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STP 1239
Atmospheric Corrosion
W. W. Kirk and Herbert H. Lawson, Editors
ASTM Publication Code Number (PCN):

04-012390-27
ASTM
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Philadelphia, PA 19103
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Library of Congress Cataloging-in-Publication Data
Atmospheric corrosion / W.W. Kirk and Herbert H. Lawson, editors.

(STP ; 1239)
Includes bibliographical references and index.
ISBN 0-8031-2015-X
I. Corrosion and anti-corrosives. I. Kirk, W. W., 1932-
II. Lawson, Herbert H., 1926- llI. Series: ASTM special
technical publication ; 1239.
TA418.74.A86 1995
620.I'1223--dc20 95-3231
CIP
Copyright 9 1995 AMERICAN SOCIETY FOR TESTING AND MATERIALS, Philadelphia, PA. All
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Printed in Philadelphia
March 1995
Foreword
This publication, Atmospheric Corrosion, contains papers presented at the symposium of the
same name, held in Fort Worth, TX on 15-16 Nov. 1993. The symposium was sponsored by
ASTM Committee G-l on Corrosion of Metals. W. W. Kirk of Ivanhoe, NC and Herbert H.
Lawson of Lawson Consultants, Inc. in Middletown, OH presided as symposium chairmen and
are editors of the resulting publication.
Contents
O v e r v i e w - - w . W. KIRK AND H. H. LAWSON vii
CORROSIVITY OF ATMOSPHERES
Time of Wetness and Dew Formation: A Model of A t m o s p h e r i c Heat T r a n s f e r -

s. w. DEAN AND D. B. REISER
Acid Deposition Effects of Materials: Evaluation of Electric Contact Materials after

F o u r Years of E x p o s n r e - - J . TIDBLAD, C. LEYGRAF, AND V. KUCERA II
An A p p r o a c h to the Modeling of A t m o s p h e r i c Corrosion---s. B. LYON, C. W. WONG,

AND P. AJIBOYE 26
Results of ISO C O R R A G P r o g r a m : Processing of One-Year Data in Respect to

Corrosivity Classification--D. KNOTKOVA, P. BOSCHEK, AND K. KREISLOVA 38
Analyses of F o u r Years of Exposure Data from the USA Contribution of ISO

C O R R A G P r o g r a m - - s . w. DEAN 56
WEATHERING STEELS AND COATED STEELS
Effects of Silicon and Nickel Contents on the Atmospheric Corrosion Resistance of

ASTM A588 W e a t h e r i n g SteeI--H. E. TOWNSEND 85
Atmospheric Corrosion Rates of W e a t h e r i n g Steels at Test Sites in the Eastern

United States-Effect of E n v i r o n m e n t and Test-Panel O r i e n t a t i o n -
s. K. COBURN, M. E. KOMP, AND S. C. LORE 101
Atmospheric Corrosion of Bolted Lap Joints M a d e of W e a t h e r i n g S t e e l - -

D. KNOTKOVAAND J. VLCKOVA 114
A Study of Rust Morphology, Contamination of Porosity by Backscattered

Electron Imaging--J. SIMANCAS, K. L. SCRIVENER, AND M. MORCILLO 137
Corrosion Evaluation of Automotive Trim Material--A. SABATA, G. S. DRIGEL,

AND T. L. COOPER 152
The Influence of M a r i n e E n v i r o n m e n t s on Metals and Fabricated Coated Metal

Products, Freely Exposed and Partially Sheltered---G. A. KING
AND D. J. O'BRIEN 167
METALS AND ALLOYS
Long-Term Atmospheric Corrosion in Spain: Results After 13 to 16 Years of

Exposure and Comparison with Worldwide Data--M. MORCILLO,
J. SIMANCAS, A N D S. FEL1U 195
Reaction Sequences in Atmospheric Corrosion of Zinc--1. ODNEVALL

A N D C. L E Y G R A F 215
Galvanic Protection of Steel by Zinc under T h i n Layer Electrolytes---x. G. ZHANG

A N D E. M. VALERIOTE 230
Corrosion Study of Carbon Steel and Zinc-Comparison Between Field Exposure

and Accelerated T e s t s - - E . J O H A N S S O N AND J. G U L L M A N 240
Atmospheric Corrosion in Ibero-America: The M I C A T Project--M. MORCILLO 257
Author Index 277
Subject Index 279
Overview
From the standpoint of economics, safety, and aesthetics, the importance of atmospheric
corrosion and its control is well recognized. More structures and materials are exposed to the
atmosphere than to any other environment. It is not surprising, therefore, that a vast body of
literature exists on the performance of materials in the atmosphere and the characterization of
such environments. (See the previous ASTM symposia covered in the special technical pub-
lications (STP) listed at the end of this introduction.) Society interests in the performance of
materials in the atmosphere were active well before the formation of Committee G-1 on Cor-
rosion of Metals in 1964. The International Organization for Standardization (ISO) has also
been very active in the development of standards for atmospheric testing methods and classi-
fication of atmospheres. It seemed a natural follow-up for Subcommittee G01.04 to organize
another symposium on Atmospheric Corrosion, held in November 1993 in Dallas, Texas. The
16 papers presented there are included in this STP.
The truly international scope of interest for this symposium was emphasized with three papers
each from Sweden and Spain, two from the Czech Republic, one each from the United King-
dom, Canada, and Australia, and five from the United States. All of the basic metals and alloys
used in construction: carbon steel, stainless steel, weathering steel, zinc, copper, and aluminum,
were included in the subject matter. For many years, an overwhelming desire to predict material
performance in the atmosphere has been at the heart of many research programs, two of which
are included here in an attempt to model atmospheric corrosion and corrosivity. An ISO pro-
gram to characterize different atmospheres as to corrosivity toward basic metals is also de-
scribed in two papers. Increased problems and concern with acid deposition and its effects on
corrosion, along with a study of marine corrosion as a function of location and distance from
salt water, round out the various subjects covered in this symposium.
Using symposia such as this and those previously held has permitted wide participation and
comprehensive coverage of the subject. Two continuing goals of Committee G-1 are "the
promotion and stimulation of research" and "the collection of engineering data relating to the
corrosion of metals." These are also goals of Subcommittee GO 1.04 on Atmospheric Corrosion.
As indicated by the long-term testing programs discussed herein and in previous literature, it
can be anticipated that future symposia on similar subject matter will be necessary. The diffi-
culties in determining and understanding the complexity of atmospheric variables and their
interactions are certain to provide interest and concern to the world of engineering.
The editors are grateful to their fellow members of Committee G-1 for their assistance and
encouragement in the organization of this symposium and the production of this volume. We
appreciate very much the support and guidance of the ASTM publications staff.
Listed below are six STPs resulting from various symposia held since 1956.
9 STP 175--Symposium on Atmospheric Corrosion of Non-ferrous Metals, 1956
9 STP 435--Metal Corrosion in the Atmosphere, 1968
9 STP 558--Corrosion in Natural Environments', 1974
9 STP 646--Atmospheric Factors Affecting the Corrosion of Engineering Metals, 1978
9 STP 767--Atmospheric Corrosion of Metals, 1982
9 STP 965--Degradation of Metals in the Atmosphere, 1987
W. W. Kirk H. H. Lawson
Kirk Corrosion Consulting, Lawson Consultants, Inc.,
Ivanhoe, NC; symposium chairman Middletown, OH; symposium
and editor, chairman and editor.
vii
Corrosivity of Atmospheres
Sheldon W. Dean I and David B. Reiser I
TI~ 07 ~TR88 ~ DEW FOI~WATION: l NODIL OF A~Og)HHRIC

HHAT TRANBFHR
REFERENCE: Dean, S. W. and Reiser, D. B., "Time of Wetness and Dew

Formation: A Model of Atmospheric Heat Transfer," Atmospheric Cer~
rosion, ASTM STP 1239, W. W. Kirk and Herbert H. Lawson, Eds., American
Society for Testing and Materials, Philadelphia, 1995.
Abstractx Time of wetness is a critical factor in atmospheric

corrosion. Dew is a major contributor to time of wetness. In normal
atmospheric exposures, dew formation is a result of radiative cooling
of exposed surfaces below the dew point of surrounding air. The extent
of radiational cooling of an object is affected by the effective sky
temperature, the presence of clouds, the view of other surfaces at
different temperatures, and air movement by wind or natural convection
adjacent to the cooling surfaces. This paper models the temperature of
a boldly exposed panel as a function of humidity and air current
velocity. The model predicts a maximum panel temperature depression of
approximately 16~ below ambient air temperature in still air. For
wind velocities of 4.5 m/s (i0 mph) radiational cooling lowers the
panel temperature 3~ below ambient air temperature.
Ke~rdsz atmospheric corrosion, time of wetness, radiational

cooling, dew formation, wind velocity
Atmospheric corrosion is an important degradation process affecting

metallic materials. Most investigators agree that atmospheric
corrosion takes place only during the time that the metal is wet with
liquid moisture. Dew is an important contribution to the formation of
surface moisture films.
Vernon [i] proposed that surface wetness occurs when a critical

relative humidity (RH) is exceeded. His work suggested that this
critical RH is between 80 and 90%. Mansfeld [i] and others have
proposed lower critical RH values depending on the hygroscopicity of
iAir Products Fellow and lead materials engineer, respectively, Air

Products and Chemicals, Inc., 7201 Hamilton Blvd., Allentown, PA 18195.
3
Copyrigh~1995by
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4 ATMOSPHERIC CORROSION
the salts on the metal surface. C o r r o s i o n of m e t a l s and alloys:

C l a s s i f i c a t i o n of c o r r o s i v i t y c a t e g o r i e s of a t m o s p h e r e s (ISO 9223)
s p e c i f i e s that time of w e t n e s s be c a l c u l a t e d from RH data as the time
for w h i c h RH > 80% and the t e m p e r a t u r e is above 0~
G r o s s m a n [~] p r o p o s e d a model w h e r e dew f o r m a t i o n r e s u l t e d from

r a d i a t i o n a l cooling, m a k i n g the model m o r e d e p e n d e n t on heat transfer
c o n s t r u c t s rather than h y g r o s c o p i c i t y c o n s i d e r a t i o n s . The p u r p o s e of
this p a p e r is to e x a m i n e the concept of a heat t r a n s f e r model b a s e d on
m o r e recent c o r r e l a t i o n s of sky t e m p e r a t u r e to d e t e r m i n e if this
a p p r o a c h m i g h t p r o v i d e a m o r e a c c u r a t e a p p r o a c h to e s t i m a t i n g time of
w e t n e s s from m e t e o r o l o g i c a l data.
UEAT TI~NSFZR MODZL
C o n s i d e r a object e x p o s e d to the night sky. The u p p e r s u r f a c e of the

o b j e c t w i l l b e c o m e wet w i t h dew if its t e m p e r a t u r e drops b e l o w the dew
p o i n t of the s u r r o u n d i n g air. R a d i a t i v e heat t r a n s f e r b e t w e e n the
object and the sky p r o v i d e s a m e c h a n i s m for a s u r f a c e to b e c o m e colder
than the s u r r o u n d i n g air. W h e t h e r this local c o o l i n g r e s u l t s in dew
f o r m a t i o n d e p e n d s on b o t h the amount of s u b c o o l i n g p o s s i b l e and on the
h u m i d i t y of the s u r r o u n d i n g air. The s u b c o o l i n g itself is a f f e c t e d by
the local h u m i d i t y a n d by w i n d or n a t u r a l convection. As a s u r f a c e
cools, w i n d a n d n a t u r a l c o n v e c t i o n will s u p p l y heat to the surface,
c o u n t e r a c t i n g the r a d i a t i v e transfer to the sky. For a h o r i z o n t a l l y
e x p o s e d panel, the e n e r g y b a l a n c e is:
(I)
A
where:
Q= heat flux, W
A= area, m2
~= Stefan-Boltzmann constant = 5.6686 x 10 -8 W m -2 K -4

= 0.1713 x 10 -8 Btu hr -I ft -2 ~
F = v i e w factor for r a d i a t i v e exchange = 1 for this g e o m e t r y
s = emissivity of r a d i a t i n g (panel) surface, dimensionless

assumed constant = 0.8 for this w o r k
Tai r = a b s o l u t e air temperature, K
Tsky = absolute sky temperature, K
Tpane I = a b s o l u t e panel temperature, K
hc = c o n v e c t i v e h e a t transfer coefficient, W m -2 K -I
DEAN AND REISER ON TIME OF WETNESS AND DEW FORMATION 5
For the p u r p o s e of r e a r r a n g i n g equation (1), define two temperature

d e p r e s s i o n terms :
ATp = Tair- Tpanel (2)
ATs = Tair - Tsk7 (3 )
Using equation (2):
T~aneI =
(T ~ - ATp )' (4)
And considering that AT << T:
T~ane1 ~-~ Tair 1 -~T ~ - 4T~ATp (51
Similarly,
T2ky T,i4~--4 T ~3A T s (6 )
At s t e a d y state the net heat flux, Q, is zero. S u b s t i t u t i n g equations

(5) and (6) into e q u a t i o n (i) and solving for ATp at s t e a d y state
gives:
3
4s s
(7)
AT~ - 4~pOT~ + h e
Equation (7) will answer the question of h o w m u c h colder than

surrounding air a panel will become, p r o v i d e d we can supply the sky
temperature d e p r e s s i o n and the convective heat transfer coefficient.
Fortunately, the subject of e f f e c t i v e sky temperature has b e e n studied
extensively with respect to passive cooling of buildings. [~] [~] [~]
Berdahl and M a r t i n [4] m e a s u r e d the clear sky e m i s s i v i t y in a number of
cities in the U.S. and d e t e r m i n e d a c o r r e l a t i o n b e t w e e n dew point
temperature and emissivity:
e ky= 0.711 + 0.561100,/ + 0.73

iT,p)2 (8)
where:
s = 24 hour average total clear sky emissivity, dimensionless
Tdp = d e w point temperature, ~
6 ATMOSPHERICCORROSION
F u r t h e r m o r e , the s k y t e m p e r a t u r e d e p r e s s i o n c a n b e d e t e r m i n e d f r o m the
e m i s s i v i t y [~] :
AT, =
(1--~sky') T
T~ (9)
The convective heat transfer coefficient, h c, w i l l be f u n c t i o n of air

v e l o c i t y o v e r the plate. If t h e r e is n o wind, t h e n o n l y n a t u r a l
c o n v e c t i o n c o u n t e r a c t s the r a d i a t i o n a l cooling. F o r a cooled,
h o r i z o n t a l p a n e l f a c i n g u p [~]:
- .0.20
h~=0.61, , , units = W (lO)

L2 )
where
L = the c h a r a c t e r i s t i c l e n g t h of the panel, m
T h e n a t u r a l c o n v e c t i o n h c is w e a k l y d e p e n d e n t on t e m p e r a t u r e d e p r e s s i o n
w e w o u l d like to c a l c u l a t e . R a t h e r t h a n r e t a i n the a d d i t i o n a l
c o m p l e x i t y in the model, w e u s e d e q u a t i o n s (7)-(10) to s o l v e for ATp b y
trial a n d e r r o r a n d s e l e c t a n a p p r o x i m a t e l y c o n s t a n t h c. F o r a 0.3 m
(i ft.) s q u a r e panel:
h e = 1.7 W m -2 K -I (0.3 B t u hr "I ft -2 ~ (ii)
T h i s v a l u e of h c is lower t h a n n u m b e r s t y p i c a l l y e s t i m a t e d for h e a t
transfer by natural convection. The difference can be rationalized by
c o n s i d e r i n g the small p a n e l s i z e a n d the small t e m p e r a t u r e d r i v i n g
force.
F o r c o n v e c t i v e h e a t t r a n s f e r to the e x p o s e d p a n e l in the p r e s e n c e of
wind, w e u s e d the w e l l k n o w n h e a t t r a n s f e r c o r r e l a t i o n [~]:
N u x = 0 . 3 3 2 Pr 1/3 R e 1/2 (12)

where:
hxx
Nux = local Nusselt number = --, dimensionless
k
Pr = P r a n d t l number, d i m e n s i o n l e s s = 0.7 for a i r at a m b i e n t
conditions
Re = Reynolds number = pvx, dimensionless
hx = local c o n v e c t i v e h e a t t r a n s f e r c o e f f i c i e n t , W m -2 K -I
x = d i s t a n c e f r o m the l e a d i n g e d g e of t h e flat plate, m
k = t h e r m a l c o n d u c t i v i t y = 0.0263 W m -I K -I for a i r
p = d e n s i t y = 1 . 1 6 1 k g m -3 for air
v = velocity, m s -1
= v i s c o s i t y = I.S5 x 10 -5 k g m -1 s -1 for air
properties for a i r are at 300 K, 1 b a r
In addition, the average convective heat transfer coefficient is twice

the local h x at the trailing edge of the panel [ 8 ] . Rearranging
equation (12) and substituting the constants for air:
112
or, for the 0.3 m panel considered in this model:
h e = 8.35 v 1/2, W m "2 K -1 (14)
Examination of equations (ii) and (14) shows that at a wind velocity of

less than 0.i m/s, the effect of the forced convection (wind) is
greater than the contribution of natural convection. This result
simplifies evaluation of equation (7) by allowing consideration of only
one of the convective heat transfer coefficients at a time.
Substituting equation (9) into equation (7) produces:
4epdl'~ (1 -- ~sky
'"~)
ATp = (15)
4epoT~ + h~
where s is given by equation (8), and h e is given by equation (ii) if
there is no wind or equation (14) if wind is present.
Equation (15) allows one to calculate the temperature depression

expected for a horizontal panel exposed to a cloudless night sky
provided the air temperature, the dew point temperature, and wind
velocity are known. Before discussing the results, two other
conditions and assumptions which affect the calculations should be
noted:
i. The back of the panel is insulated. There is no radiative exchange

between the panel and the ground. And there is no natural or forced
convection affecting the underside of the panel.
2. Heat transfer resulting from condensation is not considered. At

this stage, the model should predict if dew will form, but not how m u c h
dew will collect on the panel. With some additional assumptions the
quantity of dew could be calculated from this model.
RESULTS .i~l'D DISCUSSION
The solution of equation (15) for a variety of air temperatures and

wind velocities (Fig. i) shows that wind velocity has a much stronger
influence on the maximum panel temperature depression than the air
temperature or dew point. Remember that the model only accounts for
maximum cooling in the absence of condensation. For example, in still
air, Tair = 1.7~ (35~ 0 < Tdp < 1.7~ the model predicts a panel
temperature depression of approximately 15~ In reality, those
c o n d i t i o n s w o u l d r e s u l t i n h e a v y f r o s t r a t h e r t h a n a 15 ~ t e m p e r a t u r e
drop. G r o s s m a n [2] m e a s u r e d a m a x i m u m t e m p e r a t u r e d e p r e s s i o n of 8~ o n
a n 8 i n c h s q u a r e p a n e l , i n s u l a t e d o n the b o t t o m a n d e x p o s e d t o a
~clear, c l o u d l e s s s k y a n d n o w i n d . " T h e p r e s e n t m o d e l p r e d i c t s g r e a t e r
temperature depressions than Grossman measured. The differences
s u g g e s t i n v e s t i g a t i n g t h e v a l i d i t y of t h e n a t u r a l c o n v e c t i o n h e a t
t r a n s f e r c o e f f i c i e n t c o r r e l a t i o n at t h e l o w t e m p e r a t u r e d i f f e r e n c e
conditions characteristic of these atmospheric exposures. A higher h c
for natural convection reduces the AT predicted by the model.
It is w e l l k n o w n t h a t w i n d i n h i b i t s d e w f o r m a t i o n , a n d t h i s m o d e l
p r e d i c t s t h e m a g n i t u d e of t h a t e f f e c t . E v e n a s l i g h t w i n d o f 1.3 m / s
(3 mph) d e c r e a s e s t h e p r e d i c t e d A T p b y m o r e t h a n a f a c t o r o f t w o o v e r
the still air condition.
Maximum Cooling of Panels in the Atmosphere
20 , , i , , i , , ! ~ , , , , , , , , , , ,
Talr Vwlnd
oC m/s
O 1.7 0
15 ----O--- 1.7 1.3
O - -e- - - 1.7 4.5
o.4 .- - • - 7.2 0
c i --""*. i - -+- -7.2 1.3
10 9~ - - 7.2 4.5
i i - -e 12.8
- 0
. ~ + . ~ - - . ~ -~ Vwind =1'3 m/s
--" - 12.8 1.3
,~ 12.8 4.5
5
9 - 18.3 0
-- o- -18.3 1.3
Vwind=43 n~s -i
- -~- - 18.3 4.5
i , , J I i i i , i , i , i i , i i , , i i
0
-5 0 5 10 15 20
Dewpoint (~
FIG. 1 - - M a x i m u m c o o l i n g of a n e x p o s e d panel for several air temperatures
and wind velocities.
T h e m o d e l c a n a l s o b e u s e d to p r e d i c t t h e m i n i m u m h u m i d i t y a t w h i c h d e w
c a n b e e x p e c t e d f o r a g i v e n a i r t e m p e r a t u r e a n d w i n d v e l o c i t y (Fig. 2).
I n s t i l l a i r d e w w i l l f o r m a t h u m i d i t i e s c o m m o n i n m i d l a t i t u d e sites.
A t m o d e r a t e w i n d v e l o c i t i e s , d e w w i l l f o r m if t h e h u m i d i t y is a b o v e
some value around 75-85%. The agreement between the heat transfer
model a n d the model b a s e d on h y g r o s c o p i c i t y of salts a n d c o r r o s i o n

products is p u r e l y coincidental.
M i n i m u m RH for D e w Formation
100 . . . . . . . . I .... I . . . . . . . .
Dew forms i "rair=18.3~
80 ....................... L ......................... i ............. ' ......... ! .......................
Z"
60
E / /
~D 40
.>_
ID
20
i i i i I i i i = I i = i = i = i t = i i i
0 1 2 3 4 5
Wind velocity (m/s)
FIG. 2 - - M i n i m u m RH at w h i c h d e w will form as a function

of w i n d v e l o c i t y for two air temperatures.
In its p r e s e n t form, the heat transfer model represents a r u d i m e n t a r y

v i e w of the physical processes taking place during the formation of
liquid m o i s t u r e films on e x p o s e d panels. Logical extensions of this
w o r k w o u l d consider effects of c o n d e n s a t i o n rates and v a r y i n g cloud
cover on the heat transfer system. If such extensions could be made,
it might be p o s s i b l e to determine time of wetness m o r e a c c u r a t e l y from
existing a t m o s p h e r i c data than can be e s t i m a t e d from a critical
h u m i d i t y concept. Also, the e x t e n d e d model might be suitable for
independent v a l i d a t i o n of the o p e r a t i o n time of wetness sensors such as
the one d e f i n e d in A S T M S t a n d a r d Practice for M e a s u r e m e n t of Time-of-
Wetness on Surfaces E x p o s e d to W e t t i n g C o n d i t i o n s as in A t m o s p h e r i c
C o r r o s i o n T e s t i n g (G 84).
The model also only considers dew formation, not the e v a p o r a t i o n of

water. Interactions b e t w e e n heat transfer and h y g r o s c o p i c i t y of salts
m a y control the d r y i n g p o r t i o n of the largely diurnal nature of time of
wetness in outdoor exposures.
The v a r i a b i l i t y of atmospheric c o r r o s i o n rates indicates that m a n y

m e c h a n i s m s are at work. The more c l o s e l y the physical system can be
described, the m o r e likely it is that the v a r i a b i l i t y can be explained.
CONCLUBZON
A heat transfer model has been developed to describe the process of dew
formation in atmospheric exposures. The model considers convective
heat transfer and radiation to the night sky. Standard convective heat
transfer coefficient correlations were used. Recent measurements of
sky emissivity as a function of ground level humidity were used to
determine the radiative heat transfer contribution. Wind velocity has
a much stronger effect on panel cooling than either air temperature or
humidity.
ACXNOWLEDGEMBNT
The authors wish to thank Air Products and Chemicals, Inc. for
permission to publish this paper.
RZFZI~.ulgCR8
[i] Vernon, W. H. J., ~Reports to the Atmospheric Corrosion Committee,

Laboratory Study of the Atmospheric Corrosion of Metals,"
Transactions of the Faraday Society, 27, 265, (1931); and 31, 1668,
(1935).
[~] Mansfeld, F., ~Electrochemical Methods for Atmospheric Corrosion
Studies," Atmospheric Corrosion, Ailor, W. H., ed., John Wiley and
Sons, 139-160, (1982).
[~] Grossman, P. R., "Investigation of Atmospheric Exposure Factors
that Determine Time-of-Wetness of Outdoor Structures," Atmospheric
Factors Affecting the Corrosion of Engineering Metals, A S T M S T P
646, S. K. Coburn, ed., American Society for Testing and Materials,
5-16, (1978).
[4] Berdahl, P., and Martin, M., ~Emissivity of clear skies," Solar
Energy, 32(5), 663-664, (1984).
[~] Martin, M. and Berdahl, P., ~Characteristics of Infrared Sky
Radiation in the United States," Solar Energy, 33(3/4), 321-336,
(1984).
[~] Loxsom, F. M. and Kelly, B., ~Evaporative Cooling: Roofs as
Dissipators," Passive Cooling Handbook, Miller, M., ed., pp. 77-106
Center for Energy Efficient Design, Berkeley, (1981).
[~] Holman, J. P., Heat Transfer, 4th ed., McGraw-Hill, New York,
(1976), p. 253.
[~] Eckert, E. R. G. and Drake, R. M., Jr., Analysis of Heat and Mass
Transfer, Hemisphere, (1987).
Johan Tidblad, I C h r i s t o f e r Leygraf, I and V l a d i m i r K u c e r a 2
ACID DEPOSITION EFFECTS ON MATERIALS: EVALUATION OF ELECTRIC

CONTACT MATERIALS AFTER 4 YEARS OF EXPOSURE
REFERENCE: Tidblad, J., Leygraf, C., and Kucera, V., "Acid D e p o s i t i o n

E f f e c t s on Materials: E v a l u a t i o n of E l e c t r i c C o n t a c t M a t e r i a l s a f t e r
Four Years of E x p o s u r e , " A t m o s p h e r i c Corross A S T M STP 1239, W. W~
K i r k and Herbert H. Lawson, Eds., A m e r i c a n S o c i e t y for T e s t i n g and
Materials, Philadelphia, 1995.
ABSTRACT: In 1987 a c o - o p e r a t i v e field e x p o s u r e p r o g r a m w i t h i n the
UN Economic Commission for E u r o p e was i n i t i a t e d . T h e a i m of the
p r o g r a m is to e v a l u a t e the effect of sulfur p o l l u t a n t s in c o m b i n a t i o n
with NO• a n d o t h e r pollutants on the a t m o s p h e r i c corrosion of
i m p o r t a n t m a t e r i a l s . This w o r k p r e s e n t s r e s u l t s from the e v a l u a t i o n of
the e l e c t r i c contact m a t e r i a l s nickel, copper, silver and tin after 4
y e a r s of exposure.
D r y d e p o s i t i o n of SO 2 d o m i n a t e s the c o r r o s i o n of nickel, w h i c h
forms a m o r p h o u s and c r y s t a l l i n e basic nickel sulfate, w h e r e a s b o t h 03
and NO 2 a c c e l e r a t e the dry d e p o s i t i o n of SO 2 on copper. S i l v e r forms
Ag2S as the d o m i n a t i n g c o r r o s i o n product. Since H2S is not m e a s u r e d
within the program it has not been possible to e s t i m a t e its
c o n t r i b u t i o n . The f o r m a t i o n of oxides w i t h d i f f e r e n t s t o i c h i o m e t r i e s
d o m i n a t e s the c o r r o s i o n of tin and no e q u a t i o n has b e e n found that
r e l a t e s the w e i g h t increase of tin to e n v i r o n m e n t a l data. P a r t i c u l a t e
a m m o n i u m sulfate c o n t r i b u t e s to the weight increase of all metals.
KEYWORDS: Atmospheric corrosion, Acid deposition, International

cooperation, nickel, copper, silver, tin, XPS, S t a t i s t i c a l analysis.
INTRODUCTION
T h i s study is part of an e x t e n s i v e field e x p o s u r e p r o g r a m w i t h i n

the U n i t e d N a t i o n s E c o n o m i c C o m m i s s i o n for E u r o p e (UN ECE). T h e
p r o g r a m s t a r t e d in S e p t e m b e r 1987 and involves 39 exposure sites in 12
E u r o p e a n c o u n t r i e s and in the U n i t e d States a n d C a n a d a [l]- The aim of
the p r o g r a m is to e v a l u a t e quantitatively the e f f e c t of s u l f u r
pollutants, in c o m b i n a t i o n w i t h NO x and o t h e r p o l l u t a n t s , as well as
climatic parameters on the atmospheric corrosion of important
m a t e r i a l s . G a s e o u s pollutants, p r e c i p i t a t i o n and c l i m a t i c p a r a m e t e r s
at or n e a r b y each test site are measured, and the c o r r o s i o n effects on
d i f f e r e n t groups of m a t e r i a l s are evaluated.
iDr. and Professor, respectively, D e p a r t m e n t of M a t e r i a l s S c i e n c e and

Engineering, Division of C o r r o s i o n Science, Royal Institute of
Technology, S-I0044 Stockholm, Sweden.
2Dr., S w e d i s h C o r r o s i o n Institute, Roslagsv. i01, Bldg. 25, S-I0405

