Galvanic Corrosion of Dental Alloys

Galvanic Corrosion of Dental Alloys Summary A combination of two or more dental alloys in the oral environment can react and form diverse compounds, which could lead to oral problems. Corrosion is one of the phenomena occurring in the oral environment. An understanding of galvanic corrosion, enables the choice of alloys to be used in combination with each other to be better evaluated, especially when used for suprastructures on titanium implants. Galvanic corrosion is an accelerated corrosion which is induced when different metals come into contact in a corrosive medium. The electrical current induced by corrosion, or the quantity of released metallic ions can be measured to quantify the alloys resistance to corrosion under different conditions. Galvanic corrosion tests were conducted on the alloys Implantalloy 1, Implantalloy 2 and Implantalloy 3 coupled with Grade 2 and Grade 5 Titanium, the material used primarily for implants. For the three alloys tested, ion release in the oral cavity is well below the accepted limit and the galvanic corrosion is negligible. Implantalloy 1, Implantalloy 2 and Implantalloy 3 can be recommended for constructions on titanium implants.

Introduction
In the oral environment, all materials (ceramics, metals, alloys, cement) can react with the saliva and form different metallic, organic or mineral compounds. Saliva is more or less aggressive in relation to its composition and its pH, which varies during the day and from patient to patient. Depending on the compound released and its quantity, adverse biological reactions can be induced. The fact that oral problems such as gingival swelling and erythema, mucosal pain and lichenoid reaction can be caused due to the degradation of materials used orally is not clearly proved [1, 2]. In order to minimize risks, it is indispensable to use highly corrosion-resistant materials for oral applications. Generally, precious metal alloys have a higher resistance to corrosion than non-precious metal alloys [3]. To know the resistance to corrosion of dental alloys is all the more essential whether different alloys are used to make the dental restoration because the corrosion can be amplified if the materials in direct contact are not correctly chosen. Galvanic corrosion can occur. The objective of this paper is to provide some technical knowledge about galvanic corrosion in order to choose the alloys that are least prone to galvanic corrosion especially when they are used on Titanium implants. Numerous parameters such as the surface condition, surface area ratio and the corrosive media all influence the corrosion speed. Through different examples of coupling, their influence will be shown. The results of galvanic tests will be presented for the three alloys (Implantalloy 1, 2 and 3) and Titanium samples. Titanium was chosen due to its predominant use in Implantology. The concentrations of impurities Carbon and Oxygen, which are the differentiating factors of the four grades of pure Titanium, only influence the mechanical properties of Titanium but have no notable influence on their resistance to corrosion. Thus, pure Titanium grade 2 was used for the experiments and an usual Titanium alloy, Titanium grade 5. All the values of galvanic current density were measured using a Voltalab Model 21 (Radiometer Analytical) potentiometer/ galvanometer and the Evans diagrams method.

Without coupling M1n+ M1n+ M2n+ M2n+

M1n+ M1 ERest M1

M2n+ M2 ERest M2 Conductive media

With coupling M1n+

M1n+ M1 EMixed M2 EMixed Conductive media

Anodic behaviour

Cathodic behaviour

ERest M1 < EMixed < ERest M2

Accelerated corrosion for M1 Figure 1: Corrosion and Galvanic corrosion between two metals

Definition
Corrosion affects all materials and induces dissolution of materials, more or less significantly according to their resistance to corrosion. Galvanic corrosion is not a natural corrosion, but an accelerated corrosion induced when metallic materials, not having a similar resistance to corrosion are placed in contact in a corrosive media. The material which is the least resistant will be more corroded because it is submitted to a higher electrical potential than its characteristic

electrical potential. Indeed, when a metallic material is immersed in a conductive media, it is possible to measure its electrical potential. This potential has different names as Rest potential (ERest), Open Circuit potential or potential of corrosion. When metallic materials are coupled in a conductive media, they have all the same electrical potential named the Mixed potential (EMix). This potential is different to the Rest potential of material alone. A schematic drawing is represented in Figure 1. If the material M1 has a Rest potential ERest M1 lower than the Rest potential of the material M2, then when they are in direct contact, M1 will exhibit anodic behaviour. The material M1 will be corroded and will release more metallic ions in presence of M2 than alone.

