Corrosion of welds in automotive fuel tanks

Thomas Trickl and Gregor Mori

Department of General and Analytical Chemistry, University of Leoben, Franz-Josef-Strae 18, A-8700 Leoben, Austria Abstract Various kinds of examination were used to predict the corrosion behaviour of a CrMnNaustenitic stainless steel and three types of welded joints, produced by different welding procedures. Optical and scanning electron microscopy (SEM) was used to investigate surface and microstructure. Immersion tests in a number of test fuels and salt spray tests were carried out to simulate conditions inside and outside of the fuel tank, respectively. None of the test fuels caused any form of corrosion, whereas salt spray testing resulted in corrosion only 1 hour after test begin. Potentiodynamic polarization tests in 3.56 % NaCl solution revealed the changes in electrochemical behaviour. Corrosion effects appeared in the fusion zone or in the heat-affected zone of the welds during salt spray testing and electrochemical testing. The presence of heat-tints in the vicinity of the welds has a detrimental effect on the active corrosion behaviour. Keywords: corrosion, welds, heat tint, stainless steel, salt spray testing Introduction Many car manufacturers are forced by new legislation demanding the diminution of evaporative emissions to replace plastics for steel in the production of fuel tanks. Conceivable alternatives for plastics are sheet steel with different coating systems and stainless steel. Choice of material for fuel tank production depends on many aspects like manufacturability, safety, weight, cost, design, recyclability and corrosion [1]. As far as corrosion is concerned, there are two main factors: corrosion inside the tank, caused by fuel, and corrosion on the outside caused by atmosphere and environment. This paper is part of a study [2] that examined corrosion properties of the investigated materials and especially the influence of welding procedures on the corrosion behaviour. Materials investigated were a CrMnN-austenitic stainless steel, a zinc-nickel coated steel and a galvannealed steel. This paper presents the results concerning only corrosion behaviour of the CrMnN-austenitic stainless steel and the effects of different welding procedures on corrosion properties. Experimental Materials The sheet material examined in this study is a CrMnN-alloyed austenitic stainless steel (chemical composition given in Table 1). Different welding procedures were used to produce three types of welded joints: plasma welding, spot welding and stud welding (Fig. 1,a-d). The stud material is an AISI Type 304 CrNi-alloyed austenitic stainless steel.

Fig. 1a: Plasma weld

Fig. 1b: Spot Weld

Fig. 1c: Stud weld Fig. 1d: Stud weld, reverse

Methods Optical microscopy and scanning electron microscopy with an energy dispersive X-ray spectroscopy were used to characterize microstructure and surface of the samples. Table 1: Chemical composition of CrMnN-austenitic stainless steel (in wt%) C 0,042 Cr 18,26 Ni 3,71 Si 0,36 Mn 6,51 Mo 0,25 Cu 0,15 P 0,031 S 0,005 N 0,18

Salt spray tests were carried out in an Ascott CC1000 salt spray chamber after DIN 50021 SS. The tests were stopped after 1, 2, 5, 10, 20, 50, 100, 200, 500 and 700 hours for visual inspection of specimens. All samples were taken out of the salt spray chamber, and the progress of corrosion was documented by stereomicroscopy. Immersion tests of samples were carried out in several test fuels (Table 2). The samples were put into screw cap glasses and filled with the test fuel, until half of the sample and the weld was immersed. The maximum duration of immersion tests was 20 weeks. Testing temperature was 60 C. All test fuel were single-phase. Table 2: Composition of test fuels used for immersion tests Fuel Abbrev. composition remarks No Fuel 1 BIO Biodiesel Fuel 2 ROZ 98 Gasoline 98 Octane (ROZ 98) Fuel 3 E22 78 vol% ROZ 98, 22% Ethanol Water content ethanol: min. 3% Fuel 4 M25 75 vol% ROZ 98, 25% Methanol Water content methanol: min. 0.5% 78 vol% reference fuel C, Reference fuel C: 22 vol% aggressive ethanol 50 vol% iso-octane, 50 vol% toluene aggressive water: aggressive ethanol: Fuel 5 CE22A 1000 ml distilled water 995 ml anhydrous ethanol 0.990g NaCl (600 ppm Cl-) 5 ml aggressive water 20.888g Na2SO4 (600 ppm SO4 ) 0.028 ml formic (or acetic) acid 0.828g NaHCO3 (600 ppm HCO3-) Potentiodynamic polarization tests on sheet material and on different welds as well were done using a three-electrode cell. A saturated calomel electrode (SCE) served as reference electrode, a platinum sheet as counter electrode. The specimens were taken from differently

