12 Effects of Acid Deposition on Poultice-Induced Automotive Corrosion 1
R. C. Turcotte, T. C. Comeau , and Robert Baboian
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Texas Instruments Incorporated, 34 Forest Street, Attleboro, M A 02703
The chemistry of wet poultice deposits (road dirt and debris) on automobiles is affected by factors such as road salts and the composition of wet and dry deposition. The rate of metallic corrosion where poultice deposits accummulate on automobiles is highly dependent on this chemistry. The composition of aggressive species in poultice deposits was determined by sampling in Montreal, Detroit, Boston, and Dallas. A correlation between the corrosivity and the poultice chemistry was made by mounting corrosion test coupons on vehicles in each city and by simulating poultice effects in the laboratory. Results show that corrosion damage increases in a complex manner in areas of heavy road salt use and acid deposition. F a c t o r s a f f e c t i n g t h e c o r r o s i o n o f auto-body s t e e l and t r i m a r e i n two major c a t a g o r i e s , d e s i g n a n d e n v i r o n m e n t a l . Design f a c t o r s i n c l u d e the choice o f material o f construction, galvanic coupling o f d i s s i m i l a r m e t a l s , t h e c r e a t i o n o f l i p s o r c u p s t h a t may h o l d a g g r e s s i v e environments and o t h e r entrapment a r e a s . Environmental f a c t o r s i n c l u d e a l l the v a r i o u s c h e m i c a l s p e c i e s t o which t h e a u t o m o b i l e i s s u b j e c t e d ; major c o n t r i b u t o r s i n c l u d e r o a d s a l t s such as sodium c h l o r i d e and c a l c i u m c h l o r i d e , s e a s a l t a e r o s o l s , a n d p r e c i p i t a t i o n , e s p e c i a l l y i f i t has been a c i d i f i e d . Figure 1, which g r a p h i c a l l y d e p i c t s t h e a u t o m o t i v e c o r r o s i o n m i l e s t o n e s t h a t h a v e a c c o m p a n i e d r o a d s a l t u s a g e i n t h e U n i t e d S t a t e s ( 1 - 2 ) , and F i g u r e 2 , which superimposes automobile c o r r o s i o n r a t e s a n d average r a i n pH i n t h e U n i t e d S t a t e s (JO, s u p p o r t t h e s e c l a i m s . P o u l t i c e d e p o s i t s a r e a c c u m u l a t i o n s o f road d i r t , v e g e t a t i o n , t a r , a n d o t h e r d e b r i s which c o l l e c t s i n c r e v i c e s around t r i m m a t e r i a l s , i n w h e e l w e l l s , a n d i n o t h e r e n t r a p m e n t a r e a s (3,). S i n c e t h e b a s i c design i n those l o c a t i o n s allows p o u l t i c e d e p o s i t s t o become wetted w i t h o u t b e i n g washed away, p o u l t i c e s r e m a i n f o r a c o n s i d e r a b l e p e r i o d o f t i m e and can cause s e v e r e c o r r o s i o n l e a d i n g 'Current address: University of Rhode Island, Kingston, RI 02881 0097-6156/ 86/ 0318-0200$06.00/ 0 © 1986 American Chemical Society
Baboian; Materials Degradation Caused by Acid Rain ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
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12. TURCOTTE ET AL.
0· 1945
Effects of Acid Deposition
1
1
I
1950
1955
1960
on Automotive
I
1965 YEAR
Corrosion
201
I
I
I
I
1970
1975
1980
1985
F i g u r e 1. Automobile c o r r o s i o n m i l e s t o n e s a s a f u n c t i o n o f road s a l t usage.
Acid Rain —
pH
5.0 6.0 5.0 4.7 4.3
•
Severe
Hfljj
Moderate
HI
Mild
•
Negligible
F i g u r e 2. Geographic c o r r o s i o n i n the United
distribution States.
o f a c i d r a i n and a u t o m o b i l e
Baboian; Materials Degradation Caused by Acid Rain ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
202
M A T E R I A L S D E G R A D A T I O N C A U S E D BY A C I D R A I N
even to p e r f o r a t i o n ( 4 ^ . T h i s paper examines the c h e m i s t r y o f a g g r e s s i v e s p e c i e s i n p o u l t i c e samples from Boston, D a l l a s , D e t r o i t , and M o n t r e a l . A c o r r e l a t i o n b e t w e e n c o r r o s i v i t y and p o u l t i c e chemistry i s presented.
