Chapter 7

Galvanic Corrosion Behavior of Dental Alloys

Hamoon Zohdi, Mohammad Emami and
Hamid Reza Shahverdi
Additional information is available at the end of the chapter
http://dx.doi.org/10.5772/52319
1. Introduction
There is a wide variety of dental alloys, ranging from nearly pure gold and conventional
gold-based alloys to alloys based on silver, palladium, nickel, cobalt, iron, titanium, tin, and
other metals (Table 1). The types of dental alloys have increased significantly since 1980s in
order to change the market price of gold and palladium. Although gold alloys are the mate
rials of choice in this area because of their high mechanical properties, good corrosion resist
ance and excellent biocompatibility, their price still poses the essential challenge to
dentistry. So that, alternative materials such as Ag-Pd alloys, Co-Cr alloys and Ti alloys
have been introduced into dentistry [1,2].
Alloy type Uses in dentistry Major elements
Gold-based Restorations, solders Au, Ag, Cu, In, Pd, Pt, Zn
Palladium-based Restorations Pd, Ag, Ga, Cu
Silver-based Restorations, solders Ag, Pd
Cobalt-based Restorations Co, Cr, Mo, Fe, C, Si, Mn
Nickel-based Restorations, orthodontic materials Ni, Mo, Fe, C, Be, Mn
Titanium-based Implants Ti, O, N, C, Fe, H
Iron-based Implants, orthodontic materials Fe, C, Ni, Cr
Mercury-based Amalgam Hg, Ag, Sn, Pd, Cu, In
Table 1. Common types of alloys in dentistry and their major component elements [1]
2012 Zohdi et al.; licensee InTech. This is an open access article distributed under the terms of the Creative
Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,
distribution, and reproduction in any medium, provided the original work is properly cited.
Dental alloys can be classified into a variety of applications such as restorations, amalgam,
implants, solders and orthodontic materials. The used alloys should have suitable physical,
mechanical and chemical properties for mentioned applications. For example, an orthodon
tic wire is required to have a relatively high flexibility (a low modulus) and the ability to be
bent and shaped. However, the alloy for a dental restoration should have almost no flexibili
ty (a high modulus) and be hard and difficult to deform.
Biocompatibility is an important measuring property which should be evaluated first. The
word biocompatibility is defined as the ability of a material to perform with an appropriate
host response in a specific situation [3]. Although the biological compatibility of dental al
loys inclined to be considered separately from the other properties, biocompatibility is rath
er related to other properties of the alloys such as corrosion resistance which is estimated by
measuring the release of the corrosion products themselves. The higher the corrosion rate of
the alloy, the greater the metal ion release and the greater the risk of undesirable reactions in
the mouth. These reactions may include unpleasant metallic tastes, allergy, irritation or an
other reaction. Since the release of metal ions depends on electrochemical rules, many efforts
have been made to evaluate the biocompatibility of dental alloys via electrochemical analy
ses [1, 4, 5].
As was mentioned earlier, the corrosion behavior of dental materials is important because
poor biocompatibility of the products may render the materials inappropriate for implanta
tion. In general, the word corrosion stands for material or metal deterioration or surface
damage in an aggressive environment. The oral environment is also favorable for corrosion
in which the metal is attacked by presence of natural agents (air and water), temperature
fluctuations (hot and cold meals) and pH changes because of diet (milk products or orange
juice), resulting in partial or complete dissolution, deterioration, or weakening of any solid
substance [4, 6]
One of the problems associated with the use of metallic materials in dentistry is the proba
bility of galvanic corrosion [2, 4, 7-10]. Generally, galvanic corrosion is either a chemical or
an electrochemical corrosion. This phenomenon is attributed to a potential difference be
tween two different metals connected through a circuit for current flow to occur from more
active metal (more negative potential) to the more noble metal (more positive potential). In
addition, galvanic corrosion is a very complex phenomenon. Six basic factors are involved in
galvanic corrosion: (1) potentials, (2) polarization, (3) electrode areas, (4) resistance and gal
vanic current, (5) the electrolyte medium, (6) aeration, diffusion and agitation of the electro
lyte [11]. Galvanic coupling is a galvanic cell in which the more negative metal (anode) is the
less corrosion resistant metal than the more positive metal (cathode) [12]. The resulting gal
vanic couple achieves a mixed potential that reaches between the corrosion potentials of the
uncoupled metals (Fig. 1). Due to mutual polarization, the anodic corrosion rate of the
anode will be accelerated, while the anodic rate of the cathode will be reduced [10].
