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Ming, X.; Wu, Y.; Zhang, Z.; Li, Y. Micro-Arc Oxidation in Titanium and Its Alloys. Encyclopedia. Available online: https://encyclopedia.pub/entry/55794 (accessed on 17 November 2024).
Ming X, Wu Y, Zhang Z, Li Y. Micro-Arc Oxidation in Titanium and Its Alloys. Encyclopedia. Available at: https://encyclopedia.pub/entry/55794. Accessed November 17, 2024.
Ming, Xinwei, Yan Wu, Ziyue Zhang, Yan Li. "Micro-Arc Oxidation in Titanium and Its Alloys" Encyclopedia, https://encyclopedia.pub/entry/55794 (accessed November 17, 2024).
Ming, X., Wu, Y., Zhang, Z., & Li, Y. (2024, March 04). Micro-Arc Oxidation in Titanium and Its Alloys. In Encyclopedia. https://encyclopedia.pub/entry/55794
Ming, Xinwei, et al. "Micro-Arc Oxidation in Titanium and Its Alloys." Encyclopedia. Web. 04 March, 2024.
Micro-Arc Oxidation in Titanium and Its Alloys
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This entry is adapted from the peer-reviewed paper 10.3390/coatings13122064

Titanium (Ti) and its alloys are widely recognized as preferred materials for bone implants due to their superior mechanical properties. However, their natural surface bio-inertness can hinder effective tissue integration. To address this challenge, micro-arc oxidation (MAO) has emerged as an innovative electrochemical surface modification technique. Its benefits range from operational simplicity and cost-effectiveness to environmental compatibility and scalability. Furthermore, the distinctive MAO process yields a porous topography that bestows versatile functionalities for biological applications, encompassing osteogenesis, antibacterial, and anti-inflammatory properties.

titanium (Ti) micro-arc oxidation surface modification

1. Introduction

The latest statistics show that by mid-century, the global population aged 65 or over is expected to more than double to a staggering 1.6 billion people [1]. An aging population means a larger population base of chronic diseases, and bone and joint diseases. In dentistry and orthopedics, implants, with titanium (Ti) and its alloys as the preferred choice among various materials, have become a common approach for treating conditions due to their exceptional biocompatibility and mechanical properties [2]. Despite the vast potential for Ti and its alloys, there are still limitations to surface bioactivity. They often exhibit biological inertness, limiting the close integration of implants with surrounding tissues. Furthermore, Ti alloys are susceptible to microorganisms, increasing the risk of postoperative infections, and threatening the prognosis of patients. To tackle these issues, apart from alloying [3][4][5], surface treatment proves to be an effective approach as well. Common methodologies encompass atmospheric plasma spraying [6], laser treatment [7], anodizing [8], micro-arc oxidation (MAO), and biomimetic deposition of apatite [9] or other biomaterials [10]. Among the various surface modifications available, MAO has garnered significant attention due to its simplicity of operation, cost-effectiveness, and applicability to complex devices. Through MAO, the surface of Ti-based implants can undergo alterations in microstructural features and chemical composition, rendering them more suitable for tissue adhesion and effectively reducing the risk of infections [11].

