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Materials Science Forum Vols. 488-489 (2005) pp. 787-791 online at http://www.scientific.

net © (2005) Trans Tech Publications, Switzerland

Protection of Mg Alloys Against Galvanic and Other Forms of Corrosion Wenyue Zhenga, C. Derushieb and Jason Loc
CANMET Materials Technology Laboratory, Natural Resources Canada, 568 Booth Street, Ottawa, Canada K1A 0G1

Keywords: automotive, structural application, galvanic corrosion, coating, conversion coating, stress corrosion, compatibility, cyclic salt-spray testing, AM 50/60, AE alloy.

Abstract. Galvanic corrosion is a particularly important form of corrosion for Mg alloys used in automobiles. Our research work focuses on corrosion protection using cost-effective Cr-free coatings. The top-tanking coatings are found to be effective in preventing general corrosion; some of these coatings are also good for reducing galvanic corrosion and stress corrosion. A practical approach for mitigating galvanic corrosion is to increase the electrolytic resistance between the coated steel and the Mg surfaces. This has been demonstrated in the case of a conversion coating plus a powder coat applied on the surface of a magnesium alloy and in the case of a thin Mylar isolation layer installed between the Mg and the steel surfaces. Introduction Mg castings of appropriate compositions used in the automotive interior condition can resist well general corrosion. In terms of general corrosion rates modern Mg alloys can perform quite satisfactorily in clean atmospheric conditions. For example, in the study by Hillis etal. [1], the measured corrosion rate of AZ91D was less than 4 micrometers per year. In this type of alloys, the harmful impurity elements are Ni, Fe and Cu. To increase the resistance to corrosion in natural environment, rare-earth additions have shown to be beneficial [2] and the good corrosion resistance of AE alloys, along with their increased creep resistance, has made them the top candidate materials for many applications. However, the automotive exterior conditions in cold-climate countries can be very corrosive due to the use of de-icing salts on the road. The most challenging form of corrosion is galvanic corrosion. Under the sponsorship of the USAMP (US DOE) and the Canadian Lightweight Materials Research Initiative (CLIMRI), a research project was initiated at the Materials Technology Laboratories (MTL) of CANMET to identify cost-effective measures for protecting magnesium alloys used as structural components such as an engine cradle [3,4]. The susceptibility of Mg to stress-corrosion cracking (SCC) is also investigated; this part is relevant to a typical structural application where certain localized sites may be subject to high stresses. Evaluation of advanced Chromate-free coating systems Coating Selection. Although chromate conversion coatings were widely used for Mg alloys used in aggressive conditions, their future use in automobiles is limited due to the environmental and health concerns. In this work, a total of eighteen different types of Cr-free coatings were selected [4]. In selecting a coating, consideration was given to the technical performance, commercial availability as well as the effects of the coating materials on the recycling of the component [5]. Screening Test Results. ASTM B117 standard was used as a screening tool for the coated and uncoated Mg samples [4]. Visual examination of the test plates was performed at preset time intervals. In the case of the scribed samples, the creeping of corrosion from the scribe line and degree of disbondment underneath the coating were the criteria for assessing a coating. Based on the ranking of the test samples after 1000 hours testing, the top coatings were selected for the validation phase. These coating are: (1) Alodine 5200 with an epoxy powder coat and Magpass

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Polyurea [9] is a fast-curing polymer resulting from the reaction of an isocyanate prepolymer and a blend of primary and secondary amines.000 Ohms*cm2. As the galvanic corrosion is driven by the difference in the corrosion potential of the two coupling metals. the main advantage of this coating is that it can resist chipping and impact damage of the road sand and gravels when used as a topcoat. The LPR resistance of AM60 in 1 M NaCl solution is about 170 Ohms*cm2 and AA6061 alloy had a resistance of 23. The selection of this product for this project is based on its good elasticity and adhesion to magnesium and to an epoxy-type topcoat.2 V (SCE). Although it can be quite useful for protecting Mg alloy to a certain extent by itself. 1 A micrograph of the cross-section of the Mgcoating interface taken with a FIB microscope.1 M NaOH solution. A Solatron 1287 system controlled with a Corrware software was used. Galvanic corrosion testing Using the GM9540 Test Method GM9540P was chosen as the method for evaluating the galvanic corrosion susceptibility of Mg (coated and uncoated) fastened with M8 and M10 fasteners. AM60 showed a corrosion potential of –1. The coating consists mostly of a hard magnesium oxide with minor surface deposition of fused silicates. In this work the typical thickness is between 10 and 15 micrometers. The solution consisted of a 1 M NaCl solution with the pH adjusted to 11 by adding appropriate amount of 0. (2) Tagnite anodizing with an epoxy topcoat.788 Magnesium – Science. [7] Tagnite is a Cr-free equivalent of the Dow 17 and HAE anodizing coating. Magpass by AHC is a new Cr-free conversion coating product with a very comparable performance. indicating a similarity in long-term corrosion resistance. similar. Compatibility testing by electrochemical technique Potentiodynamic polarization testing is a fast way to compare the galvanic compatibility of different materials. An epoxy powder coat was used as the topcoat. Anomag [8] is another anodizing coating for magnesium. Technology and Applications with an epoxy topcoat. (3) Anomag anodizing with Ecoat and (4) Polyurea topcoat Alodine 5200 [6] is an organometallic titanium based primer used as a chromate-replacement conversion coating. it is conceivable that the galvanic current flow between Mg alloys and the new Al-Mg alloy would be much smaller than that between Mg and A356.5 V (SCE) and the A356 sample showed a potential of about – 1. The new experimental Al-Mg alloy showed a corrosion potential in the vicinity of that of the AM60 alloy. The new alloy had a LPR resistance slightly greater than that of AA 6061 but they are generally in the same range. which was taken with a focused ion beam microscope as the conversion layer is less than 0.5 micrometers in thickness. Figure 2 shows the polarization curves for A356. 2 Polarization measurements for feature of this comparison is that in the more anodic AM60. Another interesting Fig. Mg alloy AM60 and a new experimental alloys in a salt solution. A Singleton CCT-10C cyclic corrosion . the latest version of Anomag and Tagnite coatings can be made thinner. A356 and a new Al-Mg alloy potential range the behavior of the new Al-Mg alloys is very similar to that of A356. Figure 1 shows a micrograph of the cross-section cut of the Mg-coating interface. The application processes of the various conversion coatings are by and large Fig.