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Theory When o r g a n i c f u e l s a r e burned, carbon d i o x i d e and water vapor a r e r e l e a s e d a l o n g w i t h v a r i o u s amounts o f s u l f u r d i o x i d e and n i t r o g e n o x i d e s . The s u l f u r and n i t r o g e n o x i d e s i n the atmosphere a r e then f u r t h e r o x i d i z e d w i t h the a s s i s t a n c e of u l t r a v i o l e t solar r a d i a t i o n ; when t h e s e g a s e s a r e s c r u b b e d f r o m t h e a i r by p r e c i p i t a t i o n , a d i l u t e s o l u t i o n o f s u l f u r i c a c i d and n i t r i c a c i d forms. C a r b o n d i o x i d e i t s e l f hydro l y ζ es to c a r b o n i c a c i d and i s i m p o r t a n t i n the marine carbonate b u f f e r s y s t e m ; h o w e v e r , i t i s a weak o r g a n i c a c i d and a t m o s p h e r i c c o n c e n t r a t i o n s t y p i c a l l y lower the pH o f d i s t i l l e d water o n l y t o about 5.7 ( 5 - 6 ) . M e t a l o x i d e s a r e t y p i c a l l y more s o l u b l e i n a c i d i c m e d i a . Hence, low pH s o l u t i o n s s h o u l d a d v e r s e l y a f f e c t t h e f o r m a t i o n o f p r o t e c t i v e f i l m s on m e t a l s u r f a c e s . C h l o r i d e s , on t h e o t h e r h a n d , are known t o induce c o r r o s i o n through a c a t a l y t i c mechanism. C h l o r i d e i o n s a r e s m a l l and m o b i l e and t h e r e f o r e a f f e c t the p r o t e c t i v e f i l m s on m e t a l s c a u s i n g l o c a l breakdown and p i t t i n g . Once p i t t i n g has i n i t i a t e d , m i g r a t i o n o f c h l o r i d e i o n i n t o t h e p i t c a u s e s a l o w e r i n g o f pH w i t h i n t h e r e s t r i c t i o n by t h e f o r m a t i o n o f HC1 h y d r o l y s i s p r o d u c t s . This o c c u r s i n b o t h p i t s and c r e v i c e s and i s shown i n F i g u r e 3 ( 7 ) . A d d i t i o n a l l y , calcium c h l o r i d e i s deliquescent, absorbing m o i s t u r e f r o m t h e a i r a n d m a i n t a i n i n g a wet s u r f a c e a b o v e a c r i t i c a l humidity. I t i s known t h a t c a l c i u m c h l o r i d e i s h i g h l y c o r r o s i v e t o a u t o m o b i l e s , a t l e a s t p a r t l y because o f t h i s d e l i q u e s c e n c e (8). The mechanism o f p o u l t i c e c o r r o s i o n i s shown d i a g r a m a t i c a l l y i n F i g u r e 4. C o r r o s i o n i n i t i a l l y o c c u r s u n i f o r m l y o v e r the whole m e t a l s u r f a c e . However, as t h e p r o c e s s c o n t i n u e s , t h e o x y g e n r e d u c t i o n c a t h o d i c r e a c t i o n may become r e s t r i c t e d t o a band near the s u r f a c e where oxygen i s r e a d i l y a v a i l a b l e . C o r r o s i o n o f m e t a l t h e n t a k e s p l a c e p r e f e r e n t i a l l y s l i g h t l y below the band. The pH r i s e s i n t h e c a t h o d i c r e a c t i o n area due t o an i n c r e a s e i n h y d r o x y l i o n c o n c e n t r a t i o n w h i l e the a n o d i c a r e a decreases i n pH due t o t h e h y d r o l y s i s of metal c h l o r i d e r e a c t i o n products. Wet
P o u l t i c e Chemistry
F i g u r e 2 shows t h a t the n o r t h e a s t e r n U n i t e d S t a t e s s u f f e r s e s p e c i a l l y severe automotive c o r r o s i o n . Annual automobile c o r r o s i o n s u r v e y s c o n d u c t e d by T e x a s I n s t r u m e n t s I n c . have i n d i c a t e d t h a t M o n t r e a l , Canada i s a l s o h i g h l y c o r r o s i v e . T h e r e f o r e B o s t o n , D e t r o i t , and M o n t r e a l were chosen as i d e a l s a m p l i n g s i t e s t h a t s h o u l d have the g r e a t e s t a m o u n t s o f c o r r o s i v e s p e c i e s ; f o r c o m p a r i s o n , D a l l a s , Texas was chosen as t y p i c a l o f what s h o u l d be a mildly corrosive area. R e p r e s e n t a t i v e samples (100 grams) o f p o u l t i c e s were c o l l e c t e d from c a r s i n each c i t y ( M o n t r e a l 31, D e t r o i t 24, Boston 15, D a l l a s 4 ) . S o l u b l e s p e c i e s were t h e n e x t r a c t e d i n t o d i s t i l l e d water by means o f a b a l l m i l l , which r a n 8 hours on and 16 h o u r s o f f f o r 3
Baboian; Materials Degradation Caused by Acid Rain ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
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TURCOTTE
ETAL.
