Biomaterials 24 (2003) 1575–1582

Surface characterization of passive film on NiCr-based

dental casting alloys
Her-Hsiung Huang*
Institute of Dental Materials, Chung Shan Medical University, No. 110, Sec.1, Chien-Kuo N. Road, Taichung 402, Taiwan
Received 24 July 2002; accepted 6 November 2002

Abstract

Surface characterization of passive film formed on different NiCr-based dental casting alloys in an acidic artificial saliva was
investigated by using electrochemical impedance spectroscopy (EIS) measurement and potential decay test. The polarization
resistance (Rp ), which is inversely proportional to corrosion rate, of passive film was obtained from the EIS data. The stable passive
current density, passivating rate, and passivity decay rate of passive film were evaluated by potential decay test. Surface chemical
analyses of passive film were performed by using X-ray photoelectron spectrometer and Auger electron spectrometer. Results
showed that the Rp ; stable passive current density, passivating rate, and passivity decay rate, respectively, were significantly different
among the various NiCr-based alloys (po0.001). The presence of higher Cr (maximum 31–37 at%; mainly as Cr2O3) and Mo
(maximum 10–11 at%; mainly as MoO3) contents in the passive film led to a higher Rp ; lower stable passive current density, faster
passivating rate, and lower passivity decay rate. The presence of Be (>20 at%; mainly as BeO) in the passive film was detrimental to
both the corrosion resistance and the stability of passive film. The presence of small amount of Ti (o6 at%; mainly as TiO2) in the
passive film did not show any influence on the characterization of passive film.
r 2002 Elsevier Science Ltd. All rights reserved.

Keywords: Passive film; Polarization resistance; Passive current density; Passivating rate; Passivity decay rate; NiCr-based alloy

1. Introduction
For dental clinical applications, the NiCr-based
casting alloys are developed as an alternative to gold-
based alloys [1]. When applying the NiCr-based alloys,
their corrosion resistance in oral environment is an
important topic if biocompatibility is of great concern.
Benatti and his coworkers [2] reported that the NiCr-
based alloy presents good resistance to corrosion in both
in vitro and in vivo tests. Metwally et al. [3] found that
the NiCr-based alloy has a superior corrosion resistance
in 1% NaCl solution under deaerated conditions.
Furthermore, the positive effect of Cr and/or Mo
element on the corrosion resistance of NiCr-based
dental alloys has been proposed [4–8]. However, Gil
et al. [9] found that the Ni–24Cr–10Mo–2Be alloy
exhibits corrosion releasing a large quantity of metal
ions. The corrosion resistance of Ni–25Cr–10Mo alloy
decreases even by the addition of only 0.6% Be content
*Tel: +886-4-2471-8668  5509; fax: +886-4-2475-9065.
E-mail address: hhhuang@csmu.edu.tw (H.H. Huang).
[10]. Pan et al. [11] also reported that the NiCr-based
alloy is prone to localized corrosion in artificial saliva
when the Be content exceeds 0.6%. Goff and his
coworkers [12] found that the presence of small amount
of Be (higher than 0.6%) in the Ni–Cr–Mo dental alloy
can promote crevice corrosion. Furthermore, a con-
siderable range of corrosion rate (between 0.54 and
3.261 mg/cm2) among different NiCr-based alloys is
observed after 5 weeks of immersion test in lactic acid-
containing NaCl solution [13].
According to the literature mentioned above, the
corrosion resistance of NiCr-based alloys varies with
different chemical compositions in the alloys bulk. On
the other hand, reports have shown that variations in
chemical compositions of the alloy bulk can affect the
formation and composition of passive film on NiCr-
based casting alloy [5,7]. When a dental alloy is
embedded in the acidic oral cavity, the corrosion
resistance of passive film formed on the alloy should
be of great concern due to the biological considerations.
The proper characterization of passive film is the first
step in evaluating the biocompatibility [14]. If the

