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materials
Dental Materials 19 (2003) 188±198
www.elsevier.com/locate/dental
Abstract
Objectives: The most common metals and alloys used in dentistry may be exposed to a process of corrosion in vivo that make them
cytotoxic. The biocompatibility of dental alloys is primarily related to their corrosion behavior. The aim of this work was to evaluate the
corrosion behavior and thus the biocompatibility of the uncoated and coated stainless steels and compare the effect of type of coatings on
corrosion behavior.
Methods: Three types of coatings, hydroxyapatite (HA), titanium (Ti), and a double-layer HA/Ti on AISI 316L stainless steel were made.
HA coating was produced using plasma-spraying technique and Ti coating was made using physical vapor deposition process. In order to
perform a novel double-layer composite coating, a top layer of HA was plasma-sprayed over a physical vapor deposited Ti layer on AISI
316L stainless steel. Structural characterization techniques including XRD, SEM and EDX were used to investigate the microstructure,
morphology and crystallinity of the coatings. Electrochemical potentiodynamic tests were performed in physiological solutions in order to
determine and compare the corrosion behavior of the coated and uncoated specimens as an indication of biocompatibility.
Results: Double-layer HA/Ti coating on AISI 316L SS had a positive effect on improvement of corrosion behavior. The decrease in
corrosion current densities was signi®cant for these coated specimens and was much lower than the values obtained for uncoated and single
HA coated specimens. Ti coating on AISI 316L SS also has a bene®cial effect on corrosion behavior. The results were compared with the
results of corrosion behavior of HA coated commercially pure titanium (cpTi) and uncoated cpTi.
Signi®cance: These results demonstrated that the double-layer HA/Ti coated 316L SS can be used as an endodontic implant and two goals
including improvement of corrosion resistance and bone osteointegration can be obtained simultaneously.
q 2003 Academy of Dental Materials. Published by Elsevier Science Ltd. All rights reserved.
Keywords: AISI 316L stainless steel; Corrosion; HA coating; Ti coating
Fig. 1. XRD patterns of the coatings: (a) plasma-sprayed HA coating on cpTi; (b) plasma-sprayed HA coating on 316L SS; (c) double-layer HA/Ti coating on
316L SS.
the body [9]. It has been demonstrated that metallic ions these ions in vivo not only causes toxic effects in mouse
resulting from the in vitro corrosion of austenitic stainless testicular seminiferous epithelium but also alterations in the
steels cause alteration of the expression of human lympho- spleen cellular population [11].
cyte-surface antigens and inhibit the immune response as A number of investigations have demonstrated that metal
assessed by lymphocyte proliferation [10]. The presence of ions can be released from metallic materials as the result of
190 M.H. Fathi et al. / Dental Materials 19 (2003) 188±198
Fig. 1. (continued)
corrosion [2,3,8±10,12±14]. Local adverse tissue reactions logical results of hydroxyapatite coated/uncoated metallic
or elicit allergy reactions caused by metallic implants implants in animals [36]. In this previous work, endodontic
originate from the release of metal ions. This release of implants consisting of plasma-sprayed HA coated and
ions depends upon the corrosion rate of the alloy and the uncoated substrates of various materials, namely 316L
solubility of the ®rst formed corrosion products [15]. Inten- stainless steel and Co±Cr±Mo alloy, were prepared. These
sive investigations have been carried out on biomaterials in implants were subsequently implanted in the mandibular
order to study their corrosion behavior, ion release and its canine of cats. After a healing period of 4 months, osteo-
effects [14,16±25], and toxicity and immunity of alloys integration evaluation and histopathological interpretation
[6,16±18,26±29]. The studies have been more intensive were carried out by using scanning electron microscopy
for stainless steels due to their corrosion behavior [14,19± (SEM). The results showed that different substrates had
29]. It has been suggested that metal ions associated with pronounced effects on the histopathological response to
316L stainless steel are toxic to osteogenic cells, affecting different HA coated implants [36].
their proliferation and differentiation [19]. Stainless steel The aim of the present work was to evaluate the corrosion
corrosion products above certain concentrations may disturb behavior and therefore biocompatibility of the uncoated and
the normal behavior of osteoblast-like bone marrow cell coated stainless steels. In order to design and produce
cultures [20±22,25]. Advanced techniques have been used a desired coating for improvement of histopathological
for determining toxicity and tissue reaction around metal response, tissue reaction and bone osteointegration around
implants [24,27,29]. For this purpose, in vivo animal tests dental implants, the effects of three types of coatings on the
have been performed [28]. behavior of substrates were compared.
