1671
J. Cheng, B. Liu, Y.H. Wu, and Y.F. Zheng, Comparative In Vitro Study on Pure Metals (Fe, Mn, Mg, Zn and W) as Biodegradable Metals, J. Mater. Sci. Technol., 2013, 29(7), p 619–627. https://doi.org/10.1016/j.jmst.2013.03.019
H. Li, L. Xin, K. Zhang, X. Yin, and S. Yu, Fluorine-Free Fabrication of Robust Self-Cleaning and Anti-corrosion Superhydrophobic Coating with Photocatalytic Function for Enhanced Anti-biofouling Property, Surf. Coat. Tech., 2022 https://doi.org/10.1016/j.surfcoat.2022.128406
J. Venezuela and M.S. Dargusch, The Influence of Alloying and Fabrication Techniques on the Mechanical Properties, Biodegradability and Biocompatibility of Zinc: A Comprehensive Review, Acta Biomater., 2019, 87, p 1–40. https://doi.org/10.1016/j.actbio.2019.01.035
X. Liu, J. Sun, F. Zhou, Y. Yang, R. Chang, K. Qiu, Z. Pu, L. Li, and Y. Zheng, Micro-alloying with Mn in Zn-Mg Alloy for Future Biodegradable Metals Application, Mater. Design., 2016, 94, p 95–104. https://doi.org/10.1016/j.matdes.2015.12.128
K. Wang, X. Tong, J. Lin, A. Wei, Y. Li, M. Dargusch, and C. Wen, Binary Zn-Ti Alloys for Orthopedic Applications: Corrosion and Degradation Behaviors, Friction and Wear Performance, and Cytotoxicity, J. Mater. Sci. Technol., 2021, 74, p 216–229. https://doi.org/10.1016/j.jmst.2020.10.031
Z.Z. Shi, X.X. Gao, H.J. Zhang, X.F. Liu, H.Y. Li, C. Zhou, Y.X. Yin, and L.N. Wang, Design Biodegradable Zn Alloys: Second Phases and their Significant Influences on Alloy Properties, Bioact. Mater., 2020, 5(2), p 210–218. https://doi.org/10.1016/j.bioactmat.2020.02.010
C. Chen, S. Fan, J. Niu, H. Huang, Z. Jin, L. Kong, D. Zhu, and G. Yuan, Alloying Design Strategy for Biodegradable Zinc Alloys Based on First-Principles Study of Solid Solution Strengthening, Mater. Des., 2021 https://doi.org/10.1016/j.matdes.2021.109676
H. Yang, B. Jia, Z. Zhang, X. Qu, G. Li, W. Lin, D. Zhu, K. Dai, and Y. Zheng, Alloying Design of Biodegradable Zinc as Promising Bone Implants for Load-Bearing Applications, Nat. Commun., 2020, 11(1), p 401. https://doi.org/10.1038/s41467-019-14153-7
Z. Tang, J. Niu, H. Huang, H. Zhang, J. Pei, J. Ou, and G. Yuan, Potential Biodegradable Zn-Cu Binary Alloys Developed for Cardiovascular Implant Applications, J. Mech. Behav. Biomed. Mater., 2017, 72, p 182–191. https://doi.org/10.1016/j.jmbbm.2017.05.013
J. Huang, Y. Lai, H. Jin, H. Guo, F. Ai, Q. Xing, X. Yang, and D.J. Ross, Preparation and Properties of Zn-Cu Alloy for Potential Stent Material, J. Mater. Eng. Perform., 2020, 29(10), p 6484–6493. https://doi.org/10.1007/s11665-020-05167-0
G. Li, H. Yang, Y. Zheng, X.H. Chen, J.A. Yang, D. Zhu, L. Ruan, and K. Takashima, Challenges in the Use of Zinc and Its Alloys as Biodegradable Metals: Perspective from Biomechanical compatibility, Acta Biomater., 2019, 97, p 23–45. https://doi.org/10.1016/j.actbio.2019.07.038
Y.X. Yin, C. Zhou, Y.P. Shi, Z.Z. Shi, T.H. Lu, Y. Hao, C.H. Liu, X. Wang, H.J. Zhang, and L.N. Wang, Hemocompatibility of Biodegradable Zn-0.8 wt% (Cu, Mn, Li) alloys, Mater Sci Eng C Mater Biol Appl., 2019, 104, p 109896. https://doi.org/10.1016/j.msec.2019.109896
P.K. Bowen, J.M. Seitz, and R.J. Guillory, Evaluation of Wrought Zn-Al alloys (1, 3, and 5 wt% Al) Through Mechanical and In Vivo Testing for Stent Applications, J. Biomed. Mater. Res. B, 2018, 106(1), p 245–258. https://doi.org/10.1002/jbm.b.33850