0142-9612/02/$ - see front matter r 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 1 4 2 - 9 6 1 2 ( 0 2 ) 0 0 5 4 4 - 6
1576 H.H. Huang / Biomaterials 24 (2003) 1575–1582
passive film, normally in the form of oxides, of the
dental alloy is damaged, increased metal ions and/or
corrosion products may be released to adjacent and
systemic tissues. The passivity decay rate and the
following repassivating rate of the destroyed passive
film will be very important in evaluating the character-
ization of passive film.
In the previous study, the effect of chemical composi-
tion on the corrosion behavior of NiCr-based dental
casting alloys in an acidic artificial saliva has been
investigated [15]. The results showed that the NiCr-
based alloys with a higher Cr and Mo content have a
much higher passive range on the polarization curve and
are immune to pitting corrosion. It is assumed that the
corrosion behavior of NiCr-based alloys in the oral
cavity depends not only on the chemical composition in
alloy bulk, but also on the characterization of passive
film on the alloys. Therefore, further study on the
surface characterization, including corrosion resistance
and stability, of passive film formed on NiCr-based
alloys is inevitable. In the present study, the corrosion
resistance of passive film formed on NiCr-based dental
casting alloys in an acid artificial saliva was investigated
by using electrochemical impedance spectroscopy (EIS)
measurement which is a non-destructive electrochemical
method. The corresponding passivating rate and passiv-
ity decay rate of passive film were evaluated by using
potential decay test. Surface chemical analyses of
passive film were correlated with the characterization
of passive film.
2. Materials and methods
2.1. Materials
Six different NiCr-based dental casting alloys used in
this study were Verabond (Aalba Dent Inc., USA),
Berabond (Bego, Germany), Wiron 99 (Bego, Ger-
many), NiTi-8 (Giliga Co Ltd., USA), Talladium-P
(Talladium Inc., USA), and Titani (Jeneric/Pentron
Inc., USA), which were designated as VB, BB, W99,
NiTi8, TA, and TIT, respectively. All test specimens
represented solidification dendrites with a laminar
eutectic structure after argon gas casting (Argoncaster-
C, Shofu, Japan). Chemical compositions (in wt%) of
the NiCr-based casting alloys were reported elsewhere
[15] and listed as follows: VB/Ni–12.4Cr–4.9Mo–2.9Al–
1.6Be–0.4Co; BB/Ni–21.1Cr–8.42Mo–3.52Nb–1.0Fe–
0.1Ti–0.07Al; W99/Ni–21.71Cr–8.28Mo–0.85Si–0.83Nb
–0.33Mn–0.01Al; NiTi8/Ni–13.68Cr–3.80Mo–3.63Ti–3.1Cu
–1.88Al–1.02Mn–0.85Si–0.44Co; TA/Ni–12.96Cr–5.23Mo
–2.17Al–0.26Ti–0.14Co; TIT/Ni–13.65Cr–8.05Mo–
2.43Al–0.25Ti–0.11Co. Casting specimens, with a di-
mension of 10 mm  10 mm  1 mm, were cold mounted
with epoxy resin (Epofix Kit, Struers A/S, Denmark).
The exposed metal surface (area: 1 cm2) of each speci-
men was ground with silicon carbide paper (Nikken,
Nihonkenshi Co., Ltd., Japan) to P2000 grit, polished
with 1 mm deagglomerated Al2O3 powder (AP-D Pow-
der, Struers A/S, Denmark), washed in distilled water
and then rinsed with alcohol before the following
electrochemical tests.
2.2. Electrochemical impedance spectroscopy
measurement
A potentiostat (AUTOLAB PGSTAT 30, Eco Che-
mie BV, The Netherlands) combined with a frequency
response analyzer (FRA 2, Eco Chemie BV, The
Netherlands) was used to perform the EIS measure-
ments. Modified Fusayama artificial saliva [16–18] (pH
5) was used as the electrochemical test electrolyte which
consisted of NaCl (400 mg/l), KCl (400 mg/l),
CaCl2
2H2O (795 mg/l), NaH2PO4
H2O (690 mg/l),
KSCN (300 mg/l), Na2S
9H2O (5.6 mg/l), and urea
(1000 mg/l). The electrolyte was deaerated with pure
nitrogen gas before and during the EIS measurements,
and maintained at 37711C. A saturated calomel
electrode (SCE) and platinum sheet were used as the
reference and counter electrode, respectively. To pro-
duce a stable passive film on specimens before the EIS
measurements, all specimens were maintained at an
applied potential of 0.125 V (SCE), located on the
passive region of the polarization curves as described
elsewhere [15], for 2 h after dipping the specimens into
the test electrolyte. Then, the EIS measurements were
carried out at the passive potential of 0.125 V (SCE) to
evaluate the corrosion resistance of passive film formed
on NiCr-based alloys. The frequencies for EIS measure-
ment were chosen in the range from 100 kHz to 1 mHz
with an applied sinusoidal potential of 10 mV. The
polarization resistance (Rp ) of the specimens, which is
inversely proportional to the corrosion rate [19,20], was
obtained by applying the non-linear least squares
(NLLS)-fit technique [21] to the experimental EIS data.
The number of specimens used for every EIS test
condition was five. After the EIS measurements, the
specimens were removed from the electrolyte, rinsed
with deionized water, and dried by nitrogen gas blasting.
Then surface chemical compositions of passive film on
the specimens were determined by using X-ray photo-
electron spectrometer (XPS) (ESCA 210, Kevex Instru-
ment Inc., USA). The compositional depth profile of
passive film was analyzed by using Auger electron
spectrometer (AES) (Microlab 310D, Kevex Instrument
Inc., USA).
2.3. Potential decay test
As for potential decay tests, a potentiostat (AUTO-
LAB PGSTAT 30, Eco Chemie BV, The Netherlands)
 H.H. Huang / Biomaterials 24 (2003) 1575–1582 1577

