Recent Progress on Nanocrystalline Metallic Materials for Biomedical Applications
Abstract
:1. Introduction
2. Bio-Inert NC Metallic Materials
2.1. Biomedical NC Pure Ti and Its Alloys
2.2. Biomedical NC SMAs
2.3. Biomedical NC Stainless Steels (SSs)
2.4. Other Types of Bio-Inert NC Metallic Materials
3. Biodegradable NC Metallic Materials for Biomedical Applications
4. Conclusions
- Biomedical NC metallic materials, such as Ti and its alloys, TNTZ, NiTi SMAs, SS, and biodegradable Fe and Mg alloys have significantly improved tensile yield strength, ultimate tensile strength, and hardness without significant reduction in ductility.
- Biomedical NC metallic materials, such as Ti and its alloys, TNTZ, NiTi SMAs, SS, and biodegradable Fe and Mg alloys have better corrosion resistance than their conventional CG metallic materials.
- Nanocrystallization of metallic biomaterials can improve their biocompatibility due to the unique nanostructures on their surfaces.
- In future research, the relationships between grain size, microstructural characteristics, and material properties of NC metallic materials should be systematically investigated. More research and development should be devoted to zinc-based degradable NC alloys, iron-based degradable NC alloys, and Mg and plural NC alloys.
Author Contributions
Funding
Conflicts of Interest
References
- Gatina, S.; Semenova, I.; Leuthold, J.; Valiev, R. Nanostructuring and Phase Transformations in the β-Alloy Ti-15Mo during High-Pressure Torsion. Adv. Eng. Mater. 2015, 17, 1742–1747. [Google Scholar] [CrossRef]
- Liu, Y.; Li, K.; Luo, T.; Song, M.; Wu, H.; Xiao, J.; Tan, Y.; Cheng, M.; Chen, B.; Niu, X.; et al. Powder metallurgical low-modulus Ti–Mg alloys for biomedical applications. Mater. Sci. Eng. C 2015, 56, 241–250. [Google Scholar] [CrossRef]
- Pérez-Prado, M.; Gimazov, A.; Ruano, O.; Kassner, M.; Zhilyaev, A. Bulk nanocrystalline ω-Zr by high-pressure torsion. Scr. Mater. 2008, 58, 219–222. [Google Scholar] [CrossRef]
- Valiev, R.Z.; Semenova, I.P.; Latysh, V.V.; Rack, H.; Lowe, T.C.; Petruželka, J.; Dluhos, L.; Hrusak, D.; Sochova, J. Nanostructured Titanium for Biomedical Applications. Adv. Eng. Mater. 2008, 10, B15–B17. [Google Scholar] [CrossRef]
- Semenova, I.P.; Klevtsov, G.V.; Klevtsova, N.Y.A.; Dyakonov, G.S.; Matchin, A.A.; Valiev, R.Z. Nanostructured Titanium for Maxillofacial Mini-Implants. Adv. Eng. Mater. 2016, 18, 1216–1224. [Google Scholar] [CrossRef]
- An, B.; Li, Z.; Diao, X.; Xin, H.; Zhang, Q.; Jia, X.; Wu, Y.; Li, K.; Guo, Y. In vitro and in vivo studies of ultrafine-grain Ti as dental implant material processed by ECAP. Mater. Sci. Eng. C 2016, 67, 34–41. [Google Scholar] [CrossRef]
- Li, H.; Nie, F.; Zheng, Y.; Cheng, Y.; Wei, S.; Valiev, R. Nanocrystalline Ti49.2Ni50.8 shape memory alloy as orthopaedic implant material with better performance. J. Mater. Sci. Technol. 2019, 35, 2156–2162. [Google Scholar] [CrossRef]
- Sheng, J.; Wei, J.; Li, Z.; Man, K.; Chen, W.; Ma, G.; Zheng, Y.; Zhan, F.; La, P.; Zhao, Y.; et al. Micro/nano-structure leads to super strength and excellent plasticity in nanostructured 304 stainless steel. J. Mater. Res. Technol. 2022, 17, 404–411. [Google Scholar] [CrossRef]
- Nie, F.L.; Zheng, Y.F.; Wei, S.C.; Hu, C.; Yang, G. In vitro corrosion, cytotoxicity and hemocompatibility of bulk nanocrystalline pure iron. Biomed. Mater. 2010, 5, 065015. [Google Scholar] [CrossRef] [PubMed] [Green Version]
