J O U R N A L O F M AT E R I A L S S C I E N C E L E T T E R S 1 8 ( 1 9 9 9 ) 4 1 9 4 2 1

Corrosion resistance of automotive exhaust materials

S. CHANG Pohang Iron & Steel Co., Ltd., P.O. Box 36, Pohang, Korea J. H. JUN Research Institute of Industrial Science & Technology, P.O. Box 135, Pohang, Korea E-mail: pc553603@smail.posco.co.kr

The material in an automotive exhaust system is one of the parts that is subject to severe corrosion. The typical corrosion that exhaust parts undergo includes condensate corrosion, salt-induced corrosion, and high-temperature oxidation. The corrosion of exhaust parts is promoted in heavy snow areas due to deicing salts on the road. In addition, high engine heat efciency and extended guarantee terms for new automobiles created the necessity for the extended corrosion life of exhaust materials. Aluminized mild steel has been widely used for the exhaust parts, but it is gradually being replaced by the materials of higher corrosion resistance, such as stainless steel and aluminized stainless steel (STS) [15]. The present study was conducted to compare the corrosion resistance of various exhaust materials and to develop new materials systems. The tested materials were aluminized mild steel, plain STS 409L, and STS 409L coated with aluminum. Aluminum coatings on STS 409L were prepared with three different processes: direct hot dip, precoating followed by hot dip, and vapor deposition. Table I shows the specimens and their coating processes. Direct hot dip coating was conducted by a hot dip coating simulator with a controlled-inert gas, 90%H2 10%N2 (dew point lower than 60 8C). STS 409L was also pre-coated with Ni3 wt %Co prior to hot dip coating. The pre-coated sheet was hot dip aluminized in a gas atmosphere of 15%H2 85%N2. As for the vapor deposition of aluminum on STS 409L, four kinds of deposition systems were prepared, with aluminum at the top for all the
TA B L E I Test specimens and their coating processes Material 409L AM AS(20) AS(40) ANC ADS Ti=Al Cr=Al Si=Al
a

systems: 1) single-layer deposition of aluminum, 2) double-layer deposition of Cr=Al, 3) double-layer deposition of Ti=Al, and 4) double-layer deposition of Si=Al. Chromium, titanium, and silicon were reported to have benecial effects on the corrosion resistance of materials for automotive exhaust systems [68]. An aluminum bond coating of 1 m was specially applied to enhance the adhesion of silicon for the double-layered Si=Al vapor deposition. The coating thickness by vapor deposition was 3 m for the underlayer and 17 m for the top aluminized layer. These specimens were corrosion-tested in various environments. Corrosion resistance was evaluated by condensate corrosion, NaCl-induced corrosion, and cyclic oxidation tests, respectively. For the condensate corrosion test, all specimens were placed just above a test solution in a chamber. The chamber was heated up to 200 8C at the rate of 3 8C min1 , maintained for 2 h, and cooled at the rate of 1 8C min1 . This thermal cycle was repeated as many times as necessary. The composition of the simulated solution 2 was as follows; 5000 ppm SO2 4 , 3000 ppm CO3 , 2000 ppm NH4 , 150 ppm NO3 , and 1000 ppm Cl . The NaCl-induced corrosion test consisted of immersing the test specimens in a 5% NaCl solution, followed by exposure to a temperature of 650 8C for a given number of cycles. The cyclic oxidation test was performed in atmospheric conditions. For each cycle, the specimens were maintained at 900 8C for 20 h, and then taken out of the furnace and cooled at room temperature for 4 h. The weight change and

Type STS 409L Aluminized Aluminized Aluminized Aluminized mild steel STS 409L STS 409L Ni-Co ash STS 409L

Process 11% Cr containing steel Hot dip Al coating directly on mild steel Hot dip Al coating directly on STS 409L Hot dip Al coating directly on STS 409L Ni-Co ash coating by electroplating on STS 409L, then hot dip Al coating Evaporated Al coating on STS 409L Evaporated Ti=Al double coating on STS 409L (Ti for bottom) Evaporated Cr=Al double coating on STS 409L (Cr for bottom) Evaporated Si=Al double coating on STS 409L (Si for bottom)

Coatinga 20 20 40 20 10 3=17 3=17 3=17

Al deposited STS 409L Ti=Al deposited STS 409L Cr=Al deposited STS 409L Si=Al deposited STS 409L

coating thickness per one side in m.

