dental materials

Dental Materials 19 (2003) 188198 www.elsevier.com/locate/dental

In vitro corrosion behavior of bioceramic, metallic, and bioceramic metallic coated stainless steel dental implants
M.H. Fathi a,*, M. Salehi a, A. Saatchi a, V. Mortazavi b, S.B. Moosavi b
a

Department of Materials Engineering, Isfahan University of Technology, Isfahan 84154, Iran b School of Dentistry, Isfahan University of Medical Sciences, Isfahan, Iran Received 4 July 2001; revised 26 November 2001; accepted 18 December 2001

Abstract Objectives: The most common metals and alloys used in dentistry may be exposed to a process of corrosion in vivo that make them cytotoxic. The biocompatibility of dental alloys is primarily related to their corrosion behavior. The aim of this work was to evaluate the corrosion behavior and thus the biocompatibility of the uncoated and coated stainless steels and compare the effect of type of coatings on corrosion behavior. Methods: Three types of coatings, hydroxyapatite (HA), titanium (Ti), and a double-layer HA/Ti on AISI 316L stainless steel were made. HA coating was produced using plasma-spraying technique and Ti coating was made using physical vapor deposition process. In order to perform a novel double-layer composite coating, a top layer of HA was plasma-sprayed over a physical vapor deposited Ti layer on AISI 316L stainless steel. Structural characterization techniques including XRD, SEM and EDX were used to investigate the microstructure, morphology and crystallinity of the coatings. Electrochemical potentiodynamic tests were performed in physiological solutions in order to determine and compare the corrosion behavior of the coated and uncoated specimens as an indication of biocompatibility. Results: Double-layer HA/Ti coating on AISI 316L SS had a positive effect on improvement of corrosion behavior. The decrease in corrosion current densities was signicant for these coated specimens and was much lower than the values obtained for uncoated and single HA coated specimens. Ti coating on AISI 316L SS also has a benecial effect on corrosion behavior. The results were compared with the results of corrosion behavior of HA coated commercially pure titanium (cpTi) and uncoated cpTi. Signicance: These results demonstrated that the double-layer HA/Ti coated 316L SS can be used as an endodontic implant and two goals including improvement of corrosion resistance and bone osteointegration can be obtained simultaneously. q 2003 Academy of Dental Materials. Published by Elsevier Science Ltd. All rights reserved.
Keywords: AISI 316L stainless steel; Corrosion; HA coating; Ti coating

1. Introduction Biocompatibility is the ability of a material to perform with an appropriate host response in a specic application [1]. This means that the tissue of the patient that comes into contact with the materials does not suffer from any toxic, irritating, inammatory, allergic, mutagenic, or carcinogenetic action [25]. Since the oral environment is particularly favorable for the biodegradation of metals due to its ionic, thermal, microbiological, and enzymatic properties, it can be presumed that the patient is exposed to a certain extent to the products of the corrosion process [6]. The
* Corresponding author. Tel.: 198-311-8912750; fax: 198-3118912752. E-mail addresses: fathi@cc.iut.ac.ir, fathimoh@yahoo.com (M.H. Fathi).

biocompatibility of dental alloys is primarily related to their corrosion behavior [7]. The higher the corrosion of an alloy, the more its elements will be released and the risk of unwanted reactions in the oral tissues may be increased. These unwanted reactions include unpleasant tastes, irritation, allergy or other reaction [7]. Surgical implants are usually made of metallic materials, such as austenitic stainless steel, cobaltchromium alloys, and titanium and its alloys. Among all the metallic materials, the austenitic stainless steels are the most popular materials because of their relatively low cost, ease of fabrication and reasonable corrosion resistance [8]. However, the austenitic stainless steels are prone to localized attack in long-term applications due to the aggressive biological effects. The corrosion products include iron, chromium, nickel and molybdenum, etc. Ions can accumulate in tissues surrounding the implant or be transported to distant parts of

0109-5641/03/$30.00 + 0.00 q 2003 Academy of Dental Materials. Published by Elsevier Science Ltd. All rights reserved. PII: S01 09- 5641( 02) 0002 9-5

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Fig. 1. XRD patterns of the coatings: (a) plasma-sprayed HA coating on cpTi; (b) plasma-sprayed HA coating on 316L SS; (c) double-layer HA/Ti coating on 316L SS.

