Coll. Antropol. 27 Suppl.

2 (2003) 99106
UDC 616-74:615.465:616.314-089.27
Original scientific paper
Corrosion Behaviour of the Co-Cr-Mo
Dental Alloy in Solutions of Different
Composition and Different pH Values
Nives Rin~i}
1
, Ivo Bau~i}
2
, Slobodan Miko
3
, Milan Papi}
4
and Esad Prohi}
5
1
Public Health Center Centar, Zagreb, Croatia
2
Department of Prosthodontics, School of Dental Medicine, University of Zagreb, Zagreb,
Croatia
3
Institute of Geology, Zagreb, Croatia
4
Faculty of Practical Sciences, Split, Croatia
5
Faculty of Science, Zagreb, Croatia
A B S T R A C T
The purpose of this study was to examine how Co-Cr-Mo dental alloy behaves in the
solutions of different pH value and different composition over a relatively long period of
time. Co-Cr-Mo dental alloy was exposed in vitro to either simulated saliva (phosphate
buffer pH 6.0), a highly acidic medium resembling the extreme conditions in the oral
cavity (phosphate buffer pH 3.5), and in lactic acid at pH which occurs under the dental
plaque (lactic acid pH 3.5). The alloy samples were immersed in these three solution for
1, 2, 3, 4, 5, 6, 7, 14, 21, and 30 days. Solutions were analysed with the ICP-AES. The
analysis showed that during one month cobalt (Co), chromium (Cr), iron (Fe), zinc (Zn)
and nickel (Ni) ions had been released from tested samples in all three solutions. The re-
sults of this study indicate that the leaching of the Co, Cr, Fe, Zn and Ni ions in the solu-
tion was dependent both upon the nature of the solution in wich the alloy was immersed
and the duration of the immersion (p<0.001).
Key words: pH value, corrosion of Co-Cr-Mo alloy, time of exposure
Introduction
Dental alloys are in direct contact
with oral tissues and because of that they
must be completely biocompatible: biolog-
ically tolerant (without causing antigen-
-antibody reaction), biochemically indif-
ferent (remains unchanged in the body
without causing any effect on the organ-
ism), electrically and magnetically inert
99
Received for publication April 28, 2003
(without causing a galvanic current or
magnetic field)
1
.
As the price of gold significantly in-
creased in the 1970s, alternative cheaper
cobalt-chromium alloys came to dental
market
2
. Thanks to modern tehnology of
casting and polishing dental alloys, co-
balt-chromium alloys today are widely
used in prosthetic dentistry for the fabri-
cation of removable partial dentures and
also for the fabrication of some fixed pros-
thetic appliances. Advantages of using
these dental alloys for casting prosthetic
appliances are their low weight and good
mechanical properties, such as high
hardness, strength, resistance to tarnish
and high temperature and also resistance
to corrosion.
Many dental casting alloys which have
good mechanical properties, on the other
hand arent good enough from the aspect
of corrosion because of their complex
structure
2
. The materials employed in
the mouth must be completely tarnish-re-
sistant, they must not react with the
many alkaline and acid foods that are
taken into the mouth, and they must not
be affected by mouth fluids
3
. Organic ac-
ids, which are created after disintegra-
tion of food remains decrease pH value
inside the oral cavity and may have a
negative effect on ione release from den-
tal alloys.
Many recent studies showed that the
alternative alloys, which appeared on the
market as a result of the high price of
gold, release much more ions than the
conventional alloys with a high share of
gold
4,5
. Metal ions which are released
from dental alloys in the oral cavity can
lead to either toxic or allergic responses
6
.
Furthermore, they can be transferred to
distant organs, thereby causing different
changes
7
.
The purpose of this research was to
examine how Co-Cr-Mo alloy behaves in
the phosphate buffer at pH 6.0 and pH
3.5 and in the lactic acid at pH 3.5 as
wellas to establish the type and amount
of ions released from the alloy. Another
aim of this study was to establish the in-
fluence on ion release of the nature of the
solution and of the time period during
which the alloy was exposed to the solu-
tion.
Materials and Methods
Commercial samples of Co-Cr-Mo al-
loy (WIRONIT
R
, BEGO, Germany) which
came as standard rollers (8.0 mm in di-
ameter and 15.8 mm in height) were
tested. The declared metal composition of
the alloy is shown in Table 1. In order to
eliminate superficial impurity the sam-
ples were disinfected with alcohol and
then thoroughly washed twice with ster-
ile water. Subsequently the samples were
dried with sterile gauze.
