Materials Science and Engineering A 432 (2006) 111

Review

Corrosion of alloys used in dentistry: A review

Deepti Upadhyay a, , Manoj A. Panchal b , R.S. Dubey b , V.K. Srivastava c,1
Department of Chemistry, UP College, Varanasi 221001, Uttar Pradesh, India Department of Chemical Engineering & Technology, Center of Advanced Study, Institute of Technology, Banaras Hindu University, Varanasi 221 005, Uttar Pradesh, India c Department of Mechanical Engineering, Institute of Technology, Banaras Hindu University, Varanasi 221 005, Uttar Pradesh, India
b a

Received 19 February 2006; received in revised form 14 April 2006; accepted 4 May 2006

Abstract For regaining the normal functions of the dentition, articial materials are often used to restore the missing part or structure, these are known as dental materials. Metals and alloys, e.g., gold alloys are commonly used dental materials, due to their high strength and other desirable properties. Due to high cost of gold, alloys are being increasingly used in dental applications. Many substitutes for gold alloys have also been employed and some of them possess superior mechanical properties. Increasing knowledge about interaction of dental materials with oral tissues has resulted in evolution of high performance dental materials to meet the various requirements of the oral environment. Leaching of metallic ions and food habits are the main cause of corrosion of metallic dental implants and restorations. Therefore, corrosion has been considered as the most important factor in the selection of metallic materials, hence it deserves special emphasis and must be evaluated in ever-changing oral environment. The main objective of the present review is to describe the importance of corrosion of dental metals and alloys. Different dental materials together with oral environments and various types of corrosion have been described and related reported ndings have also been reviewed briey. 2006 Published by Elsevier B.V.
Keywords: Dental; Metal alloys; Corrosion; Pitting; Leaching; Cavitation

Contents
1. 2. 3. 4. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Metals and alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Oral environment and effects on metals and alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 4.1. Uniform or general corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 4.2. Galvanic or two-metal corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 4.3. Crevice corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 4.4. Pitting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 4.5. Intergranular corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 4.6. Selective leaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 4.7. Erosion corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 4.8. Stress corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

5.

Corresponding author. Tel.: +91 542 2368427; fax: +91 542 2368428. E-mail addresses: upadhyay deepti@rediffmail.com (D. Upadhyay), vk sa@yahoo.co.in (V.K. Srivastava). Tel.: +91 542 2368157; fax: +91 542 2368174.

0921-5093/$ see front matter 2006 Published by Elsevier B.V. doi:10.1016/j.msea.2006.05.003

D. Upadhyay et al. / Materials Science and Engineering A 432 (2006) 111

1. Introduction The eld of dental materials is highly catholic in nature, in the sense it covers a wide variety of materials from fairly exotic resin systems, elastomers, metals, alloys to ceramic materials, and many others. Metal alloys have high strength and have been found to be competitive among other dental materials. For selecting a material for dental application, it is necessary to remember that the choice of material depends on a number of factors like corrosion behavior, mechanical properties including strength and fabricability, cost, availability, biocompatibility, and aesthetic values. The corrosion behavior of metallic materials usually is the most important property because of biocompatibility and cytotoxicity of the products of the corrosion process. However, from aesthetic considerations, appearance is the most important factor to be considered. The mechanical properties of the materials are equally important even though the materials may have enough corrosion resistance. Cost and availability are also important for the selection of the materials. To better understand the effect of corrosion in the mouth, it is essential to become familiar with metals and alloys normally used, their composition, the environment in which they must function and also its effect. The main interest of the present article is to review briey the corrosion behavior of various dental alloys as reported by various research workers. 2. Metals and alloys Metals have been used as dental materials for over a century. Generally, most metals are strong enough to withstand maximum possible oral forces. Despite the fact that metals showed deterioration, before the availability of techniques to evaluate materials performance in biological systems, other high performance materials could not be developed to improve implant life and properties. Advent of innovative technologies and aseptic surgical procedures enabled researchers to ascertain the reason of failure of dental materials and consequentially development of high performance and cost effective materials. The irritability or cytotoxicity of a metal to cells is closely related to its location in the periodic table. Gold is the commonly used metal because of its high resistance to tarnish and corrosion [1]. In its pure form, gold is too soft for most dental applications. Under certain circumstances where mechanical properties are not important, pure gold is used in the form of gold leaf, powTable 1 Types and classes of metallic dental materials and their applications [2,3] S. no. 1. 2. Type Amalgam Noble alloys Class Low copper High copper Gold (non-heat-treatable) Gold (heat-treatable) Palladiumsilver Nickel Cobalt Iron