the body [9]. It has been demonstrated that metallic ions resulting from the in vitro corrosion of austenitic stainless steels cause alteration of the expression of human lymphocyte-surface antigens and inhibit the immune response as assessed by lymphocyte proliferation [10]. The presence of

these ions in vivo not only causes toxic effects in mouse testicular seminiferous epithelium but also alterations in the spleen cellular population [11]. A number of investigations have demonstrated that metal ions can be released from metallic materials as the result of

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Fig. 1. (continued)

corrosion [2,3,810,1214]. Local adverse tissue reactions or elicit allergy reactions caused by metallic implants originate from the release of metal ions. This release of ions depends upon the corrosion rate of the alloy and the solubility of the rst formed corrosion products [15]. Intensive investigations have been carried out on biomaterials in order to study their corrosion behavior, ion release and its effects [14,1625], and toxicity and immunity of alloys [6,1618,2629]. The studies have been more intensive for stainless steels due to their corrosion behavior [14,19 29]. It has been suggested that metal ions associated with 316L stainless steel are toxic to osteogenic cells, affecting their proliferation and differentiation [19]. Stainless steel corrosion products above certain concentrations may disturb the normal behavior of osteoblast-like bone marrow cell cultures [2022,25]. Advanced techniques have been used for determining toxicity and tissue reaction around metal implants [24,27,29]. For this purpose, in vivo animal tests have been performed [28]. Ion release rates in vitro can be used to determine the proportionality of release in vivo [3032] but long-term in vivo studies have been made and results indicate that metal ion release increases with the exposure time [33,34]. Release of metal ion in vivo analysis did not demonstrate any consistent differences in the concentrations of metallic elements next to stressed and nonstressed miniplates and screws of stainless steels [35]. A previous in vivo study by the present authors has shown that the type of metallic implants had signicant effects on the clinical success, bone tissue response and histopatho-

logical results of hydroxyapatite coated/uncoated metallic implants in animals [36]. In this previous work, endodontic implants consisting of plasma-sprayed HA coated and uncoated substrates of various materials, namely 316L stainless steel and CoCrMo alloy, were prepared. These implants were subsequently implanted in the mandibular canine of cats. After a healing period of 4 months, osteointegration evaluation and histopathological interpretation were carried out by using scanning electron microscopy (SEM). The results showed that different substrates had pronounced effects on the histopathological response to different HA coated implants [36]. The aim of the present work was to evaluate the corrosion behavior and therefore biocompatibility of the uncoated and coated stainless steels. In order to design and produce a desired coating for improvement of histopathological response, tissue reaction and bone osteointegration around dental implants, the effects of three types of coatings on the behavior of substrates were compared.

2. Materials and methods 2.1. Substrates and coatings Commercially pure titanium (cpTi) and AISI 316L stainless steel were used as substrates. The composition (wt%) of stainless steel was C 0.03, Si 0.80, Mn 1.2, Cr 17.55, Ni 13.65, Mo 3.1, P # 0.040, S # 0.030 and Fe as the balance. The composition (wt%) of cpTi was Ti . 99.5%.

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Fig. 2. SEM micrograph of the coatings: (a) plasma-sprayed HA coating surface showing partially melted with some porosity and microcracks; (b) the top layer of a double-layer HA/Ti coating shows some porosity and microcracks; (c) a physical vapor deposited Ti coating on a 316L SS.

Ti coating (37 mm thickness) was made using physical vapor deposition process on AISI 316L stainless steel. Crystalline hydroxyapatite coatings with 4060 mm were produced using plasma-spraying technique on two types of substrate, i.e. AISI 316L stainless steel and commercially pure Ti. A double-layer composite coating composed of a hydroxyapatite top layer (4060 mm thickness) and a Ti under layer (35 mm thickness) was prepared using a plasma-spraying and a physical vapor deposition process, respectively, on AISI 316L stainless steel. 2.2. Experimental procedure X-ray diffraction (XRD) technique (Philips X'Pert-MPD ) was used to System with a Cu ka wavelength of 1.5418 A analyze the crystalline structure and phases present in the coatings. This technique was also used to estimate the percentage of the crystallinity of the HA coating. SEM and energy dispersive X-ray analysis (EDX) techniques