- Wu, Q.; Miao, W.-S.; Zhang, Y.-D.; Gao, H.-J.; Hui, D. Mechanical properties of nanomaterials: A review. Nanotechnol. Rev. 2020, 9, 259–273. [Google Scholar] [CrossRef]
- Valiev, R.Z.; Prokofiev, E.A.; Kazarinov, N.A.; Raab, G.I.; Minasov, T.B.; Stráský, J. Developing Nanostructured Ti Alloys for Innovative Implantable Medical Devices. Materials 2020, 13, 967. [Google Scholar] [CrossRef] [PubMed] [Green Version]
- McCracken, D.M. MSBE, Dental Implant Materials: Commerciallv Pure Titanium and Titanium Alloys. J. Prosthodont. 1999, 8, 40–43. [Google Scholar] [CrossRef]
- Dick, J.C.; Bourgeault, C.A. Notch Sensitivity of Titanium Alloy, Commercially Pure Titanium, and Stainless Steel Spinal Implants. Spine 2001, 26, 1668–1672. [Google Scholar] [CrossRef]
- Aparicio, F.J.G.C.; Fonseca, C.; Barbosa, M.; Planell, J.A. Corrosion behaviour of commercially pure titanium shot blasted with different materials and sizes of shot particles for dental implant applications. Biomaterials 2003, 24, 263–273. [Google Scholar] [CrossRef]
- Filho, A.D.A.M.; Sordi, V.L.; Kliauga, A.; Ferrante, M. The effect of equal channel angular pressing on the tensile properties and microstructure of two medical implant materials: ASTM F-138 austenitic steel and Grade 2 titanium. J. Phys. Conf. Ser. 2010, 240, 012130. [Google Scholar] [CrossRef] [Green Version]
- Polyakov, A.V.; Dluhoš, L.; Dyakonov, G.S.; Raab, G.I.; Valiev, R.Z. Recent Advances in Processing and Application of Nanostructured Titanium for Dental Implants. Adv. Eng. Mater. 2015, 17, 1869–1875. [Google Scholar] [CrossRef]
- Fellah, M.; Hezil, N.; Leila, D.; Samad, M.A.; Djellabi, R.; Kosman, S.; Montagne, A.; Iost, A.; Obrosov, A.; Weiss, S. Effect of sintering temperature on structure and tribological properties of nanostructured Ti–15Mo alloy for biomedical applications. Trans. Nonferrous Met. Soc. China 2019, 29, 2310–2320. [Google Scholar] [CrossRef]
- Hussein, M.A.; Suryanarayana, C.; Al-Aqeeli, N. Fabrication of nano-grained Ti–Nb–Zr biomaterials using spark plasma sin-tering. Mater. Des. 2015, 87, 693–700. [Google Scholar] [CrossRef]
- Bhaskar, P.; Dasgupta, A.; Sarma, V.S.; Mudali, U.K.; Saroja, S. Mechanical properties and corrosion behaviour of nanocrystalline Ti–5Ta–1.8Nb alloy produced by cryo-rolling. Mater. Sci. Eng. A 2014, 616, 71–77. [Google Scholar] [CrossRef]
- Shahmir, H.; Pereira, P.H.R.; Huang, Y.; Langdon, T.G. Mechanical properties and microstructural evolution of nanocrystalline titanium at elevated temperatures. Mater. Sci. Eng. A 2016, 669, 358–366. [Google Scholar] [CrossRef] [Green Version]
- González-Masís, J.; Cubero-Sesin, J.M.; Campos-Quirós, A.; Edalati, K. Synthesis of biocompatible high-entropy alloy TiNbZrTaHf by high-pressure torsion. Mater. Sci. Eng. A 2021, 825, 141869. [Google Scholar] [CrossRef]
- Purcek, G.; Yapici, G.G.; Karaman, I.; Maier, H.J. Effect of commercial purity levels on the mechanical properties of ultrafine-grained titanium. Mater. Sci. Eng. A 2011, 528, 2303–2308. [Google Scholar] [CrossRef]
- Elias, C.N.; Fernandes, D.; De Biasi, R.S. Comparative study of compressive and fatigue strength of dental implants made of nanocrystalline Ti Hard and microcrystalline Ti G4. Fatigue Fract. Eng. Mater. Struct. 2016, 40, 696–705. [Google Scholar] [CrossRef]