dered gold, and crystalline gold. Although no other metal can withstand the uctuating oral conditions like gold but the alternative alloys available in the market also possess the properties approaching near to the ideal properties needed for dentistry. A variety of alloys with physical properties suitable for specic applications have been developed to meet the requirements of various functions and properties. A general classication of dental materials, their class and broad application areas are listed in Table 1 and their compositions are given in Table 2 [2,3]. 3. Oral environment and effects on metals and alloys Structures in the mouth are constantly exposed to an everchanging physical and chemical environment that includes temperature and components like saliva, salts, foods, liquids, and drugs. Plaques and food adhere to teeth and lling materials, which means several forms of bacteria and their products are always present inside mouth. Mechanical forces also vary with respect to the type of food consumed, temperament of person, and location in the mouth. The average biting force of a person with natural dentition is approximately 77 kg in the posterior part of mouth. It represents approximately 0.193 GPa on a single cusp of molar tooth. Similarly the temperature in the mouth uctuates rapidly. When one drinks coffee immediately after ice cream, change in temperature is as great as 65 C and pH also changes widely in the mouth. Moist environment in the mouth also varies and affects dental materials. Under these circumstances, corrosion of metals and alloys in the mouth is expected and it does occur. Some experimental observations reported by different researchers are summarized below. Laing et al. [4] observed that the tissue reaction was proportional to the amount of constituent elements released by corrosion of a pure metal or alloy. On the other hand, intermetallic compounds, e.g., AgSn and CuSn have oxidized lms on their surface protecting them from corrosion in living tissue [5]. Also, electro-deposited gold is provided with a passive protective surface [6]. Several corrosion products of metal alloys like nickel carbonyl, nickel subsulde, and nickel sulde have been shown to produce carcinogenesis [7,8]. The presence of components of the posts in dark gingival discolorations has been reported adjacent to restorations [9]. Many heavy metals likes nickel, chromium, and beryllium are classied as carcinogenic, hazardous, and priority toxic pollutants

Principal application Posterior restoration of teeth Posterior restoration of teeth Restoration of single teeth Fixed bridges Restoration of single teeth Restoration of single and missing teeth, partial denture frameworks Partial denture framework and implants Orthodontic appliances and endodontic instruments

3.

Base alloys

D. Upadhyay et al. / Materials Science and Engineering A 432 (2006) 111 Table 2 Composition of dental restorative materials [2,3] S. no. 1. Type Amalgam Class Low copper High copper 2. Noble alloys Gold (non-heat-treatable) Gold (heat-treatable) Gold (heat-treatable) Gold (heat-treatable) Palladiumsilver Nickel base Cobalt base Iron base Composition 6370% Ag, 2628% Sn, 27% Cu, 02% Zn, Mercury100% Hg, set amalgam contains Ag2 Hg3 , Ag3 Sn, and Sn8 Hg 4060% Ag, 2230% Sn, 1330% Cu, 05% In, 01% Pd Mercury100% Hg, Set amalgam contains Ag2 Hg3 , Ag3 Sn, AgCu eutectic, and Cu6 Sn5 7678% Au, 13% Pd, 38% Ag, 812% Cu, 1% Zn maximum 7375% Au, 24% Pd, 915% Ag, 1218% Cu, 1% Zn maximum 5062% Au, 13% Pd, 1626% Ag, 811% Cu 3550% Au, 310% Pd, 03% Pt, 1330% Ag, 1130% Cu 5460% Pd, 2838% Ag, 79% Sn 17% Cr, 5% Mo, 5% Al, 5% Mn, 0.5% Fe, 0.1% C, 1% Be, 0.5% Si, balance Ni 2730% Cr, 013% Ni, 45% Al, 11.5% Fe, 0.20.5% C, 0.50.6% Si, 0.50.7% Mn, 00.05% Ga, balance Co 18% Cr, 8% Ni, 0.080.2% C, minor % of Ti, Mn, Si, Mo, balance Fe

3.