(Philips XL 30) were used to study the microstructure and morphology of the coatings. EDX analysis was utilized to estimate the ratio of Ca/P of the HA coating and the composition of the coatings. Commercially pure titanium (cpTi) and AISI 316L stainless steel (316L SS) were selected as the sample materials. Coupons of two types of alloys were cut and surface preparations were carried out by wet grinding with a series of SiC papers to 4000-grit followed by thorough cleaning in distilled water, degreasing with acetone and air drying. An electrochemical corrosion polarization test cell was used for in vitro potentiodynamic corrosion tests in physiological solutions. Graphite was used as the counter electrode and saturated calomel electrode (SCE) as the reference electrode. The physiological solutions were the Ringer's solution and physiological normal saline (0.9 wt% NaCl) and the potentiodynamic corrosion tests were performed at 37 ^ 1 8C. Dynamic polarization curves were recorded at a potential scanning rate of 0.5 mV s 21 initiated at 2250 mV

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Fig. 3. SEM EDX of the coatings: (a) HA coating, desirable Ca/P is obtained; (b) and (c) HA layer and Ti layer, respectively, of a double-layer HA/Ti coating.

below the open circuit potential and the atmosphere was open to air. Five replicate tests of each group of specimens were performed. To compare the corrosion behavior between the uncoated and HA coated cpTi, the uncoated 316L SS, HA coated 316L SS and double-layer HA/Ti coated 316L SS, specimens were dynamically polarized in two different types of physiological solutions. Potentiodynamic polarization curves were determined at 37 ^ 1 8C using a EG and G model 263A potentiostat/galvanostat interfaced with a computer and a recorder. The tests were started after a steady open-circuit potential was attained (not more than ^5 mV drift in 5 min). The anodic and cathodic polarization curves were obtained for each specimen and corrosion potentials and corrosion current densities were determined by Tafel extrapolation and linear polarization methods. The mean value and standard deviations of the results were calculated. It is noticeable that two kinds of electrochemical tests were utilized in this investigation. The rst test was referred to as a potentiodynamic anodic polarization-scan because it is dynamic or continuous. It represented a prole of the behavior of the alloy when scanned in a forward direction from anodic to cathodic potential and spans a range of 1 V or more. The straight line segments of these scans are iden-

tied by the Tafel equation. DE b logi=I0 : The expanded form of this equation shows linearity where b is slope and log i0 is the Y intercept. The scans are plotted as potential, E (mV, SCE), vs. log current density, log i (mA cm 21), and are often referred to as Evans Diagrams. The reverse scan was obtained by reversing the direction of the scan, thus obtaining a reverse Evans Diagram. Curve shape, potentials at current discontinuities and absolute values are all important in characterizing corrosion behavior. The second test involved potentiodynamic or continuous scanning but over a much smaller potential range than anodic polarization. Typically, a scan is started 10 mV anodic to the corrosion potential and terminates 10 mV cathodic to it. The scan is plotted directly as E vs. i and is referred to as a linear polarization plot. The slope of the linear segment of the DE vs. Di plot is expressed by the formula: DE=DiDE!0 RP B=icorr where RP is polarization resistance (kV cm 2), (DE/Di) is slope (mV cm 2/mA) and Bconstant b a bc =2:3ba 1 bc where ba and bc are Tafel slopes for the anodic and cathodic proles, respectively. One way to nd the value of the equation involves the determination of Tafel bc and ba from

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Fig. 3. (continued)

potentiodynamic polarization curves and calculation of the resulting value of B.

3. Results 3.1. Structural characterization The XRD patterns of the plasma-sprayed HA coatings on cpTi and 316L SS are shown in Fig. 1(a) and (b), respectively. In the plot of intensity vs. 2u , there are numerous sharp peaks and a low background indicative of highly crystalline HA coating. Fig. 1(c) also shows the XRD pattern of a double-layer HA/Ti coating on 316L SS which is very similar to the XRD pattern of HA coating on 316L SS. The SEM micrograph showing a typical plasma-sprayed HA coating on a metallic substrate is shown in Fig. 2(a). The structure appears to be partially melted and porous and microcracks can be observed scattered throughout the structure, probably as a result of a very rapid cooling rate during the deposition process. Fig. 2(b) is a SEM micrograph showing a typical double-layer HA/Ti coating on 316L SS substrate which also shows that the coating consists of a

porous surface and some microcracks. Fig. 2(c) is a SEM micrograph showing a physical vapor deposited Ti coating on a 316L SS. The porosity of the coating is less than HA coating but microcraks cannot be seen. The result of EDX analysis of HA coating surface is shown in Fig. 3(a). The Ca/P 2 is the desired ratio. Fig. 3(b) and (c) show EDX analysis of HA layer and Ti layer of double-layer HA/Ti coating. 3.2. Corrosion behavior The potentiodynamic polarization curves of the uncoated, HA coated, Ti coated, double-layer HA/Ti coated 316L SS and HA coated/uncoated cpTi in the normal saline solution are shown in Fig. 4. The similar curves that are obtained in Ringer's solution are plotted in Fig. 5. These curves are selected because their extracted data were the most nearest to the mean values of the current densities of each group of specimens. The corrosion current densities of various specimens were determined from the potentiodynamic polarization curves (Figs. 4 and 5) by Tafel extrapolation method. These results align with corrosion potentials, summarized