- Javadhesari, S.M.; Alipour, S.; Akbarpour, M. Biocompatibility, osseointegration, antibacterial and mechanical properties of nanocrystalline Ti-Cu alloy as a new orthopedic material. Colloids Surf. B Biointerfaces 2020, 189, 110889. [Google Scholar] [CrossRef]
- Nie, F.L.; Zheng, Y.F.; Wei, S.C.; Wang, D.S.; Yu, Z.T.; Salimgareeva, G.K.; Polyakov, A.V.; Valiev, R.Z. In vitro and in vivo studies on nanocrystalline Ti fabricated by equal channel angular pressing with microcrystalline CP Ti as control. J. Biomed. Mater. Res. Part A 2013, 101A, 1694–1707. [Google Scholar] [CrossRef] [PubMed]
- González, M.; Peña, J.; Gil, F.J.; Manero, J.M. Low modulus Ti–Nb–Hf alloy for biomedical applications. Mater. Sci. Eng. C 2014, 42, 691–695. [Google Scholar] [CrossRef]
- Yilmazer, H.; Niinomi, M.; Nakai, M.; Hieda, J.; Akahori, T.; Todaka, Y. Microstructure and Mechanical Properties of a Biomedical β-Type Titanium Alloy Subjected to Severe Plastic Deformation after Aging Treatment. Key Eng. Mater. 2012, 508, 152–160. [Google Scholar] [CrossRef]
- Lin, Z.; Wang, L.; Xue, X.; Lu, W.; Qin, J.; Zhang, D. Microstructure evolution and mechanical properties of a Ti–35Nb–3Zr–2Ta biomedical alloy processed by equal channel angular pressing (ECAP). Mater. Sci. Eng. C 2013, 33, 4551–4561. [Google Scholar] [CrossRef]
- Yilmazer, H.; Niinomi, M.; Akahori, T.; Nakai, M.; Todaka, Y. Effect of high-pressure torsion processing on microstructure and mechanical properties of a novel biomedical β-type Ti-29Nb-13Ta-4.6Zr after cold rolling. Int. J. Microstruct. Mater. Prop. 2012, 7, 168–186. [Google Scholar] [CrossRef]
- Yilmazer, H.; Niinomi, M.; Nakai, M.; Hieda, J.; Todaka, Y.; Akahori, T.; Miyazaki, T. Heterogeneous structure and mechanical hardness of biomedical β-type Ti–29Nb–13Ta–4.6Zr subjected to high-pressure torsion. J. Mech. Behav. Biomed. Mater. 2012, 10, 235–245. [Google Scholar] [CrossRef] [PubMed]
- Xie, K.Y.; Wang, Y.; Zhao, Y.; Chang, L.; Wang, G.; Chen, Z.; Cao, Y.; Liao, X.; Lavernia, E.J.; Valiev, R.Z.; et al. Nanocrystalline β-Ti alloy with high hardness, low Young’s modulus and excellent in vitro biocompatibility for bio-medical applications. Mater. Sci. Eng. C 2013, 33, 3530–3536. [Google Scholar] [CrossRef] [PubMed]
- Hao, Y.L.; Zhang, Z.B.; Li, S.J.; Yang, R. Microstructure and mechanical behavior of a Ti–24Nb–4Zr–8Sn alloy processed by warm swaging and warm rolling. Acta Mater. 2012, 60, 2169–2177. [Google Scholar] [CrossRef]
- Kent, D.; Wang, G.; Yu, Z.; Ma, X.; Dargusch, M. Strength enhancement of a biomedical titanium alloy through a modified ac-cumulative roll bonding technique. J. Mech. Behav. Biomed. Mater. 2011, 4, 405–416. [Google Scholar] [CrossRef] [PubMed]
- He, G.; Eckert, J.; Dai, Q.; Sui, M.; Löser, W.; Hagiwara, M.; Ma, E. Nanostructured Ti-based multi-component alloys with potential for biomedical applications. Biomaterials 2003, 24, 5115–5120. [Google Scholar] [CrossRef]
- He, G.; Hagiwara, M. Ti alloy design strategy for biomedical applications. Mater. Sci. Eng. C 2006, 26, 14–19. [Google Scholar] [CrossRef]
- Yilmazer, B.D.H.; Niinomi, M.; Nakai, M. Electrochemical Impedance Spectroscopy(EIS) Evaluation of Biomedical Nanostructured Β-Type Titanium Alloys. In Proceedings of the 1st International Symposium on Light Alloys and Composite Materials, Karabük, Turkey, 22–24 March 2018. [Google Scholar]