Base alloys

[10]. The corrosion products of copperaluminum alloys are easily removed by brushing [11,12]. According to Anusavice [13] alloys with chromium in their formulation must contain a minimum of 12% of this element to achieve an adequate passivating lm. Lucas and Lemons [14] have reported that the formation of oxide lm on titanium provides corrosion-resistance under static conditions, but the oxide lm is not sufciently stable to prevent galling and seizing under loading conditions. Titanium is attractive in dentistry due to its low weight to volume ratio, high strength to weight ratio, fatigue resistance, and corrosion resistance [15]. The titanium forms a relatively stable oxide layer, and this is the basis for the corrosionresistance property and biocompatibility. Titanium is a reactive metal but the thin oxide lm that instantly and spontaneously forms in air on its surface transforms the metal from an active to a passive condition. Corrosionfatigue life of pure titanium and Ti6Al4V alloys in different storage environments indicated no signicant difference between the corrosionfatigue life for dry specimens of either metal. But, fatigue life got signicantly reduced when aqueous solutions were present probably because of the production of corrosion pits caused by supercial reactions [16]. A passive layer of oxide or sulde and a protective colloidal membrane from saliva gradually covers the surfaces of restorations [17,18]. Mateer and Reitz [19] reported a layer-like corrosion product at the tooth-restoration interface, which suggested that the compounds were formed gradually by reaction of the amalgam and oral uids. The metal alloys could release nickel and beryllium as a result of corrosive activity at various pH levels [20]. The interaction of dental plaque with restorative materials has been studied using Auger spectroscopy [21]. Adsorbed layers of plaque on gold alloy, dental amalgam, and composites formed in vivo were found to contain copper, tin, and silicon, respectively, indicating an interaction with the restorative materials. However, the biodegradation of metals within the complex in vivo milieu has, for the most part, been found to be less in amount and rate than determined for the same specimens in vitro test systems. This phenomenon has been generally held to reect the presence of various proteins and other organic substances in vivo that coat and protect the metals. Published literature has supported this general nding [22,23]. Therefore,

emphasis has recently been placed on adding proteins and/or other organic species to saline for in vitro electrochemical corrosion solutions. This provides the opportunity to more fully evaluate possible in vivo correlations [24]. 4. Corrosion Discussed in earlier section that the corrosion behavior is important because poor biocompatibility and toxicity of the products may make the materials worst for implantation purposes. This section discusses the corrosion behavior of metals and alloys used in dentistry. Corrosion is dened as the destruction or deterioration of a material because of reaction with its environment [25]. Also, corrosion shows the oral environment as a chemical or electrochemical process through which a metal is attacked by natural agents, such as air and water, resulting in partial or complete dissolution, deterioration, or weakening of any solid substance [13]. Fontana [25] and Jones [26] have classied corrosion into eleven distinct forms as shown in Fig. 1. Out of these only those occurring in the oral environment will be discussed in the following pages. Furthermore, it is important to know that the purity, casting and melting techniques also affect the corrosion behavior of alloys. Corrosion resistance of stainless steel posts changes with the heat treatment and it is reported that prefabricated posts after burnout procedures had a noticeable reduction in corrosion resistance [27]. 4.1. Uniform or general corrosion This type of corrosion is dened as a chemical or electrochemical reaction that proceeds uniformly over the entire exposed surface or over a large area. This produces the normal ux of ions from an implant, which can interact with tissue. Nagai et al. [28] tested the corrosion resistance of some alloys and concluded that the spherical-particle amalgam was more resistant to corrosion than the conventional amalgam. The corrosion resistance of conventional alloy, spherical-particle alloy, and dispersion-phase alloy was clinically evaluated and it was concluded that dispersion-phase alloy offered more resistance to corrosion than either the conventional or the spherical-particle

D. Upadhyay et al. / Materials Science and Engineering A 432 (2006) 111

Fig. 1. Schematic representation of various forms of corrosion.