Effects of Acid Deposition on Automotive Corrosion 203
F i g u r e 3·
Initial
A u t o c a t a l y t i c p i t t i n g mechanism.
Advanced
F i g u r e 4. Mechanism o f p o u l t i c e c o r r o s i o n o f a u t o s t e e l i n i t i a l and advanced s t a g e s .
Baboian; Materials Degradation Caused by Acid Rain ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
showing
204
M A T E R I A L S D E G R A D A T I O N C A U S E D BY A C I D RAIN
days; t h e s o l u t i o n was t h e n f i l t e r e d (0.45 jum) b e f o r e a n a l y s i s (9). Q u a l i t a t i v e a n a l y s e s were done u s i n g D C - P l a s m a emission s p e c t r o s c o p y and a s e r i e s o f a n i o n i c s p e c i f i c methods. The p r i m a r y c h e m i c a l c o n s t i t u e n t s were t h e n q u a n t i t a t i v e l y d e t e r m i n e d by methods l i s t e d i n T a b l e I ( 9 - 1 0 ) . EPA water q u a l i t y s t a n d a r d s were used as a check on the methods used.
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Table I .
Methods o f A n a l y s i s
Species
Technique Employed
CATIONS
Na+ Ca2+ K+ Mg2+
ATOMIC ABSORPTION SPECTROSCOPY OR ATOMIC EMISSION SPECTROSCOPY
ClANIONS
NOo-
ION SELECTIVE ELECTRODE ION SELECTIVE ELECTRODE UV-VISIBLE SPECTROSCOPY UV-VISIBLE SPECTROSCOPY TITRIMETRY TITRIMETRY
S0]J2P0 34
HCOo-
C0 23
F i g u r e 5 c o m p a r e s t h e i o n s t h a t might be a t t r i b u t e d t o road s a l t use and a c i d i c d e p o s i t i o n i n t h e n o r t h e r n c i t i e s . T h e s e i n c l u d e s o d i u m , c a l c i u m , c h l o r i d e , and s u l f a t e ; they were major constituents. W h i l e t h e n o r t h e r n c i t i e s have e x p e c t e d l y h i g h l e v e l s o f these i o n i c s p e c i e s , t h e l e v e l s i n D a l l a s were unexpected. F u r t h e r o b s e r v a t i o n p o i n t e d o u t i m p o r t a n t d i f f e r e n c e s i n t h e c h e m i s t r y o f t h e environments as d e s c r i b e d below. Comparisons o f t h e p e r t i n e n t i o n i c s p e c i e s i n t h e p o u l t i c e s a r e shown i n F i g u r e 6. I n B o s t o n , D e t r o i t , and M o n t r e a l , t h e r e i s an a p p r o x i m a t e b a l a n c e b e t w e e n e q u i v a l e n t s o f c h l o r i d e s a n d s u l f a t e s v e r s u s e q u i v a l e n t s o f c a l c i u m and sodium; i n D a l l a s , t h e r e i s an o v e r a b u n d a n c e o f c a t i o n s , i n d i c a t i n g t h a t u n i d e n t i f i e d anionic species e x i s t . The p o u l t i c e s f r o m d i f f e r e n t c i t i e s a l s o h a v e v a r y i n g c h a r a c t e r i s t i c soluble species. Montreal p o u l t i c e s a r e t y p i c a l l y v e r y h i g h i n s u l f a t e and c a l c i u m i o n s w i t h s i g n i f i c a n t l e v e l s o f c h l o r i d e and sodium. D e t r o i t p o u l t i c e s a r e h i g h e s t i n c h l o r i d e and c a l c i u m i o n s w i t h s i g n i f i c a n t l e v e l s o f s u l f a t e and sodium i o n s . Boston, while possessing l e s s o f these s o l u b l e s p e c i e s , c o n t a i n s m a i n l y s u l f a t e and c a l c i u m i o n s w i t h a f a i r p r o p o r t i o n o f c h l o r i d e and s o d i u m i o n s . D a l l a s has high c a t i o n l e v e l s , e s p e c i a l l y c a l c i u m , b u t c h l o r i d e and s u l f a t e l e v e l s were s i m i l a r t o those o f Boston.