In dentistry application, galvanic corrosion occurs when two or more dental prosthetic devi
ces with dissimilar alloys come into contact while subjected to oral liquids like salvia; the
difference between the corrosion potentials results in a flow of electric current between
them. Therefore, the galvanic cell is formed and causes the increasing corrosion rate of the
Environmental and Industrial Corrosion - Practical and Theoretical Aspects 158
anode and enhancing the amount of ion metal released. The galvanic current passes not only
through the metal/metal connections, but also through the tissues, which may cause pain.
Galvanic currents in the oral environment may cause sharp pain when they exceed 20 mA
[13]. Geis-Gerstorfer et al. [14] believes that the galvanic corrosion of dental devices is im
portant in two respects: 1) the biological effects which may result from the dissolution of al
loys and 2) the current flow resulting from galvanic cell that could cause bone destruction.
The galvanic corrosion may be started due to the interaction of prosthetic devices. For exam
ple, a restoration or prosthesis in physical contact with amalgam in an adjacent tooth or be
tween dental implants, fillings or crowns [9].
Figure 1. Schematic of data acquired during continuous potential measurement [8].
2. Methods
The measurement of the biocompatibility of dental alloys is a complicated issue. However,
tests for biocompatibility assessment are classified as either in vitro or in vivo tests. In vitro
tests are performed outside a living organism, while in vivo tests are conducted in an ani
mals body. In vitro tests are the cheapest and fastest of the biocompatibility tests, but be
cause they are not performed in a living system, their significance is often subjected.
Conversely, in vivo tests are more informative than in vitro due to the fact that the device is
subjected to all dimensions of the biological response, but they are also expensive and high
ly complex to control and interpret.
In addition, biocompatibility is relatively related to other properties of the alloys such as
corrosion having a direct relationship with the release of metal ions. The presence of metal
Galvanic Corrosion Behavior of Dental Alloys
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159
ions in the body may cause various phenomena such as transportation, metabolism, allergy,
carcinoma and accumulation in organs. Therefore, measuring the metal ion release of bio
materials (dental alloys) is important as well as other biocompatibility tests, which is done
by methods like atomic absorption spectroscopy, inductively coupled plasma mass spectro
scopy, or X-ray fluorescence spectroscopy.
Moreover, since the release of metal ions depends on electrochemical rules, many efforts
made to evaluate the biocompatibility of dental alloys by corrosion tests in in vitro and in
vivo studies. For this specific case, as was discussed earlier, galvanic corrosion can enhance
the corrosion rate of the anode resulting in high amount of metal ion released. Zero Resist
ance Ammetry is the main method used to evaluate galvanic corrosion behavior of dental
alloys; with ZRA probes, two electrodes of dissimilar metals are exposed to the process flu
id. When immersed in solution, a natural voltage (potential) difference exits between the
electrodes. The current generated due to this potential difference relates to the rate of corro
sion which is occurring on the more active of the electrode couple. A schematic of the exper
imental setup is shown in Fig. 2. Besides, the measurement of currents and potentials in
galvanic couple or uncoupled electrodes has been made to obtain more information. More
over, the electrochemical corrosion tests like open circuit potential, cyclic and linear polari
zation, potentiostatic polarization or electrochemical impedance spectroscopy (EIS) have
been developed for many years to estimate the degree of corrosion on dental alloys by meas
uring the current flow during the corrosion process, or change in potential of the alloy rela
tive to some standard.
Figure 2. Schematic diagram for the galvanic cell set-up [8].