2. Applications

MAO coatings, particularly with specific functional additives, possess remarkable biological functionalities including bone promotion, antimicrobial properties, and anti-inflammatory effects. Though clinical applications of Ti-based implants with MAO-modified functional coatings are limited, animal experiments have validated several implants with such coatings (Table 1). Presently, surface modification techniques like sandblasting, acid etching, and anodization, along with the introduction of bioactive materials such as calcium phosphate, hydroxyapatite, and calcium nanoparticles, are widely employed to optimize implant surface microstructure and topography. These modifications primarily aim to enhance biocompatibility and promote osseointegration. For example, MAO techniques have been utilized to create rough and porous surfaces on dental implants and femoral stems, facilitating improved tissue bonding [12].
Table 1. Coatings contain different components with different biological functions and are validated in vitro and in vivo.
Number Biologic Function Adding Substances Technique In Vitro In Vivo Conclusion/Remark Reference
Cell Bacterium Animal Parts
1 Osteogenesis Ca, Sr MAO hBMSCs     Simultaneously incorporating Ca and Sr demonstrated superior promotion of hBMSC proliferation. [13]
2 Osteogenesis/Angiogenesis Zn MAO HUVECs and BMSCs     In the Zn2+ environment, angiogenesis and osteogenesis mutually promote each other. [14]
3 Osteogenesis/Angiogenesis Hydroxyapatite nanotubes (HNTs) MAO HUVECs and MC3T3-E1 cells     HNT specimens promote both angiogenesis and osteogenesis on cellular and molecular levels. [15]
4 Osteogenesis B MAO, hydrothermal treatment, and heat treatment SaOS-2 cells     Nanorods inhibit SaOS-2 cell activity, whereas nanoparticles promote it. [16]
5 Osteogenesis Hierarchical coatings MAO, electrochemical reduction BMSCs   Beagle dogs, the shaft of the canine femur The hierarchical coatings show higher osteogenesis rates compared to the ordinary MAO group. [17]
6 Osteogenesis HA, BMP-2 MAO, dip coating MC3T3-E1 cells   Beagle femur The interface bonding strength between HA/BMP-2 coating and surrounding new bone tissue is higher than that of Ca/PMAO coating. [18]
7 Osteogenesis/Angiogenesis Ca, P, BMP-2 3D printing, sandblasting etching, MAO, electrochemical deposition BMSCs   New Zealand White Rabbit Skull MAO-CaP-BMP-2 is superior to the MAO and MAO-CaP groups in new bone formation. [19]
8 Osteogenesis/Antibacterial Ca, P MAO hFOBs E. coli and S. aureus   Volcanic-crater-like and needle-like CaP structures form at 350 V and 450 V, respectively. The former exhibits superior antibacterial performance and biocompatibility. [20]
9 Bioactivity/Antibacterial Ca, P MAO, UV catalysis HGFs S. sanguinis   Photofunctionalization reduces hydrocarbons and enhances surface protein adsorption. [21]
10 Osteogenesis/Antibacterial Zn MAO MC3T3-E1 cells E. coli   Incubation with salt solution converts Zn ions into zinc oxide, which helps with long-lasting antibacterial activity. [22]
11 Antibacterial/Osteogenesis/Angiogenesis Sr, Zn MAO HUVECs, BMSC MRSA and P. gingivalis Rat femoral model The surface osteogenesis of samples doped with Sr and Zn is superior to other groups. (No in vivo antibacterial test conducted.) [23]
12 Antibacterial Ag, Cu NPs MAO MC3T3-E1 cells MRSA Mouse femur ex vivo experiment Ag and Cu ions synergistically kill bacteria, allowing a 10-fold reduction in Ag ion concentration with consistent antibacterial efficacy. [24]
13 Osteogenesis/Antibacterial Ag, Zn 3D printing, MAO MC3T3-E1 cells MRSA Mouse femur ex vivo experiment The synergistic effect of Ag and Zn reduces the concentration of Ag+ by 120 times. [25]
14 Osteogenesis/Antibacterial Ag, Zn MAO MC3T3-E1 cells S. aureus   Ag and ZnO synergy enhances antibacterial performance and promotes CaP phase formation. [26]
15 Osteogenesis/Antibacterial Ag, Zn MAO MC3T3-E1 cells S. aureus   Ag and Zn ion release is above the antibacterial threshold yet well below cytotoxic levels. [27]
16 Osteogenesis/Antibacterial Ag, Zn MAO   S. aureus   Ag and Zn have good synergistic antibacterial effects. [28]
17 Osteogenesis, Antibacterial Cu, Zn MAO MG63 E. coli, S. aureus, and MRSA   Orthogonal experiments explore electrolyte effects on coatings, with phytic acid supplying the P element. [29]
18 Skin-integration/Antibacterial Cu, Zn MAO Fibroblasts (L-929) S. aureus   The synergistic effect of Cu and Zn facilitates skin integration and antibacterial activity. [30]
19 Osteogenesis, Anti-tumor/Antibacterial Se MAO BMSCs, cancerous osteoblasts S. aureus and E. coli   Se doping enhances osteogenic, anti-tumor, and antibacterial properties. [31]
20 Osteogenesis/Antibacterial Mn MAO MC3T3-E1 cells E. coli Rabbit femur The coating induces osteogenesis and promotes osseointegration. [32]
21 Antibacterial Bi MAO MG63 cells A. actinomycetemcomitans, MRSA   Bismuth nitrate has excellent antibacterial activity compared to bismuth acetate, bismuth gallate, and silver nitrate. [33]
22 Osteogenesis/Antibacterial Ce MAO BMSCs P. gingivalis, S. aureus Osteoporotic rat hind legs Ce-TiO2 coating has excellent antibacterial and anti-inflammatory properties. [34]
