Biomaterials Translational ›› 2021, Vol. 2 ›› Issue (3): 214-235.doi: 10.12336/biomatertransl.2021.03.005
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Yu Lu1, Subodh Deshmukh2, Ian Jones1, Yu-Lung Chiu1,*(
)
Received:2021-06-01
Revised:2021-07-14
Accepted:2021-08-16
Online:2021-09-28
Published:2021-09-28
Contact:
Yu-Lung Chiu
E-mail:y.chiu@bham.ac.uk
About author:Yu-Lung Chiu, y.chiu@bham.ac.uk.Lu, Y.; Deshmukh, S.; Jones, I.; Chiu, Y. Biodegradable magnesium alloys for orthopaedic applications. Biomater Transl. 2021, 2(3), 214-235.
Figure 1. (A) Locking compression plate. (B) Radiograph of distal tibial fracture treated with a locking plate. Reprinted from Bastias et al.11 Copyright 2014 European Foot and Ankle Society. (C) Interlocking nail. (D) Radiograph of femoral fracture treated with locking nail. Reprinted from Hsu et al.12 Copyright 2019, with permission from Elsevier.
Figure 2. (A-C) Principles of locking compression plate (A), intramedullary nailing (B), and screw (C).8
| Yield strength (MPa) | Ultimate tensile strength (MPa) | Elongation (%) | |
|---|---|---|---|
| CP Ti | |||
| Grade 1 | 170 | 240 | 24 |
| Grade 2 | 275 | 345 | 20 |
| Grade 3 | 380 | 450 | 18 |
| Grade 4 | 483 | 550 | 15 |
| Stainless steel | |||
| 18Cr-14Ni-2.5Mo | |||
| Annealed | 190 | 490 | 40 |
| Cold-worked | 690 | 860 | 12 |
| Co-28Cr-6Mo | |||
| Annealed | 517 | 897 | 20 |
| Hot-worked | 700 | 1000 | 12 |
Table 1 Mechanical performance of commercial pure (CP) titanium, stainless steel and cobalt-chromium alloys for surgical implant application.
| Yield strength (MPa) | Ultimate tensile strength (MPa) | Elongation (%) | |
|---|---|---|---|
| CP Ti | |||
| Grade 1 | 170 | 240 | 24 |
| Grade 2 | 275 | 345 | 20 |
| Grade 3 | 380 | 450 | 18 |
| Grade 4 | 483 | 550 | 15 |
| Stainless steel | |||
| 18Cr-14Ni-2.5Mo | |||
| Annealed | 190 | 490 | 40 |
| Cold-worked | 690 | 860 | 12 |
| Co-28Cr-6Mo | |||
| Annealed | 517 | 897 | 20 |
| Hot-worked | 700 | 1000 | 12 |
| Density (g/cm3) | Elastic modulus (GPa) | Tensile strength (MPa) | Fracture toughness (MPa1/2) | Total elongation (%) | |
|---|---|---|---|---|---|
| Cortical bone | 1.8﹣2.1 | 3﹣20 | 35﹣283 | 3﹣6 | 1.07﹣2.10 |
| Cancellous bone | 1.0﹣1.4 | NA | 1.5﹣38 | NA | NA |
| Magnesium alloys | 1.74﹣2.0 | 41﹣45 | 150﹣400 | 15﹣40 | 2﹣20 |
Table 2 Summary of the physical and mechanical properties of magnesium alloys in comparison with human bone.
| Density (g/cm3) | Elastic modulus (GPa) | Tensile strength (MPa) | Fracture toughness (MPa1/2) | Total elongation (%) | |
|---|---|---|---|---|---|
| Cortical bone | 1.8﹣2.1 | 3﹣20 | 35﹣283 | 3﹣6 | 1.07﹣2.10 |
| Cancellous bone | 1.0﹣1.4 | NA | 1.5﹣38 | NA | NA |
| Magnesium alloys | 1.74﹣2.0 | 41﹣45 | 150﹣400 | 15﹣40 | 2﹣20 |
Figure 3. Optimal degradation behaviour of a magnesium-based implant in bone fracture healing. The blue and yellow lines indicate the mechanical integrity and biodegradation rate, respectively.
