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Strategies to improve the corrosion resistance of MAO coatings on Mg and its alloys 259
corrosion resistance when immersed in simulated body fluid (SBF) (with no refreshment of the solution) at 37
evolution, which is limited to w1ml/cm
Mg, the volume of hydrogen evolution increased rapidly with an increase in immersion time from 0 to 60 h and reached w 8 ml/cm
C for 132 h, as evidenced by the volume of hydrogen
2
from 0 to 132 h. Conversely, for uncoated
2
at 60 h; beyond 60 h, it exhibited a
very slow increase until 132 h.
Gao, Guan, et al. (2011) have explored a multifunctional approach of depositing
rod-like nano hydroxyapatite (RNHA) by electrodeposition (ED) on MAO-coated
Mg alloy so that it would be possible to increase the corrosion resistance of MAO
coating as well as its biocompatibility. The MAO-ED RNHA composite coating
exhibits a much higher bonding strength of 12.3 MPa when compared to ED HA
coating, which has a bond strength of 6.2 MPa (Ban and Hasegawa, 2002). The
pinning force generated by the accommodation of RNHA within the pores of MAO
coating and similarity in chemical bonding between these two coatings are considered
to be responsible for the increase in bonding strength. Plugging of the pores by RNHA
decreased the permeation of the corrosive medium, while the better compatibility
between the MAO and HA coatings eliminates peeling of the coating and provides
a better stability. In addition, the RNHA coating induced rapid precipitation of calcium
orthophosphates on the HA rods, follow ing their ability to increase the specific surface
area to promote absorption of Ca
2þ
and PO
3
from SBF solution (Gao, Guan, et al.,
4
2011). Hence, ED of RNHA on MAO-coated Mg alloy appears to be a good strategy
because it not only increases the corrosion resistance by three orders of magnitude but
also increases the bonding strength and promotes apatite growth.
Shi, Qi, Chen, and Shi (2011) have also used a similar multifunctional approach to
deposit DCPD by ED to increase the corrosion resistance and bioactivity of
MAO-coated Mg alloy. The porous nature of the MAO coating provides an anchoring
effect for the flake-like DCPD crystals and improves the bonding between the top
DCPD layer and the inner MAO layer. Plugging of the pores by DCPD enables a significant improvement in corrosion resistance of MAO-DCPD composite coating in
SBF (pH: 7.4) at 37
C. In addition, DCPD enables an increase in apatite-forming abil-
ity when compared to the MAO coating.
Chen et al. (2012) explored ED of HA as a strategy to seal the pores of the MAO
coating on Mg alloys. The MAO-ED HA composite-coated Mg alloy effectively slows
down the rate of degradation. In vivo studies indicate that during the early period, the
MAO-ED HA composite-coated Mg alloy decreased the extent of release of Mg
2þ
ions and induced the growth of bone cells when compared to that of the uncoated
one, thus satisfying one of the important requirements of degradable implants. The
ability to show good bioactivity and rapid bone response that is evident from the newly
formed bone tissues and its faster maturity, improved adhesion strength (>40 MPa),
and complete degradability of all the components of the coating (i.e., HA, octacalcium
phosphate, Mg
(PO4)2, and MgO) are some of the important attributes of this type of
3
composite coatings.
Formation of a composite coating using a methodology that fundamentally
combines the advantages of MAO coating and ED has been addressed by
260 Surface Modification of Magnesium and its Alloys for Biomedical Applications
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Zhao et al. (2013). The combination of MAO coating and ED HA coatings lead
to a four-fold decrease in i
when compared to the uncoated Mg alloy. The
corr
multifunctional ability of the MAO-ED HA composite coating not only improves
the corrosion resistance but also endows the Mg alloys with a potential bioactivity following the chemical and b iological similarity of HA to human bone
tissues.
9.4 Summary and concluding remarks
The formation of pores and cracks in MAO coatings is inevitable. The pores in MAO
coatings can be considered to be an opportunity because they could significantly
improve the mechanical interlocking effect, the bonding area, and stress distribution
across the adhesiveesubs tr ate inte rf ace of the jo ints, resulting in higher bond
strength. However, it is a serious limitation in terms of the corrosion resistance of
the resultant coatings. Several stra tegies were explored to improve the corrosion
resistance of MAO coatings. The concern of the researchers is to employ a suitable
strategy to overcome t he deleterious influence of pores and cracks on the corrosion
resistance of MAO coatings. The cho ice of suitable electrical parameters appears to
hold a key because a hybrid (unipolar followed by bipolar) current mode, increase in
cathodic current pulse, and increase in frequency enabled the formation of goodquality coatings with a considerable reduction in pore size and density. Because
the MAO coatings are invariably porous, increasing the thickness of the barrier layer
is very critical to imparting a better corrosion resistance.
