2Department of Mechanical Engineering, National University of Singapore, 9 Engineering Drive 1, Singapore 117576, Singapore
Keywords: Magnesium; Metal matrix composites; Corrosion; Biomaterial; Temporary Implants
Titanium is a bioactive material widely used for the manufacture of orthopaedic and dental implants, and is a preferred reinforcement to improve bioactivity of composite materials owing to its high mechanical strength, excellent fatigue and tensile strength, chemical inertness, superior corrosion resistance, wear resistance, biocompatibility, low modulus of elasticity, good hardness and most importantly comes at low cost [27-33]. Similarly, titanium-based ceramics have also been used in multiple bio-applications qualifying them to be used a reinforcement [28]. Bordji et al. developed magnesium-based composites using Titanium dioxide (TiO2) particles reinforcement (45 μm) in various amounts (4 wt. %, 8 wt. %, 12 wt. %, 16 wt. %, and 20 wt. %) using powder metallurgy technique [27]. By increasing the amount from 4 wt. %, to 20 wt. % the microhardness increased from 37 HV to 50 HV. Similarly, the ultimate compressive strength (UCS) increased up to 330 MPa for 20 wt. % TiO2 reinforcement containing composite.Aydin et al. demonstrated that addition of TiB2particulates (40 μm) to magnesium matrix in the amount of 10, 20 and 30 wt.%, increased the hardness of the matrix to 65 HV for 30 wt.%, when compared to that of pure Mg of 40 HV [34]. Titanium dioxide (TiO2) nanoparticulates (∼21 nm) reinforced magnesium matrix composite was synthesised using powder metallurgy technique coupled with hot extrusion by Meenashisundaram et al.[29]. The addition of (TiO2) with different amounts (1.5, 2.5 and 5 wt. %) showed a 21% decrease in grain size. The grain size of pure Mg was 34 μm. With increasing the amount of TiO2 from 1.5% to 5%, grain size decreased from 32 to 27 μm. Well-defined grain boundaries and grain boundary pinning effect was reported by investigators [35]. Mg reinforced with 0.58, 0.97, 1.98 and 2.5 vol. % titanium nitride (TiN) nano particulates of ~20 nm size were successfully synthesized by disintegrated melt deposition (DMD) technique followed by hot extrusion by Meenashisundaram et al. [30]. Addition of TiN reinforcement progressively reduced the grain size with 2.5 vol. % reinforcement addition showing the minimum grain size accounting to 57 % reduction (Table 1)[36]. Meenashisundaram et al. synthesised Mg–Ti nanocomposites using DMD followed by hot extrusion with Ti (30–50 nm) amounts 0.58, 0.97 and 1.98 vol. %. The room temperature tensile properties of the synthesized nanocomposites revealed a significant increase in the 0.2%YS (∼79% to ∼112%) and UTS (∼ 46% to ∼81%) when compared to pure magnesium, with decrease in ductility. The addition of 0.97Ti increased the 0.2%CYS of Mg by ∼59% and with 0.58Ti, the UCS of Mg increased by ∼34% with an inappreciable decrease in the ductility [37]. Magnesium matrix (AZ91D) reinforced with TiC-Ti2-AlC-TiB2 (R-Mg) particulates (< 59 μm) was fabricated using an in-situ reactive infiltration technique by Gobara et al. [38]. Electrochemical Impedance Spectroscopy (EIS) and Potentio Dynamic Polarization (PDP) showed that the reinforcing particles greatly increased the strengthened alloy’s corrosion resistance in a 3.5% percent NaCl solution. Potentio Dynamic polarization showed that AZ91D is vulnerable to localized corrosion and a passivating activity was demonstrated by the composite alloy. Polarization resistance values obtained from the EIS study suggested that the composite alloy, R-Mg, showed high activity on the first day of immersion in NaCl due to the initial dissolution of alpha magnesium from the R-Mg surface leaving a more corrosion resistant enhanced matrix (titanium carbides and borides) [38]. Mg60Zn35Ca5 BMGC, 40 vol. % of Ti (75- 105 μm) particles showed a more stable and lower corrosion rate relative to that of the other composites suggesting that the Mg60Zn35Ca5 BMGC releases its Mg ions gradually and uniformly [39]. Meenashisundaram et al.[34] researched Mg 1 vol. % Ti and Mg 1 vol. % of TiB2 composites including Ti (30-50 nm) and TiB2 (~60 nm) nanoparticles which were synthesized using the technique of disintegrated melt deposition (DMD) followed by hot extrusion. Determination of corrosion rates by weight loss technique in Dulbecco’s Modified Eagle’s Medium (DMEM) + 10% Fetal Bovine Serum (FBS) solution revealed that after 28 days of immersion testing, Mg 1 vol.% Ti exhibited the best corrosion resistance followed by pure magnesium and finally by Mg 1 vol.% TiB2 composite. Mg ~ 1 vol. % Ti nanocomposite exhibited zero degradation whereas for pure Mg, after 24 h of immersion, the corrosion rate increased to a maximum of ~ 0.69 mm/year and gradually decreased. The average corrosion rate of Mg -1 vol.% Ti nanocomposite was found to be ~ 0.1150 mm/year for 28 days which is ~ 71% lesser than that of pure Mg [40].