welded joints by cutting off small pieces with areas of 3-5 cm. The cut edges of the specimens were protected by a lacquer. All samples were tested in aerated 3.56 % NaCl-solution at room temperature. Measurement of the samples was done by immersing specimens in the solution for 30 minutes at open circuit potential. After having reached stable conditions, the potential was raised from a value 100 mV below the open circuit potential, with a constant sweep rate of 600 mV/h, until a current density limit of 1 mA/cm was reached. For assessing the influence of heat tints on corrosion properties samples of sheet material were annealed for five minutes at different temperatures resulting in different colours (Table 3) and tested potentiodynamically under same conditions as mentioned above. Table 3: Heat tints after annealing of sheet samples at different temperatures for five minutes temperature [C] 500 colour light yellow Results Surface and Microstructure Optical examinations were carried out to get information about how the corrosion properties of the materials are affected by changes in microstructure, caused by welding operations. Fig. 2a shows the microstructure of the CrMnN-austenitic stainless steel sheet material, which is mainly austenitic with little amount of delta-ferrite (dark coloured). The surface of the sheet material, as shown in Fig. 2b, is uneven, revealing great roughness that most likely has been generated by pickling and a preferable attack of grain boundaries at the surface. 550 straw 575 dark yellow 595 crimson 615 violet 650 blue

Fig. 2a: Microstructure of CrMnN austenitic stainless steel, austenite (bright phase), and delta-ferrite (dark)

Fig. 2b: Surface of sheet material

Fig. 3a shows a micrograph of the fusion zone of the plasma welding. Here, the amount of delta-ferrite is larger, compared to the sheet material. Furthermore, the visual appearance of austenite in the fusion line is dendritic, which is also visible on the surface of the plasma weld (Fig. 3b). Fig. 4 is a SEM image of the surface of a spot weld. The photo exhibits a bright, Cu-rich phase deposited on the rough surface of the material, caused by electrode burning during the spot welding process.

Fig. 3a: Microstructure of plasma weld

Fig. 3b: Surface of plasma weld with dendritic structure

The structure of a typical stud weld is shown in Fig. 5. It shows the presence of a crevice between sheet and weld, formed by liquid metal that has been squeezed out of the welding zone during pressing the stud onto the plate.

Fig. 4: Surface of spot weld, Cu-rich deposit (bright phase) at grain boundaries

Fig. 5: Cross-sectional view of stud weld

Salt spray testing Salt spray tests were carried out to examine the performance of the samples in an environment similar to conditions given on the road. Test results were, that the sheet material unaffected by the welding procedure did not show any form of corrosion. However, those areas of the specimens affected by welding procedure, suffered corrosion already after a short time of exposition in the salt spray. Corrosion started always at heat tints, as can be seen in Fig. 6 (stud weld) and Fig. 7 (spot weld). Immersion tests The immersion tests in several test fuels were performed to examine the corrosion properties inside the fuel tank. None of the test fuels caused any form of corrosion. Neither the liquid phase nor the steam phase were aggressive enough to cause damage of the samples.

Fig. 6: Time dependency of corrosion of stud weld in salt spray test acc. DIN 50021 SS

Fig.7: Time dependency of corrosion of spot weld in salt spray test acc. DIN 50021 SS Potentiodynamic polarization tests The results of the potentiodynamic polarization tests are shown in Figs. 8. The I-U-curve of the sheet metal (Fig. 8a) shows an open circuit potential (Ecorr) of about 135 mVSCE and almost no passivity range. Ecorr of the stud material (Fig. 8d) is about 60 mVSCE. In comparison to Ecorr of the sheet material, Ecorr of all types of welds (Fig. 8, a-f) are shifted to less noble potentials, in numbers about 80 to 110 mV. The results of the experiments concerning the influence of the presence of heat tints on corrosion properties are summarized in Fig. 9a and Fig. 9b. The diagrams show, that the effect on Ecorr of the sheet material is pronounced on heat tints formed at 500 and 650 C, resulting in a significant shift into less or more noble direction respectively. Fig. 9b shows the serious decrease of corrosion resistance of the sheet material in the presence of heat tints. Each of the artificially produced heat tints causes a significant drop of corrosion potential at an anodic current density of 1 mA/cm. Discussion In general, single phase microstructures are favourable over multi-phase alloys when considering corrosive properties [3]. The content of delta-ferrite in the investigated steel has positive effects on the welding behaviour of the material by reducing hot cracking susceptibility [4]. Dirt and mud particles can easily adhere to rough surfaces, as shown in Fig. 1b.The same is valid for particles from the welding electrode (Fig. 3a), resulting in the formation of crevices or local elements, respectively. The dendritic structure of the plasma welds (Fig. 2b) indicates possible inhomogenities in the distribution of the alloying elements, therefore differences in corrosion behaviour might occur [5].