the nut was removed and no sign of corrosion can be seen underneath the Mayler sheet. The experimental alloy washer. After 40 cycles of testing. Similar results were observed on the test plate coated with a Magpass conversion layer and then a powder coat as the topcoat.12]. The fastener unit which did not contain a washer showed perforation by corrosion in the vicinity of the bolt.6 AM60 plate coated with Magpass and a topcoat after 40 cycles of testing. There were a few spots of red-rust emerging on the duplex GM3359 coating on the bolt head itself. Figure 6. 488-489 789 chamber was used [4]. the best results were observed with the anodized and sealed Fig. In this case. whereas the units with a washer showed much reduced corrosion damage. In comparison with the bare AM60 plate. On the bare magnesium test plates.11. This series in which anodized plates were bolted with various Fig. the performance of a coated Mg AM60 plate fastened with various combination of fastening units showed no visible corrosion on the Mg plate after 40 cycles of testing. Magoxide without any topcoat. 4 Effectiveness of a Mylar sheet under the washer (bottom center) in preventing galvanic attack on the Mg plate AA6061 washers. A ring of corrosion product can be seen to occur immediately adjacent to the Ti washer.3 Appearance of uncoated AM60 plate after 40 cycles of GM9540 testing. Figure 3 shows the appearance of the uncoated AM60 plate after 40 cycles of GM9540 testing. Each fastening unit consists of one bolt (M8 or M10). two washers and a hex nut. Fig. 5 AM60 plate coated with Alodine5200 and a topcoat after 40 cycles of testing. Fig. A number of in-house made prototype washers made of the Al-Mg chemistries were also evaluated. Magpass with a powder coat [Fig. The effect of a thin (about 50 micrometer thickness) layer of Mylar sheet on preventing galvanic attack is shown in Figure 4.Materials Science Forum Vols. Alodine 5200 with a powder coat [Fig.6]. The effects of washers on the galvanic corrosion of Mg are demonstrated very clearly. likely due to damage during the application of the torque loading. 5]. The selection of washer materials and their coatings were based on the current industry recommendations and published performance data [10. Exp2091 showed little effects of galvanic corrosion. an uncoated steel washer was bolted against the uncoated Mg plate with the insulating Mylar sandwiched between them. . Test results Bare Mg plate.

90 to take into account of any possible load fluctuation in the practice. In the preliminary SCC tests conducted so far. For example.4 million load cycles in a GM9540 .0 Hz. Some of the conversion treatments are known to significantly reduce the formation of hydrogen gas on the Mg surface [13]. Galvanic corrosion between fasteners and Mg alloys can be effectively mitigated though the use of a high-resistance insulating layer that separates the magnesium from the cathode material. Specifically. samples were coated with an Alodine 5200 conversion coating with an epoxy topcoat. the other series was tested as-cast. The coated sample survived 2. The load frequency used was 1. Figure 8 shows a picture of the LPDC developed along the main fracture surface. and the solution used was the GM9540 solution composition. Hydrogen embrittlement is thought to be the responsible SCC mechanism in Mg alloys. The resistance to SCC of the sample coated with Alodine 5200 may be related to the reduction in hydrogen generation rendered by the presence of the conversion product. The maximum stress used was 130% of the yield stress and the R value was 0. Summary and conclusions Results from completed tasks of this on-going project are very encouraging for future wide-scale application of Mg alloys as structural components. 8 A uncoated SCC test sample showing cracks cycles. In this work. 2. Stress corrosion tests Stress corrosion tests were carried out using Fig. the following conclusions can be drawn at this stage: 1.790 Magnesium – Science. a thin Mylar sheet sandwiched between a steel washer and a magnesium plate as well as a layer of powder coating on top of a Mg conversion film could effectively prevent the galvanic attack. Some of the commercially available coating systems for Mg alloys can satisfactorily protect Mg alloys against aggressive testing conditions established by the industry. AM50 samples coated with a conversion product and a topcoat did not exhibits visible cracking even after 2. two uncoated samples showed significant cracking after about 0. On the other hand. Figure 7. that without an organic topcoat the semi-conducting oxide layer produced by anodizing was not sufficient to prevent galvanic attack by the coated steel bolts. chromatefree conversion coatings. can last sufficiently long to survive the 1000 hours in the ASTM B117 test chamber. Technology and Applications combinations of bolts and nuts showed. One series of the anodized Mg plate. 7 Galvanic attack in along the washer on the LPDC AM50 samples. such as Alodine 5200 and Magpass with an epoxy powder coat as well a sealed anodizing coating.4 million cycles without the formation of any visible cracks on the sample surface. 3. AM50 alloys containing stress-corrosion cracks. Note that a good anodizing film such as Magoxide can very effectively prevent general corrosion in the environments such as that in the GM9540 and B117 conditions. surprisingly.4 million Fig.