Figure 4. Schematic illustration of the corrosion of magnesium in an aqueous environment:45 (A) The dissolution of magnesium via the anodic reaction. The cathodic reaction increases the pH and produces H2, while hydrolysis reduces the pH. Intermetallic particles act as cathodic sites and consume the electrons produced by the anodic reaction. (B) Chloride ions in the solution attack and dissolve the Mg(OH)2 film.
| Recommended dietary allowances for magnesium (mg) | Tolerable upper intake levels for supplemental magnesium (mg) | ||||
|---|---|---|---|---|---|
| Age (year) | Male | Female | Male | Female | |
| 19﹣30 | 400 | 310 | 350 | 350 | |
| 31﹣50 | 420 | 320 | 350 | 350 | |
| 51 or more | 420 | 320 | 350 | 350 | |
Table 3 Intake allowances for magnesium.
| Recommended dietary allowances for magnesium (mg) | Tolerable upper intake levels for supplemental magnesium (mg) | ||||
|---|---|---|---|---|---|
| Age (year) | Male | Female | Male | Female | |
| 19﹣30 | 400 | 310 | 350 | 350 | |
| 31﹣50 | 420 | 320 | 350 | 350 | |
| 51 or more | 420 | 320 | 350 | 350 | |
| Element | Solubility limits (wt%) | Growth restriction factor | Effects on mechanical properties | Effects on corrosion behaviour | Biological impact | Maximum daily allowable dose (mg) |
|---|---|---|---|---|---|---|
| Aluminium (Al) | 12.7 | 4.32 | Improves strength and ductility Grain refinement Increases castability | Decreases corrosion rate | Neurotoxic; Decreases osteoclast viability | 14 |
| Calcium (Ca) | 1.34 | 11.94 | Improves strength Grain refinement Increases castability | Decreases corrosion resistance | Most abundant mineral in the human body; Is tightly regulated by homeostasis | 1400 |
| Zinc (Zn) | 6.2 | 5.31 | Improves strength Reduces ductility at high concentration | Essential trace element (immune system, co-factor); Neurotoxic at higher concentration | 15 | |
| Manganese (Mn) | 2.2 | 0.15 | Improves strength and ductility Grain refinement | Decreases corrosion rate by removing iron and other heavy metal elements into relatively harmless compounds | Essential trace element; Important role in metabolic cycle and for the immune system; Neurotoxic at higher concentration | 5 |
| Lithium (Li) | 5.5 | Reduces strength Improves ductility | Reduces corrosion resistance | Possible teratogenic effects | ||
| Zirconium (Zr) | 3.8 | 38.29 | Improves strength and ductility Grain refinement | |||
| Silicon (Si) | ~0 | 9.25 | Reduces ductility and castability | Reduces corrosion resistance | Essential mineral in human body Helps to build the immune system | |
| Strontium (Sr) | 0.11 | 3.51 | Improves strength and ductility; Grain refinement | Deceases corrosion rate | Trace element in human body; Stimulates bone formation | 5 |
| Yttrium (Y) | 12.4 | 1.7 | Improves strength | Same standard electrochemical potential as Mg; Decreases corrosion rate by purifying the alloy and forming a passive film | May exhibit anti-carcinogenic properties | 0.016a |
| Neodymium (Nd) | 3.6 | Improves strength | Decreases corrosion rate by creating less noble intermetallic phase (‘scavenger effect’ on impurities) | May exhibit anti-carcinogenic properties | 4.2a | |
| Copper (Cu) | Increases strength | Causes hypotension, jaundice, etc. |
Table 4 The physical properties and influence of alloying elements on properties and biological impact of magnesium-based alloys.
| Element | Solubility limits (wt%) | Growth restriction factor | Effects on mechanical properties | Effects on corrosion behaviour | Biological impact | Maximum daily allowable dose (mg) |
|---|---|---|---|---|---|---|
| Aluminium (Al) | 12.7 | 4.32 | Improves strength and ductility Grain refinement Increases castability | Decreases corrosion rate | Neurotoxic; Decreases osteoclast viability | 14 |
| Calcium (Ca) | 1.34 | 11.94 | Improves strength Grain refinement Increases castability | Decreases corrosion resistance | Most abundant mineral in the human body; Is tightly regulated by homeostasis | 1400 |
| Zinc (Zn) | 6.2 | 5.31 | Improves strength Reduces ductility at high concentration | Essential trace element (immune system, co-factor); Neurotoxic at higher concentration | 15 | |
| Manganese (Mn) | 2.2 | 0.15 | Improves strength and ductility Grain refinement | Decreases corrosion rate by removing iron and other heavy metal elements into relatively harmless compounds | Essential trace element; Important role in metabolic cycle and for the immune system; Neurotoxic at higher concentration | 5 |
| Lithium (Li) | 5.5 | Reduces strength Improves ductility | Reduces corrosion resistance | Possible teratogenic effects | ||
| Zirconium (Zr) | 3.8 | 38.29 | Improves strength and ductility Grain refinement | |||
| Silicon (Si) | ~0 | 9.25 | Reduces ductility and castability | Reduces corrosion resistance | Essential mineral in human body Helps to build the immune system | |
| Strontium (Sr) | 0.11 | 3.51 | Improves strength and ductility; Grain refinement | Deceases corrosion rate | Trace element in human body; Stimulates bone formation | 5 |
| Yttrium (Y) | 12.4 | 1.7 | Improves strength | Same standard electrochemical potential as Mg; Decreases corrosion rate by purifying the alloy and forming a passive film | May exhibit anti-carcinogenic properties | 0.016a |
| Neodymium (Nd) | 3.6 | Improves strength | Decreases corrosion rate by creating less noble intermetallic phase (‘scavenger effect’ on impurities) | May exhibit anti-carcinogenic properties | 4.2a | |
| Copper (Cu) | Increases strength | Causes hypotension, jaundice, etc. |
Figure 5. The tensile strength and elongation of various magnesium alloys. (A) Reprinted from Lu.45 (B) Reprinted from Chen et al.84 Copyright 2014, with permission from Acta Materialia Inc.