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Fig. 3. (continued)

in Tables 1 and 2 in normal saline solution and Ringer's solution, respectively. The standard deviations of the corrosion current densities are shown in parentheses in Tables 1 and 2. The corrosion current densities as determined by linear polarization method are also shown in Tables 1 and 2. According to Table 1 and Fig. 4, the uncoated 316L SS possesses lower corrosion resistance and thus higher corrosion current density (icorr 265 nA cm 22) in the normal saline solution. The similar trend can be observed in the Ringer's solution (Table 2). The HA coating decreased the corrosion current density of the HA coated 316L SS (icorr 68 nA cm 22) and HA coated cpTi (icorr 43 nA cm 22). The double-layer HA/Ti coating had a signicant effect on the corrosion behavior of 316L SS so that the corrosion current density of HA/Ti coated 316L SS decreased (icorr 44 nA cm 22) and was exactly similar to single HA coated cpTi (icorr 43 nA cm 22) in normal saline solution. The Ti coating could decrease the corrosion current density of the Ti coated 316L SS in both types of the physiological solutions (Table 1 and 2). 4. Discussion The single HA coating had a positive effect on corrosion

resistance of metallic substrate, i.e. 316L SS and cpTi and decreased the corrosion current density of each type of coated metallic substrate. The polarization curve, (b) in Fig. 4, of the HA coated 316L SS was shifted to the left upper area, compared with curve (a), which is the uncoated 316L SS specimen. It means that the HA coated 316L SS (Ecorr 2105 mV, icorr 68 nA) was more corrosion resistant than the uncoated 316L SS (Ecorr 2174 mV, icorr 265 nA). The corrosion behavior of the HA coated cpTi (Ecorr 2256 mV, icorr 43 nA) was better than uncoated cpTi (Ecorr 2334 mV, icorr 72 nA) up to 200 mV, as manifested by a shift of the polarization curve (f) to the left upper of the uncoated cpTi curve (e). A similar trend can be observed in the Ringer's solution (Fig. 5, curves (a), (b), (e) and (f), Table 2). Therefore, single HA coating on metallic substrate caused signicant changes on corrosion behavior of substrate. This result was in agreement with the results of the other researchers [37]. Single HA coating could decrease the corrosion current density of 316L stainless steel substrate in physiological solutions (Tables 1 and 2 and Figs. 4 and 5) but this effect was not adequately complete. This was due to the fact that the structure and surface morphology of single HA coating consists of a porous surface and some microcracks (Fig. 2) and could not act as a barrier to the release of metal ions

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Fig. 4. Potentiodynamic polarization curves of: (a) the uncoated; (b) HA coated; (c) Ti coated; (d) double-layer HA/Ti coated 316L SS; (e) the HA coated cpTi; (f) uncoated cpTi in the normal saline solution (0.9 wt% NaCl) at 37 8C.

Fig. 5. Potentiodynamic polarization curves of: (a) the uncoated; (b) HA coated; (c) Ti coated; (d) double-layer HA/Ti coated 316L SS; (e) the HA coated cpTi; (f) uncoated cpTi in the Ringer's solution at 37 8C.

from metallic implant to physiological solutions and corrosive environment. The HA coating acted simply as a semi-mechanical barrier. The corrosion rate in this case was drastically reduced, although in the microcracks and pores of the HA coating the substrate came into contact with the solution and some corrosion occurred. Earlier work by the present authors showed that the histoTable 1 Mean values (standard deviation) of corrosion current densities and corrosion potentials in normal saline solution (0.9 wt% NaCl) at 37 8C Material Ecorr (mV) Icorr (nA/cm 2) Tafel Uncoated 316L SS Uncoated cpTi HA coated 316L SS HA coated cpTi HA/Ti coated 316L SS Ti coated 316L SS 2174(20) 2334(11) 2105(10) 2256(10) 2153(15) 288(20) 265 (16) 72 (7) 68 (2) 43 (6) 44 (5) 27 (5) Linear 194 (16) 63 (9) 52 (1) 34 (7) 32 (3) 26 (5)