Multiple reconstructions

Mesial/distal contact Single reconstructions

Opposing dentition

Different alloys within the same reconstruction and titanium implants Figure 2: Examples of galvanic corrosion in oral environment

Some examples of galvanic corrosion in mouth

In the oral environment it is the saliva which is responsible for the degradation of materials. Galvanic corrosion can occur in different cases such as when two casting crowns with different alloys are in direct contact or when non resistant to corrosion materials are used in combination with titanium implants. Some examples are represented in Figure 2.

It is clear that the Rest potential value must be measured in the same operating conditions (media, reference electrode, pH, Temperature). In the Figure 3, the Rest potentials of different types of alloys are shown. On the left of the figure, the Rest potential values are given in the same conditions as described in the ISO Standard. Before immersion in the corrosive solution of Sodium chloride, each sample is polished in order to have a reproducible surface state. The Rest potential is recorded after two hours of immersion. The Rest potential of Titanium is negative, comparable to the Rest potential of non precious alloys because Titanium is not covered by its protective oxide layer. After polishing and in this very corrosive media, the natural formation of Titanium oxides is difficult. The Rest potentials of precious metals alloys are the highest, meaning they are very resistant to corrosion. On the right of the figure, after some days of immersion, the Rest potentials of all materials are stable. The Rest potential of Titanium is comparable to the Rest potentials of precious metals alloys. Once covered by its natural oxide layer, Titanium is very resistant to corrosion. On the other hand, some non precious alloys do not have an adapted composition to form a protective oxide layer. Their Rest potentials stay very negative. They are not resistant to corrosion. As the media is very corrosive, it is possible to consider that this scale of Rest potentials is similar in mouth in the worst oral conditions.

Compatible materials versus Rest potential

Galvanic corrosion only occurs when the materials put in direct contact do not have a comparable resistance to corrosion. Thereby, it is important to know the resistance to corrosion of materials alone before coupling them. The corrosion tests proposed in the ISO 10271 Standard [4] for the dental alloys are very useful to judge the resistance to corrosion of materials. In this standard, the Rest potential for each alloy is recorded for two hours. In a first approach, this value of Rest potential for each alloy used is essential to forecast galvanic corrosion. The greater the difference between the Rest potentials of the coupled metallic material is, the more significant the galvanic corrosion. Thereby, it is important to choose materials having similar Rest potentials.

Rest potential after 2 hours of immersion

Rest potential after 3 days ERest / SCE

200 mV

ERest / SCE Precious dental alloys Titanium Formation of an oxide layer for Titanium and some non precious metal alloys

200 mV

Precious dental alloys

Deaerated solution: NaCl 9 g/l pH= 7.3, ISO 10271 Standard Samples are initially polished

100 mV

100 mV Some CoCr, NiCr dental alloys 0 mV

0 mV

-100 mV CoCr dental alloys -200 mV Titanium -300 mV NiCr dental alloys

-100 mV Some CoCr dental alloys -200 mV Some NiCr dental alloys

-300 mV

-400 mV

-400 mV

Figure 3: Rest potentials of different types of alloys

Thereby, some non precious metals coupled with Titanium could induce a non negligible galvanic corrosion whether they are not resistant to corrosion. After stabilisation, the value of Rest potential is a good indicator of the resistance to corrosion. To avoid galvanic corrosion, it is important to choose materials for which the difference of Rest potentials is low. Examples of couplings between different alloys and Titanium Grade 5 are shown in Figure 4. If the difference of Rest potential is high, the galvanic corrosion is significant. The galvanic current density is characteristic of corrosion speed. The higher the galvanic current density is, the more significant the galvanic corrosion. The alloys A, B, C, D and Titanium covered by its natural oxide layer had a similar Rest potential. Thus, they are not prone on an accelerated corrosion. On the contrary, the alloy E had a lower Rest potential than the Rest potential of Titanium. It is corroded regards to Titanium and faster than when it is not in direct contact with another metallic material, in a conductive media. Through different experiments, it has been noticed that for a difference of Rest potentials equal or less than 100 mV, the galvanic corrosion was negligible because it was comparable to natural corrosion (50 nA/cm2).