was used to apply an anodic passive potential of
0.125 V (SCE) to the specimens for 2 h in the artificial
saliva as used in the EIS measurements. In the mean-
time, the current density was recorded as a function of
time. The final current density, namely the stable passive
current density, was designated as Ipass ; and used to
evaluate the corrosion resistance of passive film. A lower
Ipass corresponded to a higher corrosion resistance of the
passive film. The time taken to reach Ipass was
designated as tpass which was used to evaluate the
passivating rate of specimen. A lower tpass corresponded
to a higher passivating rate of specimen. Subsequently,
the externally applied passive potential was removed,
and then the free potential, namely open circuit
potential (OCP), was measured as a function of time.
The OCP of specimens would immediately decrease
from the passive potential of 0.125 V (SCE) down to
an actively stable value, designated as Eact : The time
taken to reach Eact was designated as tact which was used
to evaluate the passivity decay rate of passive film. A
larger tact corresponded to a higher stability of passive
film.
2.4. Statistical analyses
Table 1, the Rp of BB and W99 specimens was over
2 MO-cm2, while that of other NiCr-based specimens
was less than 0.2 MO-cm2.
3.2. Potential decay test
Fig. 2(a) showed the variation of current density of
different NiCr-based alloys under an applied passive
potential of 0.125 V (SCE) in the acidic artificial saliva
as a function of time. A higher magnification of Fig. 2(a)
is shown in Fig. 2(b). The corresponding values of Ipass
and tpass are listed in Table 1. As shown in Fig. 2(a), for
all specimens except BB and W99, the current density
initially increased up to a critical value, then decreased
gradually to a stable value, Ipass : As shown in Table 1,
the Ipass of BB and W99 specimens was around 0.2–
0.3 mm/cm2, while that of other NiCr-based specimens
was over 2.5 mm/cm2. The tpass of BB and W99 speci-
mens was around 2  103 s which was about half of that
of other specimens.
Fig. 3 showed the variation of OCP of different NiCr-
based alloys in the acidic artificial saliva as a function of
time after removing the applied passive potential of

The experimental data, including Rp ; Ipass ; tpass ; Eact ;

and tact ; were statistically analyzed by one-way ANOVA
for analyzing the factor of material. Tukey’s test
(a=0.05) was chosen as the following multiple-compar-
ison technique when necessary.