alloys [29]. Corrosion process released tin ions from tin based alloys to form 2 (Sn8 Hg) phase, which then reacted with nonmetallic ions in saliva to produce tin salts [19,30]. Copper and zinc alloys showed large corrosion in non-self-cleaning sites in the mouth, such as proximal surfaces [31]. Nickelchromium alloys exhibited good corrosion resistance in the oral cavity [32], where as, copperzinc alloy (Progold) showed appreciable corrosion when it was immersed in a chloride solution [33]. But, corrosion resistance of low gold casting alloys decreased in chloride solutions using potentiodynamic polarization measurements when compared with other conventional gold alloys [34]. The effect of chloride ions was observed on the corrosion behavior of ve silverpalladium dental casting alloys in a 1% NaCl solution using potentiodynamic polarization measurements and microstructure analysis [35]. Gettleman et al. [36] measured in vivo corrosion rate in baboons, and correlated with in vitro rates. Corrosion rates of metal alloys were observed in vitro and in vivo in articial

saliva [37,38], whereas corrosion of stainless steel, gold-plated stainless steel, and cast gold pins were studied in vitro and in vivo [39]. Guastaldi [40] studied potentiostatic polarization of copperaluminum alloys and observed passivation in articial saliva and Na2 S (5 g/L) solutions. Copper and silver-enriched alloys were readily corroded because of the action of sulde ions. Benatti Oscar et al. [32] studied in vitro and in vivo corrosion of nickelchromium and copperaluminum based alloys and reported high resistance to corrosion for nickelchromium alloy and considerable corrosion of copperaluminum alloy in the sulde solution. 4.2. Galvanic or two-metal corrosion This type of corrosion occurs due to the galvanic coupling of dissimilar metals involved. Less corrosion-resistant metals become anode and usually corrode. The dentist knows about the danger of this type of corrosion and asks for homogeneous

D. Upadhyay et al. / Materials Science and Engineering A 432 (2006) 111

metals with respect to chemical composition and metallurgical state. Researchers reported that the galvanic current could be suspected of having a harmful effect on soft tissues [41]. However, this was contradicted by clinical observations, which found no difference between gum tissues adjacent to and away from such dissimilar metals that were in contact with each other [42]. Schoonover and Souder [43] reported that gold restorations were corroded by mercury released from amalgam llings because of an electrochemical reaction. The corrosion of gold and amalgam placed in contact with each other was also investigated and it was observed that silver-colored stains formed on the surface of gold inlays that had got into contact with fresh amalgam mix or llings. Researchers demonstrated that the 2 phase (Snx Hgy ) of the silver amalgam was most susceptible to breakdown by electrolytic action [44,45]. According to Jorgensen [30], concentration cell currents occurring along the margins of amalgam restorations are, in part, responsible for marginal breakdown and ditching that are commonly seen in dental amalgams in the mouth. Dental amalgam subjected to high pressure resulted in the complete disappearance of 2 phases by the transfer of tin to 1 phase. Rotating ring-disc electrode was used to detect the soluble species produced during anodic polarization of dental amalgam [46]. The degradation interactions between oral uids and brazed joints were mostly attributed to galvanic coupling due to differences in the composition of castings and brazed alloys [47]. The metallic restorations in contact allow the release of components into the oral environment because of the formation of an electrogalvanic cell. Shigeto et al. [48] evaluated corrosion properties of solder joints using galvanic current analysis between dental solder and dental nickelchromium alloy and concluded that in soldering NiCr alloy, use of gold solder and a high-resistance NiCr alloy should be preferred for corrosion resistance. They also studied corrosion properties of solder joints by analyzing corrosion pattern of dental solder and dental nickelchromium alloy and conformed the previous ndings of combination of gold solder and a high-resistance NiCr alloy for corrosion resistance [49]. Angelini et al. [50] explained inuence of corrosion on brazed joints strength using 60 days immersion experiments and observed dramatically reduced tensile strength for the samples brazed with the gold alloy because of galvanic corrosion phenomena. Palaghias et al. [51] studied in vivo behavior of gold-plated stainless steel titanium dental retention pins, and reported that in vivo corrosion resistance of the titanium pins was superior to that of gold-plated stainless steel pins. 4.3. Crevice corrosion Crevices on the material surface cause the regions of stagnant solutions, and attack the material. This type of attack is generally dened as crevice corrosion. Crevices are unavoidable with surgical implants where a screw or plate contacts the bone. The local ux of ions is drastically enhanced at crevice sites and tissue impregnation follows. Implants never have simple shapes and are never exposed to a homogeneous environment. The contact region of a screw or