Galvanic corrosion density (nA/cm2) 500 450 400 350 300 250 200 150 100 50 0 A: B: C: D: E: F: A B C D E F ? 100 mV Difference of Rest potentials 365 mV

Pd-base alloy (Cerapall 2) / Ti grade 5 Au-Pt-Pd alloy (Implantalloy 1) / Ti grade 5 Au-Pt alloy (V-Gnathos Plus) / Ti grade 5 Au-Pd alloy (Implantalloy 2)/Ti grade 5 Au-Ag-Cu Alloy (Implantalloy 3) / Ti grade 5 NiCr Alloy / Ti grade 5

Figure 4: Galvanic corrosion and difference of Rest potentials (Surface area ratio 1:1, NaCl 9 g/l, pH = 7.3, T = 37C, deareated solution)

Quantification of corrosion
The knowledge of the material Rest potentials allows forecasting their anodic or cathodic behaviour when they are coupled. However, it is more difficult to determine precisely the amount of corrosion. Two ways can be used to measure corrosion. It is possible to measure the electrical current induced by corrosion (electrochemical testing) or to measure the quantity of metallic ions released (chemical testing). In theory, Faradays law (1) links the quantity of dissolved metal and the electrical current produced by corrosion. However, for alloys containing several metals, it is difficult to know the quantity dissolved regards to the electrical current because some parameters such as number of electrons

exchanged, are unknown and the electrical current is not stable versus time.

I x t = n x F x (m / M) I: t: n F: m: M:

(1)

electrical current (A) time (s) number of electrons exchange Faraday number: 96500 C/mole quantity dissolved (g) Molar mass (g/mole)

Therefore, instead of deducing the amount of corrosion from electrochemical parameters, the actual quantity of metallic ions released in the test solution can be directly measured by an accurate method of analysis such as Induced Coupled Plasma spectrometry (ICP). The higher the electrical current or the quantity of metallic ions released are, the more significant the corrosion. The values of the galvanic current density or the quantity released depend on several parameters such as the surface state of materials, the surface areas ratio, the conductive media and additional current density due to other type of corrosion (Crevice corrosion). The influence of each parameter will be shown separately through concrete examples in the following paragraphs.

200 mV/SCE 0 200 400 600 0 2 24 Time (Hours) 48

Galvanic current density and surface state of materials Oxide layer The experiment consisted of measuring the galvanic current density between samples of Titanium and a Au-Pt-Pd precious alloy (Implantalloy 1) in a deaerated solution of Sodium Chloride 9 g/l, pH 7.3, at 37C (the same electrolyte as defined in the ISO 10271 Standard). Just before immersion in the solution, the two samples were polished with Silicon Carbide grinding papers and diamond paste, and then ultrasonically cleaned in demineralised water. Figure 5 shows the galvanic current density and the Rest and Mixed potentials of the samples when measured at different times of immersion. 48 According to its surface state, the Rest potential of a material can be different. After polishing the surface of titanium, for example, the titanium is no longer protected by its oxide layer which causes it to have a very low Rest potential of 500 mV/SCE. As the chloride solution is very corrosive, much time is required for the protective layer of titanium oxide to be reformed. The Rest potential increases until values similar to the Rest potentials of precious metals alloys about 200 mV/SCE. The galvanic current density is negligible (5 10 nA/cm2).

Mixed potential Rest potential Implantalloy 1 Rest potential Ti grade 5

800 nA/cm2 600 400 200 0 0 2 24 Time (Hours)

Galvanic corrosion density

Figure 5: Galvanic current density and surface state of the sample (Implantalloy 1 / Ti grade 5 Surface area ratio 1:1, NaCl 9 g/l, pH = 7.3, T = 37C, deareated solution)

Overall, Titanium is covered by its oxide layer when it is introduced in the mouth, thus the risk of galvanic corrosion with precious metals alloys is limited. Porosity and saliva infiltration Galvanic corrosion and general corrosion can be more significant if the surface state of the material has defects such as porosity (see Figure 6) due to a non optimal casting or if there are small cavities where the electrolyte can infiltrate. When there is a saliva infiltration (leakage) between the supra-structure and the implants, the materials already in direct contact are then in a conductive media and galvanic corrosion can occur. In addition these alloys can undergo crevice corrosion. Crevice corrosion is induced by the geometry of the construction. The saliva is not renewed in the

cavities. This results in a decrease of dissolved oxygen, a diffusion of chloride ions and a decrease of pH which induce an accelerated dissolution of the material in the cavity. In in-vitro tests measuring the quantity of metallic ions released by galvanic corrosion, this phenomenon of crevice corrosion was involuntarily induced due to the preparation of samples. In order to have well-defined areas immersed in the corrosive solution, a sample part was embedded in an epoxy resin. However, a micro-leakage of the solution occurred in the interstice between the metal and the epoxy resin (see Figure 7). Samples without porosity and the use of another epoxy resin enabled the elimination of the interstice and associated the crevice corrosion (see sample Figures 8 and 9). Figure 10 illustrates the influence that porosity or solution infiltration can have on the quantity of metallic ions released for the same materials.