The phosphate buffer at pH 6.0, which
was composed according to the estab-
lished pharmacopeial standards, was
used as the lowest pH of freshly collected
saliva. The phosphate buffer at pH 3.5,
also composed according to the estab-
lished pharmacopeial standards, was
used to test the resistance of alloy to re-
duced pH values under extreme condi-
tions. Lactic acid at pH 3.5, which came
as a mixture of 0.1 M lactic acid and 0.1
M sodium chloride with 0.1% acetic acid
and 1% formiatic acid, was used to repre-
sent the lowest end of pH under active
plaque in oral cavity (formiatic and acetic
acid are added in small quantities be-
cause of bacterial metabolism in dental
plaque).
Six samples of Co-Cr-Mo alloy (n = 6)
were immersed in every solution for ei-
ther 1, 2, 3, 4, 5, 6, 7, 14, 21 or 30 days, i.e.
a total of 180 samples were tested. The
samples were secured in 15 mL sterile
test tubes of very fine glass. 10 mL of
each solution was added to the test tubes
which were then sealed with plastic
100
N. Rin~i} et al.: Corrosion Behaviour of Dental Alloy, Coll. Antropol. 27 Suppl. 2 (2003) 99106
seals. The test tubes were marked and
placed into a thermostat at 37C to mimic
the temperature of the oral cavity envi-
ronment.
The type and amount of metal leached
into the solution was assessed with the
inductively coupled plasma atomic emis-
sion spectrophotomer (ICP-AES; JY 50 P,
Jobin Yvon, France). The electronic
equipment of the device ensured the mea-
surements of concentrations of each ele-
ment in one of five ranges of potencies
(for example either from 1 mg/L to 0.1
mg/L or between 1 mg/L and 100 g/L).
SPSS for Windows was used for statisti-
cal analysis and data presentation. The
overall difference between the solutions
and exposure time was assessed by
means of ANOVA.
Results and Discussion
Five types of metal ions were released
from the samples of Co-Cr-Mo alloy
which was examined in this research: co-
balt (Co), chromium (Cr), iron (Fe), nickel
(Ni) and zinc (Zn). The presence of these
ions was recorded in all solutions (phos-
phate buffer pH 3.5, phosphate buffer pH
6.0 and lactic acid pH 3.5). Most of the
principal declared metal constituents of
the Co-Cr-Mo dental alloy did not leach
into these solutions, whereas some of the
undeclared metals did leach in the
amounts well above their detection limit.
Thus, zinc, iron and nickel leached from
the Co-Cr-Mo alloy, whereas no traces of
molybdenum, silicium, manganese or car-
bon were detected regardeless of how
long the alloy was immersed in either of
the three solutions (Table 1). The results
of previous studies indicate that the ion
release from an alloy doesnt necessarily
correlate with the abundance of this ele-
ment in the alloy. There is a selective dis-
solution so that the elements that are
present in alloys only in traces can be re-
leased from them in larger amounts
8
.
Zinc, iron and chromium leached the
most when in phosphate buffer at pH 3.5
(reduced pH value under extreme condi-
tions, Figures 2, 4, 5), whereas cobalt
leached the most when in lactic acid at
pH 3.5 (lowest end of pH under active
plaque, Figure 1). During the initial pe-
riod of exposure the nickel ions were re-
leased in all three solutions in very small
amounts (10 mg/L) while increase in the
ion release was observed on the sixth day
in the phosphate buffer at pH 3.5. Signifi-
cant nickel ions release also occurred on
the 21
st
and 30
th
day in the phosphate
buffer at pH 6.0 (lowest pH of freshly col-
lected saliva) as well as in lactic acid at
pH 3.5 (Figure 3).
101
N. Rin~i} et al.: Corrosion Behaviour of Dental Alloy, Coll. Antropol. 27 Suppl. 2 (2003) 99106
TABLE 1
DECLARED COMPOSITION AND DETECTED METALS FROM
THE Co-Cr-Mo DENTAL ALLOY LEACHED IN VITRO
Metal Declared (%) Detected
Cobalt (Co) 64.0 Detected
Chromium (Cr) 28.65 Detected
Molybdenum (Mo) 5.0 Not detected
Silicium (Si) 1.0 Not detected
Manganese (Mn) 1.0 Not detected
Carbon (C) 0.5 Not detected
Zinc (Zn) Undeclared Detected
Iron (Fe) Undeclared Detected
Nickel (Ni) Undeclared Detected
Normally, Co, Cr, Fe, Ni and Zn are
present in small concentrations in the hu-
man body as trace elements. Although
sufficiently small concentrations of these
ions were recorded in this study, for some
elements (Ni and Cr) they exceeded the
favourable daily dietary intake
9,10
. The
results of most recent epidemiological
102
N. Rin~i} et al.: Corrosion Behaviour of Dental Alloy, Coll. Antropol. 27 Suppl. 2 (2003) 99106
Days of exposure
30 21 14 7 6 5 4 3 2 1
9
5
%
C
o
n
f
i
d
e
n
c
e
I
n
t
e
r
v
a
l
f
o
r
C
o
b
a
l
t
(
C
o
)
m
i
c
r
o
g
/
L
3000
2000
1000
0
-1000
Solution:
Phosph.Buffer pH 3.5
Phosph. Buffer pH 6
Lactic Acid pH 3.5
Fig. 1. Confidence interval (95%) for the release of cobalt (Co) ions into solutions of different
composition and pH values over different time periods.