implant material can form the crevice. In the small space the liquid and oxygen exchanges are severely limited, and surface in the crevice undergoes active corrosion and cause further deterioration of the milieu. Failures in soldered joints, especially when stainless steel is soldered with silver solder, are often caused by corrosion. In this instance, either the residual uoride ux or the dissimilarity of the metals results in crevice corrosion. Crevice corrosion of silver soldered stainless steel was studied and established its convenience by using 316 L stainless steel [52,53]. 4.4. Pitting Pitting is a form of extremely localized attack that results in holes on the surface. The localized breakdown of the protecting passive layer causes pitting and this is termed a bad habit of aluminum and low-grade stainless steel. This is already discussed in the earlier section on metals and alloys that Zavanelli et al. [54] studied corrosionfatigue life of pure titanium and Ti6Al4V alloys in different storage environments, and observed no signicant difference between the corrosionfatigue life for dry specimens of either metal. But, they observed signicantly reduced fatigue life when solutions were present probably because of the initiation of corrosion pits caused by supercial reactions. 4.5. Intergranular corrosion Due to more reactive nature of grain boundaries, intergranular corrosion occurs adjacent to grain boundaries with relatively little corrosion of grains. This type of corrosion occurs due to the inhomogeneity and mainly technological errors. It has been demonstrated that heating 18-8 stainless steel between 400 and 900 C may negate its resistance to corrosion [3]. This corrosive tendency was attributed to the precipitation of chromium carbide at the grain boundaries at elevated temperatures. 4.6. Selective leaching Selective leaching is the removal of one element from a solid alloy by corrosion process. This process is generally not that important in dentistry. Tai et al. [55] studied leaching of nickel, chromium, and beryllium ions from base metal alloy in an articial oral environment for simulated 1-year period of mastication and showed that nickel and beryllium metals were released both by dissolution and occlusal wear. 4.7. Erosion corrosion Erosion corrosion is the acceleration or increase in rate of deterioration or attack on a material because of relative movement between a corrosive uid and the material surface. It includes cavitation damage and fretting corrosion. Cavitation damage is not important in dentistry. Fretting is described as the corrosion occurring at contact areas between materials under load subjected to vibration and slip. During insertion of an implant, some degree of abrasion between xing screws and implants or between tools (screw-

Table 3 Summary of the available experimental work on the corrosion of dental materials S. no. 1. Reference Fusayama et al. [44] Dental alloys Gold and amalgam restorations Medium Air, articial saliva Temp, pH, exp. period, etc. 1 day to 6 months Method In vitro and in vivo Remarks (a) Contact of gold inlays with old amalgam llings in air or saliva did not cause any signicant corrosion of the restorations but with fresh amalgam llings produced silver colored stains on the contact area (b) Contact with fresh amalgam llings less than 1 h old in saliva produced silver-colored stains of negligible thickness (c) On amalgam lling surfaces no signicant corrosion was found Steeping of chromecobalt dentures in domestic bleach had to be avoided, due to the inherently poor resistance of this alloy to attack in solutions containing chlorine (a) Amalgam made with dispersion-phase alloy maintained a signicantly higher degree of lustre than amalgam made with spherical-particle alloys. No signicant differences were evident compared with conventional alloy (b) Amalgam made with dispersion-phase alloy maintained a smooth surface texture to a signicantly greater degree than did amalgams of the conventional or spherical-particle type (c) Ditching of the margins was signicantly less evident with either conventional alloy or spherical-particle alloy (d) There was no difference in discoloration of tooth structure at the margins of the restorations Silver rather than copper appears to be the principal element rendering goldcoppersilver alloys susceptible to tarnish

D. Upadhyay et al. / Materials Science and Engineering A 432 (2006) 111

2.