0261-8028 # 1999 Kluwer Academic Publishers

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rust area (%) were measured for each test specimen to estimate corrosion resistance. Fig. 1 shows the rust area (%) of the specimens tested by condensate corrosion for 30 cycles. The performances of Ti=Al-deposited STS 409L, aluminized Ni-Co ash STS 409L, and aluminized STS 409L(40) were much better than those of STS 409L and other coated specimens. The data for aluminized STS 409L, (c) and (d) in Fig. 1, indicate that the corrosion resistance of aluminized STS 409L increased with coating weight. The rust area of Ti=Aldeposited STS 409L with good corrosion resistance was analyzed by using a scanning electron microscope and an energy dispersive spectrometer. The titanium undercoating layer was observed to protect the substrate steel in the area where the aluminum coating was locally corroded. Fig. 2 shows the weight changes of the specimens
100 90 80 70 Rust Area (%) 60 50 40 30 20 10 0 a b c d e f g h i
Figure 1 Rust area (%) of the specimens after condensate corrosion test for 30 cycles at 200 8C: (a), 409L; (b), AM; (c), AS(20); (d), AS(40); (e), ANC; (f), ADS; (g), Ti=Al; (h), Cr=Al; i;Si/Al:

tested by NaCl-induced corrosion. The plain STS 409L and Ti=Al-deposited STS 409L revealed abrupt weight gains in the initial stage and were severely corroded after 10 cycles. It was reported that Cr2 O3 on a stainless steel surface reacts with NaCl into soluble and unstable Na2 CrO4 at high temperature, which may accelerate the corrosion of stainless steel [9]. Other specimens showed lower weight gains. Si=Al-deposited STS 409L represented the best appearance in the comparison of the rust areas among the specimens tested for 40 cycles. X-ray diffraction on the coating of Si=Al-deposited STS 409L revealed -Al2 O3 and some Fe-Al intermetallics such as Fe2 Al5 and FeAl. Fig. 3 shows the weight changes of STS 409L and various coated specimens after a cyclic oxidation test at 900 8C. The oxidation properties of STS 409L and aluminized mild steel were very poor when compared with those of the aluminum-coated STS 409L specimens. The weight gain of uncoated STS 409L was about 160 mg cm2 , even after weight loss by partial spallation of the oxide layer. Aluminumcoated STS 409L specimens, however, showed much slower oxidation rates, indicating the formation of thin alumina layers on the surface. The total weight gain of every coated STS 409L was less than 20 mg cm2 . The oxide scales were analyzed with Xray diffraction for the specimens oxidized for 10 cycles at 900 8C. Only an Al2 O3 peak was strongly detected from the oxide layers of Ti=Al-deposited STS 409L and Ni-Co pre-coated aluminized STS 409L, whereas a weak Fe2 O3 peak with Al2 O3 was observed from other aluminum-coated specimens. It is, therefore, believed that a titanium or Ni-Co underlayer effectively prevented the outward diffusion of iron and the formation of its oxide. Summarizing the present study, the performances of Ti=Al-deposited STS 409L, aluminized Ni-Co ash STS 409L, and aluminized STS 409L(40) were much better than uncoated STS 409L and other

20 10 Weight Change (mg/cm2)

180 160 140 a b c d e f g h

0 0 10 20 30 40 50

10

20

30

40

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Weight Gain (mg/cm2)

120 100 80 60 40 20 0 0 1

a b c d e f g h Cycles

5 6 Cycles

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Figure 2 Weight change of the specimens after NaCl-induced corrosion test at 650 8C: (a), 409L; (b), AM; (c), AS(20); (d), AS(40); (e), ADS; (f), Ti=Al; (g), Cr=Al; (h), Si=Al.

Figure 3 Weight change of the specimens after cyclic oxidation at 900 8C: (a), 409L; (b), AM; (c), AS(20); (d), AS(40); (e), ADS; (f), Ti=Al; (g), Cr=Al; (h), Si=Al.

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coated specimens in the condensate-corrosion test at 200 8C. But NaCl-induced corrosion resistance was the best with Si=Al-deposited STS 409L, which was probably due to the Al2 O3 layer formed on the coating surface. In cyclic oxidation tests at 900 8C, all aluminum-coated STS 409L showed much slower oxidation rates than uncoated STS 409L and aluminized mild steel. As a result, most aluminized stainless steel revealed good performances for exhaust systems, with respect to corrosion. Considering the cost and process, however, the increase of coating weight seemed to be more effective than the selection of coating system for corrosion resistance.

References

1. D. A . J O N E S , in "Principles and prevention of corrosion" 2. Y. TA R U TA N I , H . F U J I K AWA , H . H O S H I , K . H I G U C H I 3. S . C H A N G , POSCO Technical Report, 1995P151 (1996). 4. W. D. E D S A L L , Chromium Rev. 9 (1988) 1. 5. J. D E C R O I X , P. M AT R E P I E R R E and B . B R A M AU D 6. 7. 8. 9.
G R AT T E AU , Rev. Metall. Cah. Inf. Tech. 83 (1986) 657. K . A S A K AWA , CAMP-ISIJ 4 (1991) 1839. N . H I R A N AT S U , ibid. (1991) 1808. H . K A G E C H I K A , Alutopia 21 (1992) 56. Y. S H I N ATA , Oxidation of Metals 20 (1987) 315.

(Macmillan, 1992).

and T. H A S H I Z U M E , Sumitomo Metals 48 (1996) 22.

Received 3 December 1997 and accepted 18 September 1998

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