Ion release rates in vitro can be used to determine the
proportionality of release in vivo [30±32] but long-term in
vivo studies have been made and results indicate that metal 2. Materials and methods
ion release increases with the exposure time [33,34].
Release of metal ion in vivo analysis did not demonstrate 2.1. Substrates and coatings
any consistent differences in the concentrations of metallic
elements next to stressed and nonstressed miniplates and Commercially pure titanium (cpTi) and AISI 316L stain-
screws of stainless steels [35]. less steel were used as substrates. The composition (wt%) of
A previous in vivo study by the present authors has shown stainless steel was C 0.03, Si 0.80, Mn 1.2, Cr 17.55, Ni
that the type of metallic implants had signi®cant effects on 13.65, Mo 3.1, P # 0.040, S # 0.030 and Fe as the balance.
the clinical success, bone tissue response and histopatho- The composition (wt%) of cpTi was Ti . 99.5%.
M.H. Fathi et al. / Dental Materials 19 (2003) 188±198 191
Fig. 2. SEM micrograph of the coatings: (a) plasma-sprayed HA coating surface showing partially melted with some porosity and microcracks; (b) the top
layer of a double-layer HA/Ti coating shows some porosity and microcracks; (c) a physical vapor deposited Ti coating on a 316L SS.
Ti coating (3±7 mm thickness) was made using physical (Philips XL 30) were used to study the microstructure and
vapor deposition process on AISI 316L stainless steel. Crys- morphology of the coatings. EDX analysis was utilized to
talline hydroxyapatite coatings with 40±60 mm were pro- estimate the ratio of Ca/P of the HA coating and the compo-
duced using plasma-spraying technique on two types of sition of the coatings.
substrate, i.e. AISI 316L stainless steel and commercially Commercially pure titanium (cpTi) and AISI 316L stain-
pure Ti. A double-layer composite coating composed of a less steel (316L SS) were selected as the sample materials.
hydroxyapatite top layer (40±60 mm thickness) and a Ti Coupons of two types of alloys were cut and surface
under layer (3±5 mm thickness) was prepared using a preparations were carried out by wet grinding with a series
plasma-spraying and a physical vapor deposition process, of SiC papers to 4000-grit followed by thorough cleaning in
respectively, on AISI 316L stainless steel. distilled water, degreasing with acetone and air drying.
An electrochemical corrosion polarization test cell was
2.2. Experimental procedure used for in vitro potentiodynamic corrosion tests in physio-
logical solutions. Graphite was used as the counter electrode
X-ray diffraction (XRD) technique (Philips X'Pert-MPD and saturated calomel electrode (SCE) as the reference elec-
System with a Cu ka wavelength of 1.5418 A Ê ) was used to trode. The physiological solutions were the Ringer's solu-
analyze the crystalline structure and phases present in the tion and physiological normal saline (0.9 wt% NaCl) and
coatings. This technique was also used to estimate the the potentiodynamic corrosion tests were performed at
percentage of the crystallinity of the HA coating. SEM 37 ^ 1 8C. Dynamic polarization curves were recorded at a
and energy dispersive X-ray analysis (EDX) techniques potential scanning rate of 0.5 mV s 21 initiated at 2250 mV
192 M.H. Fathi et al. / Dental Materials 19 (2003) 188±198
Fig. 3. SEM EDX of the coatings: (a) HA coating, desirable Ca/P is obtained; (b) and (c) HA layer and Ti layer, respectively, of a double-layer HA/Ti coating.
