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Do phosphate ions affect the biodegradation rate of uoride-treated Mg?

C. Alonso
a
, J.A. del Valle
b
, M. Gamero
a
, M. Fernndez Lorenzo de Mele
c,

a
Dto de Qumica Fsica Aplicada, Universidad Autnoma de Madrid, Madrid, Spain
b
Dto de Metalurgia Fsica, CENIM, CSIC, Madrid, Spain
c
Instituto de Investigaciones Fisicoqumicas Tericas y Aplicadas (INIFTA, CCT La Plata-CONICET), Facultad de Ciencias Exactas, UNLP, C.C. 16, Sucursal 4, (1900) La Plata,
Argentina y Facultad de Ingeniera, UNLP, Argentina
a b s t r a c t a r t i c l e i n f o
Article history:
Received 7 July 2011
Accepted 12 October 2011
Available online 20 October 2011
Keywords:
Magnesium
Powder metallurgy
Fluoride
Phosphate
Biodegradable metal
Previous studies have shown that pure Mg that is reinforced by powder metallurgy (Mg(PM)) is a promising
biodegradable material, because it circumvents the drawbacks of the toxic components of Mg alloy implants.
However, its degradation rate is high, which can be reduced with uoride coatings (Mg(PM)F). This protec-
tive effect is temporary, because chloride induces further biodegradation of Mg(PM) in biological media. The
aim of this report was to examine the effects of phosphates on Mg(PM)F in chloride-containing medium. By
surface analysis of Mg(PM)F, the aggressive activity of chlorides induced a rapid decrease in F content of the
layer. However, by electrochemical impedance spectroscopy and EDX, the surface attack was hindered in the
presence of phosphates that precipitated onto the regions where localized attack occurred and formed a
more protective P-containing layer. Our results highlight the robust activity of phosphates, which act syner-
gistically with uorides, controlling the degradation of F-coating in biological media and prolonging the ser-
vice period of temporary Mg(PM)F implants.
2011 Elsevier B.V. All rights reserved.
1. Introduction
Pure Mg overcomes the effects of the toxic components of magne-
siumalloys, but it has anexcessively highdegradationrate [16] and in-
sufcient yield strength [7]. In this study, we examined Mg that was
reinforced by powder metallurgy (Mg(PM)). Mg(PM) has a yield
strength of 280 MPa considerably higher than that of pure cast mag-
nesium and approximating that of AZ31 Mg alloy. Many reports have
demonstrated the importance of chloride ions, phosphates, and the
pH and buffer capacity of solutions on the degradation of bare Mg and
alloys in biological media [6,7].
Immersion of Mg(PM) in KF solution has been proposed to im-
prove its resistance to degradation, because it is low-cost, nontoxic,
simple, and amenable for biomedical applications [7]. After this treat-
ment a conversion coating is formed [714].
The aimof this letter was to examine the effects of phosphate ions on
the control of degradation of uoride-treated Mg(PM) (referred to as Mg
(PM)F) in chloride-containing media by electrochemical impedance
spectroscopy (EIS) and EDX analysis. To mitigate the interference of
other ions, simple synthetic solutions that are usedfrequently to simulate
biological media NaCl solution and chloride-containing phosphate-
buffered solution (PBS) were used as electrolytes.
2. Materials and methods
2.1. Materials
Magnesium powder (99.8%, 325 mesh) was supplied by Alfa
Aesar. The powder was cold-pressed, and the resulting cylindrical
compacts, 40 mm in diameter, were extruded in the form of bars at
420 C at an extrusion ratio of 16:1.
Cylindrical samples (1 cm in diameter) were cut from Mg(PM)
bars. The lateral surfaces were covered by epoxy resin, leaving a cir-
cular exposed area of 0.785 cm
2
. The samples were ground and dry-
polished with successively ne SiC paper to 1500 grit. A Philips
XL30 scanning electron microscope (SEM), coupled to an EDX DE4i
analyzer, was used to characterize the magnesium samples.
All solutions were prepared with ultrapure water from a Millipore
Milli-Q system (18.2 M
1
). The compositions of the solutions were:
0.1 M KF, 8 g L
1
NaCl, and PBS (8 g L
1
NaCl, 0.2 g L
1
KCl, 0.2 g L
1
KH
2
PO
4
, 1.15 g L
1
Na
2
HPO
4
). Analytical-grade reagents were used in
all cases. Mg(PM) electrodes were used untreated or after immersion
in 0.1 M KF for 1 h. To demonstrate the synergistic effect of phosphates
and uoride, we also performed experiments with electrodes that
were treated with 0.1 M KF for 1 h, followed by immersion in PBS for
30 min.
2.2. Electrochemical impedance spectroscopy measurements
EIS measurements were made with an Autolab PGSTAT 30 poten-
tiostat from Eco-Chemie. A sinusoidal potential modulation, 10 mV
Materials Letters 68 (2012) 149152
Corresponding author at: Casilla de Correo 16, Sucursal 4, 1900 La Plata, Argentina.
Tel.: +54 221 425 7430x148; fax: +54 221 4254642.
E-mail address: mmele@inifta.unlp.edu.ar (M. Fernndez Lorenzo de Mele).
0167-577X/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2011.10.048
Contents lists available at SciVerse ScienceDirect
Materials Letters
j our nal homepage: www. el sevi er . com/ l ocat e/ mat l et
in amplitude in the 10
5
Hz10
2
Hz frequency range, spaced loga-
rithmically (120 per 8 decades), was superimposed onto the open cir-
cuit potential of the Mg(PM)F in 8 g L
1
NaCl or PBS.
3. Results and discussion
3.1. Electrochemical results
We compared the electrochemical behavior of untreated and KF-
treated samples (Mg(PM)F) in NaCl-sol and PBS. The EIS results on
the Mg(PM) samples under the open circuit potential condition are
shown in Fig. 1. The Nyquist diagrams show a semicircle that corre-
sponds to the limiting of charge transfer resistance (R
CT
), related to
the F