porosities interstice

Figure 6: Samples with porosity

Figure 7: Interstice epoxy-resin and the alloy

Figure 8: New sample without porosity

Figure 9: Elimination of interstice

600

Galvanic corrosion density (nA/cm2)

500

800 700

400

600 500

300

400 300

200

200 100

100

0 0 2 Time
Porosity and saliva infiltration Solution infiltration Without porosity or infiltration

24 (Hours)

48

72

Na CI 9 g/l, pH = 7.3, 37C, deaerated Na CI 5,85 g/l, pH = 2.3, deaerated Figure 12: Galvanic current density measured with two corrosive solutions (Implantalloy 1 / Titanium grade 5 Surface area ratio 1:1)

Figure 10: Quantity of metallic ions released (Implantalloy 3/ Ti grade 2 Surface area ratio 1:1, NaCl 5.85 g/l, Lactic acid 9 g/l, pH = 2.3, T = 37C)

80 70 60 50 40 30 20 10 0 Implantalloy 1 / Titanium grade 2 Implantalloy 2 / Titanium grade 2 Implantalloy 3 / Titanium grade 2

Figure 11: Quantity of metallic ions released (Surface area ratio 1:1, NaCl 5.85 g/l, Lactic acid 9 g/l, pH = 2.3, T = 37C)

In normal conditions, the quantities of metallic ions released by the three alloys, Implantalloy 1, 2 and 3 are presented in Figure 11. The quantities released are well below the accepted limit of 100 g/cm2 . week. Galvanic current density and conductive media (composition, pH, temperature) According to the saliva of the patient or the solution of test, the results can be different due to the behaviour of materials in the media considered. Parameters such as composition, pH and temperature influence the values of the galvanic current density. A galvanic coupling was carried out in two different solutions used in the corrosion tests of the ISO 10271 Standard. The results are shown in the Figure 12. The galvanic current densities measured between Implantalloy 1 and Titanium grade 5 are not the same for the two solutions because the solution of the chemical test seems to be more aggressive for these materials. The test solutions indicated in the ISO 10271 Standard, are very corrosive in relation to artificial or natural saliva. Thus the measured values of galvanic current are probably higher in these tests than in mouth if all other operating conditions were respected (surface state, area ratio, etc). Galvanic current density and alloys surface areas It is important to know the ratio between the anodic surface area (the lowest Rest potential) and the cathodic surface

Galvanic corrosion density (nA/cm2) 2500

Anodic area

Cathodic area

Anodic area

Cathodic area

2000 1500 1000 500 0 0 2 24 Time

The first worst case

The second case

After the same period in a corrosive media

Anodic area

Cathodic area

Anodic area

Cathodic area

The first worst case

The second case

Ratio (Anodic: Cathodic) Ratio 1:2 Ratio 2:1 Ratio 1:3 Ratio 1:1

48 (Hours)

Figure 13: Speed of galvanic corrosion accelerated by area ratio

Figure 14: Galvanic current density versus surface area ratio (Implantalloy 1/ Ti grade 5- Surface area ratio 1:1, NaCl 9 g/l, pH = 7.3, T = 37C, deareated solution)

area (the highest Rest potential) because the current density is proportional to these surface areas (2). ia = Ia / Sa (2)

twice as large as the cathodic surface area, the galvanic current density is two times lower than it would be for two identically sized anodic and cathodic surface areas. Galvanic corrosion and materials In addition to the surface state, surface area ratio of materials and the test media, the materials themselves obviously influence the results of galvanic corrosion. Several couplings between dental alloys and Titanium grade 5 were made in the same operating conditions to compare the galvanic current density for different materials. The evolution of galvanic current density until stabilisation (48h of immersion) is also shown in Figure 15. At the beginning of the experiment, the galvanic current density was significant for all alloys tested because Titanium was not covered by its oxide layer. Its Rest potential was very different to the Rest potential of alloys. But when the surface of Titanium is stable, i.e. covered by its oxides, the galvanic corrosion with the precious metals alloys was negligible (< 50 nA/cm2). The results for Implantalloy 1, 2 and 3 were very satisfying. On the other hand, for the non precious metals alloy tested, the galvanic current stayed significant because the Rest potential of this alloy was very low. The difference of Rest potentials was always high between Titanium and this alloy. The galvanic corrosion induced an accelerated dissolution of the alloy.