Stockholm, Sweden.
11
Copyrightm1995by ASTM International
Downloaded/printed by www.astm.org
A T a s k F o r c e o r g a n i z e s the program, in w h i c h S w e d e n is the lead

country a n d the S w e d i s h Corrosion Institute serves as the m a i n
research centre. Subcentres in d i f f e r e n t countries have been
appointed, each responsible for t h e i r own group of m a t e r i a l s ,
including structural metals, stone materials, paint coatings and
electric contact materials.
This w o r k p r e s e n t s weight increase m e a s u r e m e n t s for nickel, copper,
s i l v e r and tin after I, 2 and 4 years of exposure. It a l s o p r e s e n t s
the c u r r e n t s t a t e of e v a l u a t i o n of t h e s e four electric contact
materials.
In order to o b t a i n i n f o r m a t i o n about the c o m p o s i t i o n of c o r r o s i o n
products, X-ray Photoelectron Spectroscopy (XPS) m e a s u r e m e n t s h a v e
been made on the four m e t a l s after 4 y e a r s of exposure, in a d d i t i o n to
the XPS m e a s u r e m e n t s p e r f o r m e d b e f o r e on n i c k e l a n d c o p p e r a f t e r 2
y e a r s of e x p o s u r e [~]. B u l k a n a l y s e s of the c h e m i c a l c o m p o s i t i o n of
c o r r o s i o n p r o d u c t s on n i c k e l have b e e n m a d e a f t e r 2 and 4 years of
exposure. D i f f u s e R e f l e c t a n c e I n f r a r e d F o u r i e r T r a n s f o r m S p e c t r o s c o p y
(DRIFT) and X-ray powder Diffraction (XRD) were used in t h e s e
analyses.
R e s u l t s from the e v a l u a t i o n have been p u b l i s h e d before: e v a l u a t i o n
of nickel and copper after 2 years of exposure [!], a n a l y s i s of field
e x p o s e d nickel [~], e v a l u a t i o n of silver after 4 years of e x p o s u r e [4]
and e v a l u a t i o n of nickel after 4 years of exposure [~] .
EXPERIMENTAL
Environment and exposure conditions
The program is u n d e r t a k e n by e x p o s i n g samples at or n e a r b y

stations, a l r e a d y e s t a b l i s h e d for m e a s u r e m e n t s of e n v i r o n m e n t a l data.
Environmental parameters, which are expected to influence the
investigated materials f r o m a c o r r o s i o n or d e t e r i o r a t i o n p o i n t of
view, are c o n t i n u o u s l y collected. This includes data for three g ~ 9 9 ~
~9.l]~.~D.~ (sulfur d i o x i d e (S02) , n i t r o g e n d i o x i d e (NO2) a n d o z o n e
(03)), D ~ A D A ~ A g D (total amount (mm), c o n d u c t i v i t y (Cond), a c i d i t y
(pH), s u l f a t e (S042-), n i t r a t e (NO3-), chloride (CI-), a m m o n i u m (NH4+),
s o d i u m (Na+), c a l c i u m (Ca2+), m a g n e s i u m (Mg 2+) and p o t a s s i u m (K+)) and
9~at.$~.p.a.ramete[s (temperature (T), r e l a t i v e h u m i d i t y (Rh), time of
wetness (Tow) and s u n s h i n e h o u r s (Sun)). T a b l e 1 shows the number,
l o c a t i o n and s e l e c t e d m e a s u r e m e n t s of the e n v i r o n m e n t for the 39 test
sites. It a l s o i n d i c a t e s the sites w h e r e XPS was p e r f o r m e d a f t e r 4
y e a r s of exposure. A m o r e d e t a i l e d d e s c r i p t i o n of the test sites has
b e e n p r e s e n t e d in a s e p a r a t e report, c o m p i l e d by the m a i n r e s e a r c h
c e n t r e [6]. All c l i m a t i c m e a s u r e m e n t s are r e p o r t e d to and s u b s e q u e n t l y
c o m p i l e d by the N o r w e g i a n I n s t i t u t e for Air R e s e a r c h , which also
examines the q u a l i t y of the data. Climatic data from the 4 first years
of e x p o s u r e have been p r e s e n t e d in a separate report [~].
The e l e c t r i c contact m a t e r i a l s at each test site are p l a c e d in an
a l u m i n u m b o x w i t h two v e n t i l a t i o n holes, s i t u a t e d in a l a r g e r b o x
c o n t a i n i n g all s h e l t e r e d samples and p l a c e d on the e x p o s u r e rack (Fig.
i). This extra p r o t e c t i n g a r r a n g e m e n t was c h o s e n in o r d e r to simulate
the n a t u r a l e n v i r o n m e n t for e l e c t r o n i c d e v i c e s in u n h e a t e d storage.
The w i t h d r a w a l of s p e c i m e n s was p e r f o r m e d a f t e r I, 2 and 4 y e a r s of
e x p o s u r e and will be p e r f o r m e d after 8 years of exposure. At the end
of e a c h e x p o s u r e period, 3 samples of e a c h m e t a l are w i t h d r a w n . T h e s e
three samples are from now on r e f e r r e d to as triplicates.
TIDBLAD ET AL. ON ACID DEPOSITION EFFECTS ON MATERIALS 13
T A B L E 1 - - T e s t s i t e number~, l o c a t i o n a n d s e l e c t e d e n v i r o n -
m e n t a l p a r a m e t e r s t o a e t h e r w ~ t h an i n d i c a t i o n if X P S a n a l y s e s
w e r e m a d e a f t e r 4 y e a r s of exposure.
Country: Tow SO 2 NO 2 03 Cond pH XPS a n a l y s e s

No Name h/yr._ < - - ~ / m 3 --> ~S/cm Ni Cu A ~ S n
Czech Republic:
1 Prague-Letnany 2877 67.8 36.0 70.9 4.26
2 Kasperske Hory 3261 19.6 12.6 31.2 4,13
3 Kopisty 2265 83.2 38.2 86.4 4,53
Finland:
4 Espoo 3750 14.8 20.4 35.3 4,35
5 Aht&ri 3081 3.8 4.9 52 18.1 4.54
6 Helsinki-Vallila 3776 18.0 33.8 41.3 4.32 x
Germany:
7 Waldhof-Langenbr~gge 4573 12.2 12.0 59 37.0 4.36
8 Aschaffenburg 3508 17.5 39.2 28 51.7 4,71 x x
9 Langenfeld-Reusrath 4570 23.7 45.7 38.6 4.42
10 B o t t r o p 4195 50.1 47.7 27 49.9 4.44
11 E s s e n - L e i t h e 4376 27.2 43.8 37.9 4.40
12 G a r m i s c h - P a r t e n k i r c h e n 8.9 13.3 53 18.7 4.79
Italy:
13 R o m e 34.0 68.7 24 34.1 4.69 i x x
14 C a s a c c i a 3460 6.9 14.1 51 33.9 5.00
15 M i l a n 3246 67.4 109.4 19 60.1 4.34 x x x
16 V e n i c e 4200 21.1 44.9 25 57.1 5.18 x x
Netherlands:
17 V l a a r d i n g e n 5438 32.5 55.0 30 51.6 4.44 x
18 E i b e r g e n 4911 9.0 25.3 43 30.8 5.44
19 V r e d e p e e l 5002 10.8 32.2 39 33.5 5.38 x
20 W i j n a n d s r a d e 4895 12.0 29.8 41 33.7 4.80
Norway:
21 O s l o 2783 10.9 50.6 19 32.7 4.55 x x
22 B o r r e g a a r d 3449 40.5 17.7 67.6 3.97
23 B i r k e n e s 4296 I.i 3.5 56 35.3 4.30 x x
Sweden:
24 S t o c k h o l m S o u t h 3272 ii.0 29.3 45 25.9 4.41 x x x
25 S t o c k h o l m C e n t r e 3272 16.0 42.5 25.9 4.41
26 A s p v r e t e n 3681 2.4 4.6 57 32.0 4.34
United Kingdom:
27 L i n c o l n C a t h e d r a l 5908 18.2 46.1 55.2 4.24
28 W e l l s C a t h e d r a l 5991 6.5 23.3 64.4 5.44
29 C l a t t e r i n g s h a w s L o c h 3.9 3.8 55 4.73 x x x x
30 S t o k e O r c h a r d 5188 16.1 41.8 3.66 x x
Spain :
31 M a d r i d 1620 15.5 24.7 26 27.5 5.44 x x
32 B i l b a o 4193 37.3 37.8 65.1 4.86 x
33 T o l e d o 1813 8.0 14,2 12.1 5.46
Russian Federation:
34 M o s c o w 2562 25.8 61.2 35.4 5.47 x
Estonia :
35 L a h e m a a 4076 0.6 3.8 17.1 4.63
Portugal :
36 L i s b o n 9.1 30.3 34 56.8 5.56 x x
Canada :
37 D o r s e t 3231 3.3 1.7 59 25.3 4.33
USA :
38 R e s e a r c h T r i a n g l e Park 9.2 25.7 53 22.1 4.36 x
39 S t e u b e n v i l l e 1737 59.3 44.5 39 49.6 3.96 x x
Shelterin~ roof A l u m i n u m box
/ Aluminum
box
\
i year 2 year lJ
samples samples
II
Exposure 4 year 8 year
of other samples samples
materials
Ventilation holes
FIG. 1 - - S c h e m a t i c d r a w i n g of the a l u m i n u m box and its posi-

tion under the s h e l t e r i n g roof.
Sample p r e p a r a t i o n and analvsis
F r o m s h e e t s of p u r e m e t a l s (>99% for nickel and tin, > 9 9 . 8 % for

c o p p e r a n d > 9 9 . 9 % for silver), s a m p l e s m e a s u r i n g 50 x 10 x 0.5 mm 3
were prepared, followed by d e g r e a s i n g in a c e t o n e and isopropyl
alcohol. In order to e v a l u a t e the c o r r o s i o n effect on nickel, copper,
s i l v e r and tin, w e i g h t increase m e a s u r e m e n t s w e r e m a d e by m e a n s of a
m i c r o b a l a n c e w i t h an e s t i m a t e d p r e c i s i o n of 1 ~ g / c m 2. B e f o r e weighing,
the e x p o s e d s a m p l e s w e r e b l o w n by a jet s t r e a m of n i t r o g e n gas in
order to remove dust and other loose particles.
C a t h o d i c r e d u c t i o n m e a s u r e m e n t s of copper and s i l v e r samples were
also p e r f o r m e d and the results have been p r e s e n t e d e l s e w h e r e [~,~].
A f t e r 4 y e a r s of exposure, metal samples from s e l e c t e d sites w e r e
a n a l y z e d by XPS (Table i). The XPS s p e c t r a were o b t a i n e d by m e a n s of a
L e y b o l d H e r a e u s LH2000 s p e c t r o m e t e r for silver, a Perkin Elmer 5000 LS
for nickel and c o p p e r and a KRATOS AXIS HS for tin. All samples w e r e
i r r a d i a t e d w i t h A1 Ke X-rays. D e t a i l e d scans of Ni2p/Cu2p/Ag3d/Sn3d,
Ols, Nls, Cls, C l 2 p and S2p p e a k s w e r e r e c o r d e d for e a c h s a m p l e
investigated. S e n s i t i v i t y factors w e r e taken f r o m B r i g g s a n d Seah,
[~], for samples a n a l y s e d w i t h the LH2000 and from an a n a l y s i s p r o g r a m
for s a m p l e s a n a l y s e d w i t h the 5000 LS and the A X I S HS. B i n d i n g
e n e r g i e s w e r e c a l c u l a t e d by a s s u m i n g the Cls p e a k f r o m h y d r o c a r b o n
c o n t a m i n a t i o n to be located at 284.6 eV [~].
DRIFT spectra were obtained using a Biorad FTS60A spectrometer
e q u i p p e d w i t h a S p e c a c or B i o r a d d i f f u s e r e f l e c t a n c e a c c e s s o r y . The
s p e c t r o m e t e r was p u r g e d w i t h air r e d u c e d in w a t e r and c a r b o n d i o x i d e
to m i n i m i z e i n t e r f e r e n c e of a t m o s p h e r i c a b s o r p t i o n bands. S a m p l e s for
D R I F T a n a l y s e s w e r e p r e p a r e d by r e m o v i n g the c o r r o s i o n p r o d u c t s from
the e x p o s e d nickel coupons, m i x i n g w i t h p o t a s s i u m b r o m i d e in a m o r t a r
and g r i n d i n g for a couple of minutes. S p e c t r a w e r e o b t a i n e d by adding
500 scans at r e s o l u t i o n of 2 cm -I, n o r m a l l y u s i n g a b r o a d b a n d m e r c u r y
c a d m i u m t e l l u r i d e (MCT) detector.
The X R D p h o t o g r a p h s w e r e o b t a i n e d u s i n g a G u i n e r - H & g g c a m e r a w i t h
m o n o c h r o m a t i c CuK~ r a d i a t i o n (I=1.5405981 A). The films w e r e m e a s u r e d
w i t h a c o m p u t e r c o n t r o l l e d single b e a m m i c r o d e n s i t o m e t e r [i0], and the
e-scale was calibrated by the i n t e r n a l standard technique using
silicon.
RESULTS AND DISCUSSION
Weiaht increases
T a b l e 2 shows m e a n v a l u e s of the nickel, copper, s i l v e r a n d tin

t r i p l i c a t e s after i, 2 and 4 years of exposure, for the 39 test sites.
In e x a m i n i n g Table 2, a common o b s e r v a t i o n is that the s a m p l e s e x p o s e d
for 4 y e a r s have h i g h e r w e i g h t increases, per year, than the s a m p l e s
e x p o s e d for I year, e s p e c i a l l y in the case of nickel and tin. A closer
e v a l u a t i o n of t h e . 4 y e a r t r i p l i c a t e samples reveals a systematic
d i f f e r e n c e . W i t h i n e a c h triplicate, the s a m p l e c l o s e s t to the lower
v e n t i l a t i o n h o l e often show higher weight increases than the other two
(Fig. i). T h i s o c c u r s m o r e f r e q u e n t t h a n one w o u l d e x p e c t f r o m a
r a n d o m v a r i a t i o n of three s a m p l e s and is true for all four m e t a l s .
T h i s m a k e s it v i r t u a l l y i m p o s s i b l e to e x t r a c t the k i n e t i c b e h a v i o r
from the w e i g h t i n c r e a s e d a t a a f t e r i, 2 a n d 4 y e a r s of e x p o s u r e .
However, w h e n the w e i g h t i n c r e a s e s a f t e r 8 y e a r s of e x p o s u r e are
a v a i l a b l e , it will be p o s s i b l e to e v a l u a t e if the c o r r o s i o n rate of
the d i f f e r e n t m e t a l s increases or not.
Correlation analysis
T a b l e 3 shows the Pearson c o r r e l a t i o n m a t r i x c a l c u l a t e d for w e i g h t

i n c r e a s e s a f t e r 4 y e a r s of e x p o s u r e and a v e r a g e 4 y e a r v a l u e s of
s e l e c t e d e n v i r o n m e n t a l p a r a m e t e r s . The e n v i r o n m e n t a l p a r a m e t e r s are
not i n d e p e n d e n t . For example, S02, NO 2 and 03 c o r r e l a t e w i t h e a c h
other, w h i c h m a k e s it d i f f i c u l t to s e p a r a t e the e f f e c t s of t h e s e
p a r a m e t e r s on p u r e s t a t i s t i c a l grounds. In the c a s e of the metals,
w e i g h t i n c r e a s e s of nickel and s i l v e r c o r r e l a t e fairly well, w h e r e a s
copper and tin exhibit a different behavior.
The two most important explanatory variables are SO2 a n d
c o n d u c t i v i t y of p r e c i p i t a t i o n . $02 c o r r e l a t e s w i t h n i c k e l and s i l v e r
and conductivity c o r r e l a t e s w i t h all m e t a l s but tin. The p o s s i b l e
e f f e c t s of g a s e o u s pollutants, p r e c i p i t a t i o n and c l i m a t i c p a r a m e t e r s
on the c o r r o s i o n b e h a v i o u r of the four m e t a l s w i l l be d i s c u s s e d
s e p a r a t e l y in the following.
Gaseous pollutants--Fig. 2 shows the w e i g h t i n c r e a s e of nickel,

copper, s i l v e r a n d tin a f t e r 4 y e a r s of e x p o s u r e v s . the a v e r a g e
concentration of SO 2. T h e s e r e l a t i o n s h i p s f o r m the b a s i s of the
f o l l o w i n g d i s c u s s i o n of gaseous pollutants.
The w e i g h t increase of nickel c o r r e l a t e s very s t r o n g l y w i t h the SO 2
c o n c e n t r a t i o n . In fact, this is the best single factor r e l a t i o n s h i p in
the e n t i r e e x p o s u r e program, i n c l u d i n g all s t r u c t u r a l metals, stone
m a t e r i a l s and paint coatings.
The w e i g h t increase of copper depends on the SO 2 c o n c e n t r a t i o n in a
m o r e c o m p l i c a t e d way. High weight increases are o b s e r v e d b o t h at h i g h
p o l l u t a n t levels and at b a c k g r o u n d sites. At h i g h p o l l u t a n t levels,
the a d d e d effect of SO 2 and NO 2 is a p r o b a b l e cause of the c o r r o s i o n
a t t a c k on c o p p e r [II]. At the b a c k g r o u n d sites, the SO 2 c o n c e n t r a t i o n
is f a i r l y low but the 03 c o n c e n t r a t i o n is h i g h since 03 c o r r e l a t e s
n e g a t i v e l y to NO 2 and thus to SO 2. At equal c o n c e n t r a t i o n s of 03 and
NO2, laboratory experiments h a v e s h o w n that 03 e n h a n c e s the SO 2
d e p o s i t i o n rate on c o p p e r to a larger e x t e n t than NO 2 [12], w h i c h
c o u l d e x p l a i n this behavior.
T w o e x t r e m e cases are observed, site 35 L a h e m a a and 22 Borregaard.
At the latter site, chlorine gas is a m a j o r pollutant. The h i g h weight
increase on copper at site 35 are not yet understood.
The w e i g h t i n c r e a s e of silver c o r r e l a t e s w i t h the SO 2 c o n c e n t r a -
tion, but not to the same extent as nickel.
T A B L E 2 - - M e a n v a l u e s of w e i a h t i n c r e a s e of nickel, CoPPer,
s i l v g r a n d %in in u a / c m 2 ~ f t e r I. 2, and 4 y e a r s of e x p o s u r e
for the 39 test sites.
Site nickel copper silver tin

No 1 2 4 1 2 4 1 2 4 1 2 4
1 186.4 540.1 1450 14.6 28.3 60.2 8.7 14.7 44.3 7.8 12.1 36.4
2 35.0 87.5 391.2 13.0 34.4 56.8 4.8 6.2 32.1 6.1 11.6 37.7
3 243.8 811.6 2182 12.5 25.0 97.3 19.7 43.1 105.9 4.6 11.7 44.8
4 19.6 30.6 138.1 9.0 15.7 32.5 3.0 2.3 16.0 9.4 9.1 28.6
5 4.1 7.8 22.0 6.5 10.6 43.7 1.8 2.2 14.2i 1.6 3.8 45.0
6 125.7 155.1 417.9 12.0 20.0 61.1 8.1 8.2 30.7 8.8 17.5 123.1
7 27.2 65.8 239.1 14.3 26.3 70.9 6.1 9.3 29.1 11.3 20.1 111.7
8 55.5 111.4 358.0i 9.7 12.0 34.0 8.6 15.2 34.8 5.2 6.0 26.0
9 121.2 154.5 326.01 13.9 22.6 38.3 i0.4 13.9 38.1 7.7 16.0 42.1
i0 103.0 259.7 892.2 9.7 19.1 48.7 16.4 27.0 84.9 6.2 12.3 39.6
ii 103.7 172.4 518.5 12.7 17.8 44.0 12.0 19.5 43.2 6.0 10.2 35.2
12 14.4 22.4 30.4 8.6 21.4 26.9 4.9 5.8 14.9 2.1 9.1 16.2
13 28.4 110.8 465.2 7.6 13.6 50.8 7.5 12.8 39.2 0.9 7.2 45.6
14 13.1 25.2 150.1 12.7 24.6 71.5 4.2 7.3 40.8 5.1 14.9 102.3
15 112.9 503.8 1507 11.8 22.0 74.7 11.6 23.9 52.7 5.0 ii.0 46.1
16 19.8 53.2 222.5 14.5 24.3 87.8 13.1 25.4 86.5 7.0 37.6 56.1
17 106.6 173.4 571.0 8.4 12.6 31.3 13.7 22.3 60.1 5.5 10.6 29.6
18 19.1 37.9 66.3 9.5 19.1 58.9 8.3 18.5 35.5 8.2 35.0 156.6
19 60.1 73.6 189.5 39.9 38.3 66.0 20.9 35.1 88.5 19.4 26.6 95.4
20 26.9 56.3 163.9 11.3 18.6 38.3 7.9 11.7 51.6 3.9 9.2 28.2
21 16.9 48.4 153.4 5.1 7.2 19.2 3.8 5.5 16.0 1.6 3.6 16.3
22 173.1 341.5 902.0 59.7 101.7 146.2 10.8 15.3 43.0 10.7 23.8 49.2
23 2.9 3.9 12.6 5.7 14.5 79.4 2.6 2.7 20.8 4.2 6.2 24.1
24 68.6 137.6 295.9 12.1 20.8 37.3 5.3 5.2 31.5 4.9 9.6 24.9
25 79.9 162.8 298.0 7.8 11.9 25.5 5.0 7.1 29.6 3.8 6.1 21.4
26 4.6 5.4 20.6 6.2 8.4 41.6 2.8 2.4 13.0 5.6 11.7 96.0
27 53.1 198.1 643.3 30.0 44.1 75.4 8.5 16.0 50.9 6.2 12.4 42.2
28 50.2 135.0 254.8 25.3 61.2 109.9 5.9 18.4 42.2 8.4 37.3 136.6
29 4.7 10.9 44.8 i0.3 48.1 72.5 2.5 4.1 19.9 9.2 25.2 90.2
30 88.2 137.8 371.6 18.8 42.6 66.3 8.5 11.5 38.8 8.5 20.2 143.6
31 88.9 230.6 603.6 10.4 21.0 64.1 6.5 10.9 35.0 7.0 9.8 34.3
32 105.1 281.5 1083 9.6 17.9 84.1 i0.i 25.8 107.6 59.6 199.0 559.1
33 5.0 8.6 41.4 4.7 17.7 25.8 3.9 6.6 13.6 4.4 31.2 38.0
34 38.2 137.3 388.0 9.4 21.7 42.5 7.3 13.9 30.7 3.4 10.7 26.6
35 15.5 17.6 53.5 233.0 283.7 297.8 4.2 6.1 24.4 30.4 86.0 166.3
36 16.8 75.4 279.4 16.9 35.2 87.1 6.4 8.1 32.8 18.8 25.9 87.0
37 3.4 12.3 21.6 5.0 15.9 52.7 1.4 2.9 25.9 i 1.9 6.0 20.5
38 8.8 19.6 95.1 ii.i 49.0 59.9 3.4 4.6 19.9 6.9 33.9 87.9
39 133.4 532.0 1347 12.2 27.7 71.9 17.9 35.2 60.9 4.2 ii.i 45.8
TABLE 3--Pairwise Pearson correlation matrix, s h o w i n q R-

v a l u e s for w e i a h t increases of nickel. CoPPer. s i l v e r a n d tin
as w e l l as s e l e c t e d e n v i r o n m e n t a l p a r a m e t e r s .
Ni Cu I A~ Sn T Rh Tow SO~ NO~ 0% mm Ccnd pH

Ni 1.0 0.4 0.6 0.i 0.2 -0.2 -0.3 1.0 0.5 -0.6 -0.2 0.8 -0.3
Cul 0.4 1.0 0.4 0.3 0.2 0.i 0.2 0.3 -0.i 0.I 0.0 0.7 0.0
Ag 0.6 0.4 1.0 0.4 0.4 0.0 0.2 0.6 0.4 -0.5 -0.1 0.7 0.i
Sn 0.i 0.3 0.4 1.0 0.2 0.i 0.2 0.0 -0.i 0.3 0.i 0.2 0.i
T 0.2 0.2 0.4 0.2 1.0 -0.5 0.0 0.2 0.4 -0.5 0.0 0.3 0.4
Rh -0.2 0.i 0.0 0.I -0.5 1.0 0.8 -0.2 -0.2 0.4 0.0 0.1-0.2
Tow -0.3 0.2 0.2 0.2 0.0 0.8 1.0 -0.3 0.0 0.2 0.0 0.1 0.0
SO2 1.0 0.3 0.6 0.0 0.2 -0.2 -0.3 1.0 0.6-0.6 -0.i 0.7 -0.3
NO 2 0.5-0.1 0.4-0.1 0.4 -0.2 0.0 0.6 1.0-0.8 -0.i 0.4 0.0
O3 -0.6 0.i -0.5 0.3 -0.5 0.4 0.2 -0.6 -0.8 1.0 0.4 -0.6 -0.2
mm -0.2 0.0 -0.i 0.i 0.0 0.0 0 . 0 - 0 . i -0.i 0.4 1.0 -0.2 -0.1
Cond 0.8 0.7 0.7 0.2 0.3 0.i 0.1 0.7 0.4 -0.6 -0.2 1.0 -0.I
pH -0.3 0.0 0.i 0.i 0.4 -0.2 0.0 -0.3 0.0-0.2 -0.1 -0.i 1.0
iSite No 35 L a h e m a a excluded.
S O 2 t a r n i s h e s s i l v e r [13] but the m e t a l is r e l a t i v e l y i n s e n s i t i v e

to SO 2 as c o m p a r e d to H2S [ 1 4 , 1 5 ] . C a t h o d i c r e d u c t i o n s h o w s t h a t
s i l v e r s u l f i d e (Ag2S) is a m a j o r part of the c o r r o s i o n p r o d u c t s on the
39 t e s t s i t e s a n d p a r t l y a c c o u n t s for the c o r r e l a t i o n w i t h SO 2 [i] 9
T h i s is s u r p r i s i n g , b e c a u s e one w o u l d e x p e c t the SO 2 c o n c e n t r a t i o n to
b e r e l a t e d to S042- a n d not to s u l f i d e (S 2-) f o r m a t i o n . In fact, the
reaction of silver with S02 to f o r m s u l f i d e a n d o x i d e is n o t
thermodynamically favourable [15]. A r e d u c t i o n p a t h for SO 2 w i t h
s u l f i d e as a p o s s i b l e e n d p r o d u c t w a s p r o p o s e d by R o z e n f e l d a n d
involves dithionite, $2042-, as an i n t e r m e d i a t e s p e c i e [13]. T h i s
m e c h a n i s m h a s b e e n u s e d to e x p l a i n or d e s c r i b e s u l f i d e f o r m a t i o n on
i r o n a n d c o p p e r at SO 2 l e v e l s h i g h e r t h a n t h o s e of t h e p r e s e n t
exposure conditions [ 1 6 , 1 7 ] . To t h e b e s t of o u r k n o w l e d g e , the
mechanism has not been examined in c o n n e c t i o n with silver. An
a l t e r n a t i v e e x p l a n a t i o n of the d e p e n d e n c e of s u l f i d e f o r m a t i o n u p o n
S O 2 w o u l d be a c o r r e l a t i o n b e t w e e n SO 2 a n d H2S. No e v i d e n c e of s u c h a
c o r r e l a t i o n w a s f o u n d in a N o r d i c r e s e a r c h p r o j e c t on c o r r o s i o n of
e l e c t r o n i c s w h e r e b o t h SO 2 a n d H2S w e r e m e a s u r e d in a b r o a d s p e c t r u m
of n e a r l y 50 d i f f e r e n t i n d o o r test s i t e s [18]. A c o r r e l a t i o n b e t w e e n
SO 2 a n d H2S w a s found, h o w e v e r , w h e n o n l y s i t e s w i t h l o w (<2 ~ g / m 3)
c o n c e n t r a t i o n of H2S w e r e c o n s i d e r e d . R e d u c e d s u l f u r c o m p o u n d s , s u c h
as H2S, m a y o r i g i n a t e f r o m a n u m b e r of n a t u r a l b i o l o g i c a l s o u r c e s ,
s u c h as m a r s h e s a n d v o l c a n o e s , a n d a n t h r o p o g e n i c s o u r c e s f r o m e . g .
c r u d e oil p r o c e s s i n g [14]. S i n c e H2S is not m e a s u r e d in this program,
it has not b e e n p o s s i b l e to c o m p a r e its c o n t r i b u t i o n to the t o t a l Ag2S
f o r m a t i o n w i t h that of SO 2.
T h e w e i g h t i n c r e a s e of tin does not c o r r e l a t e at all w i t h the SO 2
c o n c e n t r a t i o n . Fig. 2 s h o w s t w o c l e a r l y d i s t i n g u i s h a b l e g r o u p s of
s i t e s for tin: o n e g r o u p is c h a r a c t e r i z e d by w e i g h t i n c r e a s e v a l u e s
below 60 ~ g / c m 2 a n d a w e a k SO 2 d e p e n d e n c e ; the other group is
c h a r a c t e r i z e d by v a l u e s a b o v e 80 ~ g / c m 2 a n d l o w SO 2 c o n c e n t r a t i o n s . So
far, no p a r a m e t e r s m e a s u r e d in the p r o g r a m can e x p l a i n the d i f f e r e n c e
b e t w e e n t h e s e two groups, nor the v a r i a t i o n w i t h i n the groups, e x c e p t
the w e a k SO 2 d e p e n d e n c e in the g r o u p w i t h the l o w w e i g h t i n c r e a s e
values.
2500
' Nickel '.3 15~ 15 262 C o p p e r
2000
28
15 10q
1500 16 36 32
23" " 9
&- 32
~9 1 29147.27 39.15
"~',38 " 1
iooo i0 38, 3 L 2 13
U ~2 " 5, i P ,/i" 10
3~711~7
:i
i,-, 50C 9.~ :~ ..~ 13
9 ~. "16 21
M
i i I I I l I
150 i , i , 200 , , i
U Silver Tin
35 32
.18
32
9 3 150 28 9 30
i00
16. 19 i0 .6
7
14"
i00 , ~& 19
17 39 2"9;38
20 27 15
50 9.11 .22 I 31 16
~. :. " "13 1 50 o . 3.22
"% "@ "34 1377.o,. ~12/.1..h7 ~.o "1
.: .
0 I I I I 0 /" 12211 I I I
0 20 40 60 80 i00 0 20 40 60 80 I00
Sulfur dioxide [gg/m 3 ]
FIG. 2 - - W e i g h t i n c r e a s e of nickel, copper, s i l v e r and tin
after 4 y e a r s of e x p o s u r e v s . the SO 2 c o n c e n t r a t i o n . Numbers
indicate the test site a c c o r d i n g to Table i.
Precipitation Parameters--One might argue that precipitation

p a r a m e t e r s are of no interest b e c a u s e the samples are sheltered, but
the c o m p o s i t i o n of the p r e c i p i t a t i o n reflects properties of the
e n v i r o n m e n t a n d is linked to p a r t i c u l a t e s and gases of the atmosphere,
some of which are not measured in the program. Especially,
conductivity of p r e c i p i t a t i o n is a p a r a m e t e r that gives a good
d e s c r i p t i o n of the o v e r a l l p o l l u t a n t level a n d c o r r e l a t e s w i t h all
important ions in p r e c i p i t a t i o n .
F o r copper, conductivity of p r e c i p i t a t i o n is the s i n g l e m o s t
i m p o r t a n t v a r i a b l e that e x p l a i n s the w e i g h t i n c r e a s e v a r i a t i o n (Table
3). Fig. 3 shows the w e i g h t i n c r e a s e of c o p p e r v s . conductivity of
precipitation with symbols corresponding to high and low 03
c o n c e n t r a t i o n s . Since 03 is only m e a s u r e d on a p p r o x i m a t e l y half of the
39 test sites, it was e s t i m a t e d by the NO 2 c o n c e n t r a t i o n on the
r e m a i n i n g sites (Fig. 3).
150 60
9 Ozone high r
0 Ozone low
50 9 o
o .
%
high range
"" 100 [] %4o
@ O
Q o
@ mm 00o ~30
I,i @
m %r'] o []
o o 15
"~ 50 9 0 o g~20
g m I Q
9 8
I0 9 measured
CI oestimated
i I .I I [ i I I I
20 40 60 80 100 20 40 60 80 i00 120
Conductivity [~S/cm] Nitrogen dioxide [~g/m 3 ]
FIG. 3--Weight increase of c o p p e r vs. conductivity of

p r e c i p i t a t i o n , w i t h symbols c o r r e s p o n d i n g to h i g h and low 03
c o n c e n t r a t i o n s (left), m e a s u r e d and e s t i m a t e d by NO 2 (right).
To i n v e s t i g a t e m o r e s p e c i f i c a l l y the p o s s i b l e c o n t r i b u t i o n of
conductivity, the d i f f e r e n t ions in p r e c i p i t a t i o n were examined
individually. In this evaluation, site 35 L a h e m a a was excluded. The
three ions that c o r r e l a t e most s t r o n g l y w i t h w e i g h t i n c r e a s e data are
S042-, CI- a n d NH4 + (Table 4), F o r n i c k e l and silver, the SO 2
d e p e n d e n c e was c o m p e n s a t e d for p r i o r to the calculation, u s i n g outputs
from r e g r e s s i o n s of only SO 2 on the metal w e i g h t increases.
NH4 § c o r r e l a t e s more w i t h silver than w i t h the other metals. No ion
is d o m i n a t i n g in the c o r r e l a t i o n m a t r i x w i t h r e s p e c t to c o p p e r and
nickel. Tin c o r r e l a t e s not at all w i t h the ions in p r e c i p i t a t i o n .
TABLE 4--Pairwise P e a r s o n c o r r e l a t i o n matrix, s h o w i n q R-

v a l u e s for w e i a h t increases of nickel. C O D D e r and s i l v e r vs.
S042- , NO3- , CI- and NH4 § in p r e c i p i t a t i o n . For n i c k e l a n d
s i l v e r the SO 2 d e p e n d e n c e was c o m p e n s a t e d for P r i o r to the
calculation.
.... I SO42- NOy- CI- NH4+