The mechanical and corrosion results discussed above shows that Mg-Ti composite systems can be used in clinical scenario for orthopaedic and dental applications. However, a more systematic approach is required to equally balance the triangle of biocompatibility, mechanical integrity and corrosion resistance. (Table 1) provides a summarized view of different types of titanium-based reinforcements in different magnesium-based matrices.
Traditional Ceramic Reinforcements
Traditional ceramic reinforcements are used due to their wider availability, low cost and chemical inertness in physiological mediums. Accordingly, they are investigated by many researchers. Guo et al. [48] synthesised a (SiC/TiC)p/AZ91 hybrid nanocomposite using slow extrusion speed (1, 0.5 and 0.1 mm/s, ) and at low temperature (270 oC). The addition of 1 wt. % (SiC/TiC)p (40 and 50 nm) nanoparticles hindered the movement of grain boundaries leading to grain refinement. With the addition of nano reinforcements, they reported an enhancement in tensile strengths (YS 345.6 MPa and UTS of 397.2 MPa) of AZ91 alloy [48]. Deng etal.[49]used 1 wt.% SiCp (40 nm) as reinforcement in magnesium matrix and the composite exhibited high strength (∼441MPa) and high modulus (∼60 GPa). The research work conducted so far has established that the size or length scale of the reinforcement significantly influences the strength of the end composite. For example, within micron length scale, smaller the size of the micron particles, better the mechanical strength of the composites [49]. This was also supported by Chen et al. [50,51] who added SiCp particles of 1-2 μm size range to AZ91 alloy and observed a finer grain size and increased strength
Material |
Condition |
UCS (MPa) |
UTS (MPa) |
Ref. |
Pure Mg |
|
326 ±1 |
130.3 ± 4.4 |
[35, 37] |
Mg/0.58Ti |
DMD |
431 ±8(↑32%) |
190 ± 7(↑46%) |
|
Mg/0.97Ti |
|
413 ± 15(↑26%) |
197 ± 8(↑51%) |
|
Mg/1.98Ti |
|
415 ± 4(↑27%) |
231 ± 12(↑77%) |
|
Pure Mg |
|
142 ± 6 |
275 ± 4 |
[41] |
Mg/1.98 TiO2 (∼ 21 nm) |
(PM+MW) |
132 ± 8 (↓5%) |
245 ± 8 (↓9%) |
|
Mg/2.5 TiO2 |
|
134 ± 7 (↓5%) |
233 ± 6 (↓14%) |
|
Mg-4% TiO2 |
|
292 |
|
[42] |
Mg-8% TiO2 |
|
307 |
|
|
Mg-12%TiO2 |
|
312 |
|
|
Mg-16%TiO2 |
|
321 |
|
|
Mg-20%TiO2 |
|
330 |
|
|
ACB (30.82 μm) |
|
|
155 |
[43] |
ACC |
|
|
190 |
|
HACB |
Hybrid Method |
|
201 |
|
HACC |
|
|
231 |
|
|
|
|
|
|
Mg60 |
|
580 |
|
[39] |
Mg67 |
As-cast |
440 |
|
|
Mg60T40 |
|
800 |
|
|
Mg67T40 |
|
700 |
|
|
|
|
|
|
|
Mg-0.58(vol%)TiO2 |
|
285 |
128 |
[44] |
Mg-0.97(vol%)TiO2 |
DMD |
278.4 |
154 |
|
Mg-1.98(vol%)TiO2 |
|
297 |
165 |
|
Mg-2.5(vol%)TiO2 |
|
305.5 |
170 |
|
AZ91 |
As-cast |
|
165 |
[45] |
TiB2/AZ91(30 nm) |
As-cast |
|
207 |
|
AZ91 |
Homogenized |
|
201 |
|
TiB2/AZ91 |
Homogenized |
|
237 |
|
Mg-0.58(vol%)TiO2 (20-30 nm) |
|
285 |
128 |
[46]
|
Mg-0.97(vol%)TiO2 |
PM |
278.4 |
154 |
|
Mg-1.98(vol%)TiO2 |
|
297 |
165 |
|
Mg-2.5(vol%)TiO2 |
|
305.5 |
170 |
|
Pure Mg |
DMD |
332±10 |
157±5 |
[40] |
Mg - 1Ti |
|
413±15 |
197±8 |
|
Mg - 1TiB2(60 nm) |
|
333±9 |
173±8 |
|
Pure Mg |