Environmental and Industrial Corrosion - Practical and Theoretical Aspects 160
3. In vitro and in vivo tests
The aim of this section is to evaluate and compare, in vitro and in vivo, the galvanic corro
sion behavior of dental alloys such as restorations, amalgam, implants or orthodontic mate
rials when they are used in a mouth at the same time. It was indicated in the previous
section that the simultaneous using of these devices can cause some biologic problems due
to the galvanic corrosion effect.
Nowadays, titanium and titanium alloys are widely used in odontology because of their ex
cellent characteristics such as good mechanical behavior, low density, high corrosion resist
ance in body fluids and excellent biocompatibility. The high biocompatibility of these alloys
is attributed to the formation of the passive film (TiO
2
) on the surface, which is highly pro
tective. As these alloy implants and prosthetic devices become more common, the galvanic
interaction with other metallic materials may become an issue [9, 11, 15, 16]. Studies of gal
vanic cells of titanium with dental alloys indicated either almost no interaction, or very
small galvanic currents [11, 15, 17]. R. Venugopalan and L. C. Lucas [8] used continuous cor
rosion potential monitoring in coincidence with Zero Resistance Ammetry to achieve gal
vanic corrosion properties of restorative and implant materials coupled with titanium. All
tests were carried out in artificial salvia solution. The composition of the electrolyte is shown
in Table 2. They found that noble restorative (Au-, Ag-, and Pd-based) alloys coupled to tita
nium are least susceptible to galvanic corrosion, while the NiCrBe alloy showed unstable
galvanic corrosion behavior. Also findings of N. M. Taher and A. S. Al Jabab [2] indicated
that the highest galvanic corrosion resistant alloys coupled with titanium implant abutment
material were Pontallor (Au-based), Ternary Ti, R800 (Co-Cr alloy) and Jelstar (Ag-Pd alloy),
respectively. But, RCS (NiCr) alloy was found to be highly susceptible to galvanic corro
sion, which is in accordance with former study. In general, it should be mentioned that tita
nium was anodic to noble alloys and cathodic to iron and nickel-based passivating alloys. It
is also worth noting that other researchers could obtain relatively similar results [11, 18].
Compound Composition (g/dm
3
)
K
2
HPO
4
0.20
KCl 1.20
KSCN 0.33
Na
2
HPO
4
0.26
NaCl 0.70
NaHCO
3
1.50
Urea 1.50
Lactic acid Up to pH = 6.7
Table 2. Chemical composition of the artificial salvia
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Dental amalgams are still the most common metallic direct filling materials. However, be
cause of mercury toxicity, low-mercury and mercury-free gallium-based direct filling alloys
have been developed in recent years. Both dental amalgams and gallium-based filling alloys
are passivating materials with less protective passive film in comparison with titanium or
most other passivating dental alloys. Researchers [9, 19] have considered the galvanic inter
action between titanium and direct filling alloys like gallium and variety of copper contain
ing amalgams. They reported that the galvanic interaction between titanium and direct
filling alloys is small. The gallium alloy was the most sensitive to galvanic corrosion among
the samples when in contact with titanium, which is ascribed to relatively poor corrosion re
sistance of gallium alloys [20]. It was shown that the galvanic corrosion resistance of men
tioned alloys coupled to Ti from the highest to lowest are as follows: High copper dental
amalgam > Low copper dental amalgam > Gallium-based direct filling.
Nitinol (Nickel titanium) is a very attractive material for use as an orthodontic wire due to
its unique shape memory and superelasticity properties. Researchers evaluated the galvanic
corrosion of these orthodontic wires with dental alloys in artificial saliva. They found that
placing stainless steel brackets or Aristaloy (Ag-Cu-Sn ) amalgam in direct contact to nitinol
arch wire is not recommended, because it causes enhanced corrosion rate of nitinol arch
wire. They also suggested that using ceramic brackets instead of stainless steel brackets
could help to get rid of the occurrence of galvanic corrosion [21].
Another group of metals used in dentistry is chromium based alloys. Ciszewski et al. [4] in
vestigated the galvanic corrosion behavior of Remanium GM 380 (chromiumcobalt alloy)
and Remanium CS (chromiumnickel alloy) when bound together or coupled with Amalcap
plus (silver-based amalgam) in an artificial saliva solution at 37C. It was found that a bi
metallic cell consisting of Remanium CS and Remanium GM 380 alloys has a very low EMF
(electromotive force) which is not a potential source of galvanic currents in the oral cavity.