| Alloy | Condition | In vitro corrosion rate (mm/year) | In vivo corrosion rate (mm/year) | Reference |
|---|---|---|---|---|
| Mg-0.8Ca | As-extruded | - | 0.5 | |
| Mg-1Ca | As-cast | ﹣ | 1.27 | |
| Mg-1Al | As-cast | 2.07 | ﹣ | |
| Mg-1Zn | As-cast | 1.52 | ﹣ | |
| Mg-1Zn | As-rolled | 0.92 | ﹣ | |
| Mg-1Zr | As-cast | 2.2 | ﹣ | |
| Mg-1Zr | As-rolled | 0.91 | ﹣ | |
| Mg-1Sn | As-cast | 2.45 | ﹣ | |
| Mg-2Sr | As-rolled | 0.37 | 1.01 | |
| Mg-3Zn | Solution treated | 1.53 | ﹣ | |
| Mg-6Zn | As-extruded | 0.07 | 2.32 | |
| Mg-8Y | As-cast | 2.17 | ﹣ | |
| AZ31 | As-cast | 2 | 1.17 | |
| AZ31 | As-extruded | 0.21 | ﹣ | |
| AZ61 | As-cast | 0.73 | ﹣ | |
| AZ91D | As-cast | 2.8 | 1.38 | |
| WE43 | As-cast | 0.26 | 1.56 | |
| Mg-1.2Mn-1Zn | As-cast | ﹣ | 0.45 | |
| Mg-1Zn-1Ca | As-cast | 2.13 | ﹣ | |
| Mg-3Zn-0.3Ca | Solution treated | 0.81 | ﹣ | |
| Mg-6Zn-1Ca | As-cast | 9.21 | ﹣ | |
| Mg-4Zn-0.5Ca-0.4Mn | As-cast | 0.25 | ﹣ | |
| Mg-3.09Nd-0.22Zn-0.44Zr | As-extruded | 0.13 | ﹣ | |
| Mg-2Zn-1.53Y | As-extruded | 0.7 | ﹣ | |
| Mg-11.3Gd-2.5Zn-0.7Zr | As-extruded | 0.17 | ﹣ |
Table 5 Bio-corrosion properties of magnesium-based alloys.
| Alloy | Condition | In vitro corrosion rate (mm/year) | In vivo corrosion rate (mm/year) | Reference |
|---|---|---|---|---|
| Mg-0.8Ca | As-extruded | - | 0.5 | |
| Mg-1Ca | As-cast | ﹣ | 1.27 | |
| Mg-1Al | As-cast | 2.07 | ﹣ | |
| Mg-1Zn | As-cast | 1.52 | ﹣ | |
| Mg-1Zn | As-rolled | 0.92 | ﹣ | |
| Mg-1Zr | As-cast | 2.2 | ﹣ | |
| Mg-1Zr | As-rolled | 0.91 | ﹣ | |
| Mg-1Sn | As-cast | 2.45 | ﹣ | |
| Mg-2Sr | As-rolled | 0.37 | 1.01 | |
| Mg-3Zn | Solution treated | 1.53 | ﹣ | |
| Mg-6Zn | As-extruded | 0.07 | 2.32 | |
| Mg-8Y | As-cast | 2.17 | ﹣ | |
| AZ31 | As-cast | 2 | 1.17 | |
| AZ31 | As-extruded | 0.21 | ﹣ | |
| AZ61 | As-cast | 0.73 | ﹣ | |
| AZ91D | As-cast | 2.8 | 1.38 | |
| WE43 | As-cast | 0.26 | 1.56 | |
| Mg-1.2Mn-1Zn | As-cast | ﹣ | 0.45 | |
| Mg-1Zn-1Ca | As-cast | 2.13 | ﹣ | |
| Mg-3Zn-0.3Ca | Solution treated | 0.81 | ﹣ | |
| Mg-6Zn-1Ca | As-cast | 9.21 | ﹣ | |
| Mg-4Zn-0.5Ca-0.4Mn | As-cast | 0.25 | ﹣ | |
| Mg-3.09Nd-0.22Zn-0.44Zr | As-extruded | 0.13 | ﹣ | |
| Mg-2Zn-1.53Y | As-extruded | 0.7 | ﹣ | |
| Mg-11.3Gd-2.5Zn-0.7Zr | As-extruded | 0.17 | ﹣ |
Figure 6. (A) As-built WE43 scaffold with diamond lattice fabricated by selective laser melting. Reprinted from Li et al.40 Copyright 2017, with permission from Acta Materialia Inc. (B) Honeycomb-structured magnesium scaffold produced by laser perforation. Reprinted from Tan et al.167 Copyright IOP Publishing. Reproduced with permission. All rights reserved. Scale bars: 1 mm.
