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 [10]. Pan et al. [11] also reported that the NiCr-based
alloy is prone to localized corrosion in artificial saliva
For dental clinical applications, the NiCr-based when the Be content exceeds 0.6%. Goff and his
casting alloys are developed as an alternative to gold- coworkers [12] found that the presence of small amount
based alloys [1]. When applying the NiCr-based alloys, of Be (higher than 0.6%) in the Ni–Cr–Mo dental alloy
their corrosion resistance in oral environment is an can promote crevice corrosion. Furthermore, a con-
important topic if biocompatibility is of great concern. siderable range of corrosion rate (between 0.54 and
Benatti and his coworkers [2] reported that the NiCr- 3.261 mg/cm2) among different NiCr-based alloys is
based alloy presents good resistance to corrosion in both observed after 5 weeks of immersion test in lactic acid-
in vitro and in vivo tests. Metwally et al. [3] found that containing NaCl solution [13].
the NiCr-based alloy has a superior corrosion resistance According to the literature mentioned above, the
in 1% NaCl solution under deaerated conditions. corrosion resistance of NiCr-based alloys varies with
Furthermore, the positive effect of Cr and/or Mo different chemical compositions in the alloys bulk. On
element on the corrosion resistance of NiCr-based the other hand, reports have shown that variations in
dental alloys has been proposed [4–8]. However, Gil chemical compositions of the alloy bulk can affect the
et al. [9] found that the Ni–24Cr–10Mo–2Be alloy formation and composition of passive film on NiCr-
exhibits corrosion releasing a large quantity of metal based casting alloy [5,7]. When a dental alloy is
ions. The corrosion resistance of Ni–25Cr–10Mo alloy embedded in the acidic oral cavity, the corrosion
decreases even by the addition of only 0.6% Be content resistance of passive film formed on the alloy should
be of great concern due to the biological considerations.
*Tel: +886-4-2471-8668  5509; fax: +886-4-2475-9065. The proper characterization of passive film is the first
E-mail address: [email protected] (H.H. Huang). 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 The exposed metal surface (area: 1 cm2) of each speci-
dental alloy is damaged, increased metal ions and/or men was ground with silicon carbide paper (Nikken,
corrosion products may be released to adjacent and Nihonkenshi Co., Ltd., Japan) to P2000 grit, polished
systemic tissues. The passivity decay rate and the with 1 mm deagglomerated Al2O3 powder (AP-D Pow-
following repassivating rate of the destroyed passive der, Struers A/S, Denmark), washed in distilled water
film will be very important in evaluating the character- and then rinsed with alcohol before the following
ization of passive film. electrochemical tests.
In the previous study, the effect of chemical composi-
tion on the corrosion behavior of NiCr-based dental 2.2. Electrochemical impedance spectroscopy
casting alloys in an acidic artificial saliva has been measurement
investigated [15]. The results showed that the NiCr-
based alloys with a higher Cr and Mo content have a A potentiostat (AUTOLAB PGSTAT 30, Eco Che-
much higher passive range on the polarization curve and mie BV, The Netherlands) combined with a frequency
are immune to pitting corrosion. It is assumed that the response analyzer (FRA 2, Eco Chemie BV, The
corrosion behavior of NiCr-based alloys in the oral Netherlands) was used to perform the EIS measure-
cavity depends not only on the chemical composition in ments. Modified Fusayama artificial saliva [16–18] (pH
alloy bulk, but also on the characterization of passive 5) was used as the electrochemical test electrolyte which
film on the alloys. Therefore, further study on the consisted of NaCl (400 mg/l), KCl (400 mg/l),
surface characterization, including corrosion resistance CaCl2
2H2O (795 mg/l), NaH2PO4
H2O (690 mg/l),
and stability, of passive film formed on NiCr-based KSCN (300 mg/l), Na2S
9H2O (5.6 mg/l), and urea
alloys is inevitable. In the present study, the corrosion (1000 mg/l). The electrolyte was deaerated with pure
resistance of passive film formed on NiCr-based dental nitrogen gas before and during the EIS measurements,
casting alloys in an acid artificial saliva was investigated and maintained at 37711C. A saturated calomel
by using electrochemical impedance spectroscopy (EIS) electrode (SCE) and platinum sheet were used as the
measurement which is a non-destructive electrochemical reference and counter electrode, respectively. To pro-
method. The corresponding passivating rate and passiv- duce a stable passive film on specimens before the EIS
ity decay rate of passive film were evaluated by using measurements, all specimens were maintained at an
potential decay test. Surface chemical analyses of applied potential of 0.125 V (SCE), located on the
passive film were correlated with the characterization passive region of the polarization curves as described
of passive film. 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
2. Materials and methods evaluate the corrosion resistance of passive film formed
on NiCr-based alloys. The frequencies for EIS measure-
2.1. Materials ment were chosen in the range from 100 kHz to 1 mHz
with an applied sinusoidal potential of 10 mV. The
Six different NiCr-based dental casting alloys used in polarization resistance (Rp ) of the specimens, which is
this study were Verabond (Aalba Dent Inc., USA), inversely proportional to the corrosion rate [19,20], was
Berabond (Bego, Germany), Wiron 99 (Bego, Ger- obtained by applying the non-linear least squares
many), NiTi-8 (Giliga Co Ltd., USA), Talladium-P (NLLS)-fit technique [21] to the experimental EIS data.