Baboian; Materials Degradation Caused by Acid Rain ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
12. TURCOTTE ET AL. Effects of Acid Deposition on Automotive Corrosion
205
3.5 3H
^
i
S
2A 2
-
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g
< °-
Na+
•
Ca 2
0
ci-
^
1
DC (Ο a
•
+
NOS
ES S04-2
15-1
Β
HC03-
1
0.5
BOSTON
MONTREAL
F i g u r e 5. C o n c e n t r a t i o n poultices.
o f road
DETROIT s a l t and
DALLAS
acid deposition ions i n
BOSTON
DALLAS S04 (10.1%) 2
cr (2.4%)
DETROIT
MONTREAL N a (10.5%) +
N a (2.4%) +
CI" (1.2%)
Figure 6.
Proportions
o f p o u l t i c e i o n s on an e q u i v a l e n t b a s i s .
Baboian; Materials Degradation Caused by Acid Rain ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
M A T E R I A L S D E G R A D A T I O N C A U S E D BY A C I D RAIN
206
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Automotive Corrosion In the winter of 1984-1985, test samples on Plexiglass plates were exposed i n each of the test c i t i e s . These included samples of bare weighed auto-body s t e e l , weighed g a l v a n i z e d s t e e l , and painted auto-body steel with s t a i n l e s s s t e e l t r i m . Where p a i n t e d panels were i n v o l v e d , cut edges were coated; i n the s t a i n l e s s s t e e l trimmed panels, the ends o f the s t a i n l e s s s t e e l b o l t s used f o r e l e c t r i c a l continuity were coated as w e l l . Nylon bolts were used to a t t a c h the other test specimens to the Plexiglass plate which was mounted on the front bumper of an automobile. Bare s t e e l from a l l s i t e s except Dallas generally had the same v i s u a l appearance, with F i g u r e 7 being t y p i c a l . Dallas steel p l a t e s showed very l i t t l e r u s t i n g . Upon r e t r i e v a l a l l the s t e e l plates were cleaned using Clarke's solution (ASTM G1) to determine the weight loss. The calculated mils per year penetration rates are l i s t e d i n Table I I . The c i t i e s may be l i s t e d i n decreasing order of aggressiveness as: Montreal >
Boston > Detroit
»
Dallas
with differences i n aggressiveness being s l i g h t i n the Northeast i n this test.
Table I I .
City
Boston
Dallas
Detroit
Montreal
Atmospheric Corrosion Rates of Bare Automotive Steel Plates During the Winter of * 84 - •85
Corrosion Rate (ropy) 1.83 2.24 2.68 0.0491 0.114 0.143 0.148 1.41 1.75 2.19 1.99 2.28 2.29 3.64
Average Corrosion Rate (mpy)
2.25
0.114
1.78
2.55
Baboian; Materials Degradation Caused by Acid Rain ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
12.
Effects of Acid Deposition on Automotive Corrosion 207
TURCOTTE ET AL.