|
347±4 |
161 |
[36] |
Mg 0.58 TiN |
|
355±5 |
151 |
|
Mg 0.97 TiN |
DMD |
365±2 |
173 |
|
Mg 1.98 TiN |
|
385±11 |
190 |
|
Mg 2.5 TiN |
|
345±1 |
197 |
|
Pure Mg |
|
332±10 |
157±5 |
[47] |
Mg0.58TiB2 |
DMD |
352±4 |
149±9 |
|
Mg0.97TiB2 |
|
333±9 |
173±8 |
|
Mg1.98TiB2 |
|
365±10 |
186±1 |
|
DMD- Disintegrated Melt Deposition, PM- Powder Metallurgy, MW-Microwave Sintering |
Calcium Phosphate Ceramics (CPC)
For more than 20 years ceramics made from calcium phosphate salts are successfully used to replace and increase bone tissue growth. Hydroxyapatite (HAP) and β-tricalcium phosphate (β-TCP) are the most widely used bio ceramics based on calcium phosphate [53-55]. Hydroxyapatite (HAP) reinforced magnesium matrix has been used for various biomedical applications. HAP reinforced magnesium composites were studied by Gu et al. and the corrosion and mechanical properties of the composites were evaluated [56, 57]. They reported an increase in tensile strength and corrosion resistance with addition of 10 wt. % HAP (2–3 μm)when compared to composites with higher amounts of HAP (20 wt.% and 30 wt.%) [56, 57]. Cui et al. investigated Mg- 2.5 Zn/HAP composites and showed that the addition of 5 and 10 wt.% HAP (60 μm) assists in decreasing corrosion rate and increases the mechanical strength [58]. They reported that addition of 5 wt.% HAP retained the tensile integrity of the structures by 34% and compressive strength by 66 % after 14 days of immersion [59]. Jaiswal et al. reported that addition of 5 wt.% HAP (30 μm) into Mg-3 Zn matrix increased the CYS by 23% and reduced the corrosion rate by 42% [60]. The addition of nano HAP (30 nm) particles to Mg66Zn30Ca4 metallic glass led to marginal improvement in the mechanical properties and increased corrosion resistance of the composite [61]. From the microstructural perspective, addition of HAP nano reinforcement reduced the grain growth and showed grain refinement [26]. Khanra et al. [62, 63] evaluated the microstructure of Mg–HAP and ZM61–HAP composites and reported grain refinement. Xu etal.[64] showed that Mg–HAP (0, 5, 10 and 15 wt.%) exhibits high compressive strength, yield strength and reduced tensile strength when compared to the base matrix (Table 2). (Figure 1) shows typical micrographs illustrating the role of β -TCP in grain boundary pinning and grain refinement (~
Material |
Results |
Reference(s) |
Mg + xHAP (2–3 μm) |
Mg/10 HAP composite sample showed higher YS but reduced UTS. Increase in amount decreased the strength and ductility. |
[57] |
Mg + xHAP(30 μm) |
Reduced grain size and grain refinement. |
[62, 63] |
Mg + xHAP (25 µm) |
Addition of HAP increased the microhardness and decreased the yield stress and ultimate compressive strength of the composites. |
[65-67] |
Mg + xHAP |
Addition of HAP increases the microhardness. Decreased the corrosion rate. |
[68] |
Mg + xHAP(32 nm) |
Fracture toughness slightly increased for composites with addition of 8% HAP. Mg + 10% HAP improved the corrosion resistance of magnesium in 3.5% NaCl solution. |