| Ion | Blood plasma | Ringer’s solution | Earle’s balanced salt solution | Hank’s balanced salt solution | Kokubo’s simulated body fluid |
|---|---|---|---|---|---|
| Na+ (mM) | 142.00 | 130.00 | 143.60 | 138.00 | 142.00 |
| K+ (mM) | 5.00 | 4.00 | 5.37 | 6.14 | 5.00 |
| Ca2+ (mM) | 2.50 | 1.40 | 1.80 | 1.26 | 2.50 |
| Mg2+ (mM) | 1.50 | NA | 0.81 | 0.81 | 1.50 |
| Cl﹣ (mM) | 103.00 | 109.00 | 125.30 | 144.8 | 147.80 |
| HCO3﹣ (mM) | 27.00 | NA | 26.2 | 4.2 | 4.20 |
| HPO42- (mM) | 1.00 | NA | 1.00 | 0.78 | 1.00 |
| SO42- (mM) | 0.50 | NA | 0.81 | 0.81 | 0.50 |
| Ca/P (mM) | 2.50 | NA | 1.80 | 1.62 | 2.50 |
| Buffer (mM) | NA | NA | NA | NA | Tris |
| pH | 7.4 | 6.5 | 6.7-6.9 | 6.7-6.9 | 7.4 |
Table 6 The concentration of ions and pH values in blood plasma and in different solutions.
| Ion | Blood plasma | Ringer’s solution | Earle’s balanced salt solution | Hank’s balanced salt solution | Kokubo’s simulated body fluid |
|---|---|---|---|---|---|
| Na+ (mM) | 142.00 | 130.00 | 143.60 | 138.00 | 142.00 |
| K+ (mM) | 5.00 | 4.00 | 5.37 | 6.14 | 5.00 |
| Ca2+ (mM) | 2.50 | 1.40 | 1.80 | 1.26 | 2.50 |
| Mg2+ (mM) | 1.50 | NA | 0.81 | 0.81 | 1.50 |
| Cl﹣ (mM) | 103.00 | 109.00 | 125.30 | 144.8 | 147.80 |
| HCO3﹣ (mM) | 27.00 | NA | 26.2 | 4.2 | 4.20 |
| HPO42- (mM) | 1.00 | NA | 1.00 | 0.78 | 1.00 |
| SO42- (mM) | 0.50 | NA | 0.81 | 0.81 | 0.50 |
| Ca/P (mM) | 2.50 | NA | 1.80 | 1.62 | 2.50 |
| Buffer (mM) | NA | NA | NA | NA | Tris |
| pH | 7.4 | 6.5 | 6.7-6.9 | 6.7-6.9 | 7.4 |
Figure 7. Micro-computed tomographic three-dimensional images of as-cast Mg-3Zn-0.3Ca alloy. (A) Before immersion test. (B) After immersion test. Scale bars: 2 mm. Reprinted from Lu et al.105 Copyright 2018, with permission from Acta Materialia Inc.
Figure 8. (A) Fluoroscopic image of cross-section of magnesium rod in a guinea pig femur. E: endosteal bone formation; I: implant residual; P: periosteal bone formation. (B) Three-dimensional reconstruction of remaining AZ91D in the femur of a guinea pig. (C) Three-dimensional reconstruction of remaining LAE442 in the femur of a guinea pig. Scale bars: 1.5 mm. A-C were reprinted from Witte et al.39, 109 Copyright 2005 & 2006, with permission from Elsevier Ltd.
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