N i / [ S O 2] 0.41 0.28 0.40 0,41
Cu 0.42 0.25 0.49 0,39
A~/[SO2]0-3 0.37 0.22 0.51 0.63
NH4+ in p r e c i p i t a t i o n reflects the air c o n t e n t of p a r t i c u l a t e a n d

g a s e o u s a m m o n i u m c o n t a i n i n g compounds. A m m o n i u m sulfate ((NH4)2SO 4) is
k n o w n to s t i m u l a t e the a t m o s p h e r i c c o r r o s i o n of s e v e r a l m e t a l s [13].
NH 3 t o g e t h e r w i t h c h l o r i n e can form a m m o n i u m c h l o r i d e (NH4CI), w i t h
s i l v e r a c t i n g as a g o o d c a t a l y s t [15]. Also, NH 3 can d i s s o l v e in the
s u r f a c e film, i n c r e a s i n g the pH and t h e r e b y i n c r e a s i n g the a m o u n t of
d i s s o l v e d SO 2 in the film [19] or p r o m o t i n g the o x i d a t i o n of SO 2 to
s042- [16].
Climatic parameters--Norse of these parameters exhibit any

s i g n i f i c a n t c o r r e l a t i o n w i t h the w e i g h t increase data (Table 3). This
m a y s e e m s t r a n g e since c l i m a t e is k n o w n to h a v e an e f f e c t on the
a t m o s p h e r i c c o r r o s i o n of m e t a l s . One clue to the lack of c l i m a t i c
e f f e c t s is the degree of sheltering. The p r o t e c t i n g a l u m i n u m b o x can
even out d r a s t i c c h a n g e s in t e m p e r a t u r e and r e l a t i v e h u m i d i t y . Also,
the p r o t e c t i o n p r o b a b l y makes mass transport of the gaseous p o l l u t a n t s
more rate limiting, shielding the e f f e c t of o t h e r e n v i r o n m e n t a l
parameters.
F o r tin, t e m p e r a t u r e has a s p e c i a l e f f e c t since the a l l o t r o p i c
transformation (~-->~) occurs at 13.2 ~ In practice, the ~ - f o r m is
s t a b l e even b e l o w 0 ~ u n l e s s s p e c i f i c f a c t o r s t r i g g e r the c h a n g e
[20]. S i n c e the two d i f f e r e n t forms of tin are e x p e c t e d to b e h a v e
q u a l i t a t i v e l y different, w i t h r e s p e c t to a t m o s p h e r i c corrosion, this
c o u l d be an e x p l a n a t i o n for the o c c u r r e n c e of the two s e p a r a t e tin
groups (Fig. 2). B e a r i n g this in mind, emphasis was made on s e p a r a t i n g
the groups, b o t h by i n v e s t i g a t i n g the t e m p e r a t u r e in m o r e d e t a i l and
by s e a r c h i n g for e x t r e m e v a l u e s in the m o n t h l y averages of all
parameters. However, the a t t e m p t was u n s u c c e s s f u l , c o n f i r m i n g the
o b s e r v a t i o n that g e n u i n e failures c a u s e d by the a l l o t r o p i c t r a n s f o r -
m a t i o n (~-->~) appear to be rare [20].
Analysis of c o r r o s i o n products
XPS and D R I F T are the two main m e t h o d s u s e d here for the a n a l y s i s

of c o r r o s i o n products. XPS is a s u r f a c e s e n s i t i v e t e c h n i q u e that only
p r o b e s the o u t e r m o s t a t o m i c layers w h e r e a s D R I F T is a b u l k a n a l y s i s
t e c h n i q u e . However, D R I F T is not as s t r a i g h t f o r w a r d as XPS w h e n it
comes to i n t e r p r e t i n g the spectra.
XPS--Fig. 4 summarizes in t h r e e ternary diagrams the XPS

m e a s u r e m e n t s m a d e on nickel, copper, silver and tin a f t e r 4 years of
exposure. I n c l u d e d are the five important c o m p o n e n t s SO42- , S 2-,
NO3-, CI- and NH4 +. Areas c o v e r i n g i n d i v i d u a l site analyses, corres-
p o n d i n g to a t o m i c c o n c e n t r a t i o n s of the components, are i n d i c a t e d as
w e l l as the t h e o r e t i c a l p o s i t i o n of (NH4)2SO4, a c o m m o n p a r t i c u l a t e
p o l l u t a n t in most atmospheres.
For nickel, the sites are p o s i t i o n e d only in the NO3--CI--SO42- and
SO42--CI--NH4 + triangles. This means that all c o m p o n e n t s except S 2- are
detected. Furthermore, in the NO 3 -CI -SO42 triangle s i t e s are
p o s i t i o n e d on the SO42--CI - line w h e r e a s in the SO42--CI--NH4 + t r i a n g l e
all sites are w i t h i n the borders of the triangle. In other words, SO42-
, CI- a n d NH4+ are always detected whereas NO 3 sometimes is
undetected. Also, the nickel areas are closer to the SO42- corner, i.e.
SO42- is the d o m i n a t i n g component.
A p p l y i n g the same r e a s o n i n g to copper, the f o l l o w i n g p i e c e s of
i n f o r m a t i o n are e x t r a c t e d from Fig. 4. C o p p e r b e h a v e s as n i c k e l in
that all c o m p o n e n t s but S 2- are detected. C o p p e r is c a p a b l e of forming
sulfides but further o x i d a t i o n to SO42- p r o b a b l y p r e v e n t s its d e t e c t i o n
[21]. Also, m o r e n i t r o g e n compounds, b o t h in the form of NO 3- and NH4+,
are found on copper, as c o m p a r e d w i t h nickel.
S i l v e r is the only metal on w h i c h S 2- has b e e n detected. This, and
the fact t h a t NO 3- has not b e e n d e t e c t e d , confirms the e a r l i e r
s t a t e m e n t that Ag2S is a m a j o r c o m p o n e n t on silver, t o g e t h e r w i t h
(NH4)2SO 4 and NH4CI.
On tin, o n l y SO42- and NH4 § has been detected, p r o b a b l y o r i g i n a t i n g
m a i n l y from p a r t i c u l a t e (NH4)2SO 4.
cf
{i{{{ikA
ln/
i
,l
No; so? s 2-
FIG. 4 - - S u m m a r y of XPS a n a l y s e s on s e l e c t e d sites (Table i).
A r e a s c o v e r i n g all s i t e s a n a l y z e d a r e s h o w n for n i c k e l ,
copper, s i l v e r a n d tin in t h r e e t e r n a r y d i a g r a m s w i t h a t o m i c
p r o p o r t i o n s of d e t e c t e d NO 3 , C1 , SO42 , NH4+ a n d S 2- .
O x i d e s a n d c a r b o n c o n t a i n i n g compounds, s u c h as c a r b o n a t e , o x a l a t e
or the c a r b o x y l a t e s a c e t a t e a n d formiate, are not d i s p l a y e d in Fig. 4
but a r e a l w a y s p r e s e n t to v a r y i n g d e g r e e s . H o w e v e r , X P S is not the
m o s t s u i t a b l e m e t h o d for i d e n t i f y i n g t h e s e c o m p o u n d s . On tin, o x i d e s
c l e a r l y d o m i n a t e in the XPS a n a l y s i s , the o x y g e n c o n t e n t i n c r e a s i n g
w i t h the SO 2 c o n c e n t r a t i o n .
It s h o u l d be n o t e d that d i f f e r e n t XPS e q u i p m e n t s w e r e u s e d in the
a n a l y s e s s u m m a r i z e d in Fig. 4. Also, s e n s i t i v i t y f a c t o r s w e r e not
determined experimentally by s t a n d a r d c o m p o u n d s , which makes the
quantification procedure more uncertain.
~IFT--For nickel, o b s e r v a t i o n s are in a c c o r d a n c e w i t h the e a r l i e r

f i n d i n g s a f t e r 2 y e a r s of e x p o s u r e that a b a s i c n i c k e l c a r b o n a t e is
f o r m e d w h i c h is m o r e a b u n d a n t at l o w e r w e i g h t i n c r e a s e s . Also, an
a m o r p h o u s and, s u b s e q u e n t l y , a c r y s t a l l i n e a n d m o r e p r o t e c t i v e b a s i c
n i c k e l s u l f a t e is f o r m e d [~]. A f t e r 4 y e a r s of exposure, c r y s t a l l i n e
b a s i c n i c k e l s u l f a t e was f o u n d on all s a m p l e s i n v e s t i g a t e d . The
p r e s e n c e of b a s i c n i c k e l s u l f a t e s is in a c c o r d a n c e w i t h the e a r l y w o r k
of V e r n o n [ 2 2 ] . T h e r e s u l t s a l s o e x h i b i t s i m i l a r i t i e s w i t h a r e c e n t l y
p r o p o s e d r e a c t i o n s c h e m e for zinc, in w h i c h b a s i c zinc c a r b o n a t e is
i n i t i a l l y f o r m e d f o l l o w e d by the f o r m a t i o n of a b a s i c z i n c s u l f a t e
and, e v e n t u a l l y , a basic zinc chlorosulfate [23]. In the c a s e of
n i c k e l , h o w e v e r , t h e c r y s t a l l i n e b a s i c n i c k e l s u l f a t e s e e m s to be
s t a b l e e n o u g h to h i n d e r the f o r m a t i o n of b a s i c n i c k e l c h l o r o s u l f a t e
e v e n a f t e r 4 y e a r s of exposure.
XRD--Measurements w e r e p e r f o r m e d in o r d e r to c o n f i r m t h a t the
c r y s t a l l i n e b a s i c n i c k e l s u l f a t e p h a s e a f t e r 4 years, a c c o r d i n g to
D R I F T m e a s u r e m e n t s , was i d e n t i c a l to the one o b t a i n e d a f t e r s h o r t e r
e x p o s u r e times. T h i s w a s i n d e e d the case; the d - v a l u e s a n d r e l a t i v e
i n t e n s i t i e s a r e i d e n t i c a l to t h o s e p r e v i o u s l y f o u n d a f t e r 2 y e a r s of
e x p o s u r e [~].
Damaae functions
H a v i n g i d e n t i f i e d the i m p o r t a n t e x p l a n a t o r y v a r i a b l e s by c o r r e -
lation a n a l y s i s and j u s t i f i e d them by a n a l y s i n g the c o r r o s i o n p r o d u c t s
it is now p o s s i b l e to derive d a m a g e functions. R e g r e s s i o n a n a l y s i s was
p e r f o r m e d and the s t e p w i s e p r o c e d u r e was u s e d for s e l e c t i n g v a r i a b l e s
to the model if more than one v a r i a b l e was appropriate.
Nickel--The following linear equation was found,
WINi = 5.5 + 15.8[SO2] R 2 = 0.78 (i)
where
WI = Weight increase after 4 years of exposure, ~g/cm2,

[so2] = SO 2 concentration, ~ g / m 3,
N i c k e l is the m a t e r i a l that is m o s t s e n s i t i v e to dry d e p o s i t i o n of

SO2. The w e i g h t increase also c o r r e l a t e s s l i g h t l y w i t h SO42-, NH4+ and
CI- in p r e c i p i t a t i o n , which indicates the effect of chlorine
c o n t a i n i n g g a s e s or of d i f f e r e n t p a r t i c u l a t e s , for e x a m p l e (NH4)2SO 4.
The a n a l y s i s of c o r r o s i o n products shows the p r e s e n c e of a m o r p h o u s and
c r y s t a l l i n e b a s i c nickel sulfate, but also, to a lesser extent, the
p r e s e n c e of carbonate, nitrate, chloride and ammonium.
C O D D e r - - A r e g r e s s i o n equation c o m p r i s i n g conductivity of p r e c i p i t a -
tion and the 03 c o n c e n t r a t i o n was obtained,
WIcu = ii + 0.031Cond[O3] R 2 = 0.59 (2)
where
Cond = C o n d u c t i v i t y of precipitation, ~S/cm,

[03] = 03 concentration, ~ g / m 3,
It s h o u l d be s t r e s s e d that, since the samples are p r o t e c t e d from rain,

the c o n d u c t i v i t y of p r e c i p i t a t i o n is not the c a u s e of the w e i g h t
increase, but an i n d i c a t i o n of the o v e r a l l p o l l u t a n t level. 03 m a y
a f f e c t the c o r r o s i o n of c o p p e r by s t i m u l a t i n g oxide f o r m a t i o n and by
a c c e l e r a t i n g the d e p o s i t i o n rate for SO 2 on copper. The 03 c o n c e n -
t r a t i o n u s e d in Eq. 2 was a m i x e d variable. The m e a s u r e d 03 c o n c e n -
t r a t i o n was u s e d w h e n available, i.e. on a p p r o x i m a t e l y half of the 39
test sites. An e s t i m a t i o n based on the NO 2 c o n c e n t r a t i o n was u s e d at
the other sites,
[03 ] = 58.2 - 0.60[NO 2] R2 = 0.77 (3)
where
[NO2] = NO 2 concentration, ~ g / m 3.
Eq. 3 was c a l c u l a t e d by r e g r e s s i o n a n a l y s i s of d a t a f r o m all test

sites w i t h s i m u l t a n e o u s m e a s u r e m e n t s of 03 and NO 2, except test site
15, M i l a n (Fig. 3,right).
Silve;-- The following equation was estimated,
WIAg = 22.6[SO2]0.21[NH4+]0.36 R2 = 0.60 (4)
where
[NH4+ ] = NH4+ c o n c e n t r a t i o n in p r e c i p i t a t i o n , mgN/l.
T h e w e i g h t i n c r e a s e is due to the f o r m a t i o n of a layer of Ag2S a n d to

the f o r m a t i o n or d e p o s i t i o n of c h e m i c a l species, p o s s i b l y NH4CI a n d / o r
(NH4)2SO 4 a n d o r g a n i c c o n t a m i n a n t s . S i n c e H2S is not m e a s u r e d w i t h i n
the p r o g r a m it has not b e e n p o s s i b l e to e s t i m a t e its c o n t r i b u t i o n to
the total Ag2S formation, as c o m p a r e d to the c o n t r i b u t i o n from SO 2.
T i n - - N o e q u a t i o n has b e e n f o u n d that r e l a t e s the c o r r o s i o n a t t a c k

to e n v i r o n m e n t a l data. T w o c l e a r l y d i s t i n g u i s h a b l e groups can be
r e c o g n i s e d . So far, no p a r a m e t e r s m e a s u r e d in the p r o g r a m can e x p l a i n
t h e d i f f e r e n c e b e t w e e n the g r o u p s , n o r the v a r i a t i o n W i t h i n e a c h
group, e x c e p t a w e a k SO 2 d e p e n d e n c e in the g r o u p that i n c l u d e s the low
w e i g h t i n c r e a s e values. A c i d i f y i n g p o l l u t a n t s are not as d o m i n a t i n g as
for o t h e r m e t a l s . The only c o r r o s i o n p r o d u c t s s e e m to be oxides, w i t h
v a r y i n g s t o i c h i o m e t r y . This a g r e e s w i t h a s t u d y by P e t e r et. al., in
w h i c h o n l y S n O 2 w a s d e t e c t e d in an u r b a n and a m a r i n e e x p o s u r e site,
w h e r e a s SnO, S n O 2 a n d 5 S n O 2 . 2 H 2 0 w e r e all d e t e c t e d in an i n d u s t r i a l
e x p o s u r e s i t e u s i n g X - r a y d i f f r a c t i o n [24]. Also, Z a k i p o u r a n d L e y g r a f
u s e d X P S to a n a l y z e b o t h f i e l d e x p o s e d t i n a n d t i n e x p o s e d to
d i f f e r e n t l a b o r a t o r y - m i x t u r e s o,f SO~, NO 2 a n d H2S. In the laboratory,
o n l y o x i d e s w e r e d e t e c t e d , w S e r e a s SO42- a n d NH4+ w e r e a d d i t i o n a l
c o m p o n e n t s on the s u r f a c e of field e x p o s e d tin [25]. T h i s c o n f i r m s the
assumption t h a t SO42- a n d NH4+ m a i n l y o r i g i n a t e from particulate
(NH4)2SO 4 9
CONCLUSIONS
E v a l u a t i o n of the e f f e c t of a c i d i f y i n g a i r p o l l u t a n t s on nickel,
copper, s i l v e r a n d tin a f t e r 4 y e a r s f i e l d e x p o s u r e in r a i n s h e l t e r e d
e n v i r o n m e n t , inside a box, p e r m i t s the f o l l o w i n g m a i n c o n c l u s i o n s :
- D r y d e p o s i t i o n of SO 2 d o m i n a t e s the c o r r o s i o n of nickel, which

forms a m o r p h o u s a n d c r y s t a l l i n e b a s i c n i c k e l sulfate.
- B o t h 03 a n d N O 2 can a c c e l e r a t e the d e p o s i t i o n of SO 2 on c o p p e r .
H i g h w e i g h t i n c r e a s e s are o b s e r v e d at p o l l u t e d sites, w h e r e b o t h the
SO 2 a n d N O 2 c o n c e n t r a t i o n s are high, a n d at b a c k g r o u n d sites, w h e r e
the 03 c o n c e n t r a t i o n is high.
- S i l v e r forms Ag2S as the d o m i n a t i n g c o r r o s i o n p r o d u c t . E v e n so, the

SO 2 c o n c e n t r a t i o n c o r r e l a t e s w i t h the w e i g h t i n c r e a s e of silver. S i n c e
H2S is n o t m e a s u r e d w i t h i n the p r o g r a m it has not b e e n p o s s i b l e to
e s t i m a t e its c o n t r i b u t i o n to the Ag2S f o r m a t i o n and its c o r r e l a t i o n to
SO 2 .
- The f o r m a t i o n of o x i d e s w i t h d i f f e r e n t s t o i c h i o m e t r i e s is the
dominating c a u s e for the w e i g h t i n c r e a s e of tin a n d no e q u a t i o n has
b e e n f o u n d that r e l a t e s the c o r r o s i o n a t t a c k to e n v i r o n m e n t a l data.
- P a r t i c u l a t e compounds, s u c h as (NH4)2SO4, c o n t r i b u t e s to the w e i g h t

i n c r e a s e of all metals.
- Conductivity of p r e c i p i t a t i o n is t h e single most important

e x p l a n a t o r y v a r i a b l e . It i n d i c a t e s the p r e s e n c e of g a s e o u s pollutants
as w e l l as p a r t i c u l a t e s .
ACKNOWLEDGEMENTS
This work is financially supported by the Swedish Environmental

Protection Agency. It is the result of c o - o p e r a t i o n b e t w e e n the
organisations listed below, which participated in the UN ECE exposure
program. Each organization was responsible for gathering
meteorological and pollution data, and for providing sites for the
exposure of materials:
National Research Institute for Protection of Materials (SVUOM), Czech
Republic; Technical Research Centre of Finland (VTT); Bayrisches
Landesamt far Denkmalpflege, Germany; Agency for Energy Sources
(ENEA), Italy; TNO Division of Technology for Society Department of
Environmental Chemistry, the Netherlands; Norwegian Institute for Air
Research; Swedish Corrosion Institute; Building Research Establish-
ment, Department of Environment, United Kingdom; Ministerio de Obras
Publicas y Urbanismo (MOPU), Spain; Institute of Physical Chemistry,
R u s s i o n Academy of Sciences (Russion Federation); M i n i s t r y of the
Environment, Estonia; Institute of Technology, Laboratory of
Mineralogy and Petrology, Portugal; National R e s e a r c h Council of
Canada and the Ministries of the Environment of Canada and of Ontario;
and United States Environmental Protection Agency.
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XLVII, 1932, p 121.
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Corrosion, A S T M STP 1239, W. W. K i r k and H e r b e r t H. Lawson,
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Stuart B. Lyon I, Chun Wai Wong ~, and Paul Ajiboye I
AN APPROACH TO THE MODELLING OF ATMOSPHERIC CORROSION
REFERENCE: Lyon, S. B., Wong, C. W., and Ajiboye, P . , "An Approach to

the Modeling of Atmospheric Corrosion, u Atmospheric Corrosion, ASTM ST~
1239, W. W. Kirk and Herbert H. Lawson, Eds., American Society for
T e s t i n g and Materials, Philadelphia, 1995.
ABSTRACT: Atmospheric corrosion is relatively complex involving interac-

tions between a metallic substrate and a dynamic atmosphere. Modelling
of other corrosion processes has been carried out with some success
however, little advance has been made on the modelling of atmospheric
corrosion. Successful models must incorporate a detailed understanding
of the corrosion under the various deposition, evaporation and condensa-
tion regimes implicit in the diurnal cycle. A good model for atmospheric
corrosion should also consider the electrochemical nature of corrosion
and be able to predict the observed changes in corrosion rate during
drying and re-wetting. This work develops a model based on a condensed
droplet model with a central anode and a peripheral cathode and considers
the effects of evaporation on the concentration of electrolyte, its
conductivity and the effects of reducing droplet size on the variation in
limiting oxygen reduction current. AS the conductivity variation permits
estimation of the anode to cathode resistance, the limiting oxygen reduc-
tion current can be used to estimate the maximum voltage drop due to
resistive effects in the droplet. The model predicts that there is n__oo
significant resistive control in an evaporating droplet assuming the
corrosion rate is that given by the limiting oxygen reduction current.
However, in a condensate or adsorbate of uniform thickness resistive
effects may become significant in layers less than 10 pm thick. In
atmospheric corrosion, this has relevance with respect to repeated
evaporation and condensation during wetting and drying, t o t h e effects of
rainwater washing and surface cleaning and also to micron or sub-micron
thick adsorbates.
KEYWORDS: modelling, atmospheric corrosion, droplet evaporation, resis-

tive control
Atmospheric corrosion is a complex process involving the interac-

tion of the atmospheric environment with metallic materials. Although
the atmospheric corrosion of metals, like other corrosion phenomena,
involves electrochemical reactions of anodic dissolution balanced by a
cathodic reduction reaction, the variability of the environment compared
with other typical environments encountered in corrosion causes substan-
tially greater difficulties in explicit analysis of the problem. As an
example, the environment of a boiler is precisely controlled to minimise
corrosion problems. In such a controlled environment modelling of
specific corrosion processes, especially crevice corrosion, has been
carried Out with some precision by workers such as Turnbull [1-3].
Unfortunately, the environment of the atmosphere is not tightly con-
ILecturer and graduate students, respectively, Corrosion and Protection

Centre, UMIST, Manchester, M60 IQD, UK.
26
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LYON ET AL. ON MODELING OF ATMOSPHERIC CORROSION 27
trolled nor is there any apparent d i f f u s i o n constraint on an e x p o s e d

metal surface. As a consequence, m o d e l l i n g of a t m o s p h e r i c c o r r o s i o n has
g e n e r a l l y focused on an empirical basis w i t h the d e v e l o p m e n t of "damage
function" or "dose response" type expressions p r e v a l e n t [4-6].
The d e v e l o p m e n t of more fundamental models of a t m o s p h e r i c c o r r o s i o n

require c o n s i d e r a t i o n of the p r i n c i p l e s of m e t a l l i c corrosion, i.e.
e l e c t r o c h e m i c a l t h e r m o d y n a m i c s and kinetics, as well as k n o w l e d g e of, or
insight to, the specific r a t e - c o n t r o l l i n g step in c o r r o s i o n (which m a y
differ from m a t e r i a l to material and as the external e n v i r o n m e n t a l
c o n d i t i o n s alter).
Thermodynamics
A l t h o u g h a study of thermodynamics cannot p r o v i d e i n f o r m a t i o n on

the rates of chemical or e l e c t r o c h e m i c a l reaction it will indicate l i k e l y
r e a c t i o n p r o d u c t s or pathways. All metals of c o m m o n interest (e.g. iron,
zinc, aluminium, copper, and lead) are t h e r m o d y n a m i c a l l y u n s t a b l e to the
f o r m a t i o n of ions (dissolution) where the cathodic r e a c t i o n is the
r e d u c t i o n of oxygen. The m o r e active metals, iron, zinc and aluminium,
are also g e n e r a l l y unstable where the cathodic reaction is the e v o l u t i o n
of hydrogen. However, direct formation of ions is not the o n l y means b y
w h i c h m e t a l s m a y react. Thus, at a s u f f i c i e n t l y high anodic p o t e n t i a l
(which differs from metal-to-metal), a stable, p r o t e c t i v e oxide film m a y
form; the p h e n o m e n o n known as passivity. Evidence from w o r k c a r r i e d out
on the c o r r o s i o n of iron under thin layers of e l e c t r o l y t e s d e m o n s t r a t e s
that, p a r t i c u l a r l y on an i n i t i a l l y u n c o r r o d e d surface but also on pre-
c o r r o d e d (rusty) surfaces, the corrosion p o t e n t i a l varies as a f u n c t i o n
of e l e c t r o l y t e thickness on the metal surface and thus appears to be
c o n t r o l l e d b y the kinetics of the oxygen r e d u c t i o n reaction. Thus, the
c o r r o s i o n p o t e n t i a l of iron in 10 3 M Na2SO 4 solution varies from about
-600 m V on the Saturated Calomel Electrode (SCE) scale under fully
immersed stagnant conditions to values in the region of 0 mV (SCE) w i t h
v e r y thin e l e c t r o l y t e s (<< i00 ~m) [7]. At the more noble potential, all
the m e t a l s m e n t i o n e d above will s p o n t a n e o u s l y p a s s i v a t e and should
corrode at v e r y low rates. It is an interesting o b s e r v a t i o n that the
typical range of a t m o s p h e r i c c o r r o s i o n rates of iron (100-250 ~m y l) is
e q u i v a l e n t to typical values for the p a s s i v e c o r r o s i o n c u r r e n t d e n s i t y on
iron (4-10 ~A cm ~) [8].
Kinetics
Chemical and e l e c t r o c h e m i c a l reaction rates are c o n t r o l l e d b y the

kinetics of the slowest reaction in a sequence of reactions, i.e. the
r a t e - d e t e r m i n i n g step. Hence, the fundamental p r o b l e m in the study of
r e a c t i o n kinetics is the d e t e r m i n a t i o n of w h i c h r e a c t i o n step is the one
w h i c h is rate-limiting. Given the w i d e l y differing e l e c t r o c h e m i s t r y and
r e a c t i v i t y of the metals of interest, it is u n l i k e l y that the same step
will be r a t e - l i m i t i n g in all cases. However, in general, the f o l l o w i n g
sequence holds true under all c i r c u m s t a n c e s for all metals:
Mass transport of species from the a t m o s p h e r e to the e x t e r i o r solid

surface of the material. In the general case, such r e a c t a n t s
include water (to p r o v i d e an electrolyte) as well as r e a c t i v e
p o l l u t a n t gases and other species d i s s o l v e d in solution.
Chemical r e a c t i o n of species at the material surface. This does

not d i r e c t l y c o n t r i b u t e to metal d i s s o l u t i o n but m a y s i g n i f i c a n t l y
alter the n a t u r e of the c o r r o s i o n or other r e a c t i o n p r o d u c t formed.
Mass transport of species w i t h i n the c o r r o s i o n p r o d u c t layer on the

m a t e r i a l surface to the u n d e r l y i n g c o r r o s i o n p r o d u c t / m e t a l inter-
face or to some point s u f f i c i e n t l y close to that interface to
o v e r c o m e the ionic or e l e c t r o n i c resistance.
A n o d i c o x i d a t i o n of the metal or lower o x i d a t i o n state oxide. This

includes direct d i s s o l u t i o n into an e l e c t r o l y t e as well as forma-
tion of solid state oxides or intermediaries and further o x i d a t i o n
of p r e - f o r m e d oxides.
C a t h o d i c r e d u c t i o n of a species at the metal p r i m a r i l y c o n s u m i n g

a t m o s p h e r i c oxygen but also p o s s i b l y involving r e d u c t i o n of pre-
formed oxides or other species and/or e v o l u t i o n of hydrogen.
Mass transport of species from the c o r r o s i o n p r o d u c t / m e t a l inter-

face to the exterior solid surface of the material.
Chemical r e a c t i o n or t r a n s f o r m a t i o n of the c o r r o s i o n p r o d u c t via

i n t e r m e d i a t e stages to a final stage w h i c h m a y include a s o l u b l e
species.
Mass transport of a species from the exterior solid surface of the

m a t e r i a l to the atmosphere. This includes d i s s o l u t i o n of s o l u b l e
species from the surface and removal by w a s h i n g as well as evapor-
ation of a species, such as water, from the surface.
Current state of m e c h a n i s t i c understandinq
W e t / d r y episodes are important in altering the n a t u r e of the

c o r r o s i o n p r o d u c t by precipitation, dissolution, and chemical changes
i n c l u d i n g dehydration. Secondly, w e t t i n g and drying causes changes in
the c o n c e n t r a t i o n of the surface e l e c t r o l y t e w h i c h alter the rate of
e l e c t r o c h e m i c a l and chemical reactions. Thirdly, w e t t i n g and drying
causes changes in the electrolyte layer thickness w h i c h changes the
m a x i m u m o x y g e n r e d u c t i o n current.
Zinc corrodes by formation of a s p a r i n g l y soluble h y d r o x i d e at a