- Lu, J.; Zhang, Y.; Huo, W.; Zhang, W.; Zhao, Y.; Zhang, Y. Electrochemical corrosion characteristics and biocompatibility of nanostructured titanium for implants. Appl. Surf. Sci. 2018, 434, 63–72. [Google Scholar] [CrossRef]
- Hussein, M.A. Synthesis, Characterization, and Surface Analysis of Near-β Ti20Nb20Zr Alloy Proceeded by Powder Metallurgy for Biomedical Applications. JOM 2022, 74, 924–930. [Google Scholar] [CrossRef]
- Otsuka, K.; Ren, X. Physical metallurgy of Ti–Ni-based shape memory alloys. Prog. Mater. Sci. 2005, 50, 511–678. [Google Scholar] [CrossRef]
- Wen, C.E.; Xiong, J.Y.; Li, Y.C.; Hodgson, P.D. Porous shape memory alloy scaffolds for biomedical applications: A review. Phys. Scr. 2010, 2010, 014070. [Google Scholar] [CrossRef]
- Hao, S.; Cui, L.; Jiang, D.; Han, X.; Ren, Y.; Jiang, J.; Liu, Y.; Liu, Z.; Mao, S.; Wang, Y.; et al. A Transforming Metal Nanocomposite with Large Elastic Strain, Low Modulus, and High Strength. Science 2013, 339, 1191–1194. [Google Scholar] [CrossRef] [PubMed] [Green Version]
- Sheremetyev, V.; Churakova, A.; Derkach, M.; Gunderov, D.; Raab, G.; Prokoshkin, S. Effect of ECAP and annealing on structure and mechanical properties of metastable beta Ti-18Zr-15Nb (at.%) alloy. Mater. Lett. 2021, 305, 130760. [Google Scholar] [CrossRef]
- Yan, B.; Jiang, S.; Sun, D.; Wang, M.; Yu, J.; Zhang, Y. Martensite twin formation and mechanical properties of B2 austenite NiTi shape memory alloy undergoing severe plastic deformation and subsequent annealing. Mater. Charact. 2021, 178, 111273. [Google Scholar] [CrossRef]
- Nie, F.; Zheng, Y.; Cheng, Y.; Wei, S.; Valiev, R. In vitro corrosion and cytotoxicity on microcrystalline, nanocrystalline and amorphous NiTi alloy fabricated by high pressure torsion. Mater. Lett. 2010, 64, 983–986. [Google Scholar] [CrossRef]
- Sharifi, E.M.; Kermanpur, A. Superelastic properties of nanocrystalline NiTi shape memory alloy produced by thermomechanical processing. Trans. Nonferrous Met. Soc. China 2018, 28, 515–523. [Google Scholar] [CrossRef]
- Baigonakova, G.; Marchenko, E.; Chekalkin, T.; Kang, J.-H.; Weiss, S.; Obrosov, A. Influence of Silver Addition on Structure, Martensite Transformations and Mechanical Properties of TiNi–Ag Alloy Wires for Biomedical Application. Materials 2020, 13, 4721. [Google Scholar] [CrossRef] [PubMed]
- Ozan, S.; Munir, K.; Biesiekierski, A.; Ipek, R.; Li, Y.; Wen, C. 1.3.3A—Titanium Alloys, Including Nitinol. In Biomaterials Science, 4th ed.; Wagner, W.R., Sakiyama-Elbert, S.E., Zhang, G., Yaszemski, M.J., Eds.; Academic Press: Cambridge, MA, USA, 2020; pp. 229–247. [Google Scholar]
- Shri, D.N.A.; Tsuchiya, K.; Yamamoto, A. Corrosion Behavior of HPT-Deformed TiNi Alloys in Cell Culture Medium. AIP Conf. Proc. 2017, 1877, 030010. [Google Scholar] [CrossRef] [Green Version]
- Nie, F.; Wang, S.; Wang, Y.; Wei, S.; Zheng, Y. Comparative study on corrosion resistance and in vitro biocompatibility of bulk nanocrystalline and microcrystalline biomedical 304 stainless steel. Dent. Mater. 2011, 27, 677–683. [Google Scholar] [CrossRef]
- Yin, F.; Hu, S.; Xu, R.; Han, X.; Qian, D.; Wei, W.; Hua, L.; Zhao, K. Strain rate sensitivity of the ultrastrong gradient nanocrystalline 316L stainless steel and its rate-dependent modeling at nanoscale. Int. J. Plast. 2020, 129, 102696. [Google Scholar] [CrossRef]