23 Antibacterial I MAO, HT, photocatalysis BMSCs S. aureus Tibial Intramedullary Infection Model of Rats Under NIR, the coating has good antibacterial and osteogenic properties. [35]
24 Antibacterial I MAO, electrophoresis BMSCs S. aureus and E. coli The rat osteomyelitis intramedullary nail model Thirty days after implantation, excellent antimicrobial ability was verified. [36]
25 Bioactivity/Antibacterial B MAO ADSCs S. aureus and P. aeruginosa   Add a small amount of sodium tetraborate to the Ca, P electrolyte system. [37]
26 Osteogenesis/Antibacterial F MAO BMSCs S. aureus and E. coli Rabbit femur Coatings with high F addition showed improved antibacterial and osteogenic abilities. [38]
27 Antibacterial/Osteogenesis/Angiogenesis Sr, Co, and F MAO BMSCs S. aureus and E. coli Rabbit femur Sr, Co, and F co-doped coatings induce osteogenesis. [39]
28 Osteogenesis/Antibacterial Mn, F MAO BMSCs S. aureus   Mn and F co-doped coatings show excellent wear and corrosion resistance, along with strong antibacterial properties. [40]
29 Osteogenesis/Antibacterial Cu, BMP-2 MAO, dip coating MC3T3-E1 cells E. coli, MRSA, Neurospora crassa, and Candida albicans Mouse craniotomy model The coating significantly promotes osseointegration. [41]
30 Osteogenesis/Antibacterial Ag, HA MAO, RF-MS MC3T3-E1 cells E. coli   This coating exhibits strong biological activity and antibacterial properties. [42]
31 Bioactivity/Antibacterial Ag NPs, polylactic acid (PLA) MAO, electrospinning MC3T3-E1 cells S. aureus   PLA ultrafine fibers produced by electrospinning can control the release of silver ions. [43]
32 Osteogenesis/Antibacterial AgNPs, polydopamine MAO, dip coating MG63 cells S. aureus New Zealand rabbit subdermal implantation This coating exhibits strong biological activity and antibacterial properties. [44]
33 Osteogenesis/Antibacterial Polydopamine, cationic antimicrobial peptide LL-3, phospholipid MAO, dip coating BMSCs and OBs S. aureus and E. coli   The coating exhibits good osteogenesis and antibacterial properties. [45]
34 Antibacterial GO MAO, EPD   S. aureus and E. coli   Achieves ~80% antibacterial activity against E. coli and 100% against S. aureus. [46]
35 Antibacterial rGO, Ag NPs MAO MC3T3-E1 cells MRSA   The coating exhibits good osseogenesis and antibacterial properties. [47]
36 Osteogenesis/Antibacterial HA, chitosan (CS) MAO, dip coating MC3T3-E1 cells E. coli   Higher usage of CS results in decreased biological performance but improved antimicrobial performance. [48]
37 Osteogenesis/Antibacterial HA, CS hydrogel containing ciprofloxacin MAO, HT, chemical grafting hBMSCs S. aureus and E. coli   The coating exhibits good osseogenesis and antibacterial properties. [49]
38 Osteogenesis/Antibacterial BMP-2/CS/HA MAO, dip coating MC3T3-E1 cells E. coli   CS encapsulation sustains BMP-2 release with added antibacterial properties. [50]
39 Antibacterial Vancomycin MAO, dip coating     The rabbit osteomyelitis model (infection with MRSA) In vivo studies demonstrate the potential of this coating to prevent MRSA infection. [51]
40 Osteogenesis/Antibacterial Vancomycin MAO, dip coating, chemical grafting BMSCs S. aureus Rat femur Functional coatings prevent prosthesis infection and promote bone integration at the interface. [52]
41 Antibacterial Mesoporous silica NPs (MSNs), octenidine (OCT) Electrophoretic-enhanced MAO OBs S. aureus and E. coli   The coating exhibits good osseogenesis and antibacterial properties. [53]
42 Bioactivity/Antibacterial N, Bi MAO, photocatalysis HGFs Streptococcus sanguinis and Actinomyces nasseri   The coating has bactericidal properties under visible light. [54]
43 Osteogenesis/Antibacterial MoSe2, CS MAO, electrospinning, photocatalysis MC3T3-E1 cells S. mutans Rat tibia Adding MoSe2 significantly enhances TiO2 coating photothermal and photodynamic capabilities. [55]
44 Skin-integration/Antibacterial β-FeOOH, Fe-TiO2 MAO, HT, photocatalysis Mouse fibroblasts (L-929) S. aureus Mouse skin infection model The β-FeOOH/FeTiO2 heterojunction prevents bacterial infection under light irradiation. [56]
45 Osteogenesis/Anti-inflammatory Ca, Si MAO SaOS-2 cells     The coating inhibits inflammation and induces M2 macrophage polarization. [57]
46 Antibacterial/Immunoregulation Cu MAO RAW 264.7 macrophages, SaOS-2 cells S. aureus   Cu boosts macrophage-driven osteogenesis and antibacterial activity in biomaterials. [58]
47 Osteogenesis/Anti-inflammatory Zn MAO RAW264.7 macrophages, BMSCs     The coating shows good osteogenic and anti-inflammatory properties. [59]
48 Osteogenesis/Anti-inflammatory Mg MAO RAW 264.7 macrophages     Mg acts as an anti-inflammatory agent, inhibiting inflammation and promoting osteogenesis. [60]
49 Anti-inflammatory Co MAO RAW 264.7 macrophages   Mouse air chamber model Cobalt-loaded Ti exhibits immune-regulatory effects on macrophages. [61]
50 Osteogenesis/Angiogenesis/Anti-inflammatory Li MAO BMDMs, mouse embryonic cell line (C3H10T1/2), HUVEC   Mouse air-pouch model Low Li doses effectively regulate immunity, and promote osteogenesis. [62]
51 Osteogenesis/Angiogenesis/Anti-inflammatory HA MAO, SHT MC3T3-E1 cells, human umbilical vein fusion cells, RAW 264.7 cells   Rabbit femur This coating promotes osteogenesis and angiogenesis, and induces M2 macrophage phenotype. [63]