Taylor and Jordan [57]

Chromecobalt alloy

Domestic chlorine bleach

9 months

In vitro

3.

Duperon et al. [29]

Conventional alloy, dispersion-phase alloy, spherical-particle alloy

Saliva, etc.

1 year

In vivo

4.

Tuccillo and Nielson [18]

Gold base alloy

0.5% sodium sulde aqueous solution

15 and 45 s

Rotating wheel with eight holes of 2.54 cm each, speed 1 rpm

5.

Holland and Asgar [7]

Amalgam restorations

Saliva

200 s

SEM and electron microprobe

The corrosion process yielding Sn ions that can react with non-metallic ions present in saliva attacks the y2 phase selectively. Sn released from this process can migrate to area within the amalgam that is continuous with the oral environment. Corrosion process yields two distinct new phases with amalgam: a dark gray phase consisting primarily of Sn and Cl and blue gray phase consisting primarily of Sn. The corrosion process yields a corrosion layer at the tooth amalgam interface consisting of Sn, S, P, and Cl The electrochemical behavior of 1 phase of dental amalgam (Ag2 Hg3 ) and 1 containing dissolved Sn is compared with that for the 2 phases in dental amalgam (Sn78 Hg). The results indicate that when tin is dissolved in 1 it did not affect the electrochemical behavior of that phase Electroplating with gold before and after silver soldering the stainless steel prevented crevice corrosion. The stainless steel surface was activated and protected by the rst layer of electro-deposited gold. The silver solder alloyed with this gold layer so a second application of electro-deposited gold was required to protect the joint from electrolytic action During anodic polarization of the dental amalgam in chloride solution, there is evidence that soluble species are formed prior to passivation An occluded corrosion cell and polarization program has been developed. It is free from unwanted crevices and gives reproducible results

D. Upadhyay et al. / Materials Science and Engineering A 432 (2006) 111

6.

Sarkar and Greener [33]

Dental amalgam (Ag2 Hg3 ) and (Sn78 Hg)

Ringers solution and KCl solution

25,000 psi, 7 days, T = 37 C

Potentiostatic anodic polarization

7.

Rogers [52]

Silver-soldered stainless steel; silver-soldered nickel-plated stainless steel; silver-soldered gold-plated stainless steel; silver-soldered stainless steel, gold plated after soldering; silver-soldered, gold-plated stainless steel, re-plated with gold after soldering

Aqueous solution containing anhydrous Fe2 (SO4 )3 , HF, dist. H2 O

4h

Accelerated corrosion test (electrochemical)

8.

Do Duc and Tissot [46]

Dental amalgam, Sn ringamalgam disc electrode

Ringers solution, 0.1 M chloride solution Deaerated Ringers solution

T = 37 C

Anodic polarization

T = 37 C, pH 7

Anodic polarization

Table 3 (Continued) S. no. 9. Reference Sarkar et al. [34] Dental alloys Dental gold alloys: (a) Forticast, (b) Midas, (c) Lab-44, (d) Minigold, (e) Midigold, (f) Maxigold, (g) Ney cast III, (h) Firmlay, and (i) Jelenko No.7 Medium 1% NaCl solution Temp, pH, exp. period, etc. 4h Method Potentiodynamic polarization (200 mv to +400 mv); controlled potential polarization at +200 mv, reverse polarization Potentiodynamic polarization Remarks Decreased chloride corrosion resistance, when compared with ADA Type III and Type IV gold alloys characterizes low-gold alloys

D. Upadhyay et al. / Materials Science and Engineering A 432 (2006) 111

10.