- Heidari, L.; Hadianfard, M.; Khalifeh, A.; Vashaee, D.; Tayebi, L. Fabrication of nanocrystalline austenitic stainless steel with superior strength and ductility via binder assisted extrusion method. Powder Technol. 2020, 379, 38–48. [Google Scholar] [CrossRef]
- Nie, F.L.; Wang, Y.B.; Wei, S.C.; Zheng, Y.F.; Wang, S.G. In Vitro Corrosion and Haemocompatibility of Bulk Nanocrystalline 304 Stainless Steel by Severe Rolling. Mater. Sci. Forum 2010, 667–669, 1113–1118. [Google Scholar] [CrossRef] [Green Version]
- Mineta, T.; Saito, T.; Yoshihara, T.; Sato, H. Structure and mechanical properties of nanocrystalline silver prepared by spark plasma sintering. Mater. Sci. Eng. A 2019, 754, 258–264. [Google Scholar] [CrossRef]
- Namus, R.; Rainforth, W.M.; Huang, Y.; Langdon, T.G. Effect of grain size and crystallographic structure on the corrosion and tribocorrosion behaviour of a CoCrMo biomedical grade alloy in simulated body fluid. Wear 2021, 478–479, 203884. [Google Scholar] [CrossRef]
- Huo, W.T.; Zhao, L.Z.; Yu, S.; Yu, Z.T.; Zhang, P.X.; Zhang, Y.S. Significantly enhanced osteoblast response to nano-grained pure tantalum. Sci. Rep. 2017, 7, 40868. [Google Scholar] [CrossRef] [Green Version]
- Fouzia, H.; Mamoun, F.; Hezil, N.; Aissani, L.; Goussem, M.; Said, M.; Mohammed, A.S.; Montagne, A.; Iost, A.; Weiß, S.; et al. The Effect of Milling Time on the Microstructure and Mechanical Properties of Ti-6Al-4Fe Alloys. Mater. Today Commun. 2021, 27, 102428. [Google Scholar] [CrossRef]
- Klinge, L.; Siemers, C.; Sobotta, B.; Krempin, H.; Kluy, L.; Groche, P. Nanocrystalline Ti13Nb13Zr for Dental Implant Applications. In Proceedings of the 60th Conference of Metallurgists, COM, Online, 17–19 August 2021. [Google Scholar]
- Aguilar, C.; Pio, E.; Medina, A.; Parra, C.; Mangalaraja, R.; Martin, P.; Alfonso, I.; Tello, K. Effect of Sn on synthesis of nanocrystalline Ti-based alloy with fcc structure. Trans. Nonferrous Met. Soc. China 2020, 30, 2119–2131. [Google Scholar] [CrossRef]
- Yilmazer, H.; Niinomi, H.M.; Nakai, M.; Cho, K.; Hieda, J.; Todaka, Y.; Miyazaki, T. Mechanical properties of a medical β-type titanium alloy with specific microstructural evolution through high-pressure torsion. Mater. Sci. Eng. C 2013, 33, 2499–2507. [Google Scholar] [CrossRef] [PubMed]
- Despang, F.; Bernhardt, A.; Lode, A.; Hanke, T.; Handtrack, D.; Kieback, B.; Gelinsky, M. Response of human bone marrow stromal cells to a novel ultra-fine-grained and dispersion-strengthened titanium-based material. Acta Biomater. 2010, 6, 1006–1013. [Google Scholar] [CrossRef] [PubMed]
- Huang, C.; Gao, Y.; Yang, G.; Wu, S.; Li, G.; Li, S. Bulk nanocrystalline stainless steel fabricated by equal channel angular pressing. J. Mater. Res. 2006, 21, 1687–1692. [Google Scholar] [CrossRef]
- Liu, H.-N.; Zhang, K.; Li, X.-G.; Li, Y.-J.; Ma, M.-L.; Shi, G.-L.; Yuan, J.-W.; Wang, K.-K. Microstructure and corrosion resistance of bone-implanted Mg–Zn–Ca–Sr alloy under different cooling methods. Rare Met. 2021, 40, 643–650. [Google Scholar] [CrossRef]
- Wang, W.; Blawert, C.; Zan, R.; Sun, Y.; Peng, H.; Ni, J.; Han, P.; Suo, T.; Song, Y.; Zhang, S.; et al. A novel lean alloy of biodegradable Mg–2Zn with nanograins. Bioact. Mater. 2021, 6, 4333–4341. [Google Scholar] [CrossRef]
- Zhang, C.; Guan, S.; Wang, L.; Zhu, S.; Chang, L. The microstructure and corrosion resistance of biological Mg–Zn–Ca alloy processed by high-pressure torsion and subsequently annealing. J. Mater. Res. 2017, 32, 1061–1072. [Google Scholar] [CrossRef]