[69] |
Mg + 20%HAP |
Addition of HAP improved the corrosion resistance. |
[70] |
Mg + xHAP(60 nm) |
HAP particles improved the grain refinement of the composites. |
[62] |
AZ91D + 20%HAP (<44 μm) |
Minor corrosion attack observed in composites when compared to alloy without HAP. HAP particles decreased the corrosion rate of the alloy matrix. |
[71] |
AZ31–nHAP |
Friction stir processing led to grain refinement. Deposition of Ca-P phase resulted in the excellent bioactivity of the composite. |
[68] |
WE43 + 20% HAP |
HAP addition weakened the alloy. |
[72] |
|
Zirconium improved the alloy properties due to grain refinement. |
[73] |
ZK60A+ xCPP (10 μm) |
Addition of CPP increased mechanical strength. Addition of CPP decreased corrosion rate in SBF solution. |
[74] |
Mg-3Zn-Ca/β-TCP |
β-TCP particles were located along grain boundaries. Decreased grain size. Increased mechanical strength. |
[75] |
Mg-1Ca-2Zn + 1% β -TCP |
Processing methods used enabled grain refinement and uniform distribution of ceramic particles. Increased mechanical strength. Decreased corrosion rate. |
[76] |
Mg-3Zn-0.8Zr + x β-TCP (100 nm ) x = 0.5; 1; 1.5% |
Addition of β -TCP significantly refined microstructure, with increasing β TCP content led to reduction in grain size. |
[77] |
MgCaxHAP/ y β-TCP |
Mechanical and corrosion properties of the composites were adjustable by the choice of HAP content. Mechanical properties increased with an increase in HAP content. |
[78] |
Mg-Ca /TCP/HAP |
Increased mechanical strength. Superior corrosion resistance. |
[79] |
Mg-Ca/ β -TCP |
Mechanical properties of the composite were lower than for Mg-Ca alloy. |
[80] |
DMD- Disintegrated Melt Deposition, PM- Powder Metallurgy, MW-Microwave Sintering, HAP-Hydroxyapatite, |
The presence of β-TCP particles (0.7–4.6 μm) assisted in the corrosion protection of pure Mg. The pH values stabilized for the composites compared to pure Mg and displayed lower corrosion rate (~9 times) with a superior protection displayed by the Mg-1.5 TCP composite as compared to pure Mg [81]. To note here that calcium phosphate ceramics, similar to traditional ceramics, assist in grain refinement, enhance the mechanical properties typically the elastic modulus and enhances corrosion response. However, not all the systems with all reinforcements and length scales will do so and experimental validation will be required for each new system. (Table 2) provides a summarized view of balancing act of different types of reinforcements in different magnesium-based matrices.
Bioactive glass, consisting of a family of glass compositions and capable to bind in a few hours to hard and soft tissues, displays the best-known bioactive actions [84]. These bioactive glasses could gradually degrade after implantation accompanied by the release of ionic products that stimulate bone-related cell proliferation. These advantageous features make the bioactive glass a preferred choice as the reinforcement phase to be added to a Mg-based biomaterial for the enhancement of bioactivity [84, 85].