s l i g h t l y alkaline pH. This r e l a t i v e l y r a p i d l y reacts w i t h CO 2 to form a
b a s i c carbonate. In the absence of pollutants, further c o r r o s i o n is
c o n t r o l l e d by d i f f u s i o n of species through the film and t h r o u g h pores in
the film. D e p o s i t i o n of pollutant results in thinning of this film b y
its c o n v e r s i o n to m o r e soluble, and less p r o t e c t i v e species, w h i c h
e v e n t u a l l y are r e m o v e d by d i s s o l u t i o n and washing. During drying the
e l e c t r o l y t e concentrates, thinning the film by dissolution. C o r r o s i o n is
s t i f l e d b y e v a p o r a t i o n of water and p r e c i p i t a t i o n of basic salts of zinc
h y d r o x i d e [9-11].
Iron corrodes initially to the ferrous state, either Fe 2§ or

ferrous hydroxide, during extended wet episodes. These species are then
f u r t h e r o x i d i s e d to an oxide (Fe304 or FelOn) or h y d r o x i d e (Fe(OH) 3 or
7-FeOOH) p a r t i c u l a r l y during drying episodes. Fe203 m a y also be r e d u c e d
b a c k to ferrous h y d r o x i d e under w e t t i n g conditions. C o r r o s i o n is s t i f l e d
by p a s s i v a t i o n of the iron surface during drying. In the l o n g - t e r m
r e l a t i v e l y u n r e a c t i v e goethite (a-FeOOH) is formed [12-14].
POSSIBLE CONTROLLING MECHANISMS
The m o s t likely factors c o n t r o l l i n g r e a c t i o n kinetics are an aspect

of the b a s i c e l e c t r o c h e m i s t r y of the system or mass transport of some
species during the r e a c t i o n process. These processes, as m o d i f i e d b y
w e t t i n g and drying of the surface, are c o n s i d e r e d below.
Diffusion control
The general k i n e t i c control of a t m o s p h e r i c c o r r o s i o n b y d i f f u s i o n

of o x y g e n through an electrolyte film can be d i s m i s s e d as u n i m p o r t a n t
though it m a y have a role in transient phenomena. Thus, if o x y g e n
diffusion was always the r a t e - c o n t r o l l i n g step, the a t m o s p h e r i c c o r r o s i o n
rates of, say zinc and iron, should differ only b y v i r t u e of their
d i f f e r e n t densities and atomic masses w h e r e a s iron corrodes approximately

i0 times faster than zinc.
K i n e t i c control via mass transport through a t h i c k e n i n g m a c r o s c o p i c

c o r r o s i o n p r o d u c t film should give p a r a b o l i c kinetics w i t h time for a
g i v e n set of exposure conditions. In fact, e x c l u s i v e l y p a r a b o l i c kin-
etics are r a r e l y o b s e r v e d w i t h exponents lying b e t w e e n 0.5 and i. Indeed
a p p r o x i m a t e l y linear d e p e n d e n c e of c o r r o s i o n rate w i t h exposure time is
often observed, e s p e c i a l l y for zinc c o r r o s i o n w h i c h implies control due
to mass transport of one or more species from the gas phase.
A n o d i c r e a c t i o n control
A n o d i c r e a c t i o n rate control of c o r r o s i o n p r o c e s s e s almost

i n v a r i a b l y involve f o r m a t i o n of a filmed surface. The surface film m a y
be an insoluble c o r r o s i o n p r o d u c t or salt or true p a s s i v a t i o n m a y occur.
If the p r o c e s s is c o n t r o l l e d by the rate of the anodic r e a c t i o n then the
i m p l i c a t i o n is that the nature of the filmed surface changes.
Resistance control
The e l e c t r o c h e m i c a l c o r r o s i o n kinetics m a y also be c o n t r o l l e d b y

the ohmic r e s i s t a n c e b e t w e e n anode and cathode. Thus, for a g i v e n anode-
c a t h o d e distance and potential difference, the m a x i m u m r e a c t i o n rate
reduces as the e l e c t r o l y t e r e s i s t a n c e increases.
This paper explores the last p o s s i b i l i t y by m o d e l l i n g of changes in

e l e c t r o l y t e concentration, and in the limiting o x y g e n r e d u c t i o n rate,
during e v a p o r a t i o n of droplets on a surface.
THE D R O P L E T MODEL
The model is d e v e l o p e d by considering e v a p o r a t i o n from d r o p l e t s of

e l e c t r o l y t e on a w e t t e d surface. This derives from the o b s e r v a t i o n that
the f o r m a t i o n of u n i f o r m films of electrolyte on a s u b s t r a t e d u r i n g
c o n d e n s a t i o n or p r e c i p i t a t i o n processes are u n l i k e l y due to the rela-
t i v e l y h i g h surface tension of water. Thus e l e c t r o l y t e droplets, of
g e n e r a l h e m i s p h e r i c a l shape, are likely to result. During drying, such
droplets u n d e r g o e v a p o r a t i o n into an a t m o s p h e r e of lower relative humid-
ity r e s u l t i n g in a c o n c e n t r a t i o n of electrolyte, a general thinning of
the a v e r a g e droplet thickness and a shrinkage in size (volume and s u r f a c e
area) of the droplet.
I tl ~%%% rb
'. . . . . . . . . . . . . . . . . . . . . . .\
%
FIGURE 1 -- C r o s s - s e c t i o n of flattened h e m i s p h e r i c a l cap and p l a n a r
cylindrical droplet geometries.
As has b e e n p o i n t e d out by Evans' in his classic d e m o n s t r a t i o n of

the d i f f e r e n t i a l aeration p h e n o m e n o n [15], anodic and c a t h o d i c p r o c e s s e s
in a droplet are well seperated w i t h the latter l o c a l i s e d at the d r o p l e t
p e r i p h e r y w h e r e o x y g e n access is more rapid through the thinner d r o p l e t

section, Figure i. In such a geometry, o x y g e n diffuses e s s e n t i a l l y
p e r p e n d i c u l a r to the surface through the p e r i p h e r y under a c o n c e n t r a t i o n
g r a d i e n t b e t w e e n the air and the cathode w h e r e d i s s o l v e d o x y g e n is
consumed. In contrast, ionic transport to the central anode is effec-
t i v e l y p a r a l l e l to the surface.
Droplet evaporation
The model considers three g e o m e t r i e s of droplet; hemispherical, a

f l a t t e n e d h e m i s p h e r i c a l cap and planar (cylindrical). The second of
these is e x p e c t e d to most c l o s e l y model a real droplet w i t h the o t h e r
g e o m e t r i e s chosen for comparison. E v a p o r a t i o n of the droplet is a s s u m e d
to be F i c k i a n into still air at an a r b i t r a r y relative h u m i d i t y of 60% and
a critical d i f f u s i o n distance of 1 mm.
Water flux = Dw/d. (I-X).C w
Dw = d i f f u s i o n coefficient of water vapour in air (0.478 cm 2 s ~)

d = c h a r a c t e r i s t i c diffusion distance (0.i cm)
x = relative h u m i d i t y of still air (60%)
Cw = s a t u r a t i o n c o n c e n t r a t i o n of water vapour in air (1.046xi0 6
mol cm 3)
Electrolyte conductivity
D u r i n g evaporation, the c o n c e n t r a t i o n of e l e c t r o l y t e in the droplet

increases in p r o p o r t i o n to the r e d u c t i o n in droplet volume. If, for
example, c o r r o s i o n in droplets was under resistive control, this m a y
result in an increase in the c o r r o s i o n rate under the droplet as a result
of an increase in solution conductivity. On the other hand, the anode-
t o - c a t h o d e r e s i s t a n c e is expected to v a r y inversely w i t h droplet thick-
ness at a given e l e c t r o l y t e conductivity. In dilute solution, the
c o n d u c t i v i t y of an electrolyte is given by the D e b y e - H u c k e l ~ O n s a g e r
e q u a t i o n [16]:
Am = Amo _ (A + B . ~ n ~ ~
Am = m o l a r c o n d u c t i v i t y of e l e c t r o l y t e solution
Am ~ = m o l a r c o n d u c t i v i t y of NaCI at infinite d i l u t i o n (126.4)
A,B = 60.2 and 0.229 r e s p e c t i v e l y for w a t e r
c = c o n c e n t r a t i o n of e l e c t r o l y t e solution (mol cm 3)
Also:
k = Am.c
k = conductivity of electrolyte solution (ohm cm) I
The above e q u a t i o n is g e n e r a l l y valid up to a c o n c e n t r a t i o n of about

0.1 M. The e l e c t r o l y t e was chosen as NaCI at an initial c o n c e n t r a t i o n of
1 0 `4 M .
Oxyqen diffusion to the cathode
As the droplet evaporates, the average thickness of the d r o p l e t

decreases, thus increasing the rate of o x y g e n d i f f u s i o n to the cathode.
This p o t e n t i a l l y increases the m a x i m u m c o r r o s i o n rate if the s y s t e m is
under c a t h o d i c control. However, during e v a p o r a t i o n the area of surface
under the droplet, including the cathode area, decreases. O x y g e n diffu-
sion at the droplet p e r i p h e r y is assumed to occur at the m a x i m u m rate
g i v e n b y Fick's law. C o n v e c t i v e effects are neglected:
LYON ET A L ON MODELING OF ATMOSPHERIC CORROSION 31
Oxygen diffusion f l u x = Dox/t. Cox
Do• = d i f f u s i o n c o e f f i c i e n t of 03 in w a t e r (2.1x10 ~ c m 2 s i)
t = t h i c k n e s s of e l e c t r o l y t e at c a t h o d e
Cox = c o n c e n t r a t i o n of 02 in w a t e r (2.64xi0 7 m o l c m 3)
Anode to c a t h o d e resistance
A c o m p l e t e s o l u t i o n f o r e v a l u a t i o n of a n o d e - t o - c a t h o d e r e s i s t a n c e
w o u l d i n v o l v e a f i n i t e e l e m e n t t r e a t m e n t of 2 - d i m e n s i o n a l o x y g e n d i f f u -
s i o n at t h e p e r i p h e r a l c a t h o d e a n d c a l c u l a t i o n of the e l e c t r o c h e m i c a l
p o t e n t i a l v a r i a t i o n f r o m t h e c e n t r e to t h e d r o p l e t edge. T h i s is b e y o n d
t h e s c o p e of t h i s c u r r e n t study. H o w e v e r , a g o o d a p p r o x i m a t i o n to t h e
r e s i s t a n c e m a y b e o b t a i n e d u s i n g the f o r m u l a d e r i v e d f r o m t h e c a p a c i t a n c e
b e t w e e n t w o c o n c e n t r i c c y l i n d r i c a l rings:
R = i/(2~tk).In(r'Jr' I)
R = resistance
k = c o n d u c t i v i t y of the m e d i u m
t = t h i c k n e s s / h e i g h t of the c o n c e n t r i c rings
r'~ = r a d i u s of o u t e r r i n g
r'~ = r a d i u s of i n n e r r i n g
Relative anode and cathode locations
T h e p e r i p h e r a l c a t h o d e w a s a s s u m e d to h a v e a l a r g e r a r e a t h a n t h e
c e n t r a l a n o d e w i t h a r a t i o of c a t h o d e to a n o d e a r e a (Ac/A a) e q u a l to 3.
Thus, t h e r a t i o of t h e c a t h o d e r a d i u s ( e f f e c t i v e l y t h e s a m e as the b a s e
r a d i u s of t h e d r o p l e t ) to the a n o d e r a d i u s (Ro/R~) e q u a l l e d 2. However,
for both the hemispherical and hemispherical cap geometries, the thick-
n e s s of t h e e l e c t r o l y t e v a r i e s as a f u n c t i o n of r a d i u s . A l s o , f o r all
g e o m e t r i e s , a n o d e a n d c a t h o d e c u r r e n t is n o t l o c a l i s e d at a s p e c i f i c
r a d i u s b u t r a t h e r is s p r e a d out. Thus, in o r d e r to u s e t h e a p p r o x i m a t e
f o r m u l a f o r t h e a n o d e to c a t h o d e r e s i s t a n c e , all the c u r r e n t p a s s i n g
b e t w e e n a n o d e a n d c a t h o d e is a s s u m e d to o r i g i n a t e from, a n d b e c o n s u m e d
at, a p a i r of c o n c e n t r i c r i n g e l e c t r o d e s p l a c e d at r a d i a l d i s t a n c e s s u c h
t h a t t h e a r e a of c a t h o d e (or anode) i n s i d e the r i n g e q u a l s t h e a r e a of
c a t h o d e (or anode) o u t s i d e the ring. T h e n o m i n a l a n o d e l o c a t i o n (r'a)
a n d n o m i n a l c a t h o d e l o c a t i o n (r'c) d e r i v e d in t h i s w a y w e r e u s e d i n t h e
resistance formula above. T h e e l e c t r o l y t e t h i c k n e s s w a s t a k e n as t h e
t h i c k n e s s of the d r o p l e t m i d w a y b e t w e e n r" c a n d r' a. S i m i l a r l y , t h e
c h a r a c t e r i s t i c d i s t a n c e f o r o x y g e n d i f f u s i o n t h r o u g h the d r o p l e t to t h e
p e r i p h e r a l c a t h o d e w a s t a k e n as the d r o p l e t t h i c k n e s s at r" c.
Droplet geometries
various formulae for e a c h g e o m e t r y u s e d in the c a l c u l a t i o n s are

reproduced below. The following symbols are commonly used:
h = m a x i m u m t h i c k n e s s (height) of the d r o p l e t
ro = t r u e r a d i u s of t h e h e m i s p h e r e
r h = b a s e r a d i u s of t h e d r o p l e t
Hemispherical: Volume = 2~/3ro 3

Surface area = 2~ro 2
Initial height = 0.I c m
Flattened cap: Volume = ~.t~(3ro - h ) / 3

Surface area = 2~roh
Base radius = 4(2rob - h 2)
ro/t = 0.i
Initial height = 0.i c m
Cylindrical: V o l u m e = ~rb2h
Surface area Krb 2
=
Initial height = 0.1 cm
Computation
The results were computed on a spreadsheet model: total e v a p o r a t i o n

was c a l c u l a t e d over a given time step after w h i c h the v a r i o u s p a r a m e t e r s
of interest w e r e r e - c a l c u l a t e d w i t h the reduced droplet volume. This
p r o c e s s was r e p e a t e d until a final a r b i t r a r y size was achieved. Thus,
the droplet volume, p e a k height, anode to cathode resistance, total
limiting o x y g e n r e d u c t i o n current (i.e. c o r r e c t e d for s h r i n k i n g c a t h o d e
area) and anode to cathode iR drop were c a l c u l a t e d at time steps of 10
seconds; chosen as a good c o m p r o m i s e b e t w e e n a large c o m p u t a t i o n a l effort
and accuracy. For example, a shorter time step of 1 second, tested on
the p l a n a r (cylindrical) droplet, resulted in less than 0.5% change in
final e v a p o r a t i o n time.
The v a r i a t i o n of droplet volume w i t h e v a p o r a t i o n time is shown in

Figure 2. F l a t t e n i n g of the h e m i s p h e r i c a l cap causes an increase in the
total e v a p o r a t i o n time to about 3800 s. The c o n c e n t r a t i o n ratio for the
e l e c t r o l y t e in the droplets, equivalent to the ratio of initial to final
volumes, was similar for b o t h h e m i s p h e r i c a l droplet g e o m e t r i e s (~ 105 )
but v e r y m u c h smaller for the p l a n a r droplet (~ 102).
0.1_--
0.01~
0.001 Cap
~" 0.0001 9
1E-05
o
>
1E-06 :
1E-07i
1 E-08~
1E-0~
o 56o l doo l gOO 2goo aooo .ooo
]]me (s)
FIGURE 2 -- Droplet v o l u m e as a function of e v a p o r a t i o n time.
RESULTS
The anode to cathode r e s i s t a n c e is p r e s e n t e d in Figure 3 w i t h the

limiting o x y g e n r e d u c t i o n current at the p e r i p h e r a l c a t h o d e in Figure 4.
B o t h the h e m i s p h e r i c a l droplets show similar behaviour. Thus, d e s p i t e
the r e d u c e d g e o m e t r i c c r o s s - s e c t i o n of e l e c t r o l y t e in the droplet, the
anode to cathode r e s i s t a n c e decreases as a function of e v a p o r a t i o n time
due to the i n c r e a s e d c o n d u c t i v i t y of the electrolyte. Likewise, a l t h o u g h
the o x y g e n r e d u c t i o n current d e n s i t y increases s u b s t a n t i a l l y d u r i n g
evaporation, the total current decreases due to the r e d u c e d c a t h o d e area.
However, s u b s t a n t i a l l y different b e h a v i o u r is d e m o n s t r a t e d b y the p l a n a r
droplet g e o m e t r y w h e r e the anode to cathode r e s i s t a n c e is almost
invariant w i t h time and the total o x y g e n r e d u c t i o n current increases as
the c a t h o d e area does not change w i t h evaporation.
1000~
100
Planar
.~,~ 10
0.1
o s6o lO'OO 1ioo 26oo 2ioo 3o'oo 2'oo 40oo
Time (s)
FIGURE 3 -- A n o d e - t o - c a t h o d e resistance as a function of evaporation

time.
100
"0
rr 0.1=
o Ca \
0.001
'~ 0.0001 Hemisphere
%
1E-05
o 56o 16oo 15oo 2600 2ioo 3obo ~oo 4000
Time (s)
FIGURE 4 -- T o t a l l i m i t i n g o x y g e n reduction current as a function of

evaporation time
10000:
g 1000
2
Q
0
100
10
Cap
/ Planar
I
0
< 0.1 Hemisphere
0.01
o 56o 16oo 1s.oo 2600 2~;oo 3o'oo 3ioo 4o00
Time (s)
FIGURE 5 -- A n o d e - t o - c a t h o d e iR v o l t a g e d r o p as a f u n c t i o n of e v a p o r a t i o n
t i m e ( e l e c t r o l y t e c o n c e n t r a t i n g w i t h time).
10000
~" 1000
g
~ 100
~0 10!
0
N 1
0
< 0.1 Hemisphere
0.01 r i i i i i = i i g = i i = =
10 100 1000
Droplet height (um)
FIGURE 6 -- A n o d e - t o - c a t h o d e iR v o l t a g e d r o p as a f u n c t i o n of d r o p l e t
h e i g h t (assume c o n s t a n t c o n c e n t r a t i o n ) .
The v a r i a t i o n in the voltage drop b e t w e e n anode and c a t h o d e as a

function of e v a p o r a t i o n t i m e , derived from the oxygen r e d u c t i o n c u r r e n t
and anode to cathode resistance, are summarised in Figure 5. In general,
the r e s i s t i v e v o l t a g e losses in all droplet geometries are i n i t i a l l y
r e l a t i v e l y low (< 10 mY). However, while the resistive losses d e c r e a s e
w i t h e v a p o r a t i o n time for the the h e m i s p h e r i c a l droplets, they increase
w i t h the p l a n a r droplet geometry. For comparison, Figure 6 shows the iR
v o l t a g e drop as a function of e l e c t r o l y t e thickness at a fixed electro-
lyte c o n c e n t r a t i o n of 10 4 M. In this case, the iR drop is invariant as
a f u n c t i o n of e l e c t r o l y t e thickness for h e m i s p h e r i c a l and h e m i s p h e r i c a l
cap g e o m e t r i e s but increases w i t h decreasing e l e c t r o l y t e thickness for
the c y l i n d r i c a l p l a n a r geometry.
DISCUSSION
The results of this model of droplet formation and e v a p o r a t i o n are

h i g h l y p e r t i n e n t to the study of atmospheric corrosion. Two p r o c e s s e s
are considered; e v a p o r a t i o n of a p r e - e x i s t i n g e l e c t r o l y t e layer of a
given initial c o n c e n t r a t i o n formed, for example, as a result of rainfall,
and f o r m a t i o n and retention of an e l e c t r o l y t e of fixed concentration, but
of v a r y i n g size, formed, for example, as a result of c o n d e n s a t i o n and
r e t a i n e d b y v i r t u e of a high local humidity. In the former case, i.e.
under e v a p o r a t i v e conditions, the e l e c t r o l y t e c o n c e n t r a t e s w h i l e in the
latter case, i.e. n o n - e v a p o r a t i v e conditions, the e l e c t r o l y t e concentra-
tion is fixed.
Evaporative conditions
These represent conditions where p r e c i p i t a t i o n or c o n d e n s a t i o n

results in a m a c r o s c o p i c electrolyte w h i c h s u b s e q u e n t l y e v a p o r a t e s w i t h
e l e c t r o l y t e concentration. R e p e a t e d w e t / d r y cycles of this n a t u r e can
increase the c o n t a m i n a n t level on a surface. However, large e p i s o d i c
q u a n t i t i e s of rainfall can reduce b u i l t - u p contaminants.
This process was m o d e l l e d by e v a p o r a t i o n of an initial d r o p l e t

c o n t a i n i n g an a r b i t r a r y q u a n t i t y of ion species and a l l o w i n g the concen-
t r a t i o n of the species to rise as the droplet evaporated. This model
predicts, Figure 6, that the a n o d e - t o - c a t h o d e r e s i s t a n c e as a hemispheri-
cal droplet evaporates does not limit the rate of corrosion. However,
w i t h an e l e c t r o l y t e of u n i f o r m thickness the c o r r o s i o n rate m a y b e c o m e
subject to r e s i s t i v e control at the latter stages of evaporation.
Non-evaporative conditions
These represent situations where a condensate or a d s o r b a t e is in

e q u i l i b r i u m w i t h the surrounding relative h u m i d i t y and the surface is
t y p i c a l l y "wet". For an u n c o n t a m i n a t e d surface this should h a p p e n at
h u m i d i t i e s of 100% and for c o n t a m i n a t e d surfaces at the e q u i l i b r i u m
h u m i d i t y of a saturated solution of the contaminant species. In prac-
tise, "time-of-wetness" occurs at s u b s t a n t i a l l y lower h u m i d i t i e s than
these due, in part, to c a p i l l a r y c o n d e n s a t i o n effects.
This process was m o d e l l e d b y varying the c o n d e n s a t e / a d s o r b a t e

thickness and size while keeping the electrolyte c o n c e n t r a t i o n at a
constant a r b i t r a r y value. Results, Figure 6, predict that for a hemi-
spherical droplet geometry, the a n o d e - t o - c a t h o d e v o l t a g e drop is c o n s t a n t
for a given c o n c e n t r a t i o n of electrolyte irrespective of droplet size.
However, the size of iR drop was c o m p a r a t i v e l y modest (i0 mV for the
h e m i s p h e r i c a l cap geometry) at a r e l a t i v e l y dilute e l e c t r o l y t e of 10 4 M.
W i t h m o r e c o n c e n t r a t e d electrolytes this effect will be g r e a t l y reduced.
More i m p o r t a n t l y for adsorbates of u n i f o r m thickness the iR drop r a p i d l y
increases w i t h r e d u c t i o n in electrolyte thickness. This latter result is
similar to the e v a p o r a t i v e condition w i t h c o n c e n t r a t i n g electrolyte, but
the v o l t a g e loss rises more rapidly.
Summary
In effect, b o t h sets of conditions predict that, for a typical

h e m i s p h e r i c a l geometry, resistive control of c o r r o s i o n does not occur in
an e v a p o r a t i n g droplet where the electrolyte is c o n c e n t r a t i n g and is
u n l i k e l y to be of s i g n i f i c a n c e at a constant e l e c t r o l y t e concentration.
This can be c o n f i r m e d by experimental evidence showing v e r y rapid cor-
r o s i o n rates during the final stages of drying of an i n i t i a l l y w e t t e d
surface [17-19]. On the other hand, c o r r o s i o n occuring in a r e l a t i v e l y
u n i f o r m c o n d e n s a t e or adsorbate, e.g. at high relative humidities, is
likely to have an element of resistive control. This has b e e n demon-
s t r a t e d b y A s k e y [20] during corrosion of iron and zinc w i t h v a r y i n g
amounts of surface c o n t a m i n a t i o n where c o r r o s i o n rates at 80% RH w e r e
s t r o n g l y r e l a t e d to the q u a n t i t y of leached ion species.
CONCLUSIONS
i. A model of droplet e v a p o r a t i o n has b e e n d e v e l o p e d to s i m u l a t e

w e t t i n g and drying effects during a t m o s p h e r i c corrosion. The
droplet size, anode to cathode resistance, oxygen r e d u c t i o n current
and iR drop were c a l c u l a t e d as a function of e v a p o r a t i o n time.
Hemispherical, flattened h e m i s p h e r i c a l cap and p l a n a r c y l i n d r i c a l
droplet g e o m e t r i e s were considered.
2. Under e v a p o r a t i v e conditions, the p r e d i c t e d a n o d e - t o - c a t h o d e resis-

tance, total o x y g e n r e d u c t i o n current and, hence, r e s i s t i v e iR
losses d e c r e a s e during c o n c e n t r a t i o n of the e l e c t r o l y t e for hemi-
spherical and h e m i s p h e r i c a l cap geometries. However, for p l a n a r
c y l i n d r i c a l droplets, the p r e d i c t e d a n o d e - t o - c a t h o d e r e s i s t a n c e is
a p p r o x i m a t e l y invariant while the total oxygen r e d u c t i o n current
increases. Thus, the resistive iR losses rise during e v a p o r a t i o n
of a u n i f o r m l y thick electrolyte.
3. In n o n - e v a p o r a t i v e conditions w i t h a constant (i.e. not concen-

trating) electrolyte, the a n o d e - t o - c a t h o d e r e s i s t a n c e is invariant
w i t h d e c r e a s i n g droplet size for h e m i s p h e r i c a l and h e m i s p h e r i c a l
cap g e o m e t r i e s but increases for the planar c y l i n d r i c a l geometry.
4. Under e v a p o r a t i v e conditions, atmospheric c o r r o s i o n is not con-

trolled b y the c o n d u c t i v i t y of the surface e l e c t r o l y t e in typical
droplets of h e m i s p h e r i c a l shape. However, r e s i s t i v e control m a y be
important in condensates or adsorbates of u n i f o r m thickness.
5. Under n o n - e v a p o r a t i v e conditions, a t m o s p h e r i c c o r r o s i o n is p o s s i b l y
c o n t r o l l e d by the c o n d u c t i v i t y of the surface e l e c t r o l y t e for
likely droplet geometries and sizes. However, r e s i s t i v e control i__~s
important in condensates and adsorbates of u n i f o r m thickness.
REFERENCES
i. Turnbull A. and Thomas, J.G.N., J. Electrochem. Soc., Vol. 129,

1982, p. 1412.
2. Turnbull, A., C h e m i s t r y and Physics of Fracture, R.M. L a t i n i s i a n

and R.H. Jones Eds., NATO ASI Series, Martinus Nijhoff, Dordrecht,
The N e t h e r l a n d s (1987), p. 287.
3. Sharland, S., C o r r o s i o n Science, Vol. 27, 1987, p. 289.
4. Spence, J.W. and Haynie, F.H., C o r r o s i o n T e s t i n q and Evaluation,

A S T M STP 1000, R. B a b o i a n and S.W. Dean, Eds., A m e r i c a n S o c i e t y for
T e s t i n g and Materials, Philadelphia (1990), p. 208.
5. Feliu, S. and Morcillo, M., Corrosion u Proteccion de los Metales

en la Atmosfera, ediciones bellaterra, Madrid (1982), especially
Ch. 6-10.
6. Haagenrud, S., Werskst. und Korros., vol. 31, (1980), p. 541.
7. Cox, A. and Lyon, S.B., Corrosion Science, vol. 36, in press.
8. Zhang, S.-H. and Lyon, S.B., Corrosion Science, vol. 35, (1993)
p. 731.
9. Barton, K. and Bartonova, Z., Proc. 3rd Int. Conqress on Metallic

Corrosion, Vol. 4, (1969), p. 403.
i0. Duncan, J.R. and Spedding, D.J., Corrosion Science, Vol. 14,
(1974), p. 271.
ii. Svensson, J.-E. and Johansson, L.-G., Corrosion and Reliability of

Electronic Materials and Devices, R.B. Comizolli and J.D. Sinclair,
Eds., The Electrochemical Society, Philadelphia (1993), p. 541.
12. Evans, U.R. and Taylor, C.A.J., Corrosion Science, vol. 12, (1972),
p. 227.
13. Misawa, T., Hashimoto, K. and Shimodaira, S., Corrosion Science,

Vol. 14, (1974), p. 131.
14. Stratmann, M., Bohnenkamp, K. and Engell, H.J., Corrosion Science,

vol. 23, (1983), p. 969.
15. Evans, U.R., Introduction to Metallic Corrosion, Edward Arnold,

London (1963), p. 31.
16. Moore, W.J., Physical Chemistry, Longman, New York (1972), p. 458.
17. Stratmann, M., Bohnenkamp, K. and Ramchandran, T., Corrosion

Science, Vol. 27, (1987), p. 905.
18. Mansfeld, F., Corrosion Processes, R.N. Parkins, Ed., Applied

Science, London, (1982), p. i.
19. Zhang, S.-H. and Lyon, S.B., Corrosion Science Vol. 36" (in press).
20. Askey, A., Lyon, S.B., Thompson, G.E., Johnson, J.B., wood, G.C.,
Sage, P.W., Cooke, M.J., Corrosion Science, Vol. 34, (1993),
p. 1055.
D a g m a r Knotkova, ~ P e t r Boschek, 2 and Katerina Kreislova 1
Results of ISO CORRAG Program:

Processing of One-Year Data in Respect to
Corrosivity Classification
REFERENCE: Knotkova, D., Boschek, P., and Kreislova, K., "Results of ISO CORRAG
Program: Processing of One-Year Data in Respect to Corrosivity Classification," Atmo-
spheric Corrosion, ASTM STP 1239, W. W. Kirk, and H. H. Lawson, Eds., American Society
for Testing and Materials, Philadelphia, 1995.
ABSTRACT: Elaboration and publishing of four International Standards Organization (ISO)

standards, 9223 to 9226, covering the classification system and criteria, the prognostic guiding
corrosion values, and the methods to be used for atmospheric corrosivity derivation, were a result
of an extensive international cooperation. During this standardization procedure, the international
testing program, ISOCORRAG, started with the aim to work out a database for statistical veri-
fication of the classification methods.
The outcome of this broad common testing, evaluation, and statistical analysis of the data is
presented in the ISO technical report elaborated in I s o f r c 156/WG 4, and in this paper.
Broad acceptance of 1SO standards, 9223 to 9226, was supported by new agreements between
ISO/TC 156/WG 4, ISO/TC 35/SC 14, and CEN/TC 262AVG 3.
KEYWORDS: atmospheric corrosion, corrosivity classification, corrosion of unalloyed steel,

zinc, copper, aluminum, flat specimens, helix specimens, statistic analysis, calculation model
The course of atmospheric corrosion varies in time and with corrosive influences. Exposure
categories and shielding systems distinctly modify the open air atmospheric effects.
The technical viewpoint, selection of materials, and protective systems, therefore, require a
set of rules helping to standardize methods for deriving the degree of stress exerted by the
atmosphere. This is why a number of different classification systems have been proposed for
defining corrosivity of atmospheres that would help in the selection of better materials and
protection Systems, and in selecting adequate testing methods, their severities, and evaluation
criteria.
The results of about ten years of activities of the ISO/TC 156/WG 4, Corrosivity Classifi-
cation of Atmospheres, are four ISO standards [1-4] approved in 1991. In the elaboration of
these standards, experiences of specialists in atmospheric corrosion were fully utilized. The
standards are based on statistical evaluation of corrosion tests performed at more than 200 sites
under different climatic and pollution conditions. Another viewpoint was technical: to find the
optimum way for extensive, practical use of the classification system. The complex of the four
ISO standards comprises the classification system, prognostic guiding corrosion values, and
t Senior research scientist and convener of ISO/TC 156/WG 4, and research scientist, respectively,
National Institute for Protection of Material (SVUOM), U Mestanskeho Pivovaru 4, 170 04 Prague, Czech
Republic.
2 Senior lecturer, Charles University, Philosophic Faculty, Hradcanske sq. 5, 118 42 Prague 1, Czech
Republic.
38
Copyright9 byby ASTM lntcrnational
Downloaded/printed www.astm.org
KNOTKOVAETAL. O N T H E I S O CORRAG PROGRAM 39
L~
',,' ..;
t,.9
I
d
ff'l . / /
! 2 --~o
methods for pollution measurements necessary for defining the corrosivity categories. The
approved system allows derivation of the corrosivity category with the help of direct one-year
corrosion tests of four standard technical metals, or on the basis of yearly means of environ-
mental classification criteria: time-of-wetness (TOW), SO2 deposition, or concentration and
airborne salinity deposition.
Even though the new ISO classification standards represent a state of the art solution of the
given problem, the working group members were well aware that the generalization of extensive
data and knowledge based on very different methodical backgrounds should be complemented
by results of a well prepared and coherent test program. Therefore, the ISO CORRAG 3 program
(Fig. 1) was started in 1987 to 1989 [5]. This program was aimed at obtaining data on corrosion
of metals, environmental characteristics, and corrosivity in a large-scale zonal concept. The
background methodology of this program is ISO 9223 to 9226.
A basis for deeper elaboration of the classification system was built. It may be expected that
these results will contribute to a better understanding of the atmospheric corrosion process as
well. At present, four-years' exposure results published by the WG 4 members [6] and sum-
marized in an extensive ISO document [7] are evaluated and analyzed.
This communication describes the next phase of analyzing the results performed in The
National Institute for Protection of Material in Prague (CR), the seat of the WG 4 secretariat,
and the main center for the ISO CORRAG program. Members of ISO/TC 156AVG 4 introduced
the first experimental results of the ISO CORRAG program during the twelfth ICC [6]. The
U.S. member of WG 4 presented the results for the U.S. sites included in the ISO CORRAG
program in a separate paper [8].
Standards ISO 9223 to 9226 together with the description of the structure of the ISO
CORRAG program and a survey of the experimental results given in the paper [6] provide
sufficient introductory information for the readers.
The applicability of the classification system for engineers as a guide in selecting materials
for atmospheric environments cannot be solved on the basis of ISO CORRAG program results,
and represents a new item (ISO/NP 11 303) in ISO/TC 156AVG 4 activity. The ISO CORRAG
program results form a basis for the next justification of the environmental classification criteria
of ISO 9223.
Specification of the Program and the Obtained Experimental Results

A. Tested Materials and Exposure Conditions
unalloyed carbon steel
zinc, minimum of 98.5
copper, minimum of 99.5
aluminum, minimum of 99.85 (aluminum 99.5 allowed)
Steel for flat and helix specimens was produced by the British Steel Corporation (0.056%
carbon, 0.060% silicon, 0.012% sulfur, 0.013% phosphorus, 0.02% chromium, 0.01% molyb-
denium, 0.04% nickel, 0.03% copper, 0.01% niobium, 0.01% titanium, 0.01% vanadium, 0.02%
aluminum, 0.005% tin, 0.004% nitrogen, and 0.39% manganese). All helix specimens were
prepared in Germany (Staatliches Materialprtifungsamt, Dortmund). Flat specimens of zinc,
3 International testing program within the ISO/TC 156AVG 4 classification of corrosivity of atmosphere
with SVUOM Praha as main center.
KNOTKOVA ET AL. ON THE ISO CORRAG PROGRAM 41
copper, and a l u m i n u m were produced by single participating countries in agreement with pre-
scribed properties.
All specimens were exposed on standard racks in open air.
B. Types of Specimens
flat specimens
metallic wire, open helix specimens
There are three specimens for each metal, sample type, and exposure sequence.
C. Exposure Sequences
6 one-year exposures (starting both in spring and autumn)
1 two-year exposure
1 four-year exposure
1 long-term exposure (eight years)
D. Measured Environmental Characteristics

M e a s u r e m e n t of the environmental characteristics is in agreement with the needs for cor-
rosivity classification, prescribed in ISO 9223 and is defined in Table 1.
Further methodic and technical data are described in the ISO C O R R A G Manual [5].
The set of data is rather extensive and has been published [7]. At this time we are trying to
better analyze one-year results, serving as mentioned, for determining corrosivity. Our work is
based on preliminary data treatment [7] that clearly proves the usefulness of the ISO C O R R A G
program and helps to specify correct questions.
TABLE l--Environmentalfactors characterizing atmospheric exposure conditions.
Types and Number Expression

Measured Value Unit of Measurements of Results
Air temperature ~ continuous or at least 3 average per month and/or

times per day per year
Relative humidity % continuous or at least 3 average per month and/or
times per day per year
AIR CONTAMINATION
SO 2 concentration mg m -3 continuous monthly average per month
SO2 deposition rate mg m 2 d- continuous monthly average per month and/or
per year
C1 deposition rate mg m z d continuous monthly average per month and/or
per year
NOTE--
1. Method of the sorption of sulfur dioxide on an alkaline surface according to ISO 9225.
2. Method of the sorption of sulfur dioxide on PbO: according to ISO 9225.
3. For C1 deposition, measurement by the wet-candle recommended method (ISO 9225).
4. For CI deposition, measurement by the NILU aerosol-trap and the inert catchment plate method as
recommended.
Summary of the First Analysis Phase of ISO CORRAG Results

The resulting database of results and their sorting according to classification criteria showed
some limits on the very extensive results:
1. Nonuniform covering of the different climatic zones with testing sites (the majority of
sites is situated in the moderate zone).
2. A few sites in other zones distinctly deviated from the set (Panama, Oymyakon).
3. Some of the included testing sites deviated from the set as not meeting the ISO 9223
validity (sites extremely polluted with specific industrial atmospheres where corrosivity
cannot be specified by the standard criteria such as TOW, SO2, NaC1, etc.).
4. Nonuniform distribution of sites representing single corrosivity categories; this is clear
from Tables 2 and 3.
Practical requirements of the international standards are to provide methods for deriving the
corrosivities on the basis of the test results or environmental data. The method of deriving
corrosivity from environmental data is realizable because air pollution data are available at the
present time, and TOW values can be derived from standard climatic data, or, within the range
of the classification category, can be estimated if the exposure locality and category of location
for the object is known. Direct determination of corrosion losses is time consuming and needs
much experience in corrosion testing and evaluation of test results. The first evaluation of the
ISO CORRAG program, however, shows that, as expected, the determination of the corrosivity
category based on one-year tests leads to more unambiguous results.
Another problem lies in the possible use of both specimen types (flat and helix). Results
show difficult comparisons or transformation abilities, and differences are found for the tested
metals and the single corrosivity categories. Flat specimens are well known and of standard
specification. Helix samples, however, can be exposed on objects that are investigated, and due
to the helix configuration no problems arise in evaluating different surfaces.
Another problem to be analyzed in more detail is the validity of the chosen classification
criteria and of their levels for the metals contained in the system. A case is aluminum. The
system and corrosion determination method do not express its tendency to pitting corrosion.
The lack of it is fully mentioned in ISO 9223 and ISO 9224.
Based on understanding of the corrosion processes, it may be assumed that classification
criterion TOW (defined as time with RH --> 80% at temperatures above the freezing point) does
not describe correctly the effect of water presence in the corrosion system, especially not for
plain (unalloyed) structural steel.
Another area needing statistical analysis of the results is the expression of the individual SO2
and NaC1 corrosion effects, that is, the effect at background level pollution of the second
pollutant and the combined effect. Published data do not provide any definite solution. The
results of the first ISO CORRAG evaluation indicate an important effect of chlorides in the
system [6].
Evaluation of the ISO CORRAG Program--Second Phase

This phase of evaluation is divided into steps differing in significance and content.
A detailed analysis of one-year corrosion loss values and environmental characteristics serves
as the base for improving the classification system.
More precise methods for deriving corrosivity will be based on attention to dispersion of the
single sequence values, and also the spring and autumn exposure starts.
KNOTKOVA ET AL. ON THEISO CORRAG PROGRAM 43
Comparison of results obtained with flat and helix specimens in different types of atmo-
spheres will be used as supplementing specific information, as discussions in the relevant ISO
and CEN working groups lead to preferred acceptance of results obtained with fiat specimens.
Present activities are trying to analyze the structures of multivariant dependencies of cor-
rosion attack on variables that characterize the atmospheric environment. Another is analyzing
the partial significance of effort factors measured in the ISO CORRAG program and of their
interactions using results of repeated one-year tests.
The joint and separate contributions of the environmental factors to the variation of the
corrosion losses of unalloyed steel, zinc, copper, and aluminum were analyzed. The set of
statistical data was represented by one-year mean corrosion losses of four structural metals for
the individual withdrawal sequences (dependent variables) and for yearly mean values of SO2
and chloride deposition rates, together with calculated time of wetness as independent variables.
Only test results with full data were included (n = 130). For inland sites environmental
characteristics the deposition rates of chlorides were included as value 1.
Two multiple regression models were used.
The first model (A) is the classical linear model based on the additivity of single effects:
CorrLoss = a + B I . S O 2 + B2.TOW + B3.C1 (A)
The second model is more sensitive to interaction (multiplicative effects) of the independent
variables:
Lg(CorrLoss) = a + B1.SO 2 + B2.TOW + B3-C1 (B)
The multiple coefficient of correlation, the coefficient of determination (measurements of

the model fitness), partial regression coefficients, and beta weights including the statistical
significance are presented for both models (Appendix Tables A1 to A8).
The results of statistical analyses will be supplemented in the future by new evaluations with
narrower target limits.
It is necessary to accept the fact that the analysis included only cases with complete infor-
mation on corrosion and environmental characteristics. This emphasized the disproportion in
processed data from the moderate climatic zone and from other already mentioned climatic
zones (the fact of more frequent complete information for sites in the moderate zone).
It was not the target of the statistical analysis to optimize the equations describing deterio-
ration of the single metals (damage functions). Two calculation models with additive processing
characteristics were selected intentionally. Model B is in principle a multiplicative one and
these models, as shown by others [9,10], are more sensitive in expressing interactions of effects.
The analysis leads to a numerical expression of statistical characteristics allowing evaluation
of the given classification system with respect to selected classification criteria:
1. Numerical expression of corrosion effect variance for the selected independent variables.
2. Expression of relative weights of the single factors of the used independent variables
(classification criteria) in the resulting corrosion effects.
The significances of these characteristics were tested.

Other new information is the calculation of the mean error estimate for prognostic application
of the functions (calculated one-year corrosion rates).
The results of the statistical analyses as summarized in the Appendix, and, in the short form
in Table 4, allow the following statements:
1. Multiple regression analyses by both selected functions brought results with comparable
correlation
Copyright by ASTM Int'l values
(all rightsasreserved);
in previously
Thu Dec published [10].
data2011
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TABLE 2--Classification o[ test sites according to ISO 9223 environmental criteria.
o
O
SO2 Pollution (um/m 3) Pollution by Airborne Salinity (mg/m 2 d) Time of Wetness (h/year) 213
O
Test Site Mean Value Category Test Site Mean Value Category Test Site Mean Value Category 60
O
Z
Birkenes 1,2 P0 Svanvik 1,0 SO Oymyakon 381 T3
Tananger 4,0 P0 Batumi 1,0 SO San Juan 855 T3
Ahtari 4,1 P0 Bergisch Glad. 1,6 SO Boucherville 1396 T3
El Pardo 4,9 P0 Oslo 2,1 SO Madrid 2060 T3
Murmansk 5,0 P0 Otaniemi 2,5 SO Tokyo 2173 T3
Kvarnvik 5,0 P0 Helsinki 3,7 SO Kopisty 2444 T3
Kattesand 5,0 P0 Tokyo 4,4 SO Svanvik 2605 T4
Oymyakon 5,0 P0 Picberande 6,5 SI Oslo 2641 T4
Cboshi 7,7 P0 Bergen 7,1 SI Jubay-Antarct. 2693 T4
Bergen 8.6 P0 Fleet Hall 7,9 SI Lagoas 2840 T4
Picherande 9, I P0 Borregaard 8,2 SI Praha 2991 T4
Kure Beach 9,6 P0 Stratford 15,1 SI Ahtari 3105 T4
Buenos Aires 9,7 P0 Auby 16,0 SI Paris 3189 T4
Stockholm Van 9,8 P0 Vladivostok 18,4 SI Kasp Hory. 3206 T4
Okinawa 11,1 P0 Murmansk 19,9 SI Batumi 3216 T4
Oslo 13,8 PI Lagoas 21,2 SI El Pardo 3223 T4
Fleet Hall 14,4 P1 St. Denis 27,8 S1 Murmansk 3227 T4
Tokyo 14,6 P1 Baracaldo 29,2 S1 Otaniemi 3256 T4
Otaniemi 15,3 P1 Camet 46,0 S1 Salin de Gir. 3311 T4
Boucherville 15,9 P1 Boucherville 59,0 S1 Borregaard 3339 T4
Svanik 16,7 P1 Cboshi 66,8 SI Helsinki 3578 T4
Kasper. Hory 17,1 P1 Kattesand 85,5 SI Ponteau Mart. 3846 T4
Bergisch Glad. 18,0 P1 Okinawa 130,0 $2 Okinawa 3852 T4
Helsi nki 18,9 P1 Ostende (B) 173,0 $2 Vladivostok 3920 T4
Stratford 19,9 P1 Salin de Gir. 184,0 $2 Los Angeles 4003 T4
P1 Kure Beach 184,0 $2 Birkenes 4138 T4
Salin de Gir. 20,0
P1 Biarritz 193,0 $2 Picherande 4171 T4
Los Angeles 20,0
PI Ponteau Mart. 241,0 $2 Bergisch Glad. 4267 T4
Rye 21,2
24,0 PI Rye 300,0 $2 St. Denis 4268 T4
Ostende (B) T4
Batumi 25,8 PI Tananger 321,0 $2 Kure Beach 4289
P1 St. Remy 378,0 $2 Baracaldo 4375 T4
Vladivostok 28,6
P1 Panama CZ 619,0 $3 Bergen 4439 T4
St. Remy 30,3
32,1 PI Kvarnvik 667,0 $3 Auby 4571 T4
Baracaldo
44,2 P2 Tananger 4583 T4
Borregaard
44,2 P2 Res Triang Park no data Buenos Aires 4645 T4
Madrid T4
48,7 P2 Point Reyes M Fleet Hall 4809
Lagoas
49,6 P2 Birkenes Iugazu 5680 T5
St. Denis
51,5 P2 Paris Choshi 5704 T5
Panama CZ
53,4 P2 Los Angeles Stratford 5783 T5
Paris
67,5 P2 Newark no data Ostende (B) 6083 T5 7~
Praha Z
87,0 P2 El Pardo Camet 6088 T5 O
Ponteau Mart.
P2 Crowthorne St. Remy 6310 T5
Kopisty 89,9 7~
188,0 P3 Stockholm Vanad Panama CZ 7598 T5 O
Auby <
Oymyakon >
no data Madrid Rye no data m
Newark
Point Reyes Kopisty Point Reyes
Res Triang Park Ahtari Newark
Biarritz Iugazu Crowthorne 0
Kasperske Hory Kattesand z
Crowthorne
San Juan Praha Stockholm Vanad
San Juan Biarritz m
lugazu
Camet Jubay-Antarct. M Kvarnvik
Judge ford 0
Jubay-Antarct. Buenos Aires M o
Judge ford Judgeford M Res Triang Park 0
NOTE--M = marine influence.
>
.Ix
O1
0")
0
co
-r
TABLE 3--Test sorting--one-year corrosion loss o,f flat speeimens (um/a) based on wdues submitted by member countries. m
Unalloyed Steel Zinc Copper Aluminum C')

O
-.n
Test Site A B Test Site A B Test Site A B Test Site A B :~
0
60
Panama CZ 373,0 C 5* Panama CZ 17,50 C 5* Panama CZ 5,46 C5 Auby 1,70 C3
Auby 106,0 C5 Auby 5,60 C5 Biarritz 3,69 Ostende (B) 1,50 Z
Ostende (B) 99,3 Ostende (B) 5,10 Kopisty 3,30 Jubay-Antarctic 1,31
Biarritz 87,2 Salin de Gir. 4,60 Salin de Gir. 3,20 St. Denis 1,20
Okinawa 75,2 C4 Biarritz 4,30 Ostende (B) 3, l0 Biarritz 1,20
Salin de Gir. 73,0 Borregaard 3,80 C4 Kure Beach 2,85 Ponteau Mart 1,00
Ponteau Mart. 72,4 Kopisty 3,50 Kvarnvik 2,80 Paris 0,90
Kopisty 70,7 Okinawa 3,40 Ponteau Mart 2,70 C4 Murmansk 0,80
Borregaard 61,7 Tananger 3,00 Res Triang Park 2,43 Salin de Gir. 0,70
Kvarnvik 61,6 Paris 3,00 Point Reyes 2,42 Kopisty 0,70
Tananger 59,6 Praha 2,80 Camet 2,23 St. Remy 0,70
Rye 58,5 Ponteau Mart. 2,60 Okinawa 2, I 0 Tananger 0,60
Praha 47,4 C3 Rye 2,54 Jubay-Antarctic 2,04 Praha 0,60
St. Remy 44, I Vladivostok 2,30 Batumi 2,00 Kvarnvik 0,60
Baracaldo 43,9 Birkenes 2,30 Kasperske Hory 2,IX) Borregaard 0,60
Choshi 43,3 Bergen 2,10 Tananger 1,90 Panama CZ 0,57 C2
Paris 41,7 Kure Beach 2,01 C3 Auby 1,90 Los Angeles 0,56
Point Reyes 40,1 Newark 1,96 Rye 1,86 Tokyo 0,54
Tokyo 39,5 Kasperske Hory 1,90 St. Remy 1,80 Kasperske Hory 0,50
Fleet Hall 39,0 C3 Jubay-Antarctic 1,87 C3 Kattesand 1,70 C4 Rye 0,42 C2
Stratford 38,7 Kvarnvik 1,80 Murmansk 1,70 Boucherville 0,40
Kure Beach 37,9 Point Reyes 1,73 Vladivostok 1,40 Kattesand 0,40
Crowthorne 37,4 Strattord 1,67 Paris 1,40 Fleet Hall 0,36
St. Denis 37,2 lugazu 1,62 Picherande 1,40 Choshi 0,33
Camel 36,8 Bergisch Glad. 1,60 Borregaard 1,40 Picherande 0,30
Jubay-Antarctic 36,6 Batumi 1,60 Newark 1,39 Vladivostok 0,30
Bergisch Glad. 36.2 Kattesand 1,50 Judge ford 1.36 Helsinki 0.30
Kattesand 35.2 St. Remy 1,50 Choshi 1.35 Bergisch Glad. 0.30
Helsinki 33.3 St. Denis 1.50 Praha 1.30 Stratford 0.29
Murmansk 30.8 Tokyo 1,50 Birkenes 1.30 Kure Beach 0.29
Batumi 28.7 Bouche,-ville 1,40 Baracaldo 1.20 C3 Newark 0.28
Bergen 27.9 Choshi 1.40 St. Denis 1.20 Okinawa 0.26
Madrid 27.7 Fleet Hall 1.34 Los Angeles 1.16 Point Reyes 0.22
Lagoas 26.9 Helsinki 1.30 Stratford I. 13 Stockholm Vana 0.20
Newark 26.4 Oslo 1,30 C,owthorne I. 10 Oslo 0,20
Kasperske Hory 26.0 Camet 1,26 El Pardo 1. I 0 Lagoas 0.20
Vladivostok 25.9 Baracaldo 1,20 Boucherville 1.10 Baracaldo 0.20
Otaniemi 25.6 C3 Crowthorne I, 10 C3 Bergen 1.00 C3 Camet 0.19 C2
Oslo 25.2 Murmansk 1,10 Lagoas 1.00 Crowthorne 0.12
Stockholm Vana 24.4 C2 Los Angeles 1,09 Fleet Hall 0.93 Res Triang Park 0.11
Boucherville 23.2 Buenos Aires 1,0 I lugazu 0.80 Birkenes 0.10 CI
Ahtari 0.10 7~
Res Triang Park 23.1 Lagoas 1.00 Otaniemi 0,80 Z
Los Angeles 21.4 Otaniemi 0.90 Svanvik 0,80 Batmni 0.10 O
-I
Svanvik 20.2 Picherande 0.90 Helsinki 0,70 Otaniemi 0.10 7r
Birkenes 19.7 Res Triang Park 0.84 Ahtari 0.70 Bergen 0.10 O
Judgeford 19.3 Svanvik 0.80 Tokyo 0,66 Svanvik 0.10
0,70 C2 Buenos Aires 0,64 Madrid 0.07 m
Buenos Aires 16.2 Ahtari --4
Picherande 16.1 Judgeford 0.66 Bergisch Glad. 0,60 C2 Oymyakon 0.07
El Pardo 15.5 Stockhohn Vana 0.60 Stockholm Vana 0.60 Judgeford 0.06
Ahtari 12.8 Madrid 0.60 Oslo 0.60 lugazu 0.05 0
2
lugazu 5.8 El Pardo 0.50 Madrid 0.50 Buenos Aires 0.05 .-I
San Juan 4.6 Oymyakon 0,40 San Juan 0.18 El Pardo 0.05 "T
m
Oyrnyakon 0.8 C 1 San Juan 0.18 Oymyakon 0.09 C 1 San Juan 0.03
0
NOTEI 0
A = corrosion loss (urn/a) 0
B = corrosivity categories (ISO 9223).
* = corrosion rate exceeding the upper limit in C5.
"in
0
-n
"4
.Ix
>
T A B L E 4--Effect of environmental variables on corrosion rates for flat and helix specimens.
0
60
Calculation Model A "13
"1"
m
Shape of Standardized Regression Coefficients
Standard
0
Metal Specimens Multiple R 2 Significance SO 2 Significance TOW Significance NaC1 Significance 0
-71
-.13
Steel fiat 0.428 P < 0.001 0.41 P < 0,001 0.19 P < 0.01 0.41 P < 0.001 O
helix 0.599 P < 0,001 0.53 P < 0,001 0.28 P < 0.001 0.46 P < 0.001 GO
Zinc flat 0.297 P < 0.001 0.38 P < 0.001 0.15 P < 0.05 0.39 P < 0.001 O
Z
helix 0.439 P < 0.001 0.51 P < OiO01 0.16 n.s. 0.36 P < 0.001
Copper flat 0.320 P < 0.001 0.25 P < 0,001 0,07 n.s. 0.55 P < 0.001
helix 0.301 P < 0.001 0,20 P < 0.01 -0.01 n.s. 0.60 P < 0.01
Aluminum flat 0.378 P < 0.001 0.55 P < 0.001 0.19 P < 0.05 0.17 P < 0.001
helix 0.300 P < 0.001 0.43 P < 0.001 -0.03 n.s. 0.40 P < 0.001
Calculation Model B
Shape of Standardized Regression Coefficients

Standard
Metal Specimens Multiple R 2 Significance SOz Significance TOW Significance NaC1 Significance
Steel flat 0.507 P < 0.001 0.52 P < 0.001 0.18 P < 0.01 0.40 P < 0.001
helix 0.520 P < 0.001 0.48 P < 0.001 0.29 P < 0.001 0.36 P < 0.001
Zinc flat 0.305 P < 0.001 0.42 P < 0.001 0.18 P < 0.05 0.26 P < 0.01
helix 0.506 P < 0.001 0.52 P < 0.001 0.25 P < 0.001 0.34 P < 0.001
Copper fiat 0.300 P < 0.001 0.24 P < 0.001 0.15 P <
0.05 0.41 P < 0.001
helix 0.396 P < 0.001 0.25 P < 0.001 0.09 n.s. 0.54 P < 0.001
Aluminum fiat 0.282 P < 0.01 0.43 P < 0.001 0.12 n.s. 0.25 P < 0.01
helix 0.398 P < 0.001 0.40 P < 0.001 0.19 P < 0.05 0.38 P < 0.001
TABLE 5~Squared coefficients of correlation for calculation

Models A and B and flat and helix specimens.
Coefficient of Correlation (R2)

for Calculation Model
Model Specimen Model A Model B
Fe fiat 0.428 0.507

Fe helix 0.599 0.520
Zn fiat 0.297 0.305
Zn 0.439 0.506
helix
Cu fiat 0.320 0.300
Cu 0.301 0.396
helix
A1 flat 0.378 0.280
A1 helix 0.300 0.398
2. The computed determination coefficients qualify steel corrosion (for both types of spec-
imens) and zinc corrosion (helix specimens) as processes with the highest explained vari-
ance using both calculation models.
3. The differences of determination coefficients for the corrosion effect are higher for steel
and zinc for both specimen types than for the other standard metals.
4. The calculation Model B does not distinctly lead to a better correlation.
5. The relative weight, Beta(i), of the calculated time of wetness showed the lowest and least
significant effect in all evaluations. This finding, however, should be corrected with re-
spect to the fact that the decisive part of TOW data was represented by the moderate
climatic zone,
6. The weight, Beta(i), of significance of SO2 deposition rate for steel and zinc corrosion
outweighs the significance of that of chlorides. With copper the situation is the opposite,
With aluminum, great differences in the chloride influence weight were found for cor-
rosion of flat and helix specimens.
7. Comparison of the calculated squared coefficients of correlation for both specimen types
does not lead to any unambiguous results (Table 5).
The next aims in the ISOCORRAG program evaluation can be formulated as follows:
1. Deeper analysis of environmental affected differences of corrosion losses measured on

fiat and helix specimens.
2. Harmonization of the atmospheric corrosivity derivation based on one-year corrosion
losses and environmental data (TOW, deposition rate of SO2, and NaCI).
3. Possible requirements for the application of other environmental characteristics not in-
cluded in ISO 9223 and not measured in ISO CORRAG program (NOx, acidity of rain,
rainfall) for classification purposes.
Conclusions
The statistical analysis confirmed that a simple corrosivity classification system based on
classified categories of TOW, SO2, and salinity deposition rates allows specification of an
atmospheric corrosivity system (namely, for moderate zone climatic conditions) that fully meets
technical requirements. Moderate zone regions are of course the most important ones as the
decisive amounts of materials are exposed there. For the future industrialization of regions
localized in the tropic zones, deeper knowledge of corrosion effects under temperature-humidity
conditions typical for those zones will be necessary.
The result of a direct corrosion test including tests with standard specimens according to
ISO 9226 expresses the effect of all environmental factors, not only those included as classi-
fication criteria.
In a direct corrosion test the full function of water in its wide variability becomes effective,
whereas TOW according to ISO 9223 is an agreed criterion. The lower statistical significance
of TOW indicates that the simplified version of TOW determination applied in ISO 9223 is
justified, at least, for the temperature-humidity complex typical for moderate zones. In extreme
conditions (Panama, Oymyacon), the factor acts differently (strong rains, frost, etc.). It can be
presumed that the influence of temperature should not be neglected in these conditions as in
moderate zone corrosion.
The target is to not only elaborate a system directly or indirectly applicable in different
technical areas defined, for example, in standards prepared by ISO/TC 156 Corrosion of Metals
and Alloys, but also by ISO/TC 35/SC 14 Protective Paint Systems for Steel Structures or by
CEN/TC 262 Corrosion Protection of Metals. For these purposes the corrosivity classification
based on corrosion losses contained in ISO 9223 should be considered final. New information,
from the present evaluations should be utilized for more realistic definitions of the environ-
mental characteristics classification levels.
The accuracy of the corrosivity category determinations should fully respect technical needs
and the practical possibilities to propose proper design and adequate protective measures. If
the diversity of design possibilities is taken into account, then five corrosivity categories appear
fully sufficient.
It would be very useful to extend the evaluation and interpretations of other international
testing programs to include better representation of testing sites in other than moderate climatic
zones. A new integrated database for the ISO CORRAG and MICAT programs is in preparation,
and negotiations with corrosion specialists in the Asia-Pacific area have been opened [11].
Comparative analysis of the results of the ISO CORRAG program (simple structure, mea-
surement of the ISO classification characteristics only) with the results of more complex pro-
grams [9,10,12] will stimulate new ideas for corrosivity classifications in the future.
The ISO CORRAG program comprises tests in open air conditions only; therefore, its results
describe middle to higher corrosivity categories. Collecting data characterizing free exposure
in low corrosivity areas is extraordinarily difficult (cold and extremely cold regions, high moun-
tains conditions, and extremely dry regions).
More informative classification criteria for the corrosivity category 1 overlapping to category
2 should be covered by new independent activities of W G 4 with orientation to indoor atmo-
spheric environments.
Acknowledgment
The realization of the international cooperative program ISO CORRAG, is the result of the
cooperation between members of ISO/TC 156/WG 4 and organizations supporting the program
in participating countries.
References
[1] ISO 9223, Corrosion of Metals and Alloys~lassification of Corrosivity of Atmospheres.
[2] ISO 9224, Corrosion of Metals and Alloys--Corrosivityof Atmospheres--Guiding Values for the
Corrosivity Categories.
[3] ISO 9225, Corrosion of Metals and Alloys--Corrosivity of Atmospheres---Measurement of