- Parfenov, E.; Kulyasova, O.; Mukaeva, V.; Mingo, B.; Farrakhov, R.; Cherneikina, Y.; Yerokhin, A.; Zheng, Y.; Valiev, R. Influence of ultra-fine grain structure on corrosion behaviour of biodegradable Mg-1Ca alloy. Corros. Sci. 2019, 163, 108303. [Google Scholar] [CrossRef]
- Gu, X.N.; Li, X.L.; Zhou, W.R.; Cheng, Y.; Zheng, Y.F. Microstructure, biocorrosion and cytotoxicity evaluations of rapid solidified Mg–3Ca alloy ribbons as a biodegradable material. Biomed. Mater. 2010, 5, 035013. [Google Scholar] [CrossRef] [Green Version]
- Kowalski, M.J.K. Ultrafine grained Mg-1Zn-1Mn-0.3Zr alloy and its corrosion behaviour. J. Achiev. Mater. Manuf. Eng. 2016, 74, 53–59. [Google Scholar] [CrossRef]
Materials | Methods | Grain Size (nm) | Mechanical Properties | Corrosion Properties | Biocompatibility | Application | Ref. |
---|---|---|---|---|---|---|---|
Pure Ti (grade 2) | ECAP + cold rolling | About 500 | σYS: Increased to 796 MPa σUTS: Increased to 876 MPa Hardness: Increased to 271 HV | - | - | Bone replacement and repair | [15] |
Pure Ti (grade 4) | ECAP | 150 | Good plasticity under compression Fatigue strength higher than conventional CG Ti G4 | - | - | Dental implant | [23] |
Pure Ti (grade 4) | SPD+TMT | 150 | σUTS: 1240 MPa σYS: 1200 MPa Elongation: 12% Fatigue strength at 106 cycles: 620 MPa | - | (Fibroblast mice cells L929) Occupied surface after 72 h conventional CP Ti: 53.0% NC CP grade 4: 87.2% | Dental implant | [4] |
CP Ti (grade 4) | ECAP | 250 | Ductility: 5% TS: 1190 MPa σUTS: 1240 MPa Elongation: 11.5% Fatigue strength at 106 cycles: 620 MPa | - | Protein adsorption: Better than CP Ti L929: Cell viability increases and growth ahead MG63: Grow well VSMCs: Not proliferate well ECV304: Grow well Hemolysis rates: Less than 5% In vivo test: Superior bone formation | Bone replacement | [25] |
Pure Ti (grade 2) | HPT | 70 | Strength: 940 MPa High hardness: 300 HV Elongation: 130% | - | - | - | [20] |
Pure Ti (grade 2) | ECAE | 300 | σYS: 620 MPa Ductility: 21% | - | - | - | [22] |
Pure Ti (grade 4) | ECAE | 300 | σYS: 758 MPa Ductility: 25% | - | - | - | [22] |
Pure Ti | ECAP-conform + Drawing | - | σUTS: 1330 MPa σYS: 1267 MPa Elongation: 11% Endurance limit: 107 cycles of 620 MPa | - | - | Dental implants | [16] |
B2 austenite NiTi shape memory alloy (Ni-49.3 at.%Ti) | SPD. + Annealing 4 h | 45 | Compressive yield stress: 2552.1 MPa Fracture strain decreased 11.7% σSIM: 267.8 MPa | - | - | - | [43] |
Ti-15Mo | High energy ball mill + Hot isostaticallypressed | 29 (1373 K) | Microhardness: 315 HV0.02 (1373 K) Elastic modulus: 95 GPa Friction coefficient: 023–0.35 (1373 K) | - | - | - | [17] |
Ti-50at.%Ni | HPT | - | - | Increase corrosion resistance in the cell culture medium (stable and protective passive film) | - | - | [48] |
Ni50Ti50 | 70% cold rolling + annealing at 400 °C for 1 h | 20–70 | σSIM: 610 MPa | - | - | - | [45] |
Ni50.2Ti49.8 | HPT | - | Hardness: 456.8 ± 14.9 HV | Superiorly higher corrosion resistance than microcrystalline Ni50.2Ti49.8 (Hanks’ solution and artificial saliva) | L-929: No cytotoxicity MG63: No cytotoxicity | - | [44] |
Ti49.2Ni50.8 | ECAP | 150–250 | - | - | Hemolysis rates: 0.1% Number of adhered platelets: Lower than microcrystalline Cell viability: Higher Better osteogenesis functions In vivo: Enhanced cell viability, adhesion, proliferation, ALP activity, and mineralization, and increased periphery thickness of new bone | Orthopedic biomaterials | [7] |