Conversely, galvanic cells prepared from Amalcap plus and Remanium CS or Remanium
GM 380 showed a much greater EMF. This obviously showed that in these latter it is possi
ble to expect some metal ions in the saliva solution as a result of galvanic currents. They also
indicated that even elements from a cathode specimen of a galvanic cell are able to dissolve
into the solution. These results, from an electrochemical point of view, are surprising.
Since in vivo tests are generally expensive, time consuming, controversial and complex to
study, there are few reports on the galvanic corrosion behavior of dental devices in a living
organism. Most researchers have performed an indirect measuring technique to determine
in vivo galvanic currents of dental alloys [22-24]. Palaghias et al. [25] investigated in vivo
behavior of gold-plated stainless steel titanium dental retention pins and showed that in
vivo corrosion resistance of the titanium pins was superior to that of gold-plated stainless
steel pins. Besides, Nilner et al. [26] found that gold-gold couples have lower galvanic cur
rents than those of amalgam-amalgam and amalgam-gold couples; they indicated that gal
vanic currents for the couples are generally below 15 mA, which is below the threshold of
pain (20 mA) [13]. It should be mentioned that the galvanic corrosion behavior of dental al
loys is expected to fluctuate over time due to various factors, including changes in the pH
and composition of saliva, disruption of the alloys passive film due to chewing, and aging
Environmental and Industrial Corrosion - Practical and Theoretical Aspects 162
of the restoration. Changes may also take place because of thermal and mechanical stresses
[10, 27, 28]. As a result, it is concluded that the interpretation of this type of test is so compli
cated and needs more time to investigate.
4. Parameters affect galvanic corrosion
One of the important factors affecting the galvanic corrosion is the surface area ratio of the
two dissimilar alloys (cathode/anode). An unfavorable area ratio, which consists of a large
cathode and small anode, may cause a higher corrosion [12]. Reports showed that the gal
vanic potential and current density increased with the increasing Ti/alloy area ratio, where
Ti plays the role of cathode. Therefore, the higher galvanic corrosion occurred [9, 29]. Be
sides, reducing the surface area of the anode by 75 percent increases the galvanic activity of
stainless steel/nitinol couple [30]. However, Iijima et al. found that the different anodic/
cathodic area ratios (1:1, 1:2.35, and 1:3.64) had little effect on galvanic corrosion behavior of
stainless steels and titanium bracket alloys coupled with four common wire alloys: nickel-
titanium alloy, -titanium alloy, stainless steel and cobalt-chromium-nickel alloy [31].
Fluoride is well known as an effective caries prophylactic agent and its systemic applica
tion has been recommended widely over recent decades to be the main method for pre
venting plaque formation and dental caries. Toothpastes, mouthwashes, and prophylactic
gels contain from 200 to 20,000 ppm F(-) and can impair the corrosion resistance of den
tal alloys in the oral cavity [32, 33]. Anwar et al. [34] considered the effect of fluoride
ion concentration on the corrosion behavior of Ti and Ti6Al4V implant alloys, when cou
pled with either metal/ceramic or all-ceramic superstructures. It was shown that in
creased fluoride concentration leads to a decrease in the corrosion resistance of all tested
couples. Moreover, findings of Johansson and Bergman showed that adding fluoride to
the solution made the titanium potential more active and enhanced the corrosion of tita
nium in combination with high-copper amalgams [29]. In fact, authors have exhibited
that increase in concentration of NaF (fluoride ion) decreases the corrosion resistance of
NiTi arch wires [35, 36] and titanium implants in different solutions [37, 38]. It is also
demonstrated that the combination of low pH and presence of fluoride ions in solution
severely affect the breakdown of the protective passivation layer that normally exists on
nitinol and titanium alloys, leading to pitting corrosion [39, 40, 41].