(Talladium Inc., USA), and Titani (Jeneric/Pentron The number of specimens used for every EIS test
Inc., USA), which were designated as VB, BB, W99, condition was five. After the EIS measurements, the
NiTi8, TA, and TIT, respectively. All test specimens specimens were removed from the electrolyte, rinsed
represented solidification dendrites with a laminar with deionized water, and dried by nitrogen gas blasting.
eutectic structure after argon gas casting (Argoncaster- Then surface chemical compositions of passive film on
C, Shofu, Japan). Chemical compositions (in wt%) of the specimens were determined by using X-ray photo-
the NiCr-based casting alloys were reported elsewhere electron spectrometer (XPS) (ESCA 210, Kevex Instru-
[15] and listed as follows: VB/Ni–12.4Cr–4.9Mo–2.9Al– ment Inc., USA). The compositional depth profile of
1.6Be–0.4Co; BB/Ni–21.1Cr–8.42Mo–3.52Nb–1.0Fe– passive film was analyzed by using Auger electron
0.1Ti–0.07Al; W99/Ni–21.71Cr–8.28Mo–0.85Si–0.83Nb spectrometer (AES) (Microlab 310D, Kevex Instrument
–0.33Mn–0.01Al; NiTi8/Ni–13.68Cr–3.80Mo–3.63Ti–3.1Cu Inc., USA).
–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– 2.3. Potential decay test
2.43Al–0.25Ti–0.11Co. Casting specimens, with a di-
mension of 10 mm  10 mm  1 mm, were cold mounted As for potential decay tests, a potentiostat (AUTO-
with epoxy resin (Epofix Kit, Struers A/S, Denmark). 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 Table 1, the Rp of BB and W99 specimens was over
0.125 V (SCE) to the specimens for 2 h in the artificial 2 MO-cm2, while that of other NiCr-based specimens
saliva as used in the EIS measurements. In the mean- was less than 0.2 MO-cm2.
time, the current density was recorded as a function of
time. The final current density, namely the stable passive 3.2. Potential decay test
current density, was designated as Ipass ; and used to
evaluate the corrosion resistance of passive film. A lower Fig. 2(a) showed the variation of current density of
Ipass corresponded to a higher corrosion resistance of the different NiCr-based alloys under an applied passive
passive film. The time taken to reach Ipass was potential of 0.125 V (SCE) in the acidic artificial saliva
designated as tpass which was used to evaluate the as a function of time. A higher magnification of Fig. 2(a)
passivating rate of specimen. A lower tpass corresponded is shown in Fig. 2(b). The corresponding values of Ipass
to a higher passivating rate of specimen. Subsequently, and tpass are listed in Table 1. As shown in Fig. 2(a), for
the externally applied passive potential was removed, all specimens except BB and W99, the current density
and then the free potential, namely open circuit initially increased up to a critical value, then decreased
potential (OCP), was measured as a function of time. gradually to a stable value, Ipass : As shown in Table 1,
The OCP of specimens would immediately decrease the Ipass of BB and W99 specimens was around 0.2–
from the passive potential of 0.125 V (SCE) down to 0.3 mm/cm2, while that of other NiCr-based specimens
an actively stable value, designated as Eact : The time was over 2.5 mm/cm2. The tpass of BB and W99 speci-
taken to reach Eact was designated as tact which was used mens was around 2  103 s which was about half of that
to evaluate the passivity decay rate of passive film. A of other specimens.