Ti-6Al-4Fe | Mechanical alloying | - | Hardness: 335 ± 17 HV0.05 (powders milled for 2 h), 387 ± 19 HV0.05 (powders milled for 6 h), 475 ± 23HV0.05 (powders milled for 12 h), 660 ± 33 HV0.05 (powders milled for 18 h) Young’s modulus: 110–197 GPa | - | - | Bone replacement | [56] |
Ti-5Ta-1.8Nb | Cryo-rolling | 20 | σYS: About 800 MPa σUTS: ~750 MPa Elongation: About 5% | - | - | - | [19] |
Ti13Nb13Zr | SPD | 200 | Young’s modulus: 72 GPa σYS: 1150 MPa Hardness: 300 HV | - | - | Dental implant | [57] |
Ti-18Zr-15Nb | ECAP at 250 °C for 7 passes | 20–100 | σYS: 962 MPa σUTS: 988 MPa Ductility: 5.4% | - | - | - | [42] |
Ti-20Nb-13Zr | SPS | - | Hardness: 660 HV | - | Stimulate new bone formation | Dental and orthopedic applications | [18] |
Ti-13Ta-xSn (x = 3, 6, 9 and 12, at.%) | Mechanical alloying | 10 | - | - | - | - | [58] |
Ti25Nd16Hf | Cold rolling at 95% reduction | 50 | Ductility: 4.0% σYS: 790 MPa σUTS: 870 MPa Elastic modulus: 42.3 GPa | The highest corrosion resistance (corrosion current density 1.52 μA/cm2) compared with Ti25Nb16Hf (0% C.R.) and Ti grade II | Cytotoxicity: ExcellentCell adhesion (MG63 cells): Lower than pure Ti Cell proliferation: Properly | - | [26] |
TiNbZrTaHf | HPT | <100 | Hardness: 564 ± 22 HV Elastic modulus: 79 ± 3 GPa Good plasticity under localized compression | - | - | - | [21] |
Ti-29Nb-13Ta-4.6Zr | HPT | 40–500 | Ductility: Decrease σUTS: Increase Hardness: Great | - | - | - | [29] |
Ti-35Nb-3Zr-2Ta | ECAP | 300–600 | Ductility: 16% σUTS: 765 MPa Elastic modulus: 59GPa | - | - | - | [28] |
Ti-24Nb-4Zr-8Sn | Warm swaging and warm rolling | - | Recoverable strain: 3.4%σUTS: 1150 MPaElastic modulus:56 GPaDuctility: 8% | - | - | - | [32] |
Ti-29Nb-13Ta-4.6Zr | HPT | - | σUTS: 800–1100 MPa Elongation: 7% Young’s modulus: 60 MPa | - | - | - | [59] |
Ti-29Nb-13Ta-4.6Zr (TNTZ) | HPT | - | Hardness: Higher than 310 HV | - | - | - | [27] |
Ti-29Nb-13Ta-4.6Zr | HPT | - | Hardness: >183 HV (Hardness values of peripheral region higher than that of central region) | - | - | - | [30] |
Ti-36Nb-2.2Ta-3.7Zr-0.3O | HPT | - | Elastic modulus: 43 GPa (30% lower than CG counterpart) Hardness: 320HV (23% higher than CG counterpart) | - | Human gingival fibroblasts: Attachment and proliferation were enhanced Human dental follicular Cells: Higher cell density | - | [31] |
Ti-25Nb-3Zr-3Mo-2Sn | Accumulative roll bonding | 130 | σUTS: 1220 MPa 0.5% proof stress: 946 MPa Ductility: 4.5% | - | - | - | [33] |
Ti60Cu14Ni12Sn4Nb10 | Arc melting and copper mold casting | - | σYS: 1052 MPa Young’s modulus: 59 GPa Strain at yield point: 2.1% | - | - | - | [35] |
Ti 60Cu14Ni12Sn4M10 (M = Nb, Ta, Mo) | Arc melting and copper mold casting | - | σYS: 1037–1755 MPa Young’s modulus: 59–103 GPa Plastic strain: Up to 21% | - | - | - | [34] |
Ti/1.3HMDS | Powder metallurgy | 365 | Hardness: 320 HVYoung’s modulus: 129 MPa σYS: 1439 MPa Breaking elongation: 7.1% | Osteogenically induced hMSC: Comparable with CP Ti and Ti6Al4V | - | Bone repair | [60] |
ASTM F-138 austenitic steel | ECAP + cold rolling | 100–200 | YS: Increased to 1055 MPa σUTS: Increased to 1059 MPa Hardness: Increased to 339 HV | - | - | Bone replacement and repair | [15] |