-containing coating/electrolyte or Mg(PM)/electrolyte interfaces.


At low frequency, we observed an inductive behavior, usually associat-
ed with ion adsorptiondesorption during dissolution (Fig. 1a).
The impedance modulus Bode diagrams (Fig. 1b) revealed a pla-
teau at high frequencies. The impedance value in this region, with
=0, yields electrolyte resistance (R
e
~108 ) for each case. At de-
creasing frequencies (10
3
Hz10 Hz), the slope can be attributed to
one capacitor in parallel with resistance, corresponding to the F

-
containing coating/electrolyte interface. In the lower frequency
range (110
2
Hz), the phase angle is close to 0, corresponding to
a plateau in the impedance modulus-versus-frequency plot. From
this region, it is possible to obtain the total resistance of the system
(R
TC
+R
e
).
The electrochemical parameters are summarized in Table 1, in
which 5 types of tests are compared. The EIS spectra that were
obtained with Mg(PM) with and without KF treatment in NaCl-sol
and PBS differed signicantly. The R
CT
value of the untreated elec-
trodes that were immersed in PBS solution (Test 1) was 218 higher
than that in NaCl solution (Test 2) (i.e., the phosphate effect).
After KF treatment (Tests 3, 4), the R
CT
values were higher than
those of Tests 1 and 2 (without treatment) (R
CT3
R
CT1
=267 R
CT4

R
CT2
=217 (KF effect)). Notably, we observed a synergistic effect be-
tween the inhibition by phosphate and uoride when the sample
was immersed in PBS for 30 min after treatment with KF. Thus, the dif-
ference between R
CT
values between Tests 4 and 5 is 691 higher
than the sum of the phosphate and uoride effects. Conversely, the
phase angles () and Z-log f slopes are consistent with an increase in
the capacity of the interface (Table 1).
0 500 1000 1500 2000 2500 3000
-400
-200
0
200
400
600
800
a
Mg / NaCl
Mg (KF) / NaCl
Mg / PBS
Mg (KF) / PBS
Mg (KF + PBS) / PBS
Z
'
'
(
o
h
m
)
Z' (ohm)
-30
-20
-10
0
10
20
30
40
50
60
-3 -2 -1 0 1 2 3 4 5 6
2.0
2.2
2.4
2.6
2.8
3.0
3.2
3.4
-
p
h
a
s
e

/

d
e
g

(
+
)
Mg (KF) / NaCl
Mg (KF) / PBS
Mg (KF + PBS) / PBS
l
o
g
(
Z
)
(
o
)
log(f)
b
Fig. 1. (a). Nyquist EIS spectra plots of Mg(PM) immersed in 8 g L
1
NaCl or PBS. Exper-
iments made without KF treatment in NaCl ( ) and PBS ( ) electrolyte solutions. Ex-
periments made with KF treatment in NaCl ( ) and PBS ( ) solutions and with KF
treatment +30 min immersion in PBS before EIS measurements in PBS ( ). (b). Bode
EIS spectra plots of Mg(PM) immersed in 8 g L
1
NaCl or PBS. Experiments made
with KF treatment in NaCl ( ) and PBS ( ) solutions and with KF treatment +30 min
immersion in PBS before EIS measurements in PBS ( ).
Table 1
Electrochemical parameters obtained from EIS measurements.
Test number
a
Electrode (treatment)/
solution
R
TC
cm
2
C
Fcm
2
b
|Z| vs. logf