3. Results

3.1. Electrochemical impedance spectroscopy

measurement

Fig. 1 showed the EIS data, in the form of Nyquist

plot, of different NiCr-based alloys in the acidic artificial
saliva. The corresponding Rp values are listed in Table
1. As shown in Fig. 1, all the specimens approximately
revealed only one semicircle. The diameter of the
semicircle for BB and W99 specimens was much larger Fig. 1. EIS data, in the form of Nyquist plot, of different NiCr-based
than that for other NiCr-based specimens. As listed in alloys in the acidic artificial saliva.

Table 1
Values of Rp ; Ipass ; tpass ; Eact ; and tact ; obtained from EIS measurements and potential decay tests (mean7SD)

Materials Rp ( MO-cm2) Ipass (mA/cm2) tpass (s) Eact (V vs SEC) tact (s)

VB 0.11070.010 2.71070.050 43337289 0.45470.004 343751

BB 3.36771.357 0.29370.040 18337153 0.42070.005 64337404
W99 2.33370.757 0.19670.015 21677259 0.43270.004 59677252
NiTi8 0.17170.004 2.69070.101 41767764 0.45270.007 507740
TA 0.18070.002 2.55070.087 41207461 0.45370.033 660753
TIT 0.12770.021 2.53370.104 40007500 0.44170.010 497745
1578 H.H. Huang / Biomaterials 24 (2003) 1575–1582

1000 -0.10
-0.125 V
900 VB -0.15

800
Current Density ( A / cm 2 )

-0.20
700

Potential (V, SCE)

TA -0.25
600
NiTi8

500 -0.30
BB
400 TIT -0.35 W99
300
-0.40 TA
TIT
200
-0.45
100 BB NiTi8
W99 VB
-0.50
0
0E+0 1E+3 2E+3 3E+3 4E+3 5E+3 6E+3 7E+3 8E+3
1E+0 1E+1 1E+2 1E+3 1E+4
Time (s)
(a) Time (s)
Fig. 3. Variation of OCP of different NiCr-based alloys in the acidic
5.0
artificial saliva as a function of time after removing the applied passive
potential of 0.125 V (SCE).
4.5

4.0 passive film for all specimens contained Cr2O3, MoO3,

Current Density ( A /cm 2 )

NiO, and Ni(OH)2. Furthermore, BeO and TiO2 could

3.5
VB be detected on the passive film for VB and NiTi8
3.0 NiTi8 specimens, respectively.
Fig. 4 showed the results of AES depth profile
2.5 TA chemical analyses (in at%) of surface passive film on
TIT
different NiCr-based alloys after EIS measurements. As
2.0
shown in Fig. 4, the Cr and Mo contents in the passive
1.5 film formed on BB and W99 specimens were around Cr:
23–37%/Mo: 2.5–11% and Cr: 21–31%/Mo: 3–10%,
1.0
respectively, while those on other specimens were lower
0.5 BB
than 20 (Cr) and 10% (Mo), respectively. Furthermore,
elements of Be (>20%) and Ti (o6%) were detected in
W99
0.0 the passive film on VB and NiTi8 specimens, respec-
1E+2 1E+3 1E+4
tively.
(b) Time (s)
Fig. 2. Variation of current density of different NiCr-based alloys 3.4. Statistical analyses
under an applied passive potential of 0.125 V (SCE) in the acidic
artificial saliva as a function of time.
The statistical analyses revealed that the factor of
material had a statistically significant influence on the
0.125 V (SCE). The corresponding values of Eact and Rp ; Ipass ; tpass ; and tact of the passive film on NiCr-based
tact are listed in Table 1. As shown in Fig. 3, the OCP of alloy (po0.001), while no significant influence on the
all specimens decreased gradually from 0.125 V (SCE) Eact (p>0.05). According to the results of Tukey’s test
to an actively stable value between 0.42 and 0.46 V for analyzing the Rp ; Ipass ; tpass ; and tact ; two different
(SCE). As shown in Table 1, the tact of BB and W99 groups, namely BB/W99 and VB/NiTi8/TIT/TA, were
specimens (B6  103 s) was around 10 times larger than observed.
that of other specimens (3–7  102 s).