Nano-SiO2particles (~20 nm) were used as reinforcement in AZ31 magnesium alloy to form AZ31/ SiO2 composites by friction stir process. Addition of the SiO2 particles increased the hardness of the matrix to 90 HV when compared to AZ31 alloy hardness of 49HV [86]. Low volume fraction SiO2 (0.5, 1, and 2 vol. %) nano particle (15 nm) reinforced magnesium composites synthesized using powder metallurgy technique showed marginal decrease in the grain size. There was 32 % decrease in the grain size for 2 vol. % reinforcement (23±1.5) when compared to pure Mg (34±2). The ultimate tensile strength (UTS) for pure Mg progressively increased with the addition of SiO2 nano- particulates and 2 vol. % SiO2 showed the maximum UTS of 171 MPa which surpassed the UTS value of pure Mg by 34 % [87]. The ultimate compressive strength (UCS) was 207 ± 3 for 2 vol. % SiO2 composite when compared to pure Mg with 174 ± 7 MPa. The addition of SiO2 showed 18.9 % increase in the UCS of the composite [88]. The AM60 magnesium alloy reinforced with 1 and 2 wt. % of SiO2 nanoparticles (~35 nm) reduced the grain size and increased the hardness of samples from 34.8 HV in AM60 to 51.5 HV in 2 wt.% composite. Improvement of the mechanical properties was attributed to a combination of Orowan, Hall– Petch and load-bearing mechanisms [89]. Corrosion resistance of pure Mg reinforced with bioglass (BG, 45S5) particles (30– 75 μm ) amounts of 5, 10, and 15 wt.% in simulated body fluid (SBF) at 37 °C was studied by Wan et al.[90]. Increasing the amount of bioglass reduced the hydrogen gas evolution from the composite. Accordingly, compared with pure Mg, hydrogen evolution from BG/Mg composites as a result of degradation, was less. Moreover, the hydrogen evolution is dependent on bioglass content. Expectedly, BG-15/Mg with the highest bioglass content showed the lowest hydrogen evolution rate among all composite samples. Addition of bioglass into Mg significantly reduced the pH value from 9.3 for pure Mg to 8.3 for BG-15/Mg [90]. Huan et al. synthesised ZK30 magnesium alloy as the matrix with 5 and 10 wt. % (40 μm) bioactive glass (BG, 45S5) as the reinforcement. Immersion tests in the minimum essential medium (MEM) at 37°C showed that the composites with 5 and 10% BG had lower rates of degradation and hydrogen evolution than the ZK30 magnesium alloy [91]. These results validated that hydrogen evolution and corrosion of BG/Mg composites can be controlled by adjusting the content of bioglass such that various clinical needs may be met.
Nano-carbon Reinforced Magnesium Composites
Carbon Nanotubes (CNTs) are considered as one of the ideal reinforcements due to their high strength, lightweight properties and also due to favourable geometrical properties such as high aspect ratio, high specific surface area and excellent mechanical properties [92-95]. Due to their excellent mechanical strength and corrosion resistance to improve the performance of composite materials, CNTs reinforced materials are widely used in artificial joints and bone fixation materials [96]. CNTs are intended to be used in the orthopaedic field as a locally implanted
biomaterial such as artificial joints or fixation devices. Various studies conducted on the CNTs have reported that the material exhibits high biocompatibility [96-98]. Li et al. [99] synthesised magnesium metal matrix composites containing carbon nanotubes (CNTs) using powder metallurgy process. They reported that addition of 4.0 wt.% CNT increased the microhardness by 43.5% and UTS by 33.4% when compared to pure magnesium samples [99]. Xian et al. fabricated magnesium alloy ZK60 composites containing low amount of graphene nano plates (GNPs) by facile melt stirring and hot extrusion processes. The composite with only 0.05 wt. % GNPs showed enhancement in yield strength up to 256 MPa. The hardness of the graphene reinforced magnesium composites was evaluated and the results showed that the microhardness increases with the increased graphene content. Pure magnesium sample hardness was 59.3±3.0 HV, while magnesium-graphene composites reinforced with 0.05 wt. % graphene showed hardness of 89.9 ± 4.5 HV indicating 51 % increases over unreinforced magnesium. This is attributed to the fact that the graphene gets aligned along the grain boundaries leading to grain boundary pinning effect. The Tensile Yield Strength (TYS) increased by 62% with 0.05 wt. % GNPs, the compressive yield strength (CYS) increased by 98% with 0.05 wt.% GNPs [100, 101]. Compared to pure Mg, Mg–GNP composites containing 0.1wt. % G-15 (15μm) and G-5 (5μm) GNPs showed the best corrosion resistance in the same corrosion environment. In situ formation of a MgH2 phase in Mg–GNP composites containing lower concentrations (0.1wt.%) of G-15 GNPs in the Mg matrices resulted in slower H2 production rates and lower Icorr values [102]. Carbon nanotubes (CNTs) assist in grain refinement and thus assist in increasing the mechanical properties typically the Tensile Yield Strength (TYS) and Compressive Yield Strength (CYS) and an addition also increase the corrosion resistance. However, not all the systems with all reinforcements and length scales will do so and experimentation validation will be required for each new system.
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