Multifunctional approaches seem to be logical in terms of achieving an acceptable
corrosion protection and biocompatibility. However, the acceptability of certain types
of coatings, such as electroless nickel coating to seal the pores of MAO coatings,
becomes a questionable issue for biomedical applications because they are carcinogenic in nature. A similar argument is also valid for many additives used to modify
the electrolyte where the toxicity of an incorporated additive or its decomposition
products is a matter of concern. Likewise, the sealants used to seal the pores of the
MAO coatings, particularly polymeric compounds, should possess an acceptable
self-degradation rate in the body fluid.
The major challenge is the susceptibility of magnesium and its alloys towards localized corrosion attacks when MAO coating or corrosion products cover their surface. In
fact, the dominance of localized corrosion mechanisms when the corrosion products
start to deposit on the surface has been the biggest challenge in developing
magnesium-based degradable implants. A combination of strategies e increasing the
thickness of the barrier layer, adopting suitable current parameters to prepare betterquality coatings, and imparting multifunctionality e could offer better corrosion resistance for MAO coatings on Mg/Mg alloys. In spite of numerous attempts to improve the
corrosion performance of MAO coatings, the difficulty in eliminating the inhomogeneous degradation and maintaining sufficient mechanical integrity of Mg/Mg alloys
for a reasonable time remains unsolved, and the quest for the perfect strategy continues.
Strategies to improve the corrosion resistance of MAO coatings on Mg and its alloys 261
Acknowledgements
Financial support provided by the National Research Foundation of Korea (NRF) under the grant
(MEST) (No. 2011e0028709), funded by the Korea government for our research program on
magnesium-based degradable biomaterials, is gratefully acknowledged.
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Biomimetic surface modifications
Данная книга находится в списке для перевода на русский язык сайта https://meduniver.com/
of magnesium and magnesium
10
alloys for biomedical applications
J. Gray-Munro
Department of Chemistry and Biochemistry, Laurentian University, Sudbury, ON, Canada
10.1 Introduction
The term “biomimetic” refers to any system that mimics a naturally occurring biological system. Many organisms have developed multifunctional surfaces with hierarchical topographies and unique surface chemistries that enable them to survive and adapt
to environmental influences. As our understanding of these processes has grown, we
have developed technologies that allow us to take advantage of nature’s elegant
solutions to everyday problems. A few examples include the following:
1. the surface patterning of aircraft materials to resemble the surface micron-scale pattern of shark
skin for reduced drag (Scardino & de Nys, 2011);
2. the development of catechol-based pol ymer derivatives that mimic natural mussel adhe-
sives, which have the remarkable ability to strongly adhere even under wet conditions
(Sedo, Saiz-Poseu, Busque, & Ruiz-Molina , 2013);
3. surface modifications of implant materials to emulate the structure and chemical composition of
the extracellular matrix (ECM) for optimized biocompatibility (Rahmany & Van Dyke, 2013); and
4. the development of superhydrophobic self-cleaning surfaces that mimic the hierarchical
topography and surface chemistry of the lotus leaf (Guo, Liu, & Su, 2011; Yan,
Gao, & Barthlott, 2011).
Biomimetic surface modifications can either mimic biology in terms of the modifi ed
surface itself or in the way that the coating is produced. The examples given above all
fit into the former category, where the surface topography and/or surface chemistry
mimic a biological system. A key example of the latter is in the deposition of calcium
phosphate coatings on the surface of orthopedic implants in order to improve osseointegration. Calcium phosphate coatings deposited under conditions that mimic physiological conditions have been shown to have increased biocompatibility in comparison
to spray-coated calcium phosphates that are deposited under far from natural
conditions (Avila, Misch, Galindo-Moreno, & Wang, 2009).
In this chapter, biomimetic surface modification of magnesium and its alloys is
discussed. To date, three key areas of research have been explored for these materials,
including the following:
1. surface modifications that mimic the ECM for control of biodegradation and biocompatibility
of magnesium alloy implant materials,
Surface Modification of Magnesium and its Alloys for Biomedical Applications. http://dx.doi.org/10.1016/B978-1-78242-078-1.00010-4
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