3.3. Surface chemical analyses 4. Discussion

Results of XPS chemical analyses of surface passive The impedance of surface film on metal can be many
film on different NiCr-based alloys after EIS measure- decades larger than that of charge transfer reaction of
ments are listed in Table 2. As shown in Table 2, the metal, leading to the disappearance of the impedance of
 H.H. Huang / Biomaterials 24 (2003) 1575–1582 1579

Table 2 metal’s charge transfer reaction in the Nyquist plot

Results of XPS chemical analyses of surface passive film on different [22,23]. In other words, when a protective surface film is
NiCr-based alloys after EIS measurements
formed on metal, the metal’s impedance shown in the
Materials Compound Nyquist plot mainly corresponds to the impedance of
Cr2O3 MoO3 NiO Ni(OH)2 BeO TiO2 surface passive film because the impedance of metal’s
charge transfer reaction is relatively small and can thus
VB + + + + + —
be neglected. In this study, the semicircle observed in the
BB + + + + — —
W99 + + + + — — Nyquist plot for each specimen (Fig. 1) was mainly
NiTi8 + + + + — + ascribed to the presence of the surface passive film, i.e.
TA + + + + — — the Cr2O3/MoO3-based compound (Table 2), on NiCr-
TIT + + + + — — based alloy. Therefore, the Rp values obtained from the
Note: ‘‘+’’ detectable; ‘‘ ‘‘not detectable. Nyquist plots mainly represented the corrosion resis-
tance of passive film.

80 80

VB W99
70 Ni 70 Ni
Cr Cr
Atomic Concentration (%)

Atomic Concentration (%)

60 Mo 60 Mo
O O
Be
50 50

40 40

30 30

20 20

10 10

0 0
0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350

(a) Time (s) (c) Time (s)

80 80

BB
70 70
Ni
Cr
Atomic Concentration (%)
Atomic Concentration (%)

60 60
Mo NiTi8
O Ni
50 50
Cr
Mo
40 40 O
Ti
30 30

20 20

10 10

0 0
0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350

(b) Time (s) (d) Time (s)

Fig. 4. AES depth profile chemical analyses (in at%) of surface passive film on different NiCr-based alloys after EIS measurements.
1580 H.H. Huang / Biomaterials 24 (2003) 1575–1582

80 resistance in the acidic artificial saliva referring to the

above-mentioned literature. The fact that BB and W99
70 specimens showed much larger Rp values than other
TA
specimens (po0.001) (Table 1) was related to the
compositional difference in the passive film as would
Atomic Concentration (%)

60
Ni
be discussed later.
Cr
50 As shown in Fig. 2, when a passive potential of
Mo
O
0.125 V (SCE) was applied to the specimens, the
40
current density of VB, NiTi8, TA, and TIT specimens
initially increased with time up to a critical value after
10–20 s, then decreased to a stable value (>2 mA/cm2),
30
namely Ipass : However, for BB and W99 specimens
under the applied passive potential of 0.125 V (SCE),
20
no obvious critical maximum value of current density
was observed. The corresponding Ipass of BB and W99
10
specimens was around 0.2–0.3 mA/cm2 which was one
order of magnitude less than that of other four NiCr-
0
0 50 100 150 200 250 300 350
based specimens (po0.001). The above phenomena
indicated that the formation of passive film on VB,
(e) Time (s)
NiTi8, TA, and TIT specimens in the acidic artificial
80
saliva began when the passive potential of 0.125 V
(SCE) was applied to the specimens for around 10–20 s.
70 However, the formation of passive film on BB and W99
specimens was believed to begin in a much shorter time
Atomic Concentration (%)