Days of exposure
30 21 14 7 6 5 4 3 2 1
9
5
%
C
o
n
f
i
d
e
n
c
e
I
n
t
e
r
v
a
l
f
o
r
Z
i
n
c
(
Z
n
)
m
i
c
r
o
g
/
L
1200
1000
800
600
400
200
0
-200
Solution:
Phosph.Buffer pH 3.5
Phosph. Buffer pH 6
Lactic Acid pH 3.5
Fig. 2. Confidence interval (95%) for the release of zinc (Zn) ions into solutions of different
composition and pH values over different time periods.
studies indicate to the fact that cobalt,
chromium and nickel, which are released
from dental alloys, are metals which most
often produce allergic responses
11
. Patch
testing has been carried out on a large
number of patients, subsequently result-
ing in positive reactions to some compo-
nents of dental alloys, particularly to
103
N. Rin~i} et al.: Corrosion Behaviour of Dental Alloy, Coll. Antropol. 27 Suppl. 2 (2003) 99106
Days of exposure
30 21 14 7 6 5 4 3 2 1
9
5
%
C
o
n
f
i
d
e
n
c
e
I
n
t
e
r
v
a
l
f
o
r
N
i
c
k
e
l
(
N
i
)
m
i
c
r
o
g
/
L400
300
200
100
0
-100
Solution:
Phosph.Buffer pH 3.5
Phosph. Buffer pH 6
Lactic Acid pH 3.5
Fig. 3. Confidence interval (95%) for the release of nickel (Ni) ions into solutions of different
composition and pH values over different time periods.
Days of exposure
30 21 14 7 6 5 4 3 2 1
9
5
%
C
o
n
f
i
d
e
n
c
e
I
n
t
e
r
v
a
l
f
o
r
I
r
o
n
(
F
e
)
m
i
c
r
o
g
/
L
2000
1000
0
-1000
Solution:
Phosph.Buffer pH 3.5
Phosph. Buffer pH 6
Lactic Acid pH 3.5
Fig. 4. Confidence interval (95%) for the release of iron (Fe) ions into solutions of different
composition and pH values over different time periods.
those containing nickel and chromium
12
.
Allenby and Goodwin determined that
the rate of 112 ppm of Ni (<0.05%
nickal-sulfat) was needed to obtain a pos-
itive allergic reaction
13
. Peltonen noted
that women were ten times more sensi-
tive to Ni compared to men
14
. In 1984 the
ADA workshop on the biocompatibility of
metals in dentistry stated that sensitivity
to chromium results from contact with
chromate salts, which result from the cor-
rosion of such alloys
15
. Experimental
studies of chromium carcinogenesis in
animals have been extensively investi-
gated. As a trivalent ion, chromium ap-
pears to be of great biologic value and
merit, forming part of the glucose toler-
ance factor. As a hexavalent ion, chro-
mium can penetrate cells easily and is
known to be a potent mutagenic and car-
cinogenic agent at low concentrations
16
.
The leaching of metal ions from the
tested Co-Cr-Mo alloy in the solution was
dependent both upon the nature of the so-
lution where the alloy was immersed and
the duration of the immersion.
Multivariate analysis of variance re-
vealed the time and solution (pH) related
significant difference for each of the reg-
istered metal ions (Co, Cr, Zn, Fe, Ni) re-
lease (p<0.001). The concentrations of all
recorded ions increased slowly during the
time of exposure. Some studies which ex-
amined the ion release from different al-
loys over several months, showed that
the amount of released ions was high at
the beginning of the examination. After a
proper time, a balance was established
with linear ion release in relation to
time
17
.