Sarkar et al. [35]

Ag Pd alloy system: (a) AgPdInZn, (b) AgPdAuInZn, and (c) AgPdAuCu. (1) CB-1, (2) CB-2, (3) Paliney CB, (4) WLW, (5) Albacast CuNiMn alloy, dental amalgams, dental casting gold alloys, wrought implant alloys, porcelain casting alloys

1% NaCl solution

4h

Silver-rich matrix is preferentially attacked in a 1% NaCl solution, the substitution of silver by gold improves the chloride corrosion resistance and the addition of copper may adversely affect the corrosion resistance Gold and chromium containing alloys corroded the least and amalgams generated the highest corrosion currents. Micro Bond NP2 and vitallium2 corroded the least, 316 L stainless steel corroded more and Ti, and Ti6Al4V corroded most Low corrosion in near neutral aqueous solutions; stainless steel 316, biocast, novanex and NP2 corrode 100 times slower than Rexillium, nickel, ultratech and ceramalloy Relative degree of corrosiveness on stainless steel burs showed Omni II and Omnicide solutions the best, Sterall and Sporicidin solutions the poorest, and Glutarex solution intermediate. Omnicide and Glutarex solutions showed the least degree Corrosiveness on the carbide burs. SEM analysis showed corrosion deposition over the soldered joint of the carbide burs

11.

Gettleman et al. [36]

Articial saliva

T = 37 C, 1080 h (45 days)

Back to 200 mv from +400 mv Linear polarization

12.

Wiegman-Ho and Ketelaar [58]

(a) Stainless steel 316, (b) Rexillium, (c) Pure nickel, (d) Bio-Cast, (e) Novanex, (f) NP2, (g) Ultratec, (h) Ceramalloy Stainless steel burs and carbide burs

Aerated articial saliva, 0.22 g CaCl2 was added before use

T = 20, 37 and 50 C, pH 6.65

Linear polarization

13.

Bapna and Mueller [59]

Buffer and activator, Sterall, Sporicidin, Glutarex, Omni II, and Omnicide

SEM, anodic polarization and energy depressive (EDX) microanalysis

14.

Shigeto et al. [48]

Dental NiCr alloys, gold and silver dental solder

Saline solution of 0.9% NaCl

pH 7, 120 days

Polarization

15.

Sorensen et al. [27]

Stainless steel posts divided into ve groups: (1) control; (2) gypsum-bonded investment, bench cooled; (3) gypsum-bonded investment, quenched; (4) phosphate-bonded investment, bench cooled; and (5) phosphate-bonded investment, quenched (Heat treatment at 300, 600 and 700 C for 30 min)

Ringers solution

30, 180 and 600 days

SEM, energy dispersive X-ray spectroscopy, optical emission spectroscopy and optical microscopy

Two groups of NiCr alloys: (a) high resistance alloy [high % of Cr], (b) low resistance NiCr alloy [low % of Cr]. Corrosion was observed in the silver solder coupled with high resistance NiCr alloy, but was not found in the gold solder coupled with both alloys

Investment and heat treatment altered the metallic structure of stainless steel posts. Heat treatment in gypsum or phosphate bonded investments negatively alters the corrosion resistance of stainless steel posts. Direct casting to stainless steel posts is contraindicated 16. Shigeto et al. [49] Dental NiCr alloy, dental solder Saline solution 100 days, pH 7, T = 37 C Immersion tests at 37 C No corrosion was observed in the high-resistant NiCr alloys with high Cr content. Pitting corrosion was seen on low resistant NiCr alloy, which had less Cr content. Elution of Ni ions was detected in all of the combination of NiCr alloys and solders with exception of the combination of high-resistant Ni-Cr alloys and gold solder. Elution of Cu ions was detected in all of the combinations with silver solder but not with gold solder The tensile strength of the samples brazed with the gold alloy was reduced because of galvanic corrosion phenomena. High short circuit currents were only produced with the gold brazing material Ti pin exhibited superior corrosion resistance than gold plated pins. Traces of Hg, Sn, Cu, S, Zn, Ca, K, Cl, P and S were observed on gold-plated pins. On tin pins only Ca and P (from dentin) were observed Ti6Al4V alloy had the highest mean values of fatigue; however, there were no signicant differences when compared with commercially pure titanium

D. Upadhyay et al. / Materials Science and Engineering A 432 (2006) 111

17.

Angelini et al. [50]

(i) Base metal alloys: Crutanium (A) and Wisil (B) (ii) Brazing materials: Au Cr I (sI) and Co/Cr (sII)

Articial saliva and Ringers solution

pH 2, T = 37 C, 60 days

In vitro, SEM with an energy dispersive electron microprobe

18.