1 Mg/NaCl 319 8.94 E-6 0.46 34


2 Mg/PBS 537 1.25 E-5 0.50 39
3 Mg (KF)/NaCl 586 6.99 E-6 0.52 42
4 Mg (KF)/PBS 754 5.03 E-6 0.57 45
5 Mg (KF+PBS)/PBS 1445 1.63 E-6 0.62 49
a
Mg(PM) without treatment in NaCl (1) and in PBS (2) electrolyte solutions. Mg(PM)
with 1 h treatment with KF using NaCl or PBS electrolytes (3, 4 respectively) and (5)
Mg(PM) with 1htreatment withKF followed by 30 min immersioninPBS, using PBS as elec-
trolyte solution.
O F Cl P
0
4
8
12
16
20
24
28
%

a
t
PBS
initial
time 20min
time 2h
O F Cl P
0
10
20
30
40
48
56
a
t
.
%
Fig. 2. (a) Inuence of immersion time of Mg(PM)F in PBS-sol on degradation of F

-
conversion coating. EDX analysis of the surface composition of Mg(PM)F (0.1 M KF
pretreatment for 1 h) after immersion in PBS-sol ( ) before immersion, (///) after
20 min of immersion, and (lll) after 2 h of immersion. (b) Inuence of composition
of solution on degradation of F

-conversion coating. EDX analysis of surface composi-


tion of Mg(PM)F (0.1 M KF solution pretreatment for 1 h) ( ) before and after 2 h of
immersion in (lll) NaCl-sol and (///) PBS.
150 C. Alonso et al. / Materials Letters 68 (2012) 149152
Fig. 2a shows that F-content decreased with immersion time, in-
dicating that uorides were removed progressively in the presence
of chlorides, with and without phosphates. Conversely, the Ocontent
of the layer increased. With regard to the behavior of 0.1 M KF coat-
ing after immersion in NaCl-sol versus PBS, uoride decreased and
oxygen increased to greater extents in Mg(PM)F-NaCl samples. The
presence of P, nonhomogeneously distributed, was detected on Mg
(PM)F-PBS (Fig. 2b). By microscopy, we observed liform attack of
Mg(PM)F-NaCl samples (Fig. 3a), with lower F levels in areas that
were covered by Cl

-containing deposits (Fig. 3bd). Mg(PM)F-


PBS had a dark coating (A) with bright circles (Fig. 3e and inset).
The contents of P and O in region B were greater than 4 times those
of region A, implicating the presence of precipitated phosphates in
region B, consistent with data on Mg alloys [15]. The inset shows
that there are blisters in the center of these regions, where hydrogen
evolution likely occurred.
The higher resistance to degradationby Mg(PM)F-PBS by EIS might be
attributed to hindrance of the activity of chlorides by the P-containing
layer [6,15,16]. The decrease in localized attack in region B might be
explained by the nding that the change in pH that is induced by hydro-
gen evolution favors the precipitation of phosphates that obstruct the ag-
gressive activity of chlorides against Mg(PM).
4. Conclusions
The F

-coating of Mg(PM) degrades quickly in Cl-containing solu-


tions. Notably, phosphates (at concentrations that approximate that
of biological media) hinder the effects of chloride and reduce the deg-
radation rate of F

-treated samples due to synergistic inhibition be-


tween uoride and phosphate anions. Thus, the service period of
temporary implants can be extended under this condition.
c d
a b
A
e
Fig. 3. (a) Optical microscopy image of liform corrosion on Mg(PM)F and (b) SEMimages of Mg(PM)F samples that were immersed for 2 h in NaCl-sol; (c) and (d) EDX mapping of
F (c) and Cl (d) of the SEM image (b); (e) (A) dark P-containing deposits obtained in PBS. The inset shows bright circles with blisters in the center (inset).
151 C. Alonso et al. / Materials Letters 68 (2012) 149152
Acknowledgments
MFLMwould like to acknowledge the nancial support by CONICET,
University of La Plata (11/I129) and ANPCyT (PICT 2010-1779) of
Argentina, JAV by the CICYT grant MAT2009-14452 awarded by
the Spanish Ministry of Science and Innovation of Spain and CA by
the CAM grant AVANSENS S2009/PPQ-1642.
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