60
50
40
30
20
10
0
0 50 100 150
(f) Time (s)
Fig. 4 (continued).
As shown in Table 1, the Rp values for all specimens
were higher than 0.1 MO-cm2, even higher than 2 MO-
cm2 (e.g. BB and W99 specimens). For surgical implants
with very low corrosion rates, the Rp may reach 1 MO-
cm2 [24]. In 0.9% NaCl solution, the Rp of commercially
pure (CP) titanium and CoCrNiMo alloy is around 0.7
and 0.003 MO-cm2, respectively [25]. Pan et al. [26]
found that the Rp of titanium in phosphate-buffered
saline (PBS) solution is around 1 MO-cm2. Huang [22]
also claimed that the Rp of CP titanium in acidic
artificial saliva (pH 5) is close to 1 MO-cm2. Therefore,
the passive films formed on various NiCr-based alloys
used in this study all exhibited an acceptable corrosion
TiT (less than 1 s) according to the data shown in Fig. 2(a).
Furthermore, the NiCr-based specimen had a significant
Ni
difference in the passivating rate (tpass ) (po0.001). The
Cr
Mo
tpass for all NiCr-based alloys used in this study was
O
around 2–4  103 s (Table 1). The fact that a lower Ipass ;
namely a higher corrosion resistance of passive film,
found for BB and W99 specimens with respect to the
others would be discussed later.
When an externally applied passive potential is
removed from the passivated alloy, the OCP of alloy
will decrease to a more active potential with respect to
the earlier applied passive potential. The decreasing rate
of OCP, i.e. the passivity decay rate, depends on the
200 250 300 350 stability of passive film on the alloy. In this study, the
OCP of all NiCr-based alloys immediately decreased to
an active value when the applied passive potential of
0.125 V (SCE) was removed (Fig. 3). The passivity
decay rate (tact ) of the NiCr-based alloys was signifi-
cantly different (po0.001). By comparing the tact value
among all specimens (Table 1), the tact of BB and W99
specimens (B6  103 s) was around 10 times larger than
that of other specimens (B3–7  102 s). In other words,
when the externally applied passive potential was
removed, which simulated the destruction of the passive
film on specimen, the BB and W99 specimens exhibited a
lower passivity decay rate, i.e. a higher stability of
passive film.
The addition of Cr to alloys can improve the
corrosion resistance of alloys in a corrosive environment
due to the formation of a Cr-rich, passive oxide film
which is highly resistant to acid attack; the addition of
Mo to the NiCr-based alloy increases the resistance to
 H.H. Huang / Biomaterials 24 (2003) 1575–1582
localized corrosion in the Cl 1-containing environment
[27]. Therefore, for NiCr-based dental alloys, the
addition of 12% Cr (minimum value) and 2–5% Mo
to the alloy bulk is well recommended from the
corrosion resistance point of view [28]. However, the
information concerning the surface characterization of
passive film formed on NiCr-based alloys is still not well
established. By comparing the results of XPS and AES
analyses (Table 2 and Fig. 4), higher Cr (21–37 at%;
mainly as Cr2O3) and Mo (2.5–11 at%; mainly as
MoO3) contents were detected in the passive film on
BB and W99 specimens with respect to other specimens
(Cro20 at%; Moo10 at%). It was believed that a
higher percentage of the protective Cr2O3 and MoO3
in the passive film could lead to a higher transfer
resistance of metal ions through the passive film. This
explained the fact that BB and W99 specimens exhibited
much higher corrosion resistance (in terms of Rp and
Ipass ), faster passivating rate (in terms of tpass ), and more
stable passive film (in terms of tact ) than other speci-
mens.
Furthermore, TIT specimen with approximately 16–
19 at% Cr and 1–10 at% Mo in the passive film did not
show good corrosion resistance and passive film stability
compared to BB and W99 specimens which contained
similar Mo content but higher Cr content in the passive
film (Fig. 4). This implied that Cr content (mainly as
Cr2O3) in the passive film on NiCr-based alloy seemed
to play a more important role in the improvement of the
passive film characterization with respect to Mo content
(mainly as MoO3).
For general applications in dentistry, Ti has the
ability to passivate by the formation of a protective
oxide layer, normally TiO2-based oxide, on metal