Fig. 8: Polarization curves in 3.56 % NaCl at room temperature of (a) CrMnN-austenitic stainless steel, (b) plasma weld, (c) spot weld, (d) AISI Type 304 stud material, (e) stud weld, (f) reverse of stud weld

Salt spray testing exhibited only after a short testing time the detrimental influence of heat tints on the corrosion behaviour. These oxidation layers are very thin, contain cracks and are porous and chromium-rich. The latter causes a depletion of chromium under the layer, leading to loss of corrosion resistance and possibly to sensitisation (Fig. 11) [6]. Corrosion was initiated already after 1 hour of salt spray testing, always emerging from these heat tints.

(a) open circuit potential after 30 min of immerison

(b) corrosion potentials at a current density of 1 mA/cm

Fig. 9: Potentials of heat tints measured in 3.56 % NaCl at room temperature No pitting corrosion was found until the end of the salt spray test. This means that the corrosion products formed during salt spraying may originate from the heat tint areas. Potentiodynamic polarization tests confirmed the effects found by optical examination and salt spray testing. As known from literature, there is significant difference in pitting resistance between base metal and weld metal of same chemical composition [7]. In this study, the reduced corrosion properties of the welds were clearly revealed by a significant decrease of the ECORR of the welds (Fig. 8 b,c,e,f). Also all pits that developed during polarization tests originated in areas affected by the welding processes, whereas the unafunaffected sheet material remained uncorroded. Potentials of electrochemically investigated specimens at a current density of 1 mA/cm are given in Fig. 10. The influence of welding processes on corrosion properties is expressed by an observable shift of the these potentials towards less noble values. Fig. 12 shows a spot welded sample after potentiodynamic polarization Fig. 10: Corrosion potentials of welds measexperiment. Pits are only visible inside and ured in 3.56 % NaCl at room temperature at a in the orbital of the welding spot. An current density of 1 mA/cm

important result is that none of the investigated samples showed a distinct range of passivity. As a consequence pitting potential and open circuit potential are in the same range, as illustrated in Fig. 13. PREN of investigated steel is 21. Due to this there may be a narrow potential range with passivity as shown in Fig. 13 [8]. The negative influence of heat tints on the corrosion properties could be proved by the potentiometric tests carried out. Obviously a certain degree of sensitisation was caused by welding and subsequent oxide layers.

Fig. 11: Decrease of chromium content under heat tint [6]

Fig. 12: Pitting corrosion in orbital of spot weld after potentiodynamic polarization in 3,56% NaCl

Fig. 13: Correlation between open circuit potential and pitting potential depending on PREN (Pitting Resistance Equivalent Number, %Cr + 3%Mo) [8]

The depletion of chromium under the oxide layers resulted in a lower PRE number of this area and yielded to a higher susceptibility to pitting corrosion. By this the missing passivity area in Fig. 8b and Fig. 8e can be explained. The anodic peak obtained at spot welds at 150 mVSCE is due to anodic dissolution of deposited copper from electrode contact zone. The stud material AISI type 304 has a PREN of 18 resulting in a lack of passivity in the investigated solution. Conclusions The aim of this study was to characterize the changes in corrosion behaviour of a CrMnNaustenitic stainless steel caused by different welding processes, by using different ways of examinations. Conclusions are as follows:

1. Test fuels used in the immersion tests did not cause any form of corrosion. 2. Salt spray tests revealed that the unaffected sheet material showed excellent corrosion resistance, whereas welds and heat-affected areas covered with heat tints showed corrosion already only after one hour of salt spray testing. Corrosion products seemed to be formed exclusively from chromium depleted areas beneath heat tints. No pitting was observed at any salt sprayed specimen. 3. Potentiodynamic polarization measurements showed that open circuit potentials of all welds were shifted towards less noble direction when compared to the value of unaffected sheet material. Heat tints have detrimental effect on the active corrosion behaviour (e.g. at an anodic current density of 1 mA/cm). References [1] [2] [3] [4] [5] [6] [7] [8] P. J. Alvardo, JOM, 48 (1996) 22-25 T. Trickl, Untersuchung der Korrosionseigenschaften von Schweiverbindungen im Kraftstoffbehlterbau, Diploma Thesis, University of Leoben (2002), in press A. J. Sedricks, Corrosion of Stainless Steel, John Wiley & Sons Inc, New York (1996) S. Anik, Schweieignung metallischer Werkstoffe, DVS-Verlag GmbH, Dsseldorf (1995) H. Schumann, Metallographie, Deutscher Verlag fr Grundstoffindustrie, Leipzig (1991) E. Wendler-Kalsch, Korrosionsschadenkunde, Springer, Berlin Heidelberg (1998) J. R. Davis (ed.), ASM Speciality Handbook Stainless Steels, ASM International, Ohio (1994) H. Zitter and D. Schaschl-Outschar, Werkstoffe und Korrosion 32 (1981) 324-331