G a l v a n i z e d s t e e l p l a t e s showed some v i s u a l d i f f e r e n c e s between c i t i e s , as seen i n F i g u r e 8. Some d i f f e r e n c e s w e r e a l s o o b s e r v e d w i t h i n t h e same c i t y ( e . g . F i g u r e 9 ) . These p l a t e s were c l e a n e d u s i n g an ammonia wash f o l l o w e d by a chromic a c i d and s i l v e r n i t r a t e d i p (ASTM G 1 ) . M i l s p e r y e a r p e n e t r a t i o n r a t e s a r e shown i n T a b l e III. Decreasing c o r r o s i v i t y f o l l o w s the order: Montreal
>
Boston > D e t r o i t
>
Dallas
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G a l v a n i z i n g n o t o n l y p r o t e c t s t h e s t e e l , b u t a c t u a l l y c o r r o d e s more slowly.
Table I I I .
Atmospheric C o r r o s i o n Rates o f G a l v a n i z i n g on Automotive S t e e l D u r i n g t h e W i n t e r o f '84 - '85
City
Boston
Dallas
Detroit
Montreal
C o r r o s i o n Rate (mpy)
Average C o r r o s i o n (mpy)
0.0590 0.0932 0.193 0.0152 0.0185 0.0202 0.0319 0.0364 0.0560 0.0626 0.198 0.238 0.284 0.319
Rate
0.115
0.0214
0.0517
0.260
Galvanic couples o f s t a i n l e s s s t e e l t r i m with painted auto-body s t e e l p r o d u c e d v e r y d r a m a t i c d i f f e r e n c e s i n c o s m e t i c c o r r o s i o n b e t w e e n c i t i e s , a s s e e n i n F i g u r e 10. N u m e r i c a l c o r r o s i o n r a t i n g s a r e l i s t e d i n Table IV. The d e c r e a s i n g o r d e r o f aggressiveness i s : Montreal >
Detroit
> Boston > D a l l a s
I n a d d i t i o n , r u s t i n g o f t h e s t a i n l e s s s t e e l t r i m m a t e r i a l was observed i n t h e n o r t h e r n c i t i e s , e s p e c i a l l y i n M o n t r e a l . To r e p r o d u c e p o u l t i c e c o r r o s i o n i n t h e l a b , s a m p l e s w e r e immersed i n washed sand s a t u r a t e d w i t h a s o l u t i o n o f i n t e r e s t , a s d e s c r i b e d p r e v i o u s l y (8). When bare s t e e l s a m p l e s w e r e t e s t e d i n
Baboian; Materials Degradation Caused by Acid Rain ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
208
M A T E R I A L S D E G R A D A T I O N C A U S E D BY A C I D RAIN
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Figure one
7.
Typical
season
Figure
8.
plates,
Visual
one season
Detroit,
9.
auto-body
steel
comparison
auto-body
steel
of t y p i c a l galvanized
exposure.
10.
Examples steel
Visual
galvanic
Boston,
of bare
following
i n Detroit.
Right
to l e f t :
steel
Boston,
auto-body
Dallas,
Montreal.
Figure
Figure
appearance
exposure
Dallas,
of the range
following
comparison
exposure
of stainless
c o u p l e s , one season Detroit,
of appearance
one season
f o r galvanized i n Detroit.
steel/painted
exposure.
Right
to
auto-body left:
Montreal.
Baboian; Materials Degradation Caused by Acid Rain ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
12.
T U R C O T T E ET AL.
Table IV.
Effects of Acid Deposition
on Automotive
Corrosion
209
R a t i n g o f SS T r i m / P a i n t e d Auto Body S t e e l Galvanic Corrosion
Average C o r r o s i o n Severity Rating
Corrosion Severity Rating
City
1.9
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Boston
2.1
2.1 2.3 1.1 1.4 1.4 1.9
Dallas
1.4
Detroit
2.2 3.3 3.6
3.0
Montreal
3.6 4.1 4.1
3.9
Note:
I n c r e a s i n g c o r r o s i o n i s 0 t o 5 w i t h 5 the most
severe.
a c i d r a i n ( d i s t i l l e d w a t e r a d j u s t e d t o pH 4 w i t h a 3:7 n i t r i c a c i d / s u l f u r i c a c i d m i x t u r e ) and 1? c a l c i u m c h l o r i d e , t h e d a t a i n Table V r e s u l t e d . T h a t l e v e l o f c a l c i u m c h l o r i d e i s more a g g r e s s i v e than a c i d r a i n ; however, i f t h e two a r e combined, t h e r e i s i n i t i a l l y a s y n e r g i s t i c e f f e c t that greatly increases corrosion. W i t h repeated w e t t i n g and d r y i n g , t h e s y n e r g i s t i c e f f e c t i s l o s t . The r e a s o n f o r t h i s phenomenon i s t h a t a l t e r n a t e w e t t i n g and d r y i n g of p o u l t i c e s can a f f e c t s o l u t i o n chemistry.