52 Osteogenesis/Anti-inflammatory HA MAO, SHT MC3T3-E1 cells, endothelial cells, RAW 264.7 cells   Rabbit femur Nanoparticle-shaped HA is beneficial for osteogenesis, angiogenesis, and immune regulation, whereas nanorod-shaped HA is the opposite. [64]
53 Osteogenesis/Anti-inflammatory SiO2, ZnPs MAO, sol-gel MC3T3-E1 cells     The coating shows good osteogenic and anti-inflammatory properties. [65]
54 Osteogenesis/Anti-inflammatory Sr, silk fibroin-based wogonin NPs MAO, electrochemical deposition, LBL RAW 264.7 cells, OBs   Osteoporotic rat femur The coating shows good osteogenic and anti-inflammatory properties. [66]
TiUnite and TiUltra surfaces(Nobel Biocare, Zurich, Switzerland), along with the Ospol implant(OspolAB, Malmö, Sweden) and the M implant(Shinhung, Seoul, Republic of Korea), are all manufactured using the MAO process and are commercially available. The TiUnite surface series by Nobel BiocareTM, introduced in the early 2000s, has undergone continuous refinement and gained worldwide acceptance. These implants, containing 7% phosphorus in the form of titanium phosphate chemical bonds, are fabricated using an electrolyte mixture with phosphorus. A comprehensive review [67] encompassing prospective studies spanning from 2000 to 2016 on the clinical performance of implants featuring the TiUnite surface affirms the high survival rates and favorable maintenance of marginal bone associated with such implants. Incidences of peri-implantitis are notably lower for implants employing the TiUnite surface. Notably, implants with this surface consistently exhibit predictable treatment outcomes across diverse indications. In 2019, Nobel BiocareTM introduced the TiUltra surface series (Figure 1), which features a progressively rough and porous surface texture extending from the implant collar to its tip, exhibiting excellent hydrophilic properties [68]. Moreover, the M implants of ShinhungTM are produced using the MAO method with an electrolyte mixture containing magnesium, resulting in a TiO2 surface containing magnesium (≤9.3%) and phosphorus (≤3%) [69]. Similarly, OspolTM implants are created using the MAO method with an electrolyte mixture containing Ca, leading to the incorporation of calcium ions (less than 11%) within the TiO2 in the form of calcium titanium oxide bonds [70].
Figure 1. Implants with TiUltra surfaces [68]. (A) Microscopic analysis of the implant system’s four regions: abutment (B–D), implant collar (E–G), transition zone (H–J), and apex (K–M). This includes an overview (B,E,H,K), high-magnification scanning electron micrographs of each region (C,F,I,L), and 3D surface profile reconstructions using white-light interferometry (D,G,J,M).
Femoral shafts treated with sandblasting and MAO coating are commercially available. For example, the Korean BencoxTM hip system (Corentec, Seoul, Republic of Korea) has cementless sandblasted femoral stems with MAO coating on the surface (Figure 2). Made from Ti-6Al-4V alloy, it is a double-wedge straight tapered stem with a rectangular cross-section. The coating method of MAO coating is as follows: After Ti plating, the sample is electrochemically oxidized using the MAO process. The sample is subjected to MAO treatment with a DC pulse power supply in an aqueous electrolyte containing Ca and P.
Figure 2. The BencoxTM stem is a collarless cementless bi-tapered rectangular Ti stem with an MAO-coated sandblasted surface [71].
In a study by Lim et al. [72], in a follow-up period of at least 5 years, the MAO-coated sandblasted surface did not demonstrate superiority over primary total hip arthroplasty (THA) with the same femoral component design. While MAO is theoretically known to promote bone growth through calcium and phosphorus binding to the titanium alloy surface, forming thick oxides and nano-porous coatings, its clinical utility has not been confirmed. In a study with 10 years of follow up [71], 309 cases of THA (involving 256 patients) were performed using the non-cemented BencoxTM hip joint system. A Kaplan–Meier survival analysis indicated a 10-year survival rate of 97.4% when using revision for any reason as the endpoint, and a survival rate of 98.7% when using aseptic loosening revision as the endpoint. While there was a decrease in the proportion of cases with bone resorption in the follow up, the absence of a control group precludes concluding the ability of MAO coatings to resist bone resorption, despite various studies suggesting their potential for preventing bone resorption. In summary, after a follow-up period of at least 10 years, the outcomes of non-cemented sandblasted and MAO-coated THA tapered wedge stems are satisfactory.
The MAO coating cannot only promote bone integration but also improve the wear and corrosion resistance of implants. Khanna et al. [73] performed cold spraying to deposit an Al metal layer onto a Ti-6Al-4V alloy substrate, followed by heat treatment to enhance adhesion. They then conducted MAO treatment to form a dense α-Al2O3 layer on the substrate surface, with a Vickers hardness matching that of sintered alumina used for femoral heads (Figure 3).
Figure 3. Ceramic/metal hybrid artificial hip joint cross-sectional design schematic, with alumina layers formed on Ti alloy for both the cup and head components [73].