Ti-Cu | Mechanical alloying and sintering | Hardness: 10 GPa | The corrosion behavior of the alloy was slightly lower than cp-Ti | 98% anti-bacterial rate against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli), excellent cell viability to MG-63 cells, and high osteoblast formation rate | Orthopedic material | [24] | |
304 stainless steel | Severe rolling | - | Strength 1280 MPa (NC 304), 640 MPa (CG 304 SS) | More corrosion resistant than the microcrystalline 304 SS in artificial saliva | Cytotoxicity (murine fibroblast cells): Better than microcrystalline 304 SS | - | [49] |
304 stainless steel | Severe rolling | 50 | Hardness: 480.0 ± 10.1 HV | Better corrosion resistance (Hanks’ solution) | Cytotoxicity (L-929, NIH 3T3): No toxic effect, Low hemolysis rate | - | [52] |
316L stainless steel | Severeplastic deformation | Around 5 at the surface | Maximum nanohardness: 6.2 GPa Young’s modulus: 200–220 GPa | - | - | - | [50] |
Stainless steel | ECAP | 74 (strain-induced martensite, BCC); 31 (austenite, FCC) | - | - | - | - | [61] |
Austenitic stainless steel | Binder assisted extrusion | - | Compressive yield strength: 824 MPa Compressive strength: 1326 MPa Uniform elongation: 50% Hardness: 339 HV | - | - | - | [51] |
Pure silver | Spark plasma sintering (sintered 600 K for 5 min) | 300 | σYS: 146 MPa Uniform elongation: 30% | - | - | - | [53] |
CoCrMo | Five-turns HPT | - | Compressive yield strength: 1.25 GPa Hardness: 9.3 GPa Elasticity modulus: 203 GPa | Reduce corrosion resistance | Improved tribocorrosion resistance | Hip and knee replacements | [54] |
Materials | Methods | Grain Size (nm) | Mechanical Properties | Corrosion Properties | Biocompatibility | Ref. |
Pure Fe | ECAP (8 passes) | - | σUTS: 470 MPa (double of CG counterpart) Hardness: 444 ± 31 kg f mm−2 (4 times of CG counterpart) | Higher corrosion resistance | Better hemocompatibility: Hemolysis less than 5% VSMCs: Inhibited (less than 60%) ECs and L929: Improved (more than 80%) | [9] |
Mg-2wt.%Zn | Hot-rolled | 70 | σYS: 223 MPa σUTS: 260 MPa | Good corrosion resistance (corrosion rate in vivo: 0.2 mm/y) | - | [63] |
Mg-1Zn-1Mn-0.3Zr | 20 h Ball milling + annealing | 45 | - | Corrosion resistance in Ringer solution improved | - | [67] |
Mg-Zn-Ca | HPT | With an increase in annealing temperature, grain size increased from 100 to 900 | Corrosion resistance increases with annealing temperature increased from 90–210 °C Corrosion resistance decreases with temperature increased after 210 °C | - | [64] | |
Mg-1Ca | HPT + Annealing | 100 | - | Increased corrosion resistance | - | [65] |
Mg-3Ca | Melt-spinning | 200–500 | - | Uniform corrosion morphology | No toxicity and improved adhesion in relation to L-929 cells | [66] |
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations. |
© 2022 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
Share and Cite
Li, H.; Wang, P.; Wen, C. Recent Progress on Nanocrystalline Metallic Materials for Biomedical Applications. Nanomaterials 2022, 12, 2111. https://doi.org/10.3390/nano12122111
Li H, Wang P, Wen C. Recent Progress on Nanocrystalline Metallic Materials for Biomedical Applications. Nanomaterials. 2022; 12(12):2111. https://doi.org/10.3390/nano12122111
Chicago/Turabian StyleLi, Huafang, Pengyu Wang, and Cuie Wen. 2022. "Recent Progress on Nanocrystalline Metallic Materials for Biomedical Applications" Nanomaterials 12, no. 12: 2111. https://doi.org/10.3390/nano12122111