Pollution.
[4] ISO 9226, Corrosion of Metals and Alloys--Corrosivity of Atmospheres--Determination of Cor-
rosion Rate of Standard Specimens for the Evaluation of Corrosivity.
[5] ISO/TC 156/WG 4---N 131, "The Cooperative Testing Programme ISO CORRAG," Technical
Manual, 1986.
[61 Knotkova, D., convener of ISO/TC 156AVG 4, "Atmospheric Corrosivity Classification--Results
of the International Testing Program ISO CORRAG," Proceeding of the 12th ICC, Houston, TX
Sept. 1993, pp. 561-573.
[7] ISO Technical Report (lst version), ISO CORRAG--International Testing Program in the Frame of
ISO/TC 156/WG 4--Classification of Corrosivity of Atmosphere, Prague, May 1993.
[8] Dean, S. W., "Analyses of Four Years of Exposure Data from the USA Contribution to ISO
CORRAG Program," Atmospheric Corrosion, ASTM STP 1239, W. W. Kirk and H. H. Lawson,
Eds., American Society for Testing and Materials, Philadelphia, 1994.
[9] Kucera, V., Henriksen, J., Leygraf, C., Coote, A., Knotkova, D., and Strcke, B., "Materials Damage
Caused by Acidifying Air Pollutants," Proceeding of the 12th 1CC, Houston, TX, Sept. 1993.
[10] Feliu, S., Morcillo, M., and Feliu, S. Jr., "The Prediction of Atmospheric Corrosion from Meteo-
rological and Pollution Parameters--I. Annual Corrosion," Corrosion Science, Vol. 34, No. 3, 1993,
pp. 403-414.
[11] Knotkova, D., "Results of Contemporary International Atmospheric Testing Programs in Respect to
Corrosivity Classification and Engineering Applications," Proceeding from Asia-Pacific Workshop
on Materials Performance in Various Environments, Bandung, Indonesia, Nov. 1993.
[12] Baedecker, P. A., Edney, E. O., et al., "Effects of Acid Deposition on Materials," State-of-Science~
Technology, Report 19, NAPAP, May 1990.
APPENDIX
Statistic Analysis of Environmental Effects in the Metal Corrosion

Explanation to Tables
B(i) Regression coefficient

SE B(i) Standard error of B(i)
Beta(i) Standardized regression coefficient (Beta weight)
SO2 SOz pollution (ug/m3)
TOW Time of wetness (hours/year)
C1 Air salinity--NaC1 deposition rate (mg/m2.day)
T A B L E A1---Multiple regression-contribution of environmentalfactors to corrosion losses of unalloyed

steel.
D E P E N D E N T VARIABLE: Corrosion Losses (p~m/year)--STEEL F L A T
Regression A n a l y s i s - - M O D E L A
MULTIPLE R = 0.654
MULTIPLE R-SQUARE = 0.428
F(df = 3126) = 31.50 (p < 0,001)
VARIABLE B(i) SE B(i) Beta(i) t-test Significance
SO 2 0.4313 0.0718 0.41 6.01 P < 0.001
TOW 0.0057 0.0024 0.19 2.37 P < 0.01
CI 0.1384 0.0264 0.41 5.25 P < 0.001
INTERCEPT 1.3269
Regression A n a l y s i s - - M O D E L B
MULTIPLE R = 0.712
F(df = 3126) = 43.24 (P < 0.001)
SO 2 0.8147E-02 0.9854E-03 0.52 8.27 P < 0.001
TOW 0.8223E-04 0.3324E-04 0.18 2.47 P < 0.01
C1 0.1972E-02 0.3621E-03 0.40 5.45 P < 0.001
INTERCEPT 2.9385
T A B L E A2--Multiple regression-contribution of environmentalfactors to corrosion losses of unalloyed

steel.
DEPENDENT VARIABLE: Corrosion Losses (ixm/year)--STEEL HELIX
MULTIPLE R = 0.774
F(df = 3126) = 62.79 (P < 0.001)
SO2 0.5908 0.0633 0.53 9.34 P < 0.001
TOW O.0O90 0.0021 0.28 4.21 P < 0,001
CI 0.1409 0.0233 0.40 6.06 P < 0,001
INTERCEPT 4.8587
MULTIPLE R = 0.721
F(df = 3126) = 45.56 (P < 0.001)
SO z 0.0082 0.0011 0.48 7.70 P < 0.001
TOW 0.1419E-03 0.3586E-04 0.29 3.96 P < 0,001
CI 0.1960E-02 0.3906E-03 0.36 5.02 P < 0,001
INTERCEPT 3.1003
T A B L E A3--Multiple regression-contribution of environmental factors to corrosion losses of zinc.
D E P E N D E N T VARIABLE: Corrosion Losses (l~m/year)--ZINC F L A T
MULTIPLE R = 0.5453
F(df = 3126) = 17.77 (P<0.001)
SO2 0.0232 0.0046 0.38 5.10 P < 0.001
TOW 0.2696E-03 0.1536E-03 0.15 1.76 P<0.05
C1 0.0059 0.0017 0.31 3.53 P<0.001
INTERCEPT 0.2098
MULTIPLE R = 0.552
F(df = 3126) = 18.48 (P < 0.001)
SOz 0.0075 0.0013 0.41 5.59 P < 0.001
TOW 0.9387E-04 0.4525E-04 0.18 2.07 P < 0.05
C1 0.1478E-02 0.4929E-03 0.26 3.00 P < 0.01
INTERCEPT -0.0680
T A B L E A4--Multiple regression-contribution of environmentalfactors to corrosion losses of zinc.
D E P E N D E N T VARIABLE: Corrosion Losses (p,m/year)--ZINC HELIX
MULTIPLE R = 0.663
F(df = 3126) = 33.95 (P < 0.001)
SO 2 0.0424 0.0055 0.51 7.67 P<0.001
TOW 0.3761E-03 0.1865E-03 0.16 2.02 P < 0.05
C1 0.0090 0.0020 0.35 4.43 P < 0.001
INTERCEPT 0.3819
MULTIPLE R = 0.711
F(df = 3126) = 43.02 (P<0.001)
SO 2 0.0092 0.0011 0.52 8.28 P < 0.001
TOW 0.1256E-03 0.3752E-04 0.25 3.35 P < 0.001
C1 0.1899E-02 0.4087E-03 0.34 4.65 P < 0.001
INTERCEPT 0.2130
TABLE A5--Multiple regression-contribution of environmental factors to corrosion losses of copper.
DEPENDENT VARIABLE: Corrosion Losses (ixm/year)--COPPER FLAT
Regression Analysis--MODEL A
MULTIPLE R = 0.565
F(df = 3126) = 19.77 (P < 0.001)
SO 2 0.0065 0.0019 0.25 3.40 P < 0.001
TOW 0.5377E-04 0.6473E-04 0.07 0.83 n.s.
CI 0.3934E-02 0.7051E-03 0.48 5.58 P < 0.001
INTERCEPT 0.9556
Regression Analysis--MODEL B
MULTIPLE R = 0.548
F(df = 3126) = 18.07 (P < 0.001)
SO: 0.0038 0.0012 0.24 3.23 P < 0.001
TOW 0.6968E-04 0.3941E-04 0.15 1.77 P < 0.05
C1 0.2006E-02 0.4293E-03 0.41 4.67 P < 0.001
INTERCEPT - 0.1738
TABLE A6--Multiple regression-contribution of environmental factors to corrosion losses of copper.
DEPENDENT VARIABLE: Corrosion Losses (tzm/year)--COPPER HELIX
MULTIPLE R = 0.549
F(df = 3126) = 18.08 (P < 0.001)
SO 2 0.0135 0.0051 0.20 2.65 P < 0.01
TOW - 0.9986E-05 0.1718 E-03 - 0.01 - 0.06 n.s.
C1 0.0113 0.0019 0.52 6.01 P < 0.001
INTERCEPT 1.4936
MULTIPLE R = 0.629
F(df = 3126) = 27.52 (P < 0.001)
SO2 0.0045 0.0013 0.25 3.63 P < 0.001
TOW 0.4881E-04 0.4221E-04 0.09 1.16 n.s.
C1 0.3037E-02 0.4598E-03 0.54 6.60 P < 0.001
INTERCEPT 0.2122
TABLE AT--Multiple regression-contribution of environmental factors to corrosion losses of

aluminum.
DEPENDENT VARIABLE: Corrosion Losses (Ixm/year)~ALUMINUM FLAT
MULTIPLE R = 0.165
F(df = 3126) = 25.54 (P < 0.001)
SO2 0.6383E-02 0.8170E-03 0.55 7.81 P < 0.001
TOW 0.6504E-04 0.2756E-04 0.19 2.36 P < 0.01
C1 0.5575E-03 0.3002E-03 0.15 1.86 P < 0.05
INTERCEPT 0.0069
MULTIPLE R = 0.531
F(df = 3126) = 16.51 (P < 0.01)
SO2 0.0115 0.0020 0.43 5.71 P < 0.001
TOW 0.9563E-00 0.6779E-04 0.12 1.41 n.s.
C1 0.2093E-02 0.7384E-03 0.25 2.83 P < 0.01
INTERCEPT - 1.9525
TABLE A8--Multiple regression-contribution of environmental factors to corrosion losses of

aluminum.
DEPENDENT VARIABLE: Corrosion Losses (txm/year)--ALUMINUM HELIX
MULTIPLE R = 0.548
F(df = 3126) = 17.99 (P < 0.001)
SO2 0.0281 0.0009 0.43 5.73 P < 0.001
TOW -0.4999E-04 0.1658E-03 -0.03 -0.30 n.s.
C1 0.0078 0.0018 0.38 4.34 P < 0.001
INTERCEPT - 0.0171
MULTIPLE R = 0.631
F(df = 3126) = 27.79 (P < 0.001)
SO2 0.0122 0.0021 0.40 5.83 P < 0.001
TOW 0.1633E-03 0.7064E-04 0.19 2.31 P < 0.05
C1 0.3646E-02 0.7694E-03 0.38 4.74 P < 0.001
INTERCEPT - 1.7159
S h e l d o n W. Dean I
ANALYSES OF FOUR YEARS OF EXPOSURE DATA FROM THE USA

CONTRIBUTION TO ISO CORRAG PROGRAM
REFERENCE: Dean, S. W., "Analyses of Four Years of Exposure Data from

the U S A C o n t r i b u t i o n to ISO CORRAG Program," Atmospheric CorrosiQn, ASTM
STp.1239, W. W. Kirk and Herbert H. Lawson, Eds., A m e r i c a n Society for
Testing and Materials, Philadelphia, 1995.
ABSTRACT: The USA part of ISO C O R R A G C o l l a b o r a t i v e A t m o s p h e r i c

Exposure Program has completed 4 years. The purpose of this worldwide
exposure p r o g r a m has been to obtain atmospheric and corrosion data on
four metals to verify that the atmospheric classification system given
in ISO standards ISO 9223, 9224, 9225, and 9226 are valid. Five sites
were included in this program; 250 m lot at Kure Beach, Newark-Kearny,
Point Reyes, Los Angeles, and the Fort Sherman coastal site in Panama.
Flat panels and wire helices were used with triplicate specimens for six
consecutive 1 year and single 2, 4 and 8 year exposures. The helices
appear to corrode at significantly higher rates than the panels. The
Fort Sherman coastal site was most corrosive to all alloys. The Newark-
Kearny site exhibited significantly lower corrosivity than in previous
exposures. Multiple regression analyses showed that the environmental
data accounted for a major portion of the variation in corrosion data
for all metals except aluminum. The ISO classification system was
accurate in 58% of the cases studied. In the other cases, it under-
estimated the corrosion rate about as often as it o v e r - e s t i m a t e d the
rate.
KEYWORDS: atmospheric corrosion, time of wetness, sulfation plate,

classification of atmospheres, chloride candle, multiple linear
regression analysis.
INTRODUCTION
One of the priority action areas for the International
IAir Products Fellow, Corporate Engineering, Air Products and

Chemicals, Inc., Allentown, PA 18195.
58
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DEAN ON U.S. CONTRIBUTION TO THE ISO CORRAG PROGRAM 57
Organization for S t a n d a r d i z a t i o n identified at the o r g a n i z a t i o n a l

meeting of T e c h n i c a l C o m m i t t e e TC156 in Riga, Latvia in 1976 was
atmospheric corrosion. At the second p l e n a r y m e e t i n g of ISO/TCI56 in
Bor~s, Sweden in 1978, it was decided that a w o r k i n g group should be
formed to d e v e l o p s t a n d a r d s to classify a t m o s p h e r i c corrosivity. As a
result, W o r k i n g G r o u p WG4 was formed under the l e a d e r s h i p of
C z e c h o s l o v a k i a n d e l e g a t i o n a n d four standards were w r i t t e n on the
subject of c l a s s i f i c a t i o n of atmospheric corrosivity: ISO 9223, 9224,
9225 and 9226. [i]
The s y s t e m of a t m o s p h e r i c corrosivity c l a s s i f i c a t i o n was b a s e d on

Czech national standards, and as a result, there was a need to test
these methods on a w o r l d w i d e basis to verify that the values u s e d would
apply throughout the world. A worldwide e x p o s u r e p r o g r a m was p r o p o s e d
in 1986 to carry out t h i s goal. This p r o g r a m was n a m e d ISO CORRAG.
ASTM Committee G-I on the C o r r o s i o n of Metals a s s u m e d r e s p o n s i b i l i t y for
this p r o g r a m in the U S A with joint oversight r e s p o n s i b i l i t y in
subcommittee G01.04 on a t m o s p h e r i c testing and s t a n d i n g subconunittee
G01.95 the TAG for ISO/TCI56. A report on the i n i t i a t i o n of exposure
was p u b l i s h e d in A S T M STP 965.[2] Thereafter, four exposure reports
have been s u b m i t t e d to A S T M d e t a i l i n g the results of the study [3-3].
The purpose of this p a p e r is to present the results of this study
including a current i n d i c a t i o n of the c o r r o s i v i t y of the sites and a
test of the a c c u r a c y of the techniques shown in the ISO standards.
Although the p r o g r a m is s c h e d u l e d to continue for several more years,
more than 80% of the results are available at this time so that such an
evaluation is a p p r o p r i a t e .
It should be n o t e d that the methods used in this study were

selected to m a x i m i z e r e p r o d u c i b i l i t y of results and s i m p l i c i t y for the
investigators. The e v a l u a t i o n methods chosen were not n e c e s s a r i l y
typical best p r a c t i c e s for e v a l u a t i n g the e n g i n e e r i n g p e r f o r m a n c e of
metals in a t m o s p h e r i c exposure. For example mass loss based penetration
of aluminum alloys does not usually relate to the actual pit depth
penetration or loss of t e n s i l e properties that these m a t e r i a l s suffer.
EXPERIMENTAL PROCEDURE
Materials
The ISO C O R R A G p r o g r a m was set up to evaluate four metals as

surrogates for w i d e l y u s e d m e t a l l i c alloys used in the atmosphere. The
metals to be t e s t e d i n c l u d e d a low carbon steel, c o m m e r c i a l l y pure
copper, c o m m e r c i a l l y p u r e zinc, and commercially pure aluminum. Two
types of specimens were to be exposed, flat panels i00 x150 m m and wire
helices. The steel p a n e l s were supplied by B r i t i s h Steel Corporation
and both the panels and wire were from the same lot. All of the helices
were produced by the D e u t s c h e s Institut f~r Normung. The zinc panels
were supplied by Platt Bros. The copper panels were s u p p l i e d by Olin
Corp. Metals R e s e a r c h Laboratories, and the a l u m i n u m panels were
supplied by Kaiser A l u m i n u m and Chemicals Corp. The steel and zinc
panel compositions are given in reference [2]. A d d i t i o n a l data on the
specimens are given in Table I.
TABLE l--Data on Materials Used in ISO CORRAG Program
Initial Diameter of
Material UNS Denslty~ 9/cm 3 Helix Wire, ram
Aluminum A91100 2.30 2.932

Copper CII0O0 8.90 3.000
Zinc Z41320 7.20 2.920
Steel GI0050 3.86 1.905
Specimens
The panels were f a b r i c a t e d f r o m r o l l e d products by the suppliers.

The m a r k i n g system is d e s c r i b e d in r e f e r e n c e [~]. Stencil s t a m p i n g was
used on the non-ferrous alloys, while a d r i l l e d hole system was u s e d for
the steel panels. The h e l i c e s were f a b r i c a t e d from a p p r o x i m a t e l y Im
lengths of 2-3 ran diameter wire and were s u p p l i e d with p o l y a m i d e holders
(see F i g u r e I). In most cases, the p a n e l s and helices were e x p o s e d
without any surface preparation. In some cases, it was n e c e s s a r y to
clean the steel panels i m m e d i a t e l y b e f o r e e x p o s u r e in order to remove
surface rust. In these cases, the p a n e l s were re-weighed before
exposure.
!-
OPEN HELIX SPECIMEN ASSEMBLY
= POLYAMIDE HOLDER AND NUT
rain
~mmD
9IN,m D , ,
q" ID,
" I I ~ ram,,
e l ' , ID , @
OPEN HELIX SPECIMEN ASSEMBLY
Fig. I--ISO C O R R A G h e l i x specimen assembly
Exposure Sites
The Kure Beach exposure site (KB) is the 250 m lot at Kure Beach
a ~ , i n i s t e r e d by LaQue Center for C o r r o s i o n Technol~qy (LQCCT). The
N e w a r k - K e a r n y Site (NK) is the A S T M site in Kearny, N e w Jersey. The

Point Reyes site (PR) is the A S T M site. The Fort S h e r m a n C o a s t a l site
(PCZ) is l o c a t e d at t h e US A r m y T r o p i c Test C e n t e r in Panama. The Los
Angeles site (LA) is l o c a t e d at the U n i v e r s i t y of S o u t h e r n California.
The exposure dates are g i v e n in Table 2.
Zea~--Em~z~z
At the c o n c l u s i o n of e a c h exposure, the s p e c i m e n s w e r e r e t r i e v e d

a n d s h i p p e d to the e v a l u a t o r . The specimens were t h e n c l e a n e d and
weighed. C a l c u l a t i o n s w e r e m a d e to d e t e r m i n e the m a s s loss of each
specimen. The t o t a l a r e a of each panel was estimated, a n d a m a s s loss
p e r unit area c a l c u l a t e d . The m a s s loss p e r unit a r e a was c o n v e r t e d to
an a v e r a g e c o r r o s i o n p e n e t r a t i o n rate.
In o r d e r to e s t i m a t e the true total area of e a c h p a n e l it was

d e c i d e d to use the i n i t i a l m a s s of the panel, t o g e t h e r w i t h the length
a n d w i d t h m e a s u r e m e n t s to e s t i m a t e the thickness. B e c a u s e the thickness
of r o l l e d p r o d u c t s is p r a c t i c a l l y constant, an a v e r a g e p a n e l t h i c k n e s s
was calculated. The area, A, of the panel in c m 2 was t h e n c a l c u l a t e d as
follows:
A = 2m+2t(t+w) (i)
pt
where
m = initial m a s s of the panel, g
p = d e n s i t y - see T a b l e I, g / c m 3
t = avarage t h i c k n e s s of the panel, cm
1 = m e a s u r e d length, cm
w = m e a s u r e d width, cm
The reason for this p r o c e d u r e was to o b t a i n a h i g h e r d e g r e e of

a c c u r a c y than was a v a i l a b l e in the length a n d w i d t h m e a s u r e m e n t s .
The helices p r e s e n t e d a somewhat d i f f e r e n t p r o b l e m in that the

area of a wire s a m p l e d e c r e a s e s s i g n i f i c a n t l y as c o r r o s i o n occurs. A
d e r i v a t i o n was p r e s e n t e d in the first exposure report [~], a n d the
r e s u l t i n g r e l a t i o n s h i p s have b e e n u s e d to c a l c u l a t e b o t h m a s s loss per
unit area and c o r r o s i o n rates for the helices. The r e l a t i o n s h i p for
a v e r a g e mass loss per unit area for the helices is:
mL
= 2 [ -V miJ
(2)
6O ATMOSPHERIC CORROSION
where
D i is the initial diameter of the helix wire, mm
mf is the final mass of the specimen, g
m i is the initial mass of the specimen, g
pis the d e n s i t y of the helix material, g / c m 3 (Table i)
mL is the mass loss per unit area, g/m 2
The average p e n e t r a t i o n rate, P, is given by a similar r e l a t i o n s h i p
(3)
2T L Vmi]
where
T is the exposure time, years
Ds mf, and m i d e f i n e d above
P is the average p e n e t r a t i o n rate, ~m/year
Standard d e v i a t i o n s were calculated from the corrosion rates m e a s u r e d

for replicate specimens from each exposure,as d e s c r i b e d in A S T M GI6. [7]
RESULTS
Mass Loss
The i n d i v i d u a l mass measurements for all the specimens have b e e n

reported in four exposure reports[l-~]. The averages and standard
d e v i a t i o n s for the corrosion rates are p r e s e n t e d in Table 3 for the
panels and Table 4 for the helices.
Environmental Data
E n v i r o n m e n t a l data have also been a c c u m u l a t e d by the LQCCT for the

Kure Beach site, and the U.S. Army for the Fort Sherman Coastal Site.
In these cases, wet candle measurements were u s e d to measure chloride
deposition rates and sulfation plates were used for sulfur dioxide
deposition a c c o r d i n g to ASTM G91[~]. No m e a s u r a b l e sulfation was found
at the KB site. Temperature and relative humidity were also m e a s u r e d
and recorded on an hourly basis. The average temperature for each month
TABLE 2--Exposure and Removal Dates for U S A ISO CORRAG Specimens
Exposure
Site Code No. Initiation Removal Days
Kure Beach A (KB) ii 13 Jan 87 14 Jan 88 366

NC 12 16 Apr 87 20 A p t 88 370
2 5 0 m lot 13 20 Oct 87 20 O c t 88 366
14 20 Apr 88 18 A p r 89 363
15 20 Oct 88 25 Oct 89 370
16 18 Apr 89 17 A p r 90 364
21 13 Jan 87 13 Jan 89 731
41 13 Jan 87 15 Jan 91 1,463
X1 13 Jan 87 8 years ---
Newark Kearny B (NK) ii 26,27 Feb 87 5 A p r 88 ~* 403

NJ 12 1 May 87 3 Jun 88 399
13 18 Nov 87 17 Jan 89 426
14 5 Apr 88 ii Jun 90 797
15 I Dec 88 I0 Oct 90 678
16 21 Jun 89 ii Jun 90 355
21 26,27 Feb 87 20 Oct 90 1,332
41 26,27 Feb 87 * 1,642
X1 26,27 Feb 87 8 years ---
Foint Reyes C (PR) ii 7 Feb 87 7 Feb 88 365

CA 12 27 M a y 87 28 M a y 88 367
13 28 N o v 87 26 N o v 88 364
14 28 M a y 88 18 Jun 89 386
15 26 N o v 88 17 Dec 89 386
16 18 J u n 89 25 A p r 92 1,042
21 7 Feb 87 5 Feb 89 729
41 7 Feb 87 25 A p r 92 1,904
X1 7 Feb 87 8 years ---
Fort S h e r m a n E (PCZ) ii 18 M a y 87 25 M a y 88 373

Coastal-Panama 12 15 Oct 87 14 Oct 88 365
13 15 A p r 88 15 A p r 89 365
14 15 Oct 88 15 Oct 89 365
15 15 A p t 89 20 A p t 90 370
16 16 Oct 89 20 Oct 90 369
21 18 M a y 87 18 M a y 89 731
41 18 M a y 87 21 A p r 91 1,434
X1 18 M a y 87 8 years ---
X1 S t e e l 18 M a y 87 18 N o v 87 184
Los A n g e l e s F (Ilk) Ii 2 Mar 87 2 M a r 88 366

CA 12P 29 May 87 31 M a y 88 368
12H 9 Jun 87 i0 Jun 88 367
13 2 Mar 88 6 Jul 89 481
14 19 Sep 88 20 S e p 89 366
15 26 Jun 89 2 Jul 90 372
16 20 Sep 89 24 Oct 90 399
21 2 Mar 87 31 M a r 89 760
41 2 Mar 87 8 M a r 91 1,467
Xl 2 Mar 87 8 years ---
* T h e 41 s p e c i m e n s from NK site w e r e r e m o v e d a c c i d e n t a l l y on 2 1 J a n u a r y 1989 and re-

e x p o s e d on 11 J a n u a r y 1990. T h e c o p p e r p a n e l s w e r e c l e a n e d and w e i g h e d and r e p o r t e d in
r e p o r t No. 2 and r e - e x p o s e d on ii J a n u a r y 1990. The o t h e r s p e c i m e n s w e r e nor c l e a n e d
and w e i g h e d , but w e r e r e t r i e v e d on 26 A u g u s t 1992 for a total of 1,642 d a y s e x p o s u r e .
T h e 41 c o p p e r s p e c i m e n s s h o u l d De r e t r i e v e d on or about ii J a n u a r y 1994 to c o m p l e t e 4
years exposure.
~ The I 3 C X ! I - 3 P p a n e l s w e r e r e m o v e d on 5 ~ r i l 1988 i n s t e a d of the I 3 B I I I - 3 P p a n e l s . The

3 3 B I I i - 3 ? p a n e l s w e r e r e m o v e d on 20 O c t o b e r 1990, and so r e p l i c a t e the I 3 B 2 1 1 - 3 P
panels.
TABLE 3--Average Corrosion Rates b~ Site t Metal

and E x p o s u r e - Panel R e s u l t s
B a s e d on 3 Panels E x c e p t as N o t e d
~m/yr~ standard deviation
Site Exposure A1 Cu Zn Fe
A (KB) ii 0.338 • 2.58 • 2.24 • 40.15 •

12 0.269 • 3.19 • 1.569 • 32.5 •
13 0.288 • 2.57 • 2.44 • 37.58 •
14 0.242 • 2.52 • 2.068 • 35.61 •
15 0.311 • 3.22 • 1.90 • 43.6 •
16 0.301 • 3.03 • 1.834 • ---
21 0.174 • 1.85 • 1.80 • ---
41 0.163 • 1.61 • 1.634 • ---
B (NK) ii 0.306 • 1.339 • 2.25 • Z7.8 •

12 0.318 • 1.375 • 1.794 • 21.59 •
13 0.278 • 1.291 • 1.961 • 29.80 •
14 0.228 • 1.133 • 1.794 • ---
15 0.311 • 1.477 • 1.850 • ---
16 0.252 • 1.740 • 2.091 • ---
21 0.219 • 1.051 • 1.86 • ---
C (PR) II 0.231 • 2.32 • 1.87 • 43.2 •

12 0.274 • 2.637 • 1.396 • 38.74 •
13 0.341 • 2.303 • 2.12 • 23.0 •
14 0.2165 • 2.38 • 1.61 • 41.23 •
15 0.139 • 2.45 • 1.649 • 37.40 •
16 0.i08 • . . . . . . . . .
21 0.143 • 1.60 • 1.95 • 27.5 •
41 O.ICI • . . . . . . . . .
E (PCZ) IX . . . . . . . . . 78.9 •
ii 0.569 • 6.14 • 19.98 • 373.5 tl.O
12 0.622 • 4.932 • 17.99 • ---
13 0.612 • 4.34 • 16.9 • ---
14 0.402 • 4.954 • 15.2 • ---
15 0.721 • 7.15 • . . . . . .
16 0.491 • 5.26 • . . . . . .
21 0.512 • 4.02 • 18.55 • ---
41 0.409 • 4.54 • . . . . . .
F (LA) ii 0.547 • 1.384 • 0.878 • 21.32 •

12 0.482 • 1.069 • 1.187 • 20.44 •
13 0.767 • I.i00 • 1.319 • 16.09 •
14 0.920 • 1.580 • 1.252 • 27.9 •
15 0.302 • 0.864 • 0.955 • ---
16 0.320 • 0.961 • 0.949 • ---
21 0.613 • 0.813 • 1.192 • 12.39 •
41 0.452 • . . . . . . . . .
I Two panel results included in this average.
2 41 C o p p e r p a n e l s e x p o s e d 27 Feb 1987 and

a c c i a e n t a l l y r e m o v e d on 21 Jan 1989.
3 6 Month Result.
4 The !3B!I!-3P panels were !eft in test for an i d e n t i c a l period and their average
corrosion rate w a s 1.90•
TABLE 4--Average Corrosion Rates by Site~ Metal

and Exposure - Helix Results
B a s e d o n 3 h e l i c e s e x c e p t as n o t e d
~m/yr~ standard deviation
Site Exposure A1 Cu Zn Fe
A (KB) II 0.690 • 3.726 • 2.549 • 63.7 •

12 0.733 • 5.73 • 3-3262 ---
13 1.039 • 3.353 • 3.58 • 67.5 •
14 0.994 • 5.06 •176 --- 112.4 •
15 0.851 • 4.528 • 5.30 • 93.6 •
16 0.890 • 5.077 • 3.67 • ---
21 0.264 • 3.52 • 3.24 • ---
41 0.416 • 1.739 • 2.43 • ---
B (NK) ii 0.602 • 1.813 • 2.144 • 28.1 •

12 0.751 • 1.847 • 1.797 • 26.5 •
13 0.598 • 2.41 • 2.317 • 27.3 •
14 0.460 • 1.593 • 2.088 • ---
15 0.512 • 1.834 • 2.365 • ---
16 0.644 • 2.150 • 2.174 • ---
21 0.454 • 1.63 • . . . . . .
41 . . . . . . . . . . . .
C (PR) ii 1.62 • 5.466 • 3.26 • 146.6 •

12 1.27 • 6.22 • 3.88 • 147.5 •
13 1.46 • 3.37 • 3.66 • 141.2 •
14 1.43 • 4.98 • 4.15 • 161.6 •
15 ii43 • 4.379 • 2,58 • 133.7 •
16 0.80 • . . . . . . . . .
21 1.40 • 3.513 • 2.68 • 122.0 •
41 1.86 • . . . . . . . . .
E (PCZ) IX . . . . . . . . . 220 •
ii 1.19 • 11.44 • 7.58 • 224 •
12 2.30 • ii.8 • --- 369.0 •
13 1.47 • 10.02 • --- 311 •
14 1.72 • ~ 9.99 • --- 283 •
15 1.97 • 15.99 • . . . . . .
16 1.23 • 10.56 • . . . . . .
21 1.34 • 6,94 • --- 435 •
41 0.76 • 6.28 • . . . . . .
F (LA) ii 1.712 • 2.173 • 1.51a 19.4 •

12 1.149 • 1.947 • 1.43 • 19.01 •
13 1.536 • 2.079 • . . . . . .
14 1.842 • 2.277 • . . . . . .
15 0.984 • 1.746 • 2.04 • ---
16 1.579 • 1.991 • 2.06 • ---
21 1.392 • 1.516 • . . . . . .
41 i.i01 • . . . . . . . . .
I Two helix results average.
2 Single helix result.
3 6 Month exposure result.
of exposure was reponted in the exposure reports. The relative h u m i d i t y

data were used to calculate a time of wetness based on the p r o c e d u r e
shown in ISO 9223. This p r o c e d u r e assumes that wetness occurs whenever
the relative humidity exceeds 80% and the t e m p e r a t u r e exceeds 0"C. The
time of wetness was c o n v e r t e d to a percent value and reported as an
average for each month of exposure.
Data from the weather stations at N e w a r k Airport (EWR) Los Angeles