Magnesium 2000: Second International Conference on Magnesium Science & Technology. Warrendale. 488-489 791 solution whereas uncoated samples showed significant cracking after about 400. Israel Feb. “Corrosion protection of magnesium materials (Original Title: Korrosions-schutz von Magnesium-Werkstoffen. 1987. Juptner. Ruden. pp 1-5. C. pp 321-338. No.Materials Science Forum Vols. G. Canada. Sannes and D. 22-24.W.). The project manager for the SCMD work. 1995. SAE Technical Paper No. H. B. Osborne. The authors wish to thank all SCMD project members who have provided materials. although such support does not constitute an endorsement by the Department of Energy of the views expressed herein. China Mechanical Engineering. 9. PA.A.1998. 1999-01-0926. Cole. Zheng. S. Sept. J. vol. G. Vol. [12]D. Dayong Shan and Wei Ke. No. “New possibilities for magnesium: Chrome-free surface treatments for magnesium”. Wei. G-T87-003. by Department of Energy Cooperative Agreement No. June. [5] P. October 13-16. Kurze. No. [4] W. Jan. The beneficial effect of the coating on SCC resistance is likely a result of its influence in reducing hydrogen generation on the Mg surface. 6. SAE. [7] http://www. Industrial Paint & Powder (USA).tagnite. Frantzeskakis. 20. pp 22-24. Proceedings of the Second Israeli International Conference on Magnesium Science & Technology. Derushie. Acknowledgement The author(s) acknowledge that this research was supported. in part. Balzer and P.000 cycles under the same test conditions. SAE. [13]En-Hou Han. IMA 2000 Magnesium Conference. Warrendale. Hydro Magnesium. Salt Lake City. Dead Sea. Singe and J. 2000.E. T. Johnston and S. Zhang. Murray 14th International Die Casting Congress and Exposition. USA. SAE. 2001-01-0421. Protection of Mg Alloys for Structural Applications in Automobiles. Davis. Wang. Hillis and R. “Galvanic compatibility of coated steel fasteners with magnesium”. Toronto. 1789-1792. References [1] J. helpful suggestions and ideas in the past three years. vol. 2002. Alliance for the Polyurethanes Industry (API) Conference. Gao. Q. USA [11]G. 21-23 May. Publ: Society of Automotive Engineers. Cai. [2] Duan. USA [6] D. pp. (b) P. Smith. pp 358-362. L.2000. pp 34-36. Cu. in Magnesium Technology 2004. Cox and P. Albright. Si and Co on the Corrosion Properties of Permanent Mould Cast Medallions and Die Cast Plates of Magnesium Alloy AZ91". no. TMS 2004. Metalloberf-lache [Metalloberflache]..I. 2001 [9] J. Bakke. Chemical Conversion Coating on AZ91D and its Corrosion Resistance. Utah. Berkmortel and J. R. Skar. Corrosion Prevention for External Magnesium Automotive Components. pp 20. Lo. vol. Metalloberflache (Germany). 1. Cole. Stwart. Proc. DE-FC05-02OR22910. PA 15096. 400 Commonwealth Dr. "Effects of Ni. 25 Oct. Wanqiu Zhou. 54. 74. S. 55. M. Diesing. Vancouver. R. Warrendale. PA. 2000. [10]G. Hawke and T. Support by the Canadian Lightweight Materials Research Initiative (CLiMRI) is also acknowledged. K. SAE Technical paper No. especially Dick Osborne of [8] T. Ricketts. Edited by Alan Luo. Korner. Seidel and U. 1995 SAE Transactions: Journal of Materials & Manufacturing. Wang. “USCAR Project on Magnesium Structural Castings”. “Effects of fastener surface on galvanic corrosion of automotive magnesium components”. 2003 [3] R. . Canada. Proc. SAE Paper # 2004-01-0133. Zhang and J. Paper No. vol.104. 14. R. B. Penrod.