[29,30]. However, the optimal range of Ti in the passive
film on NiCr-based alloy is still unknown. In this study,
small amount of Ti (o6 at%; mainly as TiO2) in the
Cr2O3/MoO3-containing passive film on NiTi8 specimen
(Fig. 4(d)) did not show any improvement in the
corrosion resistance and the stability of passive film
(Table 1) though TiO2 is well documented to be a good
corrosion resistant compound. Therefore, further in-
vestigation for finding an optimal Ti content in the
passive film on NiCr-based dental alloy is suggested to
improve the passive film characterization.
On the other hand, the addition of Be to NiCr-based
alloys is mainly to improve the castability of the alloys
[31]. In this study, the outermost passive film on the Be-
containing VB specimen revealed a Be-rich (B20 at%;
mainly as BeO) and Cr-Mo-depleted (Cr B2.5 at%; Mo
B0 at%) zone (Fig. 4(a)), as compared with the
compositions in alloy bulk. This indicated that even
small amount of Be (1.6 wt%) in the NiCr-based alloy
bulk was sufficient to cause Be segregation in the surface
passive film. The Be-rich and Cr-Mo-depleted zone on
the outermost surface of VB specimen could not provide
1581
the alloy with sufficient protection, leading to the lowest
corrosion resistance (in terms of Rp and Ipass ) and
passive film stability (in terms of tact ) for VB specimen as
shown in Table 1. Similar results have been reported by
other researchers [6,7,32]. Bumgardner et al. [6] reported
that the presence of Be-containing oxide on the surface
of NiCrMo alloy is associated with high corrosion rate
and susceptibility to accelerated corrosion process.
Bumgardner and Lucas [7] claimed that the Be-contain-
ing Ni-Cr alloys have non-uniform oxide surfaces. The
oxide surfaces of these alloys are more easily disrupted
and provide little resistance to accelerated corrosion
processes. Covington et al. [32] found that the outer
surface of NiCr-based alloy in aqueous solution is
definitely enriched in Be (around 13–30 at%) as com-
pared with the bulk composition (o2 at%). They
suggested that the small atomic radius (0.31 A) ( of Be
(
element with respect to Ni (0.69 A) and Cr (0.89 A) (
elements will facilitate such migration until oxidation
when further migration is impeded due to the increased
size of the oxide. This might explain the fact that the Cr/
Mo content was relatively depleted on the outermost
surface of Be-containing VB specimen.
5. Conclusions
The surface characterization of passive film formed on
NiCr-based dental casting alloys in the acidic artificial
saliva is ascribed to the chemical constituents. The
passive films formed on different NiCr-based alloys have
statistically significant difference in the polarization
resistance, stable passive current density, passivating
rate, and passivity decay rate (po0.001). The polariza-
tion resistance of the passive film with higher Cr2O3 (Cr:
21–37 at%) and MoO3 (Mo: 2.5–11 at%) contents is
higher than 2 MO-cm2 which is more than 10 times
larger compared to that with lower Cr2O3 (Cro20 at%)
and MoO3 (Moo10 at%) contents. The stable passive
current density of the passive film with a higher Cr2O3/
MoO3 content is around 0.2–0.3 mA/cm2 which is one
order of magnitude less than that with a lower Cr2O3/
MoO3 content. The passive film with a higher Cr2O3/
MoO3 content exhibits a higher passivating rate, and is
10 times more stable, in terms of passivity decay rate,
than the lower Cr2O3/MoO3-containing passive film.
The presence of Be-rich (Be B20 at%; mainly as BeO)
and Cr-Mo-depleted (Cr B2.5 at%; Mo B0 at%) zone
on the outermost surface of passive film leads to a
dramatic decrease in corrosion resistance (in terms of
polarization resistance and passive current density) and
stability (in terms of passivity decay rate) of the passive
film. The presence of small amount of TiO2 (Tio6 at%)
in the passive film does not provide the passive film with
higher corrosion resistance and stability.
1582 H.H. Huang / Biomaterials 24 (2003) 1575–1582
Acknowledgements
The author acknowledge the financial support by [15]
NSC 89-2815-C-040-019R-B. Thanks are also due to
Mr. M.C. Lin, Chungtai Institute of Health Sciences [16]
and Technology, Taiwan, for assistance with the speci-
men preparations.
[17]
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