T a b l e V.
C o r r o s i o n Data f o r Auto-Body S t e e l i n P o u l t i c e Test
Acid
Avg. P e n e t r a t i o n 2 weeks; no d r y i n g (mpy)
Avg. P e n e t r a t i o n 12 weeks; d r y i n g and w e t t i n g (mpy)
Rain
1.3
19.3
CaCl
2
A c i d R a i n and CaClp
12.5
26.3
87.4
82.8
Baboian; Materials Degradation Caused by Acid Rain ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
M A T E R I A L S D E G R A D A T I O N C A U S E D BY A C I D RAIN
210
A s o l u t i o n o f s u l f u r i c and n i t r i c a c i d s , w i t h and without c a l c i u m c h l o r i d e a d d i t i o n , was s u b j e c t e d t o c y c l i c d r y i n g . A f t e r t h r e e w e t / d r y c y c l e s , t h e pH o f b o t h h a d r i s e n , w i t h t h e CaCl2 s o l u t i o n r i s i n g more. A n a l y s i s o f t h e o r i g i n a l a n d o f t h e c y c l e d s o l u t i o n s i s shown i n T a b l e V I . Note t h a t t h e n i t r i c a c i d e v a p o r a t e d away and t h a t c h l o r i d e was d e p l e t e d t o v e r y l o w v a l u e s . T h i s i s due t o e v a p o r a t i o n and t h e r e a c t i o n : CaCl
2
+ H2SO4
CaSOiii +
2HC1 +
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i n w h i c h HC1 i s d r i v e n o f f upon d r y i n g .
Table VI.
E f f e c t o f Repeated W e t t i n g and D r y i n g on A c i d Rain Chemistry
S0 -2 (mg/1) 4
Sample
PH
H S0i| HNO3 CaCl
NO3(mg/1)
+2 (mg/1)
C a
ci(mg/l)
2
0.96
590
291
350
940
3 wet-dry cycles
1.57
350
6.8
390
w o u l d e x p e c t B o s t o n t o be t h e l e a s t a g g r e s s i v e o f t h e t h r e e n o r t h e r n c i t i e s . The f a c t t h a t i t i s more a g g e s s i v e than D e t r o i t i n two o f t h e f i e l d t e s t s may i n d i c a t e t h e i n f l u e n c e o f increased a c i d d e p o s i t i o n a c t i v i t y i n the Boston a r e a . In D a l l a s , CaCl2 i s used f o r dust c o n t r o l p u r p o s e s . The a b s o l u t e l e v e l s o f c h l o r i d e and s u l f a t e s a r e s i m i l a r t o t h o s e found i n B o s t o n . However, e n v i r o n m e n t a l f a c t o r s such as p r e c i p i t a t i o n and h u m i d i t y a r e d i f f e r e n t and t h e r e f o r e D a l l a s i s l e s s a g g r e s s i v e . I n a d d i t i o n , D a l l a s a n a l y s e s do n o t a p p e a r t o a c c o u n t f o r a l l i o n i c species. R e g a r d l e s s o f t h e environment, t e s t s i n d i c a t e t h a t a u t o m o b i l e m a n u f a c t u r e r s can s i g n i f i c a n t l y reduce c o r r o s i o n i n a c i d d e p o s t i o n a r e a s by u s i n g g a l v a n i z e d s t e e l . Even i n t h e v e r y s e v e r e M o n t r e a l environment, the c o r r o s i o n o f g a l v a n i z i n g i s r o u g h l y an o r d e r o f m a g n i t u d e l e s s than t h a t o f b a r e s t e e l . C o r r o s i o n performance can a l s o be improved by c a r e f u l c o n s i d e r a t i o n o f g a l v a n i c e f f e c t s i n the t r i m a r e a s .