Palaghias et al. [51]

Gold plated stainless steel and titanium dental retention pins (six paired pins)

Half pins restored with high copper admixed type

3 months

In vivo, emprobe

19.

Zavanelli et al. [54]

Pure titanium, titanium alloy (Ti6Al4V)

Air, synthetic saliva, uoride + synthetic saliva

At room temperature

Scanning electron microscope (SEM)

10 Ti pin exhibited superior corrosion resistance than gold plated pins. Traces of Hg, Sn, Cu, S, Zn, Ca, K, Cl, P and S were observed on gold-plated pins. On tin pins only Ca and P (from dentin) were observed

D. Upadhyay et al. / Materials Science and Engineering A 432 (2006) 111

drivers, grips, etc.) and implants is bound to occur. Another source, more or less continuous, of abrasion on implant structures, is functional loading, which induces relative movement between the material (screw hole) and the screw head. In fact, the (local) elasticity of the implant differs from that of the tooth material causing fretting corrosion. The mechanical component of fretting, i.e., the rubbing movement, disrupts the protective surface lms and removes metal particles. This action stimulates the chemical activities at the surface, leading to oxidation, or active corrosion, or repassivation as a result of the electrochemical aspect of the process [56]. 4.8. Stress corrosion Stress-corrosion cracking refers to cracking caused by the simultaneous presence of tensile stress and a specic corrosive medium. This process can dangerously impair the mechanical integrity of an implant. During mastication, restorations are subjected to heavy compressive shear, and bending forces. Also, burnishing of surfaces sometimes results in localized deformation. Thus, an electrolytic cell is formed between the stressed and unstressed metal portions. Grain boundaries of stressed metal are most vulnerable to corrosion. The failure of the soldered joint or the aking away of a thin margin of gold occurs due to stress corrosion. In mouth, the process of corrosion may be of several types. So, the chances of correlating in vivo clinical results with in vitro results seem less plausible. In spite of this, efforts have been made by researchers to generate experimental evidences under in vitro and vivo conditions. Some of the reported experimental works are summarized in Table 3 together with the environments and experimental methods used, and results obtained. Most of the workers have used in vitro methods and employed modern electrochemical and surface scanning techniques to examine the corrosive behavior of metallic dental materials. It is seen that a large number of workers have investigated both in vivo and in vitro corrosion of alloys and metals used as dental materials. Due to wide difference in the environmental conditions under two situations, generalized conclusions are difcult to arrive. Almost all reported work has been done by western workers where food habits and food ingredients are different than those used in India and other oriental countries. It would be interesting to study the effect, if any, of the spices, etc. used in the oriental foods on in vivo corrosion of natural and articial tooth and restorations. 5. Concluding remarks

MTS articial oral environment, in vitro

Method

In vitro

Nickel and beryllium metals were released both by dissolution and occlusal wear

Temp, pH, exp. period, etc.

Medium

NiCr alloy (75% Ni, 13% Cr and <1.8% Be), acrylic resin teeth, Crowns made of Rexillium III

Dental alloys

Benatti et al. [60]

Copperaluminum alloy, copperaluminum-zinc alloy, nickelchromium alloy

For in vitro test: (i) articial saliva; (ii) aqueous solution of 0.9% sodium chloride and (iii) 1.0% sodium sulde For in vivo test: (i) close to oral mucosa; (ii) towards the oral cavity; (iii) bottom surface exposed to the oral cavity

Amalgam, rest with BisGMA-POCl2

1 month and 3 months

T = 37 C, 1 year

In vivo

The nickelchromium alloy presented high resistance to corrosion. Both copperaluminum alloys showed considerable corrosion in the sulde solution and clinically in the non-self cleaning site

Remarks

Table 3 (Continued)

S. no.

20.

21.

The nature of dental metal alloys plays a major role in the initiation and propagation of corrosion. Though a large number of investigators have made efforts to investigate corrosion of dental materials, however, due to wide variation in the experimental conditions used, generalized correlations are difcult to arrive. Therefore, as for as possible corrosion free/least corrosive metal alloys should be used for the articial tooth and repair of the cavities for good health.

Reference

Tai et al. [55]

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11

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