Another parameter which could affect galvanic current is the initiation of localized corro
sion (pitting and crevice corrosion). Mastication and other food contents (such as chloride
ions) may initiate localized corrosion of dental alloys. This type of corrosion once initiated
the corrosion current density and therefore the galvanic current increase. The presence of
pitting on Nitinol arch wire harshly increases the galvanic corrosion rate of the anode,
which indicates that dentists and researchers should be aware of other types of corrosion as
well as galvanic one to investigate dental alloys appropriately. It was also mentioned that,
initiation of localized corrosion on anode increased the galvanic current by up to 45 times
revealing that consideration of the effect of localized corrosion on galvanic corrosion is nec
essary [21].
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5. Preventing galvanic corrosion
According to the published literature and experimental results, the set-up for an acceptable
couple combination in the mouth environment could be defined as the following: (1) the dif
ference in E
o.c.
of the two materials and the I
couplecorr
should be as small as possible; (2) the
E
couplecorr
of the couple combination should be significantly lower than the breakdown poten
tial of the anodic component and (3) the repassivation properties of the anodic component
of the couple should also be acceptable [8]. Besides, the use of some special composites, ce
ramics and metallic glasses can improve galvanic corrosion behavior of dental alloys. Metal
lic glasses, called also glassy or amorphous metals are rapidly quenched alloys explained as
a metastable class of materials with no long range periodic lattice structure. These alloys are
considered to be the materials of future [42, 43]. J.-J. Oak et al. [44, 45] developed new Ti-
based bulk metallic glassy (BMG) alloys for application as biomaterials. Ti-based amor
phous alloys containing no harmful elements (Ni, Al, Be) are expected to exhibit high
potential for dental materials. The Ti-based amorphous ribbons exhibited good bend ductili
ty, higher strength and lower Young's modulus than pure Ti and Ti6Al4V alloy. In addi
tion, Ti-based amorphous alloys had an excellent potentiality of corrosion resistance that
were passivated in wide passive range and at the lower passive current density in simulated
body fluid conditions. It is demonstrated that the Ti
44.1
Zr
9.8
Pd
9.8
Cu
30.38
Sn
3.92
Nb
2
bulk glassy al
loy has a high potentiality to be applied in dental implant devices. These materials can be
applied as coatings on the amalgams or restorative alloys to improve corrosion resistance of
substrates.
6. Summary
In this review, we have highlighted comprehensive study of galvanic corrosion behavior of
dental alloys. The titanium /titanium alloys, gold, silver-palladium and cobalt-chromium are
main classes of alloys widely used as dental implants. In general, although they have excep
tional properties which make them ideal for corrosion and wear resistance dental applica
tions, it has been reported that failures of some implants are due to the galvanic-type
corrosion. The galvanic current passes through the metal/metal junctions, which may finally
cause pain owing to release of metal ions. The oral environment is particularly favorable for
corrosion. The corrosive process is mainly of an electrochemical nature and natural saliva
presents a good electrolyte. Fluctuations in temperature (hot and cold meals), changes in pH
because of diet (milk products or acid dressings), and decomposition of food all contribute
to the process. It is also mentioned that the parameters like the surface area ratio of the two
dissimilar alloys, pH and the presence of fluoride could severely affect galvanic corrosion.
To measure galvanic corrosion, researchers have investigated direct coupling or galvanic ex
periments which are conducted on restorative and implant materials coupled to another
dental device like amalgam. They launched a comparative assessment of the electrochemical
measurements attained using different methods and different preparation to study this type
of corrosion. Zero Resistance Ammetry is the main method used to evaluate galvanic corro
Environmental and Industrial Corrosion - Practical and Theoretical Aspects 164
sion behavior of dental alloys in in vitro and in vivo. Besides, in this review, it is shown that
new types of prosthesis/implants like metallic glasses (ribbons) could be applied as new
generation of implants with excellent corrosion properties. These materials can be applied as
coatings on the dental alloys to improve corrosion resistance of substrates.
Author details
Hamoon Zohdi, Mohammad Emami and Hamid Reza Shahverdi
*
*Address all correspondence to: [email protected]
Department of Materials Engineering, Tarbiat Modares University, Tehran, Iran
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