Revolutionizing Metallic Biomaterials

doi:10.11900/0412.1961.2016.00529

Acta Metall Sin

2017, Vol. 53

Issue (3): 257-297 DOI: 10.11900/0412.1961.2016.00529

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Revolutionizing Metallic Biomaterials

Yufeng ZHENG^1,²(

),Yuanhao WU²

1 Department of Materials Science and Engineering, College of Engineering, Peking University, Beijing 100871, China
2 Center for Biomedical Materials and Tissue Engineering, Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871, China

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Yufeng ZHENG,Yuanhao WU. Revolutionizing Metallic Biomaterials. Acta Metall Sin, 2017, 53(3): 257-297.

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Abstract

Entering 21st century, the metallic biomaterials are revolutionizing. New kinds of metallic biomaterials represented by biodegradable metals, nacocrystalline metals and alloys, and bulk metallic glasses, had been explored as implantable biomaterials, and correspondingly the nature of metallic biomaterials are shifting from the bio-inert (with stainless steel, Co-based alloys and Ti alloys) to bio-active and multi-biofunctional (anti-bacterial, anti-proliferation, anti-cancer, etc.). The newly-emerging 3D printing technology and thin film technology had been applied to the advancing manufacture and intelligence of the medical devices made of metallic biomaterials. In this paper, the current research status of the revolutionizing metallic biomaterials had been reviewed, and the future research and development tendencies for newly-developed metallic biomaterials towards bio-functionalization, composite and intelligence are also proposed.

Key words: metallic biomaterial biodegradable metal bulk metallic glass nanocrystalline metal 3D printing biofunctionalization composite intelligence

Received: 22 November 2016

Fund: Supported by National Key Research and Development Program of China (Nos.2016YFC1102402 and 2016YFC1000903), National Natural Science Foundation of China (No.51431002) and NSFC/RGC Joint Research Scheme (Nos.51361165101 and 5161101031)

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https://www.ams.org.cn/EN/10.11900/0412.1961.2016.00529 OR https://www.ams.org.cn/EN/Y2017/V53/I3/257

Fig.1 Schematic diagram of the biocorrosion at biodegradable magnesium/medium interface^[2]
(a) absorption of organic moleculars on the alloys surface
(b) formation of Mg(OH)₂ during dissolution of the alloys
(c) chloride adsorption causes the breakdown of the Mg(OH)₂ protective layer and leads to pitting corrosion
(d) formation of corrosion particles and tissues

Fig.2 Considerations of element selection for developing biodegradable Mg-based alloys^[12]

Table 1 Cell viabilities of different Mg alloys^{[20,26,37,38,47,61~65]}

Table 2 In vivo evaluations of biocompatibility and corrosion behavior of Mg alloys^{[18,20,26,37,64,66~74]}

Material	Coating	Corrosion rate in vitro		Biocompatibility
Material	Coating	mma^-1		mLcm^-2d^-1
As-cast Mg^[104]	Alkali-heat treatment			No inhibitory effects on marrow cells growth. No signs of cellular lysis
As-cast Mg^[105]	Beta-TCP coating			MG63 viability about 80%
As-cast Mg^[106]	Heat-self-assembled monolayer			No inhibitory effects on marrow cells growth; hemolysis is 0
As-extruded Mg-0.8Ca^[14]	MgF₂ coating			After 10 d smooth muscle and endothelial cells around the alloys were still alive
As-cast Mg-1Ca^[87]	Na₂HPO₄ alkaliheat treatment	2.08^a	0.7^a	No obvious toxicity to L929 cells
As-cast Mg-1Ca^[87]	Na₂CO₃ alkali-heat treatment	2.27^a	0.86^a	No obvious toxicity to L929 cells
As-cast Mg-1Ca^[87]	NaHCO₃ alkali-heat treatment	2.29^a	0.48^a	No obvious toxicity to L929 cells
As-cast Mg-1Ca^[107]	Electrodeposition	0.17^b
As-extruded Mg-1Ca^[108]	Electrodeposition	0.14^b
As-extruded Mg-1Ca^[98]	Chitosan coating		0.312~0.686^a
As-extruded Mg-6Zn^[91,109]	Electrodeposition	(1.9×10^-3)^c	About 0.07^a
As-extruded Mg-6Zn^[91,109]	HA electrodeposition		About 0.06^a
As-extruded Mg-6Zn^[91,109]	FHA electrodeposition		About 0.02^a	Present more stimulation effects to hBMSCs proliferation and differentiation; can up-regulate main osteogenic genes after 21 d of culture
As-extruded Mg-6Zn^[101]	PLGA coating	0.68~1.18^a		Significantly enhanced ability of MC3T3 cell attachment
As-extruded Mg-Mn-Zn^[110]	DCPD	0.09~0.30^c		Better surface cytocompatibility than naked Mg-Mn-Zn alloy and pure Ti
As-cast Mg-Zn-Ca^[93]	Ca-deficient HA coating	0.56^a
As-cast AZ31^[111]	Ca-P coating			Hemolysis is 2.5%
As-cast AZ31^[112]	CeO₂/MgO coating	0.03^c		Good anti-clotting property equivalent to that of 316L stainless steel
As-cast AZ31^[113]	MgO anodic oxidation			Does not affect the proliferation and the bone formation of osteoblast; hemolysisis 4.3%
As-extruded AZ31^[108]	DCPD	0.06^b
As-extruded AZ31^[114]	MgF₂	2.26^b	0.0011^b
As-cast AZ91^[90,114~116]	MAO coating	(7.1×10^-4~3.4×10^-3)^a
As-cast AZ91^[117]	Laser surface melting	0.17^a
As-cast AZ91^[118]	Hydrogenated amorphous silicon	0.08^a		hFOB1.19 cells attach well on the coating and proliferate normally
As-extruded WE43^[119]	Chitosan coating	0.05^b
As-extruded LAE442^[68]	MgF₂ coating		0.77^b

