Rapid coating of AZ31 magnesium alloy with calcium deficient
hydroxyapatite using microwave energy
Yufu Ren
a,
⁎, Huan Zhou
a,b
, Maryam Nabiyouni
c
, Sarit B. Bhaduri
a,d
a
Department of Mechanical, Industrial and Manufacturing Engineering, The University of Toledo, Toledo, OH, USA
b
Institute of Biomedical Engineering and Health Sciences, Changzhou University, Changzhou, Jiangsu, China
c
Department of Bioengineering, The University of Toledo, Toledo, OH, USA
d
Division of Dentistry, The University of Toledo, Toledo, OH, USA
abstract article info
Article history:
Received 4 September 2014
Received in revised form 6 December 2014
Accepted 8 January 2015
Available online 10 January 2015
Keywords:
AZ31 magnesium alloy
Calcium deficient hydroxyapatite coating
Biocompatible coating
Microwave
Due to their unique biodegradability, magnesium alloys have been recognized as suitable metallic implant mate-
rials for degradable bone implants and bioresorbable cardiovascular stents. However, the extremely high degra-
dation rate of magnesium alloys in physiological environment has restricted its practical application. This paper
reports the use of a novel microwave assisted coating technology to improve the in vitro corrosion resistance and
biocompatibility of Mg alloy AZ31. Results indicate that a dense calcium deficient hydroxyapatite (CDHA) layer
was uniformly coated on a AZ31 substrate in less than 10 min. Weight loss measurement and SEM were used
to evaluate corrosion behaviors in vitro of coated samples and of non-coated samples. It was seen that CDHA
coatings remarkably reduced the mass loss of AZ31 alloy after 7 days of immersion in SBF. In addition, the prompt
precipitation of bone-like apatite layer on the sample surface during immersion demonstrated a good bioactivity
of the CDHA coatings. Proliferation of osteoblast cells was promoted in 5 days of incubation, which indicated that
the CDHA coatings could improve the cytocompatibility of the AZ31 alloy. All the results suggest that the CDHA
coatings, serving as a protective layer, can enhance the corrosion resistance and biological response of magne-
sium alloys. Furthermore, this microwave assisted coating technology could be a promising method for rapid sur-
face modification of biomedical materials.
© 2015 Elsevier B.V. All rights reserved.
1. Introduction
Recently, magnesium and its biodegradable alloys have been exten-
sively studied as revolutionary implant materials due to their unique
properties such as high strength/weight ratio, comparable mechanical
properties with natural bone and excellent biocompatibility [1–5]. Fur-
thermore, the Mg
2+
ion has been demonstrated to stimulate initial os-
teogenesis and promote new bone formation [6]. However, Mg and its
alloys degrade much too quickly in physiological environment due to
the high concentration of chloride ions [1,7,8]. Moreover, hydrogen
gas evolved as a corrosion by-product may cause problems against the
surrounding tissues, thus hindering the attachment of osteoblasts to
the implant surface [9].
To successfully employ these alloys, some kind of protective coating
is desirable. To date, there have been many technologies developed to
produce such coatings on magnesium and its alloys [10–12]. The most
common methods are electroplating, conversion coating, anodizing, or-
ganic coating and thermal spraying [13–17]. Although electroless nickel
plating and chromate conversion coatings have shown promising corro-
sion resistance, the toxicity in the nature of these treatment processes
restricts their application in the human body. Oxide films produced by
anodizing coatings have shown adverse results in fatigue behavior of
substrate and poor biocompatibility [18,19]. Furthermore, pinholes
and blisters formed in organic polymer coating processes and inherent
porosity produced by thermal spraying facilitate galvanic corrosion be-
tween the porous coating and magnesium substrate [10]. Besides the
disadvantages addressed above, poor biocompatibility of the deposited
coating is another shortcoming in these techniques [10]. Therefore, re-
cent publications have focused on bioactive ceramic coatings such as
calcium phosphate coatings, which presented good corrosion resistance
as well as outstanding biocompatibility and bioactivity [5,8,20–22].
Calcium phosphates (CaP), especially hydroxyapatite/calcium defi-
cient hydroxyapatite (HA/CDHA, Ca
10
(PO
4
)
6
(OH)
2
) have been broadly
used as biomedical materials for their chemical similarity to bone min-
eral. In addition, CaP exhibits non-toxicity, high biocompatibility and
superior ability to induce physicochemical bonds between the implant
and cortical bone i.e. osseointegration [23–26]. To date, several forms
of calcium phosphate coating have been developed on magnesium
and its alloys by various techniques, such as chemical precipitation
[19,27–32], electrodeposition [33–35], sol–gel [36] and hydrothermal
method [37,38]. For example, Yang et al. [29] produced hydroxyapatite
(HA) coatings on AZ31 alloy by immersing the AZ31 substrate in super-
saturated calcification solutions and applying heat treatments afterwards.
Materials Science and Engineering C 49 (2015) 364–372
⁎ Corresponding author.
E-mail address: Yufu.Ren@rockets.utoledo.edu (Y. Ren).
http://dx.doi.org/10.1016/j.msec.2015.01.046
0928-4931/© 2015 Elsevier B.V. All rights reserved.
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