larger tact corresponded to a higher stability of passive Fig. 3 showed the variation of OCP of different NiCr-
film. based alloys in the acidic artificial saliva as a function of
time after removing the applied passive potential of
2.4. Statistical analyses

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
TiT (less than 1 s) according to the data shown in Fig. 2(a).
Furthermore, the NiCr-based specimen had a significant
Ni
50 difference in the passivating rate (tpass ) (po0.001). The
Cr
Mo
tpass for all NiCr-based alloys used in this study was
40 O
around 2–4  103 s (Table 1). The fact that a lower Ipass ;
namely a higher corrosion resistance of passive film,
30
found for BB and W99 specimens with respect to the
others would be discussed later.
20
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
10
the earlier applied passive potential. The decreasing rate
of OCP, i.e. the passivity decay rate, depends on the
0
0 50 100 150 200 250 300 350 stability of passive film on the alloy. In this study, the
OCP of all NiCr-based alloys immediately decreased to
(f) Time (s) an active value when the applied passive potential of
Fig. 4 (continued). 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
As shown in Table 1, the Rp values for all specimens among all specimens (Table 1), the tact of BB and W99
were higher than 0.1 MO-cm2, even higher than 2 MO- specimens (B6  103 s) was around 10 times larger than
cm2 (e.g. BB and W99 specimens). For surgical implants that of other specimens (B3–7  102 s). In other words,
with very low corrosion rates, the Rp may reach 1 MO- when the externally applied passive potential was
cm2 [24]. In 0.9% NaCl solution, the Rp of commercially removed, which simulated the destruction of the passive
pure (CP) titanium and CoCrNiMo alloy is around 0.7 film on specimen, the BB and W99 specimens exhibited a
and 0.003 MO-cm2, respectively [25]. Pan et al. [26] lower passivity decay rate, i.e. a higher stability of
found that the Rp of titanium in phosphate-buffered passive film.
saline (PBS) solution is around 1 MO-cm2. Huang [22] The addition of Cr to alloys can improve the
also claimed that the Rp of CP titanium in acidic corrosion resistance of alloys in a corrosive environment
artificial saliva (pH 5) is close to 1 MO-cm2. Therefore, due to the formation of a Cr-rich, passive oxide film
the passive films formed on various NiCr-based alloys which is highly resistant to acid attack; the addition of
used in this study all exhibited an acceptable corrosion Mo to the NiCr-based alloy increases the resistance to
 H.H. Huang / Biomaterials 24 (2003) 1575–1582 1581

localized corrosion in the Cl 1-containing environment the alloy with sufficient protection, leading to the lowest
[27]. Therefore, for NiCr-based dental alloys, the corrosion resistance (in terms of Rp and Ipass ) and
addition of 12% Cr (minimum value) and 2–5% Mo passive film stability (in terms of tact ) for VB specimen as
to the alloy bulk is well recommended from the shown in Table 1. Similar results have been reported by
corrosion resistance point of view [28]. However, the other researchers [6,7,32]. Bumgardner et al. [6] reported
information concerning the surface characterization of that the presence of Be-containing oxide on the surface
passive film formed on NiCr-based alloys is still not well of NiCrMo alloy is associated with high corrosion rate
established. By comparing the results of XPS and AES and susceptibility to accelerated corrosion process.