(LAX) and San Francisco (SFO) were used to obtain temperature and
relative h u m i d i t y information for the Newark-Kearny, Los Angeles, a n d
Point Reyes sites respectively. Time of wetness was c a l c u l a t e d from the
relative h u m i d i t y data as d e s c r i b e d previously. A v e r a g e sulfur dioxide
concentrations were o b t a i n e d from New J e r s e y State D e p a r t m e n t of
Environment from their N e w a r k m o n i t o r i n g site, and f r o m the South Coast
Air Q u a l i t y M a n a g e m e n t D i s t r i c t m o n i t o r i n g site in LOS Angeles. Monthly
averages, C, of the daily 1 hour m a x i m u m s were reported in terms of
~ g / m 3 of SO 2. These c o n c e n t r a t i o n values were c o n v e r t e d to a d e p o s i t i o n
rate, r, in terms of mg S02/m2day by the formula below:
r = .844C (4)
This is based on the fact that l~g/m 3 i3 equivalent to 0.381 ppbv

at 25"C, and the c o n v e r s i o n of c o n c e n t r a t i o n to d e p o s i t i o n rate may be
a c c o m p l i s h e d by the r e l a t i o n s h i p given in A S T M G91 - i.e., 1 ppbv =
2.216 m g / m 2 day.
The m o n t h l y averages were u s e d to obtain exposure averages for

each exposure interval in this study. These values are reported in
Table 5. In this table, the values for time of wetness have been
reported as percent, the sulfur dioxide d e p o s i t i o n as mg SO2/m2day, the
chloride as mgNaCl/m2day and t e m p e r a t u r e is "C. The average corrosion
rates for each site by metal, specimen and length of exposure are given
in Table 6.
DISCUSSION
Variability of Corrosion Rates
It was of interest to d e t e r m i n e if there were any relationship

between the average m e a s u r e d corrosion rates and the standard deviation
of the corrosion rates. In cases where the s t a n d a r d deviation is
proportional to the average it is d e s i r a b l e to use a different technique
to analyze the data. Consequently, c o r r e l a t i o n analyses were made on
the average and standard d e v i a t i o n values. The results of these
analyses are shown in Table 7. These analyses show that except for the
steel panels there is a significant but weak correlation between the
average and standard deviation. This suggests that the coefficient of
variation, i.e., the ratio of standard d e v i a t i o n to average may be a
better gauge of variability than standard deviation. The copper
specimens seem to have the smallest ratio of standard deviation to
average for both specimen types, varying between 3.6% to 6%. The others
v a r i e d from 6% to 20%, except for steel panels.
TABLE 5--Environmental data for the CORRAG exposures
Expo-
sure KB (i) NK (2) PR (3) pCZ (4) LA (5)
[)esig Temp TOW SO2 NaCI Temp TOW SO2 NaCI Temp TOW SO2 NaCI Temp TOW SO2 NaCI Temp TOW SO2 NaCI
~C % mg/m2 mg/m 2 ~ % mg/m 2 mg/m2 ~ % mg/m 2 mg/m 2 ~C % mg/m2 mg/m 2 ~ % mg/m 2 mg/m2
]i 19.01 50.0 0 129 12.35 22.7 27.3 NA 14.26 45.2 NA NA 27.32 82.6 0 517 16.71 45.6 11.6 NA o
12 17.78 48.8 0 117 12.99 23.6 26.2 NA 14.26 44.2 NA NA 26.83 81.6 0 532 16.76 43.2 11.6 NA
m
>
13 17.55 45.2 0 149 11.45 18.4 29.7 NA 14.07 46.3 NA NA 26.35 83.7 NA 605 16.46 41.8 8.1 NA z
14 17.40 47.4 0 193 13.06 22.1 26.7 NA 13.70 49.7 NA NA 26.18 87.5 NA 724 16.44 44.0 28.1 NA
O
15 17.74 49.6 0 242 13,11 26.0 27.6 NA 13.52 53.2 NA NA 26.42 91.9 NA 764 16.71 41.4 6.3 NA z
16 18.03 50.6 0 266 12,99 28.2 26.8 NA NA NA NA NA 26.75 91.7 NA 723 17.42 38.1 6.3 NA
c
21 18.00 46.4 0 162 13.64 24.2 26.4 NA 14.10 45.7 NA NA 26.77 83.2 NA 554 16.47 43.6 10.4 NA
41 18.17 47.5 0 166 NA NA NA NA NA NA NA NA 26.73 86.1 NA 629 16.82 41.2 8.3 NA
ixl . . . . 21.24 88.4 0 93 - - O
O
z
(I) KB - SO 2 data from sulfation plates, NaCI from chloride candle, Temp and TOW from weather station. ~0
(2) NK - SO 2 from the hourly max. concentration, Temp and TOW from EWR weather station. 0o
(3) PR - T e m p a n d TOW from SFO weather station. c
14) PCZ - SO 2 from sulfa*ion plates, NaCI from chloride candle, Temp and TOW from local measurement. -4
(5) 1~ - SO 2 from ave hourly max concentration, Temp and TOW from LAX weather station.
]xl = 6 month data f o r s t e e l at PCZ. z
NA not available.
O
-r
TABLE 6--Average I, 2 and 4 ~eaz corrosion rates by site, metal and s~ecimen type~ pm/yr
m
Si~e A1 Cu Zn Fe O
SE,ec O
Y:~ I 2 4 1 2 4 I 2 4 1 2
0
~0
>
A KB P .292 ~.033 174 ~.006 163 1.003 2.85 1.33 1.85 ~.04 1.61 1.04 2.01 *.31 1.80 *.07 1.63 *.06 37.9 14.2
H .87 • 264 • 416 1.017 4.58 • 3.52 1.17 1.74 • 3.55 • 3.24 *.71 2.43 *.14 03 f20
B NK P .282 • 219 • 1.39 1,20 1.05 f.03 1.96 ~.IB 1.B6 • ~O

H .59 Z.10 455 • 1.94 • 1.63 1.26 2.15 *.20 27.3 ~.B O
I'~ P .21B t . o 8 6 143 ~.016 I01 ~.014 2.42 ~ . 1 3 1.60 1.10 1.73 t.28 1.95 *.39 36.8 17,8 27.5 .2.8 ~0
H 1.34 ~.28 .40 Z.15 .86 II.0r 4.88 11.08 3.51 1.08 3.51 t,61 2.68 1.43 1(6 ZlO 122 t1.1 >
E-PCZ P .57 1.II 512 t.010 409 • 5.46 fl.02 4.02 1.11 4.54 ~.05 17.5 22.0 18.55 *.84 373 il.O
1.65 t . 4 4 .34 *.38 76 • |1.7 *2.2 6,94 *.21 6.28 t.08 7.58 1.9| 29~ t60 435 189
I, J,A P .5] t.l, 613 10.23 452 10,25 1.16 1.27 O.@L 1.02 1.09 *.18 1.19 2.0"2 21,4 i~.@ 12,4 •
S 1,47 1.33 .39 *.36 .101 • 2.04 • 1.52 1.03 1.76 *.34 19.2 *.3 O~
Ln
TABLE 7--Correlatlon of average corrosion rate with its

standard deviation for all sites
Item Aluminum Copper Zinc Steel

Panel Helix Panel Helix Panel Helix Panel Helix
Ave Cot Rate 0.3665 1.1396 2.577 4.741 4.121 3.044 49.08 146.56
Ave SD 0.0229 0.2112 0.937 0.2427 0.3781 0.2601 1.24 15.65
R2 0.478 0.349 0.280 0.696 0.299 0.389 0.0001" 0.551
bo 0.0661 0.2030 0.0361 0.0600 0.0984 0.0901 .0078 0.1273
Sbo 0.0063 0.0270 0.0048 0.0056 0.0225 0.0127 0.0047 0.0203
DF 38 38 35 35 32 22 20 21
R 2= Correlation coefficient squared for correlation between standard deviation and

average corrosion rate.
bo= Best fit coefficient for assumed relationship SD = b O (ave corrosion rate.)
Sbo= Standard error of the best fit coefficient.
DF= Degrees of freedom for regression.
This R 2 value is not significant. All other R 2 values are significant at 99%
confidence level.
The results in Tables 3 and 4 also suggest that the Los Angeles
and Newark-Kearny sites are about equivalent in t e r m s o f c o r r o s i o n rates
for steel, zinc, and copper. T h e F o r t S h e r m a n s i t e i3 t h e m o s t
corrosive for those metals. The aluminum specimens showed higher rates
at t h e L o s A n g e l e s a n d F o r t S h e r m a n s i t e s , a n d l o w e r r a t e s at K u r e B e a c h
and Newark-Kearny. Correlation analyses between similar specimen rates
at any site did not show significant correlation in most cases.
Variation of Corrosion With Exposur~ Time
In g e n e r a l , atmospheric corrosion rates decrease with exposure

time. It h a s b e e n o b s e r v e d for many metals that the mass loss maybe
related to exposure time by an expression of t h e f o r m :
mL = aT n (5)
where
mL = mass loss per unit area

T = exposure t i m e in y e a r s
a and n are constants w h e r e n is u s u a l l y between 0 and 1
This expression implies that the average corrosion rate CR as

calculated in t h i s s t u d y h a s t h e f o r m :
C R = m_._L_L= a T n _ 1 (6)
T
Therefore, the average corrosion rates should d e c r e a s e as exposure

time increases.
The m a s s loss data in this study have b e e n u s e d to determine the

constants in Equation 5 above as follows. Only the ii, 21, and 41
exposure results were u s e d in this e v a l u a t i o n in order to have a
consistent data set. Previous workers who d i s c o v e r e d this r e l a t i o n s h i p
have u s e d exposure sequences of this nature. Furthermore, it is likely
that short exposures will be more a f f e c t e d by episodic e n v i r o n m e n t a l
events so that a v e r a g i n g several one-year exposures may give a better
estimate of a one-year performance, but will not relate to a single two
or four year exposure. O n l y the ii exposure was i n i t i a t e d at the same
time as the 21 and 41 specimens and so these specimens w o u l d have
e x p e r i e n c e d identical exposures for the first year. The mass loss per
unit areas were c o n v e r t e d to logarithmic values along with the exact
exposure intervals. A linear r e g r e s s i o n analysis was c o n d u c t e d for each
site, m e t a l - s p e c i m e n combination. The results are reported in Table 8.
The c o r r e l a t i o n coefficient square R 2 was i n c l u d e d to show the degree of
fit of the regression. In most cases, the mass loss exponent n was less
than one as is u s u a l l y noted. However, with only two or three e x p o s u r e
intervals, it is difficult to d e t e r m i n e the constants in such an
analyses with confidence. When the eight year exposures are completed,
it will be p o s s i b l e to have a better estimate of this behavior.
Comparison of Helix and Panel C o r r o s i o n Rates
E x a m i n a t i o n of the results in Tables 3 and 4 suggests that the

helix specimens corrode at a higher rate than panels. In order to
quantify this observation, plots were p r e p a r e d showing the c o r r o s i o n
rates for helices versus panels for each metal. R e g r e s s i o n analyses
suggested that there was a linear r e l a t i o n s h i p b e t w e e n the helix rate
and the panel rates with the helix rates b e i n g s i g n i f i c a n t l y g r e a t e r
than the panel rates. Table 9 shows the results of these analyses using
a regression t h r o u g h the origin. Figures 2,3,4, and 5 show the
comparison for each metal. The results c l e a r l y indicate that the
helices corrode at a higher rate than the panels. Zinc seems to show
the effect less than the other metals, while a l u m i n u m shows it
significantly, e s p e c i a l l y at Pt. Reyes. The reason for this b e h a v i o r is
not apparent.
It must also be noted that the helices showed g r e a t e r v a r i a t i o n in

corrosion rates. The ratio of standard d e v i a t i o n to average rates,
coefficient of variation, t e n d e d to be g r e a t e r for the helices as shown
by the values in Table 7. This w o u l d make the helix specimen less
desirable for s t a n d a r d i z a t i o n purposes. However, the fact that the
rates are higher suggests that it is p r o b a b l y unwise to use rates
o b t a i n e d from flat panels to estimate the p e r f o r m a n c e of wires and,
likewise, rates m e a s u r e d on wires would o v e r e s t i m a t e the rate o b s e r v e d
on flat panels.
TABLE 8--Reqresslon Analyses Results on Variation of

Corrosion Mass Loss with Exposure Time
Site Metal Specimen a n R2
KB A1 P 0.306 0.474 0.782

H 0.545 0.635 0.537
Cu P 2.50 0.650 0.965
H 4.16 0.450 0.736
Zn P 2.20 0.772 0.996
H 2.78 0.965 0.951
NK A1 P 0.314 0.720 ---

H 0.616 0.764 ---
Cu P 1.37 0.797 ---
H 1.83 0.911 ---
Zn P 2.29 0.641 ---
PR A1 P 0.220 0.508 0.968

H 1.50 1.097 0.984
Cu P 2.32 0.463 ---
H 5.47 0.360 ---
Zn P 1.87 1.060 ---
H 3.26 0.716 ---
Fe P 43.2 0.346 ---
H 149.0 0.715 ---
PCZ A1 P 0.583 0.755 0.996

H 1.343 0.667 0.837
Cu P 5.63 0.776 0.917
H 10.8 0.555 0.913
Zn P 20.0 0.890 -~-
Fe H 276.0 1.49 0.967
LA A1 P 0.585 0.868 0.960

H 1.73 0.683 0.999
CU P 1.39 0.272 ---
H 2.18 0.507 ---
Zn ? 0.577 1.42 ---
Fe P 21.4 0.257 ---
in cases where R 2 was omitted there were only two exposure periods.
a = coefficient in mass loss power function.
n = exponent in mass loss power function.
Effect of Environmental Variables on Corrosion Rates
The effect that environmental variables have on atmospheric

corrosion is an important issue. Unfortunately there were insufficient
data points at each site to carry out regression analyses that included
many variables. Therefore regression analyses were carried out using
similar results. The Point Reyes site was excluded because we did not
have good data for this site.
In order to determine what influence the environmental variables
have on the measured corrosion rates, a series of multiple linear
regression analyses were carried out starting with all five variables,
time of wetness, temperature, sodium chloride deposition, sulfur dioxide
deposition, and exposure time. The regression analysis program used
produced the following results: multiple regression coefficient R 2,
D E A N O N U.S. C O N T R I B U T I O N TO THE ISO CORRAG PROGRAM 69
TABLs 9--Results of Re~reesion Amal~sis Between

Eanel and Helix Corrosion Rates
AI Cu Zn Ee
Ave. P Rate 0.367 2.58 1.74 35.3

Ave. H Rate 1.140 4.74 2.79 94.2
R2 0.273 0.927 0.865 0.530
bo 2.74 1.923 1.56 2.73
Sb o 0.20 0.058 0.ii 0.27
DF 38 35 23 16
R2 = Correlation coefficient between P rate vs. R rate, all values significant at 99%
confidence level.
bo = Best fit coefflcient for regression line through origin.
Sb o = Standard error of b o.
DF = Degrees of freedom for regression.
Assumed relationship CRHeli x = b o CRpane I .
AI PANEL VS. HELIX

2.0
1.8
E
d. 1.6
tU
p- 1.4
< _ ~ /44. o o
n- 1.2
Z
o 1.0
(n
O .8
n-
n-
O .6
O R2 = 0 . 2 7 3
X
m .4
.J
LLI .2
'I-
0
0
i , ~2 i I
4
i 6
I i I I
8 10
PANEL CORROSION RATE ~m/yr
Fig. 2--Comparison of helix and panel corrosion rates for Aluminum
standard error for the regression, "F" value for the regression,
coefficients for all variables, standard deviations for each coefficient
and "t" values for each coefficient. At the conclusion of each
analysis, the values of the coefficients were examined and the variable
with a t value closest to zero was eliminated. The regression analysis
STEEL PANEL VS. HELIX
E
250
200
,/
W
150 -- 9 9
Z
O "
100
O R') = 0.S30
O
150
w
z / : : , , , I
50 100 150
P A N E L CORROSION RATE ~ . m / y r
Fig. 3--Comparison of helix and panel corrosion rates for Steel
COPPER PANEL VS. HELIX
10 _ R2 = 0.927 ' I v / / '

9
d.
8
W
I- 7 /
Z
6 .~r "
0 5
0 4
3
Q
0 2
x_ 1
,.J
W
0 I I I I I I
0 I 2 3 4 5 6
P A N E L CORROSION RATE ~ . m / y r
Fig.4--Comparison of helix and panel corrosion rates for Copper
was then repeated. The best regression was chosen as the analysis
containing only variables that contributed significantly to the variance
explained by the regression. The statistics for the best regression for
each metal-specimen combination are reported in Table i0.
ZINC PANEL VS. HELIX
4 J
3 9 "'/I I ;iI
X 9 R z = 0.866
"1-"
J I , I J
I 2 3
PANEL CORROSION RATE p.m/yr
Fig. 5--Comparison of h e l i x a n d p a n e l corrosion rates for Zinc
The results in Table I0 indicate that with the exception of the a l u m i n u m

data, the regressions y i e l d e d s u r p r i s i n g l y high squared correlation
coefficients, R 2. This indicates the e n v i r o n m e n t a l variables a c c o u n t e d
for most of the variation in c o r r o s i o n rates. It must be noted further
that b e c a u s e a variable was not i n c l u d e d in the best regression does not
mean it is not important, but rather that the degree of variation as
m e a s u r e d in this study did not p r o d u c e significant changes in the
m e a s u r e d corrosion rates. In the case of aluminum, it is apparent that
the set of environmental variables we have chosen to m e a s u r e accounts
for only a portion of the v a r i a b i l i t y of results. This suggests that
some other variables are c o n t r o l l i n g the corrosion of a l u m i n u m in the
atmosphere and especially in the west coast locations, Los Angeles and
Point Reyes. It may be that n i t r o g e n oxides or other related compounds
are a f f e c t i n g the aluminum c o r r o s i o n rates as suggested by Byrne and
Miller [~]. More work should be done on this issue.
The assumption in a linear r e g r e s s i o n analysis is that the

dependent variable, in this case c o r r o s i o n rate, can be p r e d i c t e d by a
linear combination of the i n d e p e n d e n t variables. This can be e x p r e s s e d
as:
y = a + b!x I + b2x 2 + b3x3, etc.
where y is the corrosion rate and x's represent the environmental

variables. The b values are the c c e f f i c i e n t s chosen to minimize the
variance of the data set. It is s u r p r i s i n g that in many cases the best
fit coefficients are negative. For example, the NaCI deposition
coefficient was negative for the a l u m i n u m panels, and time of wetness
TABLE 1 0 - - R e ~ e s e i o n Analyses of Corrosion Rates versus

Environmental Exposure Data
AI Cu Zn Fe
Coefficient Panel Helix Panel Helix Panel Helix Panel Helix
Temp Coef. -. . . . . . . . . . . 2.32 --- 84.4 ---

Std. Error . . . . . . . . . . . . 0.67 --- 19.3 ---
TOW Coef. 0.O140 O.0119 . . . . . . . 0.462 .... 15.64 ---

Std. Error 0.0037 0.0032 . . . . . . 0.158 --- 4.66 ---
SO2 Coef. -. . . . . . . . . . . . . . . . . . . . . . .
Std. Error . . . . . . . . . . . . . . . . . . . . . . . .
NaCI Coef. -0.00370 --- 0.00612 0.01327 0.0192 0.0102 --- 0.422
Std. Error 0.000317 --- 0.00038 0.00089 0.0054 O.0010 --- 0.031
Exp. Time Coef. --- -0.00048 -0.00080 -0.00278 . . . . . . . . . 0.500

StJ. Error --- 0.00020 0.00032 0.00074 . . . . . . . . . 0.099
Intercept -0.1073 0.736 1.747 3.39 -18.46 1.92 -694.6 -170.0
R2 0.396 0.428 0.908 0.897 0.881 0.852 0.837 0,946
F 9.20 10.5 132.9 118.2 56.6 97.9 28.2 114
SEE 0.150 0.402 0.554 1.298 2.35 0.606 40.7 34.4
DF 28 2~ 27 27 23 i~ l! 13
Temp A v e r a g e m o n t h l y temperature, ~
TOW C a l c u l a t e d m o n t h l y average time of wetness, %.
SO 2 = Sulfur d i o x i d e capture monthly average, mg/m 2 day.
NaCI S o d i u m c h l o r i d e capture on wet candle, monthly average, mg/m 2 day.
Exp. Time = Days of exposure.
R2 = Square m u l t i p l e regression correlation coefficient.
F = V a r i a n c e ratio of v a r i a n c e explained by regression to mean resident
variations.
SEE = Standard error cf regression.
DF = Degrees of f r e e d o m associated with r e s i d u a l .
coefficient was negative for both zinc and steel panels. In every case,
dropping the variable with the negative coefficient caused a significant
increase in the residual sum of squares. However, it is unlikely that
these effects are real, i.e., reducing the variable in question will
cause an increase in corrosion rate. It is more likely that strong
correlations among the environmental variables produces this result in
the regression analysis.
It must also be observed that the linear regression analysis is
not the proper form for a kinetic expression. It would be b e t t e r to use

a log c o n v e r s i o n on the variables. However, c o n s i d e r i n g the l i m i t e d
scope of the data at hand, it did not a p p e a r worthwhile to pursue a more
c o m p l i c a t e d relationship. When the m i s s i n g data is obtained and some
better e n v i r o n m e n t a l data is available, p e r h a p s a more rigorous approach
to regression a n a l y s i s could be undertaken. It must also be n o t e d that,
although in most cases R 2 values e x c e e d i n g 0.8 were obtained, a
comparison b e t w e e n the mean square residual and the replication error
showed that there was a significant r e m a i n i n g error in every case. This
was to be expected.
C o m p a r i s o n W i t h E a r l i e r Tests
It is of interest to compare the c u r r e n t results with results of

e a r l i e r studies. Unfortunately, there are no data on helices so that
comparisons are not possible in this case. In the case of the flat
panels, there are several studies that are of interest. The A S T M 1957
B3 study is p r o b a b l y the most c o m p r e h e n s i v e [i0]. It did include
similar aluminum, zinc, a n d copper alloys, and was run at Point Reyes,
and Newark. The Kure Beach exposure in this study was at the 25 m lot,
and so it is not comparable. The a l u m i n u m panels were e x p o s e d for 1 and
2 years, but the copper and zinc were o n l y two years.
A c o m p a r i s o n of the rates for all four alloys is given in Table II

for eastern m a r i n e sites. In the case of a l u m i n u m and copper, Daytona
Beach results are also of interest, a l t h o u g h this site is somewhat more
severe than the KB site. In any event, it is apparent from the data in
Table ii that the C O R R A G panel results are very similar to earlier
results at KB for all metals.
Table 12 provides a comparison for the N e w a r k - K e a r n y Site. Again,

for copper and a l u m i n u m alloys p u b l i s h e d data for Brooklyn and New Haven
are comparable, although the Brooklyn Site was consistently more severe
than NK. It is of interest to compare the variation in corrosion rates
inasmuch as e n v i r o n m e n t a l cleanup has c h a n g e d the environment in NK
area. The a l u m i n u m results are s i g n i f i c a n t l y lower than earlier tests.
The copper results are less convincing, although the CORRAG results
appear to be s i g n i f i c a n t l y lower than the 1957 rates for copper. The
zinc and steel C O R R A G results are also s i g n i f i c a n t l y lower than earlier
test results. These data appear to c o n f i r m that the NK site has become
less corrosive to all of these alloys and seems to indicate that the
c l a s s i f i c a t i o n c a t e g o r y of i n d u s t r i a l - u r b a n in the USA may no longer be
a more corrosive atmosphere than rural.
Table 13 shows comparisons for the w e s t e r n marine sites. None of

the alloys showed consistent deviations f r o m earlier results suggesting
that the PR site retains a relatively u n c h a n g e d corrosivity.
Comparison With C l a s s i f i c a t i o n Cateaories
The e n v i r o n m e n t a l data for the C O R R A G exposures were used to

obtain T (Time of wetness), P (S02), and S (Chloride) classes for each
metal. These classes were then used to obtain corrosion class
TABLE ll--Comparlson of CORRAG-KB Results to

Other Eastern Marine Results
All Rates in ~m/year
A1
Datona Beach
No. of years CORRAG 1987 1963 (II)
I 0.29 0.50
2 0.17 0.37
3 --- 0.25
4 0.16 ---
5 --- 0.31
Cu
Datona Beach
No. of years CORRAG 1987 KB 1958 (12) 1964 (13)
i 2.85 ---
2 1.85 1.8 2.57
4 1.6! --- 2.24
7 --- 1.7
Zn
KB 1960
No. of years CORKAG 1987 (14)
1 2.01 2.17
2 1.80 !.8-
4 !.63 1.52
Fe
KB 1970
No. of years COR~G !987 (15)
1 37 38
2 33 ---
Year noted refers to initiation of exposure.

Numbers !n parentheses are reference numbers.
estimates. These estimates were then compared to the corrosion classes

obtained by direct measurement. The corrosion class information is
presented in Table 14. It was assumed that the chloride deposition at
the PR site would cause it to be in the $2 class based on its proximity
to the Pacifc Ocean. The SFO temperature and humidity data was used to
determine the t i m e of wetness c l a s s as T4. These data probably
underestimate the time of wetness at PR, but not to the degree that a T5
class would be appropriate. There were no chloride deposition data for
the NK site. However, it is u n l i k e l y that this site has any significant
chloride deposition because it is remote from surf so the assumption of
a SO class is w a r r a n t e d .
TABLE 12-~ of C O R R A G - N K Results to

Other Eastern Industrial Results
All Rates in.~m/year
A1
New Haven Brooklyn NK
No. of years C O R R A G 1987 1963 (ll) 1963 (II) 1957 (16)
1 0.28 0.70 1,4 0.50

2 0.22 0.68 --- 0.35
3 . . . . . . 1.8 ---
4 . . . . . . 0.75 ---
5 --- 0.36 0.8 ---
Cu
New Haven Brooklyn NK
No. of years CORRAG 1987 1964 (13) 1964 (13) 1957 (16)
1 1.39 . . . . . . . . .
2 1.10 1.06 1.94 1.88
4 --- 1.06 1.86 ---
7 . . . . . . . . . 1.90
Zn
NK NYC
No. of years CORKAG 1987 1957 (16) 1944 (17)
1 1,96 --- 5.8

2 1,52 3.48 ---
Fe
NK NK
No, of years COR~AG 1987 1970 (18) 1935 (19)
i 26 50 57
2 --- 32 38,5
4 ~-- 20.2 ---
Year refers to initiation cf exposure.

Numbers in parentheses are re~e=ence numbers.
The comparison of corrosion class estimates to the measured values

is of interest as a test of the ISO 9223 and 9224 methods. It is
apparent that the estimated corrosion classes are usually within one of
the measured classes. At Kure Beach the estimated aluminum corrosion
classes were greater than the panel measurements in two cases. For
copper the estimated classes were generally lower than the measured
classes except at longer exposure times. For zinc the estimated classes
were greater than the measured panel class and occasionally lower than
the helix class. For steel the estimated classes were greater than the
measured panel classes and occasionally lower than the helix class.
TABLs 13-Comparison of CoRRAG-PR Results to

Other Western Marine Results
All Rates In]~m/year
A1
PR-B3
No. of years CORKAG 1987 1958 {161
1 0.28 0.25
2 0.22 0.19
Cu
PR-B3
No. of years CORRAG 1987 1958 (16)
1 2.42 ---
2 1.60 1.66
7 --- 1.70
Zn
PR-B3 La Joila
No. of years CORRAG 1987 1958 (!6} 1944 (17)
1 1.73 --- 1.60

2 1.95 3.48 ---
Fe
PR PR
No. of years CORRAG 1987 1956 (20) !952 (21)
1 40 36 54
2 28 31 47
4 --- 30 39
Year refers to initiation of exposure.

Numbers in parentheses are reference nUnlbers.
At NK the measured classes were greater than the estimated classes

for about one-half of the results, and the helices showed this tendency
most often.
At PR the panels generally agreed with the estimated classes with

some cases of being below. On the other hand, the helices were often
above the estimated class. This was especially true for steel and
copper.
At PCZ, the only material which did not agree with the estimated
class was aluminum. The aluminum panels showed significantly lower
rates than predicted. The aluminum helices also tended to be lower than
'FABLE 14--Co~arison of corrosion classes from environmental data and mass loss measurements according to ISO-9224
Site/
Exposure AI Cu Zn Fe
Env C P-C H-C Env C P-C H-C Env C P-C H-C Env C P-C H-C
KB ]1 3-4 3 3 4 4 5 4 4 4 4 3 4
KB 12 4 3 3 4 5 5 4 3 4 4 3 4
KB 13 3-4 3 4 4 4 5 4 4 4 4 3 4 m
>
KB ]4 3-4 3 4 4 4 5 4 3 4 4 3 5 z
KB 15 4 3 4 4 5 5 4 3 5 4 3 5
0
KB 16 4 3 4 4 5 5 4 3 4 4 z
KB 21 3-4 3 4 4 3 5 4 3 4 4
c
KB 4] 4 3 4 4 3 3 4 3 4 4
Go
NK ii 3 3 3 3 3 4 3 4 4 2-3 3 3 o
NK 12 3 3 3 3 4 4 3 3 3 2-3 2 3 0
NK 13 3 3 4 3 3 4 3 3 4 2-3 3 3 z
NK 14 3 4 4 3 3 3 3 3 4 2-3
-I
~o
NK 15 3 4 4 3 3 3 3 3 4 2-3 - -
NK 16 3 3 3 3 4 4 3 3 3 2-3 - - c
NK 21 3 4 4 3 3 3 3 3 2-3 - - -I
PR* ii
5
3-4 3 4 4 4 5 4 3 4 4 3 5 z
PR* 12 3-4 3 4 4 4 5 4 3 4 4 3 5 .-t
PR* 13 3-4 3 4 4 4 5 4 4 4 4 2 5 0
PR* 14 3-4 2 4 4 4 5 4 3 4 4 3 5
I'R ~ ]5 3-4 2 4 4 4 5 4 3 4 4 3 5 -1-
PR* 16 3-4 3 4 4 4 4 - m
PR* 21 3-4 3 5 4 4 5 4 3 4 4 4 5
PR* 4] 3-4 3 5 4 4 4 - 0
0
0
* Te[llp~ J;a t tlf e kind h u m i d i t y data taken from SFOr P class assLJmed t o be Ot S class assumed to be 2.
"4
"4
"4
(X)
>
TABLE 14--~omparison of corrosion classes from environmental data and mass loss measurements according to ISO-9224 0
(Continued) (D
-o
-r
m
Site/
Exposure A1 Cu Zn Fe
Env C P-C H-C Env C P-C H-C Env C P-C H-C Env C P-C H-C
O
O
PCZ Xl - - - 5 4 5
PCZ ii 5 3 4 5 5 5 5 5 5 5 5 5 O
PCZ 12 5 3 5 5 5 5 5 5 5 5
09
PCZ 13 5 3 4 5 5 5 5 5 5 5 O
PCZ 14 5 3 4 5 5 5 5 5 5 5 z
PCZ 15 5 3 5 5 5 5 5 5
PCZ 16 5 3 4 5 5 5 5 5
PCZ 21 5 4 5 5 5 5 5 5 5 5
PCZ 41 5 4 4 5 5 5 5 5
LA ii 3-4 3 4 3 4 4 3 3 3 3 2 2
LA 12 3-4 3 4 3 3 4 3 3 3 3 2 2
LA 13 3-4 4 4 3 3 4 3 3 - 3 2 -
IA 14 3-4 4 4 3 4 4 3 3 - 3 3 -
I~ 15 3-4 3 4 3 3 4 3 3 3 3
LA 16 3-4 3 4 3 3 4 3 3 3 3
LA 21 3-4 4 5 3 3 3 3 3 - 3 4 -
LA 41 3-4 4 5 3 3 - 3
Env C = Corrosion class estimate from environmental data.