below the open circuit potential and the atmosphere was ti®ed by the Tafel equation. DE b log
i=I0 : The expanded
open to air. Five replicate tests of each group of specimens form of this equation shows linearity where b is slope and
were performed. log i0 is the Y intercept. The scans are plotted as potential, E
To compare the corrosion behavior between the uncoated (mV, SCE), vs. log current density, log i (mA cm 21), and are
and HA coated cpTi, the uncoated 316L SS, HA coated often referred to as Evans Diagrams. The reverse scan was
316L SS and double-layer HA/Ti coated 316L SS, speci- obtained by reversing the direction of the scan, thus obtain-
mens were dynamically polarized in two different types ing a reverse Evans Diagram. Curve shape, potentials at
of physiological solutions. Potentiodynamic polarization current discontinuities and absolute values are all important
curves were determined at 37 ^ 1 8C using a EG and G in characterizing corrosion behavior. The second test
model 263A potentiostat/galvanostat interfaced with a involved potentiodynamic or continuous scanning but over
computer and a recorder. The tests were started after a a much smaller potential range than anodic polarization.
steady open-circuit potential was attained (not more than Typically, a scan is started 10 mV anodic to the corrosion
^5 mV drift in 5 min). The anodic and cathodic polariza- potential and terminates 10 mV cathodic to it. The scan is
tion curves were obtained for each specimen and corrosion plotted directly as E vs. i and is referred to as a linear
potentials and corrosion current densities were determined polarization plot. The slope of the linear segment of the
by Tafel extrapolation and linear polarization methods. The DE vs. Di plot is expressed by the formula:
mean value and standard deviations of the results were
DE=DiDE!0 RP B=icorr
calculated.
It is noticeable that two kinds of electrochemical tests where RP is polarization resistance (kV cm 2), (DE/Di) is
were utilized in this investigation. The ®rst test was referred slope (mV cm 2/mA) and
to as a potentiodynamic anodic polarization-scan because it
B
constant b a bc =2:3
ba 1 bc
is dynamic or continuous. It represented a pro®le of the
behavior of the alloy when scanned in a forward direction where ba and bc are Tafel slopes for the anodic and cathodic
from anodic to cathodic potential and spans a range of 1 V pro®les, respectively. One way to ®nd the value of the equa-
or more. The straight line segments of these scans are iden- tion involves the determination of Tafel bc and ba from
M.H. Fathi et al. / Dental Materials 19 (2003) 188±198 193
Fig. 3. (continued)
potentiodynamic polarization curves and calculation of the porous surface and some microcracks. Fig. 2(c) is a SEM
resulting value of B. micrograph showing a physical vapor deposited Ti coating
on a 316L SS. The porosity of the coating is less than HA
coating but microcraks cannot be seen.
3. Results The result of EDX analysis of HA coating surface is
shown in Fig. 3(a). The Ca/P 2 is the desired ratio. Fig.
3.1. Structural characterization 3(b) and (c) show EDX analysis of HA layer and Ti layer of
double-layer HA/Ti coating.
The XRD patterns of the plasma-sprayed HA coatings on
cpTi and 316L SS are shown in Fig. 1(a) and (b), respec- 3.2. Corrosion behavior
tively. In the plot of intensity vs. 2u , there are numerous
sharp peaks and a low background indicative of highly crys- The potentiodynamic polarization curves of the uncoated,
talline HA coating. Fig. 1(c) also shows the XRD pattern of HA coated, Ti coated, double-layer HA/Ti coated 316L SS
a double-layer HA/Ti coating on 316L SS which is very and HA coated/uncoated cpTi in the normal saline solution
similar to the XRD pattern of HA coating on 316L SS. are shown in Fig. 4. The similar curves that are obtained in
The SEM micrograph showing a typical plasma-sprayed Ringer's solution are plotted in Fig. 5. These curves are
HA coating on a metallic substrate is shown in Fig. 2(a). The selected because their extracted data were the most nearest
structure appears to be partially melted and porous and to the mean values of the current densities of each group of
microcracks can be observed scattered throughout the struc- specimens.
ture, probably as a result of a very rapid cooling rate during The corrosion current densities of various specimens
the deposition process. Fig. 2(b) is a SEM micrograph show- were determined from the potentiodynamic polarization
ing a typical double-layer HA/Ti coating on 316L SS curves (Figs. 4 and 5) by Tafel extrapolation method.