3. Challenges

Although MAO coatings have undergone extensive research and led to the emergence of related products, there are still challenges and limitations in the production and application:
  • Despite considerable progress in studying the discharge process of MAO, some micro-scale mechanisms remain unclear, such as cathodic discharge and soft spark discharge. This uncertainty affects the control of the microstructure of MAO coatings [74].
  • In the coating manufacturing process, establishing the electrolyte composition and electrical parameters still necessitates multiple experiments. Defining the optimal parameters remains challenging. Minor losses of electrolytes during usage and the settling of particulate or colloidal electrolytes can also impact coating performance [75][76].
  • The impact of coating morphology on cell bioactivity remains inconclusive. While some studies suggest that moderate roughness aids in cell adhesion and proliferation, and porous surfaces facilitate cell osteogenic differentiation, there is still debate about the optimal pore size. Different cell types may have varied requirements for morphology [77][78]. Additionally, due to cracks and interconnected pores, their durability and wear resistance require attention [79].
  • Coatings with added functionalities, such as antimicrobial and anti-inflammatory components, may exhibit toxic effects on normal cells, especially with high concentrations of antibiotics or antimicrobial agents [12][80].
  • There is a substantial amount of research on biologically functional coatings; the availability of implants in the market is relatively limited. Successfully translating these technologies into commercial products may face greater challenges [12].

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Subjects: Engineering, Biomedical
Contributors MDPI registered users' name will be linked to their SciProfiles pages. To register with us, please refer to https://encyclopedia.pub/register :
Xinwei Ming
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Yan Wu
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Ziyue Zhang
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Yan Li
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Update Date: 04 Mar 2024
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