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o
n
e
Summary and C o n c l u s i o n s R e p r e s e n t a t i v e a u t o m o b i l e p o u l t i c e s a m p l e s from B o s t o n , D a l l a s , D e t r o i t , and M o n t r e a l show a common c h e m i s t r y i n t h e n o r t h e r n s t a t e s i n v o l v i n g r o a d s a l t s and a c i d d e p o s i t i o n . There were a l s o s i g n i f i c a n t amounts o f c h l o r i d e f r o m d u s t c o n t r o l o p e r a t i o n s i n D a l l a s . However, t h e d i f f e r e n t s i t e s v a r i e d i n t h e l e v e l s o f i o n i c s p e c i e s and a l s o i n t h e i r p r o p o r t i o n s . As i n p a s t s u r v e y s , f i e l d t e s t s d u r i n g t h e w i n t e r o f 8 4 - 8 5 showed t h a t a r e a s o f h i g h road s a l t use and s e r i o u s a c i d d e p o s i t i o n are v e r y c o r r o s i v e . T o t a l t i m e o f wetness i s a l s o i m p o r t a n t . T h i s r e s e a r c h i n d i c a t e s a d e c r e a s i n g o r d e r o f a g g r e s s i v e n e s s on b a r e o r g a l v a n i z e d s t e e l t o be: f
Montreal
>
Boston
>
Detroit >
f
Dallas
Simple l a b o r a t o r y t e s t s may not be adequate t o reproduce f i e l d r e s u l t s . The r e a s o n f o r t h i s was demonstrated i n t h e l a b w i t h an a r t i f i c i a l solution containing road s a l t and a c i d rain c o n s t i t u e n t s . A l l o w i n g such a s o l u t i o n t o e v a p o r a t e d r i v e s o f f t h e v o l a t i l e n i t r i c a c i d component and h y d r o c h l o r i c a c i d f o r m e d when c a l c i u m s u l f a t e p r e c i p i t a t e s . Hence t h e h i s t o r y o f a p o u l t i c e i s important i n determining the a g g r e s s i v e n e s s o f a p a r t i c u l a r environment.
Baboian; Materials Degradation Caused by Acid Rain ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
212
MATERIALS DEGRADATION CAUSED BY ACID RAIN
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Literature Cited 1. Baboian, R. "Automotive Corrosion by Deicing Salts"; National Association of Corrosion Engineers: 1981. 2. Baboian, R. "Causes and Effects of Corrosion Relating to Exterior Trim on Automobiles;" (831835) in Proceedings of the 2nd Automotive Corrosion Prevention Conference; Society of Automotive Engineers, Inc.: Dec. 1983. 3. Rowe, L. C.; and Chance, R. L. "Fundamentals of Corrosion Testing"; in AUTOMOTIVE CORROSION BY DEICING SALTS; R. Baboian, Ed.; N.A.C.E.: 1981. 4. Baboian, R. "Chemistry of the Automotive Environment"; Society of Automotive Engineers; Reprint 780908: 1978. 5. Riley, J. P.; and Chester, R. "Introduction to Marine Chemistry"; Academic Press: N.Y., N.Y., 1971. 6. Pierce, W. C.; Haenisch, E. L.; Sawyer, D. T. "Quantitative Analysis"; 4th ed.; John Wiley & Sons Inc.: New York, N.Y., 1966. 7. Fontana, M.; Greene, N. D. "Corrosion Engineering"; McGraw -Hill Book Co., N.Y., 1967. 8. Baboian, R.; and Turcotte, R. C. "Development of Poultice Corrosion Tests for Automobiles"; National Assoc. of Corrosion Eng.: Paper Number 383, presented at N.A.C.E. Corrosion/85, March, 1985. 9. "Soil Survey: Laboratory Methods and Procedures for Collecting Soil Samples"; Soil Conservation Service, U.S. Dept. of Agriculture. 10. Franson, Μ. A. H., Managing ed. "Standard Methods for the Analyses of Water and Wastewater"; 15th edition; American Pub. Health Assoc.: 1981. RECEIVED January 2, 1986
Baboian; Materials Degradation Caused by Acid Rain ACS Symposium Series; American Chemical Society: Washington, DC, 1986.