New dental materials for clinical use
are considered as medical devices and
have to meet stringent safety and efficacy
requirements. Dental alloys for cast res-
torations are of concern where materials
remain in constant contact with living
tissues. The American National Standard
Institute (ANSI) / American Dental Asso-
ciation (ADA) provides guidelines to ex-
amine safety and biocompatibility of new
dental alloys for cast restorations
18
.
104
N. Rin~i} et al.: Corrosion Behaviour of Dental Alloy, Coll. Antropol. 27 Suppl. 2 (2003) 99106
Days of exposure
30 21 14 7 6 5 4 3 2 1
9
5
%
C
o
n
f
i
d
e
n
c
e
I
n
t
e
r
v
a
l
-
C
h
r
o
m
i
u
m
(
C
r
)
m
i
c
r
o
g
/
L
1000
800
600
400
200
0
-200
Solution:
Phosph.Buffer pH 3.5
Phosph. Buffer pH 6
Lactic Acid pH 3.5
Days of exposure
Fig. 5. Confidence interval (95%) for the release of chromium (Cr) ions into solutions of different
composition and pH values over different time periods.
Ion release, as recorded in this study,
showed that some metal ions could be de-
tected from the examined alloy, although
they are not declared by the manufac-
turer in all examined pH values (pH 3.5,
as well a in pH 6)
1921
. All detected ele-
ments are fortunatelly esential and are
usually lacking in the dict of old
people
9,10
. Concentration of Ni and Cr ex-
ceeded favourable daily intake, but were
far bellow toxic limits. Their allergogenic
potential must also be considered. Today,
the knowledge of biocompatibility of dif-
ferent metal ions in dental alloys is fun-
damentally important to ensure the
health od patients.
R E F E R E N C E S
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PHILLIPS, R.W., E.W. SKINNER: Elements of dental
materials (W.B. Saunders, Philadelphia, London,
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R. MLLER, W. DORN, J. VORMANN, S. ANKE, J.
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frequency of allergy against dental materials. Ab-
stract 19, In: Procceedings. (International Congress
on Biomaterials in Stomatology, Pretoria, South Af-
rica, 1981). 12. DOOMS-GOOSSENS, A., A.
CEUTERICK, N. VANMAELE, H. DEGREEF, Der-
matologica 160 (1980) 249. 13. ALLENBY, C.F.,
B.F. GOODWIN, Cont. Derm., 9 (1983) 491. 14.
PELTONEN, L., Cont. Derm., 5 (1979) 27. 15. Na-
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Assoc., 109 (1985) 469. 16. ROE, F.J.C., R.L. CA-
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Nives Rin~i}
Nova cesta 134, 10000 Zagreb, Croatia
KOROZIJSKO PONA{ANJE Co-Cr-Mo SLITINE U OTOPINAMA
RAZLI~ITOG SASTAVA I RAZLI~ITIH PH VRIJEDNOSTI
S A @ E T A K
Svrha ovog rada bila je ispitati pona{anje Co-Cr-Mo slitine u otopinama razli~ite pH
vrijednosti i razli~itog sastava kroz dulje vremensko razdoblje. Co-Cr-Mo slitina in vi-
tro je bila izlo`ena otopini koja je opona{ala ljudsku slinu (fosfatni pufer pH 6.0),
kiseloj otopini koja je opona{ala ekstremne uvjete u usnoj {upljini (fosfatni pufer pH
3.5) i otopini mlije~ne kiseline ~ija pH vrijednosti odgovara uvjetima koji nastaju ispod
dentobakterijskog plaka (mlije~na kiselina pH 3.5). Uzorci ispitivane slitine uronjeni
su u odgovaraju}e otopine kroz 1, 2, 3, 4, 5, 6, 7, 14, 21 i 30 dana. Otopine su
105
N. Rin~i} et al.: Corrosion Behaviour of Dental Alloy, Coll. Antropol. 27 Suppl. 2 (2003) 99106
analizirane pomo}u ICP-AES. Analiza je pokazala da su se tijekom mjesec dana iz
ispitivanih uzoraka slitine otpustili ioni kobalta (Co), kroma (Cr), `eljeza (Fe), cinka
(Zn) i nikla (Ni) i to u sve tri otopine. Rezultati ovog ispitivanja ukazuju na to da
otpu{tanje iona Co, Cr, Fe, Zn i Ni ovisi o sastavu otopine kojoj je slitina bila izlo`ena,
te o vremenu kroz koje je slitina bila izlo`ena otopini (p<0.001).
Klju~ne rije~i: pH vrijednost, korozija CoCrMo legure, vrijeme ekspozicije
106
N. Rin~i} et al.: Corrosion Behaviour of Dental Alloy, Coll. Antropol. 27 Suppl. 2 (2003) 99106