substrate which also shows that the coating consists of a These results align with corrosion potentials, summarized
194 M.H. Fathi et al. / Dental Materials 19 (2003) 188±198
Fig. 3. (continued)
in Tables 1 and 2 in normal saline solution and Ringer's resistance of metallic substrate, i.e. 316L SS and cpTi and
solution, respectively. The standard deviations of the corro- decreased the corrosion current density of each type of
sion current densities are shown in parentheses in Tables 1 coated metallic substrate. The polarization curve, (b) in
and 2. The corrosion current densities as determined by Fig. 4, of the HA coated 316L SS was shifted to the left
linear polarization method are also shown in Tables 1 and 2. upper area, compared with curve (a), which is the uncoated
According to Table 1 and Fig. 4, the uncoated 316L SS 316L SS specimen. It means that the HA coated 316L SS
possesses lower corrosion resistance and thus higher corro- (Ecorr 2105 mV, icorr 68 nA) was more corrosion resis-
sion current density (icorr 265 nA cm 22) in the normal tant than the uncoated 316L SS (Ecorr 2174 mV,
saline solution. The similar trend can be observed in the icorr 265 nA). The corrosion behavior of the HA coated
Ringer's solution (Table 2). The HA coating decreased the cpTi (Ecorr 2256 mV, icorr 43 nA) was better than
corrosion current density of the HA coated 316L SS uncoated cpTi (Ecorr 2334 mV, icorr 72 nA) up to
(icorr 68 nA cm 22) and HA coated cpTi (icorr 43 200 mV, as manifested by a shift of the polarization curve
nA cm 22). The double-layer HA/Ti coating had a sig- (f) to the left upper of the uncoated cpTi curve (e). A similar
ni®cant effect on the corrosion behavior of 316L SS so trend can be observed in the Ringer's solution (Fig. 5,
that the corrosion current density of HA/Ti coated 316L curves (a), (b), (e) and (f), Table 2). Therefore, single HA
SS decreased (icorr 44 nA cm 22) and was exactly similar coating on metallic substrate caused signi®cant changes on
to single HA coated cpTi (icorr 43 nA cm 22) in normal corrosion behavior of substrate. This result was in agree-
saline solution. The Ti coating could decrease the corrosion ment with the results of the other researchers [37].
current density of the Ti coated 316L SS in both types of the Single HA coating could decrease the corrosion current
physiological solutions (Table 1 and 2). density of 316L stainless steel substrate in physiological
solutions (Tables 1 and 2 and Figs. 4 and 5) but this effect
was not adequately complete. This was due to the fact that
4. Discussion the structure and surface morphology of single HA coating
consists of a porous surface and some microcracks (Fig. 2)
The single HA coating had a positive effect on corrosion and could not act as a barrier to the release of metal ions
M.H. Fathi et al. / Dental Materials 19 (2003) 188±198 195
Table 1 Table 2
Mean values (standard deviation) of corrosion current densities and corro- Mean values (standard deviation) of corrosion current densities and corro-
sion potentials in normal saline solution (0.9 wt% NaCl) at 37 8C sion potentials in Ringer's solutions at 37 8C
Material Ecorr (mV) Icorr (nA/cm 2) Material Ecorr (mV) Icorr (nA/cm 2)
Uncoated 316L SS 2174(20) 265 (16) 194 (16) Uncoated 316L SS 2195(20) 218 (17) 181 (20)
Uncoated cpTi 2334(11) 72 (7) 63 (9) Uncoated cpTi 2303(5) 71 (6) 61 (6)
HA coated 316L SS 2105(10) 68 (2) 52 (1) HA coated 316L SS 2110(21) 57 (3) 49 (1)
HA coated cpTi 2256(10) 43 (6) 34 (7) HA coated cpTi 2215(14) 40 (4) 29 (3)
HA/Ti coated 316L SS 2153(15) 44 (5) 32 (3) HA/Ti coated 316L SS 2182(20) 43 (5) 32 (4)
Ti coated 316L SS 288(20) 27 (5) 26 (5) Ti coated 316L SS 261(15) 24 (5) 26 (2)
196 M.H. Fathi et al. / Dental Materials 19 (2003) 188±198
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