pathological responses to uncoated 316L SS and uncoated vitallium were not acceptable [36]. These results are in agreement with the studies that have been carried out on endodontic implants [16,17]. Vitallium was originally used but its biocompatibility was questioned when it was shown to undergo surface corrosion. This is an important factor in the success of an endodontic implant. Stainless steel and vitallium have generally lost acceptance and are
Table 2 Mean values (standard deviation) of corrosion current densities and corrosion potentials in Ringer's solutions at 37 8C Material Ecorr (mV) Icorr (nA/cm 2) Tafel Uncoated 316L SS Uncoated cpTi HA coated 316L SS HA coated cpTi HA/Ti coated 316L SS Ti coated 316L SS 2195(20) 2303(5) 2110(21) 2215(14) 2182(20) 261(15) 218 (17) 71 (6) 57 (3) 40 (4) 43 (5) 24 (5) Linear 181 (20) 61 (6) 49 (1) 29 (3) 32 (4) 26 (2)

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Fig. 6. Periapical tissue response to HA coated 316L SS: (a) inammatory connective tissue can be observed ( 25); (b) the same picture ( 100).

no longer available for clinical use as endodontic implants [16,17]. On the other hand, earlier work showed that the type of metallic substrates which were HA plasma-sprayed coated and used for endodontic implants in animals had signicant effects on histopathological response [36]. Statistical analyses of the signicance of the differences between histopathological response to single HA coated vitallium and single HA coated 316L SS were carried out by KruskalWallis method. More tissue damage, inammation and irritation have been observed around single HA coated 316L SS (Fig. 6) in comparison with single HA coated vitallium [36]. This was owing to the inability of the single HA coating to act as a barrier to the release of metal ions to animal's body on the 316L SS implants. The bone osteointegration around single HA coated vitallium alloy and single HA coated 316L SS were almost the same and from the point of the clinical success and osteointegration no signicant difference were observed [36]. This result is also in agreement with the other researchers [38]. It has been observed that there are no differences between osteointegration when stainless steel is used instead of Ti alloy as metallic substrate, conrming that bone responds primarily to coating [38].

Many attempts have been made for improvement and optimization of implant surface conditions by creating a bioceramic coating on implant surface [3943]. In this case, double- or multi-layer coatings have been recently considered by a number of researchers' works [37,4446] for improvement of biomedical applications and offering potential clinical benets in orthopedic and dental surgery. Bioceramic coatings such as Al2O3, TiO2 and ZrO2 on 316L SS have already been considered to increase corrosion resistance [43,4749]. The in vitro electrochemical polarization corrosion test results indicated that novel double-layer HA/Ti coating have a benecial and desired effect on corrosion behavior of 316L SS. This can improve the corrosion resistance (Figs. 4 and 5 and Tables 1 and 2) and subsequently can decrease the release of metallic ions and deleterious effects. Therefore, two goals could be obtained simultaneously by the formation of the double-layer HA/Ti coating. First, the improvement of 316L SS corrosion resistance and decreasing of ion release and consequently prevention of tissue damages, inammation and irritation and obtain desirable histopathological response. The second improvement is in terms of bone osteointegration and bone bonding with the coated implant. The Ti coating had a positive effect on corrosion resistance of 316L SS. The polarization curve, (c) in Fig. 4, of the Ti coated 316L SS was shifted to the left upper area, compared with curve (a), which is the uncoated 316L SS specimen. The Ti coated 316L SS (Ecorr 288 mV, icorr 30 nA) was more corrosion resistant than the uncoated 316L SS. The type of physiological solution had no effect on this trend. It is noticeable that the passive current density (ip) of the Ti coated 316L SS (curve (c) in Figs. 4 and 5) was similar to HA/Ti coated 316L SS (curve (d) in Figs. 4 and 5). This means that the Ti responded primarily to environment and corrosion reaction was essentially between Ti and solution.

5. Conclusion Double-layer HA/Ti coating can have a benecial and desired effect on corrosion behavior of 316L SS and decrease the corrosion current density that is a distinct advantage for prevention of ion release. Corrosion current density of double-layer HA/Ti coated 316L SS was similar and equal to single HA coated cpTi and it suggests that double-layer HA/Ti coated 316L SS can be used as endodontic implant.

Acknowledgements The authors are grateful for the support of this research by Isfahan University of Technology.

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