analyses (Table 2 and Fig. 4), higher Cr (21–37 at%; Bumgardner and Lucas [7] claimed that the Be-contain-
mainly as Cr2O3) and Mo (2.5–11 at%; mainly as ing Ni-Cr alloys have non-uniform oxide surfaces. The
MoO3) contents were detected in the passive film on oxide surfaces of these alloys are more easily disrupted
BB and W99 specimens with respect to other specimens and provide little resistance to accelerated corrosion
(Cro20 at%; Moo10 at%). It was believed that a processes. Covington et al. [32] found that the outer
higher percentage of the protective Cr2O3 and MoO3 surface of NiCr-based alloy in aqueous solution is
in the passive film could lead to a higher transfer definitely enriched in Be (around 13–30 at%) as com-
resistance of metal ions through the passive film. This pared with the bulk composition (o2 at%). They
explained the fact that BB and W99 specimens exhibited suggested that the small atomic radius (0.31 A) ( of Be
much higher corrosion resistance (in terms of Rp and (
element with respect to Ni (0.69 A) and Cr (0.89 A) (
Ipass ), faster passivating rate (in terms of tpass ), and more elements will facilitate such migration until oxidation
stable passive film (in terms of tact ) than other speci- when further migration is impeded due to the increased
mens. size of the oxide. This might explain the fact that the Cr/
Furthermore, TIT specimen with approximately 16– Mo content was relatively depleted on the outermost
19 at% Cr and 1–10 at% Mo in the passive film did not surface of Be-containing VB specimen.
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 5. Conclusions
Cr2O3) in the passive film on NiCr-based alloy seemed
to play a more important role in the improvement of the The surface characterization of passive film formed on
passive film characterization with respect to Mo content NiCr-based dental casting alloys in the acidic artificial
(mainly as MoO3). saliva is ascribed to the chemical constituents. The
For general applications in dentistry, Ti has the passive films formed on different NiCr-based alloys have
ability to passivate by the formation of a protective statistically significant difference in the polarization
oxide layer, normally TiO2-based oxide, on metal resistance, stable passive current density, passivating
[29,30]. However, the optimal range of Ti in the passive rate, and passivity decay rate (po0.001). The polariza-
film on NiCr-based alloy is still unknown. In this study, tion resistance of the passive film with higher Cr2O3 (Cr:
small amount of Ti (o6 at%; mainly as TiO2) in the 21–37 at%) and MoO3 (Mo: 2.5–11 at%) contents is
Cr2O3/MoO3-containing passive film on NiTi8 specimen higher than 2 MO-cm2 which is more than 10 times
(Fig. 4(d)) did not show any improvement in the larger compared to that with lower Cr2O3 (Cro20 at%)
corrosion resistance and the stability of passive film and MoO3 (Moo10 at%) contents. The stable passive
(Table 1) though TiO2 is well documented to be a good current density of the passive film with a higher Cr2O3/
corrosion resistant compound. Therefore, further in- MoO3 content is around 0.2–0.3 mA/cm2 which is one
vestigation for finding an optimal Ti content in the order of magnitude less than that with a lower Cr2O3/
passive film on NiCr-based dental alloy is suggested to MoO3 content. The passive film with a higher Cr2O3/
improve the passive film characterization. MoO3 content exhibits a higher passivating rate, and is
On the other hand, the addition of Be to NiCr-based 10 times more stable, in terms of passivity decay rate,
alloys is mainly to improve the castability of the alloys than the lower Cr2O3/MoO3-containing passive film.
[31]. In this study, the outermost passive film on the Be- The presence of Be-rich (Be B20 at%; mainly as BeO)
containing VB specimen revealed a Be-rich (B20 at%; and Cr-Mo-depleted (Cr B2.5 at%; Mo B0 at%) zone
mainly as BeO) and Cr-Mo-depleted (Cr B2.5 at%; Mo on the outermost surface of passive film leads to a
B0 at%) zone (Fig. 4(a)), as compared with the dramatic decrease in corrosion resistance (in terms of
compositions in alloy bulk. This indicated that even polarization resistance and passive current density) and
small amount of Be (1.6 wt%) in the NiCr-based alloy stability (in terms of passivity decay rate) of the passive
bulk was sufficient to cause Be segregation in the surface film. The presence of small amount of TiO2 (Tio6 at%)
passive film. The Be-rich and Cr-Mo-depleted zone on in the passive film does not provide the passive film with
the outermost surface of VB specimen could not provide higher corrosion resistance and stability.
1582 H.H. Huang / Biomaterials 24 (2003) 1575–1582

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