X. Gu, Y. Zheng, Y. Cheng, S. Zhong, and T. Xi, In Vitro Corrosion and Biocompatibility of Binary Magnesium Alloys, Biomaterials, 2009, 30(4), p 484–498. https://doi.org/10.1016/j.biomaterials.2008.10.021
C. Wang, H.T. Yang, X. Li, and Y.F. Zheng, In Vitro Evaluation of the Feasibility of Commercial Zn Alloys as Biodegradable Metals, J. Mater. Sci. Technol., 2016, 32(9), p 909–918. https://doi.org/10.1016/j.jmst.2016.06.003
P.K. Bowen, J. Drelich, and J. Goldman, Zinc Exhibits Ideal Physiological Corrosion Behavior for Bioabsorbable Stents, Adv. Mater., 2013, 25(18), p 2577–2582. https://doi.org/10.1002/adma.201300226
Y.F. Zheng, X.N. Gu, and F. Witte, Biodegradable Metals, Mater. Sci. Eng. R., 2014, 77, p 1–34. https://doi.org/10.1016/j.mser.2014.01.001
K. Törne, M. Larsson, A. Norlin, and J. Weissenrieder, Degradation of Zinc in Saline Solutions, Plasma, and Whole Blood, J. Biomed. Mater. Res. B., 2016, 104(6), p 1141–1151.
J. Chen, L. Tan, X. Yu, and K. Yang, Effect of Minor Content of Gd on the Mechanical and Degradable Properties of As-Cast Mg-2Zn-xGd-0.5Zr Alloys, J. Mater. Sci. Technol., 2019, 35(4), p 503–511. https://doi.org/10.1016/j.jmst.2018.10.022
G. Singh and A. Pandey, Management of Appendix Stump: The Technique, Med. J. Dr. DY Patil Univ., 2012, 5(2), p 106. https://doi.org/10.4103/0975-2870.103328
J. Wang, Z. Shan, X. Tan, X. Li, Z. Jiang, and J. Qin, Preparation of Graphene Oxide (GO)/Lanthanum Coordination Polymers for Enhancement of Bactericidal Activity, J. Mater. Chem. B., 2021, 9(2), p 366–372. https://doi.org/10.1039/d0tb02266g
W.U. Xiao-ping, L.I. De-fu, G.U. Sheng-li, X.U. Xiao-qing, H.U. Jie, and H.E. Jin-yu, As-Cast Microstructure and Phase Structure of ZnAl10Cu2 Alloy, Chin. J. Eng., 2011, 33(10), p 1248–1252. https://doi.org/10.13374/j.issn1001-053x.2011.10.007
S. Gimmler, M. Apel, and A. Bührig-Polaczek, Selection of Dedicated As-Cast Microstructures in Zn-Al-Cu Alloys for Bearing Applications Supported by Phase-Field Simulations, Metals, 2020 https://doi.org/10.3390/met10121659
H. J. Wang, N. C. Si, G. L. Liu, Z. J. Wang, and R. Ding, Effect of Aluminium Element on Microstructures and Mechanical Properties of ZZn-Al-Cu Casting Alloy. Foundry. 2015.
R. Michalik and H. Woźnica, Structure and Corrosion Resistance of Cast ZnAl40Cu2 Alloy, Defect. Diffus. Forum., 2012, 326–328, p 555–560. https://doi.org/10.4028/www.scientific.net/DDF.326-328.555
Z. Shi, M. Liu, and A. Atrens, Measurement of the Corrosion Rate of Magnesium Alloys Using Tafel Extrapolation, Corros. Sci., 2010, 52(2), p 579–588. https://doi.org/10.1016/j.corsci.2009.10.016
T. Huang, Z. Liu, D. Wu, and H. Yu, Microstructure, Mechanical Properties, and Biodegradation Response of the Grain-Refined Zn Alloys for Potential Medical Materials, J. Mater. Res. Technol., 2021, 15, p 226–240. https://doi.org/10.1016/j.jmrt.2021.08.024
P.K. Bowen, E.R. Shearier, S. Zhao, R.J. Guillory 2nd., F. Zhao, J. Goldman, and J.W. Drelich, Biodegradable Metals for Cardiovascular Stents: from Clinical Concerns to Recent Zn-Alloys, Adv. Healthc. Mater., 2016, 5(10), p 1121–1140. https://doi.org/10.1002/adhm.201501019
IOF Standardization, Textile Fabrics: Determination of Antibacterial Activity: Agar Difusion Plate Test. ISO: 2004.