Table 3 Influences of surface modification methods on the corrosion behavior and biocompatibility of Mg alloys^{[14,68,87,90,91,93,98,101,104~119]}

Fig.3 Comparison of the coating effectiveness on corrosion resistance of Mg alloys substrates^[2] (PEI: polyethyleneimine, PSS: poly (styrene sulfonate), 8HQ: 8-hydroxyquinoline, PCL: polycaprolactone, CS: chitosan, PLLA: poly L-lactic acid)

Fig.4 Average corrosion rates of pure Zn wires after implanted in the SD rats^[120]

Table 4 Summary of the mechanical properties of pure Zn and Zn alloys^{[122,124~126]}

Table 5 Mechanical properties of potential alloys for biodegradable stents applications and 316L SS (stainless steel)^[127~138]

Fig.5 Weight loss and corrosion rate of pure iron in SBF^[142]

Table 6 In vivo studies of Fe and Fe alloys for vascular stents applications^{[132,141,144~149]}

Table 7 Summary of the mechanical properties of Ti-based metallic glasses^[171~180]

Fig.6 Compressive stress-strain curves of Ni-free Zr-based BMGs^[185] (BMG—bulk metallic glass)

Table 8 Summary of the mechanical properties of Zr-based metallic glasses^{[185,187~196]}

Fig.7 Uniaxial compressive true stress-strain curves of four Fe-Cr-Mo-P-C-B BMGs (a—Fe63Cr3Mo12-P10C7B5, b—Fe64Cr3Mo10P10C10B3, c—Fe63-Cr3Mo10P12C10B2, d—Fe71Mo5P12C10B2)^[205]

Table 9 Summary of the mechanical properties of Fe-based metallic glasses^{[185,205~209]}

Table 10 Summary of the mechanical properties of the biodegrdable metallic glasses^{[188,213~226]}

Fig.8 Structures fabricated via electron beam melting^[258]
(a) cubes with 40% relative density (60% porous)
(b) cubes with relative densities of 8.0%, 5.0% and 3.8%
(c) bending specimens with 8 mm and 6 mm cell sizes (7.3% and 11.9% relative density)
(d) hip stems with mesh configuration, hole configuration, and solid configuration

Table 11 Room temperature tensile properties of Ti-6Al-4V fabricated by different methods^{[260,264~266]}

Table 12 Comparison of Vickers hardness and tensile mechanical properties of different types of titanium alloys processed by SLM and traditional methods^{[264,274,275,277~283]}

Table 13 Tensile properties of laser direct melting deposition (LDMD) Ti alloy^[292,297]

Fig.9 Illustration of the mechanical properties of the metallic materials for biomedical applications^{[13,20,24~29,37,41,49,62,64,170~176,181~191,195,196,206~209,212~221,214~216]}
(a) Mg and Mg-based alloys
(b) Zn and Zn-based alloys
(c) Fe and Fe-based alloys
(d) BMGs

Fig.10 Novelcardiovascular stents intergrated with diagnose and therapy functions^[335]

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