ia: Anodic current density Ia: Electrical current Sa: Anodic surface area The smaller the anodic surface area as compared to the cathodic surface area, the larger is the anodic current density i.e. the corrosion speed is significant. Figure 13 represents schematically the two possible cases. For example, in the case of a solder in which the surface is small, it is not recommended to use a material with a corrosion resistance lower to that of the rest of the restoration because the soldering can be strongly degraded by galvanic corrosion. The phenomenon is less severe in cases where the surface area of the less resistant to corrosion material is larger than the other parts. For instance, if the bars of a long overdenture placed on titanium implants do not have as a high a resistance to corrosion as the Titanium, they will be degraded by galvanic corrosion but less quickly due to the large surface area as compared to the surface area of titanium implants in contact with the electrolyte. In Figure 14 galvanic current density is represented versus different surface area ratio. If the anodic surface area is

900 800 700 nA/cm2 600 500 400 300 200 100 0

Precious metals alloys (A, B, C, D, E, and F) are protected (cathodic behaviour)

Ni Cr Alloy (H) is corroded (anodic behaviour)

A A: B: C: D:

C E: F: G: H:

H 0h 2h 24h 48h

Pd-base alloy (Cerapall 2) / Ti grade 5 Au-Pt-Pd alloy (Implatalloy 1) / Ti grade 5 Au-Pt alloy (V-Gnathos Plus) / Ti grade 5 Au-Pd alloy (Implantalloy 2) / Ti grade 5

Au-Ag alloy (Aurofluid Plus) / Ti grade 5 Au-Ag-Cu alloy (Implantalloy 3) / Ti grade 5 Ag-Pd alloy (Ceradelta 2) / Ti grade 5 NiCr alloy / Ti grade 5

Figure 15: Galvanic current density versus coupled dental materials (Surface area ratio 1:1, NaCl 9 g/l, pH = 7.3, T= 37C, deareated solution)

Conclusion
Due to problems of galvanic corrosion, not all metallic materials can be used together, especially when they are immersed in a conductive and corrosive medium. The risk of corrosion is very limited when the materials have a similar resistance to corrosion. The measurement of the Rest potential of each material gives a very reliable indication of their resistance to corrosion and thus enables a forecast of their chemical stability when they are in direct contact. A first way to prevent an accelerated corrosion is to choose materials with similar Rest potentials. Experimental evidence has shown that when the difference of Rest potential is less than 100 mV, galvanic corrosion is negligible. Moreover, it is very important to avoid having a small surface area for the less noble material because it will be corroded even more. A lot of parameters influence the value of the galvanic current or the quantity of metallic ions released such as surface state, surface area ratio of materials and the conductive media (composition, Temperature, pH). Thereby, it would not be totally reliable to consider only one value to quantify galvanic corrosion. In the literature [5, 6], in vivo tests were described by some authors but the values measured strongly depended on the method of measurement not only on materials themselves. It is preferable to choose only materials very resistant to corrosion for which the risks of galvanic corrosion are negligible such as the precious metals alloys with Titanium. In relation to their results of galvanic corrosion tests, alloys such as

Implantalloy 1, 2 and 3 can be recommended for construction of dental reconstructions on Titanium implants due to the negligible galvanic corrosion and the resulting ion release in the oral environment.

References
[1] Gottfried Schmalz, Pauline Garhammer. Biological interactions of dental cast alloys with oral tissues. Dent. Mat., 2002; 18: 396406. [2] Environmental Health Policy Committee. Biocompatibility of Dental Restorative Materials. www.health-gov/ environment/amalgam1/appendixi-sectioniii.htm, 110. [3] C. Manaranche, H. Hornberger, A proposal for the classification of precious dental alloys according to their resistance to corrosion based on the ISO 10271 Standard, European Cells and Materials, Vol. 5, Suppl. 1, 2003, 3436. [4] ISO 10271 Standard: Dental metallic materials-Corrosion test methods. First edition 2001. [5] B. Johansson, L. Lundmark, Direct and indirect registration of currents between dental metallic restorations in the oral cavity, Scand. J. Dent. Res., 1984; 92 : 476479. [6] E. J. Sutow, W. A. Maillet, J. C. Taylor, K. L. Hanrahan, G. C. Hall, K. Harandi, Considerations in measuring the electrical potentials of metallic restorations in vivo, J. Oral Rehabilitation, 2000; 27: 927934.

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