H. Okamoto and T. Massalski, Binary Alloy Phase Diagrams, ASM Int. Mater. Park OH USA, 1990 https://doi.org/10.31399/asm.hb.v03.a0006247
D. Ma, Y. Li, S. Ng, and H. Jones, Unidirectional Solidification of Zn-rich Zn-Cu Peritectic Alloys—I. Microstructure Selection, Acta Mater., 2000, 48(2), p 419–431. https://doi.org/10.1016/S1359-6454(99)00365-1
M.J. Sun, T.J. Chen, H.Y. Guo, and T.Q. Duan Effect of Cu on the Solidification Structure of Zn-27Al Alloy. Spec Cast Nonferrous Alloys (2012)
J. Lin, X. Tong, Q. Sun, Y. Luan, D. Zhang, Z. Shi, K. Wang, J. Lin, Y. Li, M. Dargusch, and C. Wen, Biodegradable Ternary Zn-3Ge-0.5X (X=Cu, Mg, and Fe) Alloys for Orthopedic Applications, Acta Biomater., 2020, 115, p 432–446. https://doi.org/10.1016/j.actbio.2020.08.033
T. Freund and S.R. Morrison, Mechanism of Cathodic Processes on the Semiconductor Zinc Oxide, Surf. Sci., 1968, 9(1), p 119–132. https://doi.org/10.1016/0039-6028(68)90167-2
L. Sukhodub, Antimicrobial Activity of Ag+, Cu2+, Zn2+, Mg2+ Ions Doped Chitosan Nanoparticles, Ann. Mechnikov’s Inst., 2015, 1, p 39–43.
W.L. Du, S.S. Niu, Y.L. Xu, Z.R. Xu, and C.L. Fan, Antibacterial Activity of Chitosan Tripolyphosphate Nanoparticles Loaded with Various Metal Ions, Carbohyd. Polym., 2009, 75(3), p 385–389. https://doi.org/10.1016/j.carbpol.2008.07.039
S. Lin, Q. Wang, X. Yan, X. Ran, L. Wang, J.G. Zhou, T. Hu, and G. Wang, Mechanical Properties, Degradation Behaviors and Biocompatibility Evaluation of a Biodegradable Zn-Mg-Cu Alloy for Cardiovascular Implants, Mater. Lett., 2019, 234, p 294–297. https://doi.org/10.1016/j.matlet.2018.09.092
E. Zhang, X. Wang, M. Chen, and B. Hou, Effect of the Existing Form of Cu Element on the Mechanical Properties, Bio-corrosion and Antibacterial Properties of Ti-Cu Alloys For Biomedical Application, Mater. Sci. Eng. C Mater. Biol. Appl., 2016, 69, p 1210–1221. https://doi.org/10.1016/j.msec.2016.08.033
G. Grass, C. Rensing, and M. Solioz, Metallic Copper as an Antimicrobial Surface, Appl. Environ. Microbiol., 2011, 77(5), p 1541–1547. https://doi.org/10.1128/AEM.02766-10
Acknowledgments
This work was supported by the National Natural Science Foundation of China (No. 52001034, 51871030), Changzhou Sci&Tech Program (No. CJ20200078), Natural Science Foundation of the Jiangsu Higher Education Institutions of China (No. 20KJB430013), the Top-notch Academic Programs Project of Jiangsu Higher Education Institutions (TAPP) and the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD).
Author information
Authors and Affiliations
Corresponding author
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Zhan, J., Huang, X., Yang, Y. et al. Effects of Cu Content on the Mechanical, Degradable, and Antibacterial Properties of the As-Cast Zn-3Al-xCu Alloys. J. of Materi Eng and Perform 32, 10039–10056 (2023). https://doi.org/10.1007/s11665-023-07870-0
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11665-023-07870-0