P-C = Corrosion class determined from m a s s loss d a t a o n p a n e l s .
H-C = Corrosion class determined from mass loss data on helices.
predicted, but not by two units as was e x p e r i e n c e d with the a l u m i n u m

panels.
At LA there was g o o d a g r e e m e n t b e t w e e n the e s t i m a t e d and m e a s u r e d

classes for a l u m i n u m specimens except for the 2 and 4 year helix
results. The copper h e l i x m e a s u r e d classes e x c e e d e d the e s t i m a t e s in
most cases, while o n l y o c c a s i o n a l l y in the case of panels. On the other
hand, the steel s p e c i m e n m e a s u r e d classes tended to be lower than the
estimates except after 2 years.
Overall, there was agreement in 58% of the cases studied. In 22%

of the cases the e s t i m a t e d c o r r o s i o n class was lower than the m e a s u r e d
class, and in 20% of the cases it was higher. B a s e d on these results,
it seems likely that some a d j u s t m e n t s will be n e c e s s a r y in the setting
of the corrosion rate ranges to obtain better agreement in ISO 9224.
The worldwide d a t a b a s e will p r o v i d e a g o o d basis for this activity.
CONCLUSIONS
The c o r r o s i o n rates m e a s u r e d in the U S A - I S O C O R R A G exposure

p r o g r a m were g e n e r a l l y p r e d i c t a b l e on the basis of the m e a s u r e d
e n v i r o n m e n t a l variables. It is however d e s i r a b l e to use
consistent m e t h o d s to m e a s u r e environmental variables. The
a l u m i n u m specimens s h o w e d less dependance on m e a s u r e d
e n v i r o n m e n t a l v a r i a b l e s than the other metals.
The helix s p e c i m e n c o r r o s i o n rates were s i g n i f i c a n t l y higher than

flat panels with rates about twice that of flat panels. The
v a r i a b i l i t y in c o r r o s i o n rates of replicate helix specimens was
also s i g n i f i c a n t l y larger in most cases than that of flat panels.
Among the five sites i n c l u d e d in this study, the Fort Sherman

coastal site was the most corrosive to steel, copper, and zinc
specimens. Aluminum specimens corroded at similar rates at both
west coast sites and at the Fort Sherman Site.
The N e w a r k - K e a r n y Site is s i g n i f i c a n t l y less corrosive to all four

metals than p r e v i o u s tests have shown. The other A S T M sites have
not c h a n g e d in corrosivity.
The ISO c l a s s i f i c a t i o n s y s t e m based on e n v i r o n m e n t a l variables

b r a c k e t e d the m e a s u r e d rates in 58% of the exposures. In about
one-half of the remainder, the m e a s u r e d rates were higher than
predicted. Some adjustments in the c l a s s i f i c a t i o n system would be
desirable to achieve a higher degree of accuracy in p r e d i c t i n g
rates from e n v i r o n m e n t a l data.
The standard d e v i a t i o n in the calculated c o r r o s i o n rates was

weakly c o r r e l a t e d to the magnitude of the c o r r o s i o n rate for all
alloys.
The corrosion rates for most of the materials in this study

d e c r e a s e d with exposure time as is generally noted in atmospheric
corrosion studies.
ACKNOWLEDGMENTS
The author acknowledges with grateful appreciation the work of the

following individuals in carrying out the exposures and obtaining the
results for this program: Earl Baker and Stan Pikul of the La Que
Center for Corrosion Technology, Inc. for their work at Kure Beach; T.J.
Summerson, G. Busiere, and Ken Haase at Kaiser Aluminum and Chemicals
Corp. for their work in covering the Point Reyes Site and handling the
evaluation of the aluminum specimens; Victor Chaker of the Port
Authority of New York and New Jersey for his work at the Newark-Kearny
Site, George Downs III of the United States Army for handling the Fort
Sherman Site exposures; Professor Florian Mansfeld and his co-workers at
the Los Angeles USC Site; Delia Cuellar of CC Technologies for cleaning
and weighing the steel specimens; Murray Heine and Jim Brock of Olin
Corporation for cleaning and weighing of the copper specimens; William
Watkins, Lowell Frederick, and Barry Crownover of Air Products and
Chemicals, Inc. for the cleaning and weighing of the zinc specimens.
In addition, the author would like to acknowledge contributions of

the La Que Center for Corrosion Technology, Inc., Kaiser Aluminum and
Chemical Co., The Port Authority of New York and New Jersey, The United
States Army, Olin Corporation, CC Technology, Platt Bros. and Co., and
Air Products and Chemicals, Inc. All of these organizations have
provided support of various types, and Air Products and Chemicals, Inc.
has given permission to publish this paper.
REFERENCES
[i] Dean, S.W., "Corrosion Testing of Metals Under Natural Atmospheric

Conditions", Corrosidn Testina and Evaluation: Silver Anniversarv
Volume. ASTM STP 1000, R. Baboian and S.W. Dean, Eds., American
Society for Testing and Materials, Philadelphia, 1990, pp. 163-
176.
[2] Dean, S.W., "ISO CORRAG Collaborative Atmospheric Exposure

Program: A Preliminary Report", Dearadation of Metals in the
AtmosDhere. ASTM STP 965, S.W. Dean and T.S. Lee, Eds., American
Society for Testing and Materials, Philadelphia, 1988, pp. 385-
431.
[3] Dean, S.W., "ISO CORRAG Collaborative Exposure Program, First

Exposure Report on the United States Program", Air Products and
Chemicals, Inc., January 1989.
[4] Dean, S.W., "ISO CORRAG Collaborative Exposure Program, Second

Chemicals, Inc., December 1990.
[5] Dean, S.W., "ISO CORRAG Collaborative Exposure Program, Third

Chemicals, Inc., February 1992.
[~] Dean, S.W., "ISO CORRAG Collaborative Exposure Program, Fourth

Exposure Report on United States Program", Air Products and
Chemicals, Inc., December 1992.
[3_i ASTM G16-93 "Standard Guide for Applying Statistics to Analysis of

Corrosion Data", 1994 Annual Book of ASTM Standards~ VOI. 03.02,
American Society for Testing and Materials, Philadelphia, 1994,
pp. 78-91.
[~] ASTM G91-92 "Standard Practice for Monitoring Atmospheric S02

using the Sulfation Plate Technique", 1992 Annual Book of ASTM
~ , Vol. 03.02, American Society for Testing and Materials,
Philadelphia, 1992, pp. 374-378.
[~] Byrne, S.C. and Miller, A.C., "Effect of Atmospheric Pollutant

Gases on the Formation of Corrosive Condensate on Aluminum",
Atmospheric Corrosion of Metals, ASTM STP 767, S.W. Dean, Jr. and
E.C. Rhea, Eds., American Society for Testing and Materials, 1982,
pp. 359-373.
[i0] Allot, W.H., "ASTM Atmospheric Corrosion Testing: 1906 to 1976",

Atmospheric Factors Affecting the Corrosion of EnGineerinG
Materials". ASTM STP 646, S.K. Coburn, Ed., American Society for
Testing and Materials; 1978, pp. 129-151.
[ii] Castillo, A.P., "Unstressed Atmospheric Corrosion of Wrought

Aluminum Alloys", Olin Metals Research Laboratories, New Haven,
Ct., Confidential Report submitted to consolidated Aluminum
Corporation, 1975.
[12] Costas, L.P., "Atmospheric Corrosion of Copper Alloys Exposed for

15 to 20 Years", Atmospheric Corrosion of Metals. ASTM STP 767,
S.W. Dean, Jr. and E.C. Rhea, Eds., American Society for Testing
and Materials, Philadelphia, 1982, pp. 106-115.
[13] Herman, R.S. and Castillo, A.P., "Short-Term Atmospheric Corrosion

of Various Copper-Base Alloys - Two and Four Year Results",
Corrosion in Natural Environments. ASTM STP 558, American Society
for Testing and Materials, 1974, pp. 82-96.
[14] Legault, R.A. and Pearson, V.P., "Kinetics of the Atmospheric

Corrosion of Galvanized Steel", Atmospheric Factors Affecting the
Corrosion of EnGineerinG Metals. ASTM STP 646, S.K. Coburn, Ed.
American Society for Testing and Materials, Philadelphia, 1978,
pp. 83-96.
"[15] Townsend, H.E. and Zoccola, J.C., "Eight-Year Atmospheric

Corrosion Performance of Weathering Steel in Industrial, Rural,
and Marine Environments", Atmospheric Corrosion Qf Metals. ASTM
~TP 767, S.W. Dean, Jr., and E.C. Rhea, Eds., American Society for
Testing and Materials, Philadelphia, 1982, pp. 45-59.
[16] "Atmospheric Exposure of Nonferrous Metals and Alloys",

Proceedings of the American Society for Testing and Materials,
Vol. 59, 1959, Vol. 61, 1961, Vol. 62, 1962, and Vol. 66, 1966,
American Society for Testing and Materials, Philadelphia, pp. 1-
33.
[17] Anderson, E.A., and Reinhard, C.E., "Zinc", The Corrosion

Handbook, H.H. Uhlig, Ed., John Wiley & Sons, New York, 1948, pp.
331-347.
[18] Mannweiler, G.B., "Corrosion Test Results on Fifteen Ferrous

Metals After Seven Years Atmospheric Exposure",Metal Corrosion in
the AtmosDhereo ASTM STP 435~ American Society for Testing and
Materials, Philadelphia, 1968, pp. 211-222.
[19] Lorig, C.H. and Krause, D.E., "Phosphorous as an Alloying Element

in Low Carbon, Low Allow Steels III", Metals and Alloys, 7, 69
(1936).
[20] Thomas, H.E. and Alderson, H.N., "Corrosion Rates of Mild Steel in
Coastal Industrial and Inland Areas of Northern California", Metal
Corrosion in the AtmosPhere. ASTM STP 435, American Society for
Testing and Materials, Philadelphia, 1968, pp. 83-94.
[2,_1] Larrabee, C.P., and Ellis, O.B., Corrosiveness of Various Test

Sites as Measured by Specimens of Steel and Zinc", Proceedinqs,
American Society for Testing and Materials, Vol. 59, 1959, pp.
183-201.
Weathering Steels and Coated Steels
Herbert E. T o w n s e n d 1
EFFECTS OF SILICON AND NICKEL CONTENTS ON THE ATMOSPHERIC

CORROSION RESISTANCE OF ASTM A588 WEATHERING STEEL
REFERENCE: Townsend, H. E., "Effects of S i l i c o n and Nickel Contents

on the A t m o s p h e r i c C o r r o s i o n R e s i s t a n c e of A S T M A 5 0 0 W e a t h e r i n g Steel,"
Atmospheric Corrosion, A S T M STP 1239, W. W. Kirk and Herbert H. Lawson,
Eds., A m e r i c a n Society for Testing and Materials, Philadelphia, 1995.
ABSTRACT: Nine A S T M A588 low-alloy w e a t h e r i n g steels r e p r e s e n t i n g

three levels of silicon and nickel were p r e p a r e d by induction m e l t i n g
and hot rolling in the laboratory. Corrosion tests w e r e c o n d u c t e d for
eleven years at four atmospheric sites w h i c h included industrial, rural,
and m a r i n e locations. The results were fitted to kinetic e q u a t i o n s of
the form, C= At B, where C is the corrosion loss, t is time, a n d A a n d B
are constants in a c c o r d w i t h M e t h o d 1 of A S T M GI01 "Standard G u i d e for
E s t i m a t i n g the Atmospheric Corrosion Resistance of L o w Alloy Steels."
Both silicon and nickel are shown to have a b e n e f i c i a l effect on the
c o r r o s i o n resistance of A588 w e a t h e r i n g steel. For silicon, on average,
each 0.1% increase results in a 4% decrease in c o r r o s i o n loss after ii
years, a 6% decrease in corrosion rate after Ii years, a n d a 12%
increase in the time to reach a 10-mil(250~m) penetration. For nickel,
each 0.1% increase results in a 4% decrease in c o r r o s i o n loss after ii
years, a 7% decrease in corrosion rate after ii years, a n d a 15%
increase in the time to reach a 10-mil(250~m) penetration. By w a y of
comparison, M e t h o d 2 of A S T M GI01 predicts a 2% increase in the
c o r r o s i o n index for each 0.1% increase in silicon or nickel.
KEYWORDS: corrosion, weathering steel, silicon, nickel, steel
W e a t h e r i n g steels contain small amounts of elements such as

nickel, silicon, copper, chromium, and phosphorus. These elements
p r o m o t e the formation of adherent and p r o t e c t i v e rust layers w h i c h
increase atmospheric corrosion resistance. The p e r f o r m a n c e of
w e a t h e r i n g steels has been d o c u m e n t e d in long-term tests in a v a r i e t y of
o u t d o o r environments [1,2]. W i t h adherence to p r o p e r g u i d e l i n e s [3],
this m a t e r i a l is u s e d successfully without p a i n t i n g for a p p l i c a t i o n s
such as bridges, highway guardrails, and u t i l i t y towers.
In 1977-9, the composition limits for silicon and nickel in the
iSenior Research Consultant, Homer Research Laboratories,

B e t h l e h e m Steel Corporation, Bethlehem, PA 18016.
85
Copyrightm1995by
Downloaded/printed byA S T M International www.astm.org
A S T M A588 s p e c i f i c a t i o n for w e a t h e r i n g steels[4] were altered, see Table

I.
TABLE I--ASTM composition ranues
SpecineNon C Ih P S Sl Ni Q' C:u V
AilllJ 0.20 roll 0 . T i * 1.,Ill 0.04 mlz 0.li mill ILIll. 0.10 OJla rues 0.AO - 0 . 7 0 0.20 9 O.40 0.01 - 0 . 1 0
A?OSE40w
AUIill 0.20 rnllz 0.75.1.2S 0.04 mix 0.WI m 0.1S - ~ 0.110 m i l l 0 . 4 0 o 0.71) 0.20 - G.40 0 . 0 t 9 O.10
IITIor I o 1 9 7 9
s 0.19 mwx 0 . 8 0 - 1.2S 004 ms 0.0S imli O.lO - 0.ill 0,40 1 0 . 4 0 - 0.11iS 0.~i - 0.40 0.02 9 0.10
s
ASIIJL 0.10-0.19 0 . 9 0 . 1 . "JIc 0.04 nWll 0.1M IIIIIII 0.1S - 0,10 L 4 0 - 0.Wi 0.,~ - 0. an 0.0| 9 0.10
Plkl/IO 1 ~
These c h a n g e s included:
A588. Grade A -- an increase in the silicon range from 0 . 1 5 - 0 . 3 0

to 0.30-0.65 w/o, and a change in nickel from an u n s p e c i f i e d level to
0.40 w / o maximum.
A588. G r a d e B -- a change in the silicon range from 0 . 1 5 - 0 . 3 0 to

0.15-0.50 w/o. The nickel level of this grade r e m a i n e d u n c h a n g e d at 0.50
w / o maximum.
This w o r k was initiated in order to d e t e r m i n e the e f f e c t s of

changes in the a m o u n t s of these elements on the a t m o s p h e r i c c o r r o s i o n
r e s i s t a n c e of A588 w e a t h e r i n g steel. A l t h o u g h p r e v i o u s studies [5,6]
have shown that s i l i c o n and nickel are g e n e r a l l y b e n e f i c i a l to the
a t m o s p h e r i c c o r r o s i o n resistance of low alloy steels, none of the
e a r l i e r w o r k was p e r f o r m e d on steels w i t h i n the s p e c i f i c c o m p o s i t i o n
ranges of A 5 8 8 A and A588B.
EXPERIMENTAL METHODS
Materials
Steel compositions, Table 2, include cormnercially p r o d u c e d copper-

b e a r i n g steel, p r e - 1 9 7 9 A588 and A242 w e a t h e r i n g steels, a n d n i n e
l a b o r a t o r y - p r e p a r e d , induction-melted, A 5 8 8 - 1 i k e w e a t h e r i n g steels w i t h
v a r y i n g levels of silicon and nickel.
The steels w e r e hot rolled to 2.5-nml t h i c k n e s s and s h e a r e d into

100- x 1 5 0 - m m test panels. The panels w e r e shot b l a s t e d to r e m o v e hot-
r o l l i n g scale, s t a m p e d w i t h i d e n t i f i c a t i o n markings, degreased, a n d
w e i g h e d p r i o r to exposure.
Atmospheric Corrosion Te~8
Test panels w e r e exposed at three test locations in an a c i d - r a i n
TOWNSEND ON ASTM A588 WEATHERING STEEL 87
region where precipitation has an average pH of about 4.3 [7]:
TABLE 2--~omDositlons of Test Materials
Steel Grade Composition, w/o
C Mn P S Si Ni Cr Cu
Cu-Bearing 0.04 0.36 0.006 0.024 ,0.01 0.01 0.01 0.26
A588 0.14 1.07 0.011 0.022 0.28 0.32 0.55 0.28
A242 0.09 0.65 0.110 0.032 0.29 0.66 0.52 0.27
A588, low Si, 0.14 0.98 0.008 0.025 0.15 0.01 0.53 0.37
variable Ni 0.18 1.01 0.009 0.014 0.15 0.16 0.56 0.34
0.14 0.97 0.012 0.016 0.12 0.31 0.59 0.35
A588, med Si, 0.18 1.00 0.011 0.020 0.49 0.02 0.55 0.32
variable Ni 0.13 1.01 0.010 0.017 0.47 0.17 0.57 0.34
0.18 1.00 0.010 0.017 0.49 0.38 0.58 0.33
A588, high Si, 0.12 1.06 0.006 0.013 0.77 0.01 0.59 0.33
variable Ni 0.18 0.97 0.008 0.020 0.73 0.16 0.51 0.35
0.14 1.00 0.009 0.018 0.75 0.31 0.57 0.35
R o o f t o p site. B e t h l e h e m . Pa. -- T h i s s i t e is l o c a t e d o n t h e r o o f
o f a n o f f i c e b u i l d i n g in d o w n t o w n B e t h l e h e m , a d j a c e n t t o t h e b l a s t
f u r n a c e s o f a n i n t e g r a t e d s t e e l p l a n t . T h i s is c o n s i d e r e d to be an
i n d u s t r i a l e n v i r o n m e n t of m o d e r a t e s e v e r i t y .
Mountaintop site. B e t h l e h e m . ~ . -- T h i s s i t e is s i t u a t e d o n t h e
south slope of South Mountain overlooking the steel plant's coke works
w h i c h a r e a b o u t 3 k m away. T h i s l o c a t i o n is a l s o c o n s i d e r e d to be a
moderate industrial environment.
R u r a l site. S a v l o r s b u r a . Pa. -- This site is located in t h e

Pocono Mountains, a b o u t 50 k m n o r t h o f Bethlehem.
These materials were also exposed at a m a r i n e site at the LaQue Center

for Corrosion Technology:
M a r i n e site. K u r e Beach. N . C . -- Located 250 meters from the

A t l a n t i c O c e a n , t h i s s i t e is a m o d e r a t e m a r i n e site.
P a n e l s w e r e e x p o s e d at 30 d e g r e e s f r o m t h e h o r i z o n t a l and faced
south. T e s t s w e r e s t a r t e d in t h e S p r i n g o f 1979, a n d d u p l i c a t e p a n e l s
w e r e r e m o v e d f r o m t e s t at a p p r o x i m a t e i n t e r v a l s o f 3, 6, a n d ii y e a r s .
(Actual exposure times v a r i e d a c c o r d i n g to site, and are g i v e n by the

p o i n t s p l o t t e d on Figures 1 to 4.) After exposure, rust was r e m o v e d
from the test panels by the sodium h y d r i d e m e t h o d in the case of the 3-
and 6-year samples. Because the equipment for the s o d i u m h y d r i d e m e t h o d
is no longer r e a d i l y available, the ll-year specimens w e r e c l e a n e d by
the i n h i b i t e d h y d r o c h l o r i c acid m e t h o d (ASTM GI, D e s i g n a t i o n C.3.5).
The p a n e l s were r e w e i g h e d after rust removal to d e t e r m i n e m a s s losses,
and a v e r a g e o n e - s i d e thickness losses were c a l c u l a t e d a c c o r d i n g to A S T M
G1 [8].
Corrosion of R e f e r e n c e Steels
The c o r r o s i o n p e r f o r m a n c e of the copper-bearing, p r e - 1 9 7 9 A588B

and A242 w e a t h e r i n g steels at the four o u t d o o r test sites is shown in
F i g u r e I. C o r r o s i v i t y of the test sites increases in the o r d e r (least to
most):
Rooftop (industrial) < Mountaintop (industrial) < Rural < Marine.
These results are in a g r e e m e n t w i t h those of p r e v i o u s l y r e p o r t e d studies

at the mountaintop, rural and m a r i n e sites [i]. The g r e a t e r c o r r o s i v i t y
at the m a r i n e site is a t t r i b u t e d to salt exposure. The lesser
c o r r o s i v i t y at the industrial sites compared to the rural l o c a t i o n may
be the result of h i g h e r levels of dust w h i c h H o r t o n [9] found b e c o m e
e n t r a p p e d in rust layers, and p o s s i b l y i n c r e a s i n g thickness, d e c r e a s i n g
permeability, and p r o v i d i n g m e c h a n i c a l r e i n f o r c e m e n t to s t r e n g t h e n the
rust layer. The h i g h e r c o r r o s i v i t y of the m o u n t a i n t o p site c o m p a r e d to
the r o o f t o p site p r o b a b l y results from a g r e a t e r time of w e t n e s s for the
m o u n t a i n t o p specimens w h i c h w e r e e x p o s e d over b a r e ground.
At all sites, c o r r o s i o n resistance of these m a t e r i a l s can be

ranked in the order (best to worst):
A242 > A588B > C o p p e r - b e a r i n g .
These results are q u a l i t a t i v e l y in a g r e e m e n t w i t h p r e v i o u s l y r e p o r t e d

test results for similar m a t e r i a l s at three of these sites [i], and
they can be readily e x p l a i n e d in terms of the d i f f e r e n c e s in a l l o y
content.
In order to q u a n t i f y d i f f e r e n c e s b e t w e e n these materials,

l o g a r i t h m i c plots of the results, also shown in Figure i, w e r e p r e p a r e d
and lines were fitted to the data as set forth in A S T M GI01 (Method I)
[I0]. This a p p r o a c h assumes a linear r e l a t i o n s h i p of the form:
log C = log A + B log t (1)
w h e r e C is the c o r r o s i o n loss, A and B are constants, and t is time of

exposure. As p r e v i o u s l y d i s c u s s e d [ii], this e q u a t i o n can be r e w r i t t e n
in e x p o n e n t i a l form as:
C = At B (2)
1 F I I I 9 , . , . , "~
10
MOUNTAINTOPSITE
4 MOUNTAINTOP SITE
! !
~o
Gu~elmng
..0 " ...I
W ~ .. AS88
~ F I A588~
O" . ..... "I 9 A242
A242
r'l..."
1 J1
-4
I, I O
o_ * i . . . . . I
0 2 4 w 8 10 2 3 10 z
09
EXPOSURET1ME.I.wz EXPOSURE T~E. ~mm m
z
o
5 i i ' i i i . . . . . ! 0
lo z
co
-4
4t ~SrrE ! R O O F T O P SffE
Ol
O0
4D
- _ O - "C--0ufing
m
-- - -- A588 "''41
0-- ~176 t -~ ..a -4
-r
9 ......... ..--" A242 m
1 A242 ~o
J1 n. ..'''"
z
0- . . . . . I. I i , t J ! oo
-4
0 2 4 6 8 10 2 m
~ E TIME.
3 IO m
EXPOSURE11ME.ylmrs r-
FIG. 1--Corrosion performance of copper-bearing, A588B, and A242 CO

weathering steels. Left-linear plots. Right-logarithmic plots. ~O
co
S ......... I ! ! t I
0
10 ''-- " . . . . I
RURAL. SITE.
t
O
C.-bmsnng
"u
~ o ASBS """1 T
Ill
iG'.. - --" IlL - AZ42 .... Q
i AS,,
ft...-'' 0
1 0
0
0_-2 ~ , I ' ~ ' i i i i i h | O0
0 2 4 8 8 10 12 3 10
8
z
E X P O ~ lg~-. m EXPOSURETIME. ymul
10
4
M A R I N E SITE c,-u,,n,g
.~
! Cu-bemlng A588 Ag42
! . ~. 0 A551 "" .(3
.. " ..~
O" ~ . " .. "~ A242
..'" ... 9 "r~
mlo -'" ., 9 '
r'l..'."
1 1
0 - -
t i i A I
0 2 4 6 8 10 12
I0
~ 71ML ~ EX.mOSURE"rlME.yNm
FIG. 1--Corrosion performance of copper-bearing, A588B, and A242

weathering steels (continued).
Left-linear plots. Right-logarithmic plots.
so t h a t the corrosion rate, dC/dt, can be calculated from:
dC/dt = A B t B-I (3)
a n d t h e time, t*, to a given corrosion loss, C*, is g i v e n by,
t* = (C*/A) I/B (4)
V a l u e s c a l c u l a t e d for l l - y e a r c o r r o s i o n loss, l l - y e a r c o r r o s i o n rate,

a n d t i m e t o r e a c h a 1 0 - m i l ( 2 5 0 ~/n) l o s s a r e sununarized in T a b l e 3.
TABLE 3--Constants for t h e k i n e t i c ec~/ations a n d c a l c u l a t e d values of

ll-vear thickness losses, ll-vear rates, and times to 10-mil (250LLm)
D e n e t r a t io n ,
"...M..9.u..n..I..nP.P.L..Cl~t:elm..ng : 0.01 ~ 0.01 ~ 0.903 i 0.570 1.00 i 3.04 0.1535 08

_ ~
.......................... , " ; ~" - ~. . . . . . .~. ~ - - T - -, - ~. " E. . . . ~ o . , - ~ , - ~ , ~ i " - T
. . . . . . . . . . . . . . . . . 2,43 -0 . 0 9 8 8 - - 200
....... A242 ! 0.25 ! 0.1;5 0 655 0.414 E 0 94 1 79 0 0117"~1 7"61"----"-~
. ............... i ::: . . - : : : ~ . ~ :: f ' - - : ~ : ~ ~ - ' ~ - - - E ~ ~ - - ~ . - ; ~ ...... o . ~ 1 . . . . . . 0 5 ~ ,;~ o;~i~" ,-i~
.............. ~'~%--i.--.P...LL...i 0~.~!__/__0.es~ ~ o.%58 ~ 1.0o - aJ5 0.o7~.? - - 711
. A46 0 49 0 02 0 909 0 $82 0 99 i 2 27 0 0788 . $54-
i .............. ::::i::::~`.~:::::~:~;~-~.~.~-~.~:~o~.:..~`~;~..-~.-~.~?~ ............. 6"~,i ......................... ~ , ~ .................
........ AS0 0 77 ! 0.01 ~ 0 805 0 346 ! 0 90 ~ 1.07 0.0017 1~19
L ~ ~5~ ~ o ~ ................ " 6 . ' ~ ' " " T - ' ~ ~ e ~ .......... % ~ , ' ~ ' " ' I " " ' 6 " ~ i ' " " T " - - - s .................. 6 " ' o 5 ; , 8 " " - - ~ ............... ~;~o~ .............
:._ .t~_p. ;__Cu-belnnj~ : 0 01 ~ 0 01 0.840 0.471 1.00 2.S0 0 1111 1001

i .............. " ~ -";.~'a'i;' "T--'~:~,',;--"T--'~'E~:f~, '"[- 0 0o0 i 1 oo ~ 1 07 0 6;o0 ' ~0';~" ......
" '"'""~"'-'~i,; i ""T"""~'g'" ""-~"""E~i '""~""~ 06~'-'C-o:';oi'~--;;:~ -'C----'s ~ ............ 6-,;~b,;-"""~ ........... i'~;,7 ..............
....... ~ A4A. ~_..__J:,5 i o._o! F-~:'f~4 ~: o.~m i o.n i ~.ls o.o.~ i 75~
, ......... i-----A-4-4-----~--i~0:1.. S. L 0.15 ~ 0.755 ~ 0 0146 ~ 0.90 i 1.73 0.0045 1773
i - -- ~--'~A;I'-?-~" --~'~i~r i 0.i7 ' ~ 0 7 1 2 "~'- 0.:107 ! 0 90 i 1.71 0.'6"~'71 " 1551" -- ']
L. . . . . . . . . ~._~-:-~/~'~_ ~ o_~b 09;~ ~ 0.711 " 0.'.:17 ~ 0.00 i lee o.o;05 ? .... E'~ko . . . . !
.............. i AS0 ~ 0.77 ~ 0.01 .~ 0 683 ~ 0:172 { 0 07 ! 1 lit 0.0S601 .~ 10181 !
':-......... -~ : : " "" "['"'""~i~i-1100":~ " " ' ' ~ ~~ ' ~ ' ' ' ' ' ' ~ ' ' - " ~-~ ~ ' - " ; ""i3[ 7 ~ " "" ~ ' 0 ~ " " -~--0711"7"--" T - - ' ~ " l i ............................................
0.0547 "~'~95 ............... i
i ~ [ C~-b~m~l~ ~ 0 01 ; 0 01 0 804 ! 0 61.1 ~ I 00 i 4.21 i b:2SS0 ; 40 ..... i
_ .. ! *~,%";--'T"--E'~'--T'---6:~''--t-E~;, ' o :1o5 o.o~ 1.7o ~ o.o~i~" i i~'~'~-'----~

i "----~'--'A'4"3"'--'T"--O:'1"5"--T'~6:01- :-"'T-'~,O'Sk ~ 0~ ] 1.014 ..... ~.75 i 0"1002"---'--T -2"76--'----~
A44
{" ........................ i .................................. 0 . 15 . 0,16 ~ 0.9110 ~ 0.307 ~__I:@0 ___J.50 { 0,0785 { 558
....... ~i A45 ._~ 0:'1"2"'""~'"'"'0":3"I"'""'~'""0i'i7""'~ "0"4"~ .... O:'ii ...... 2:'$4 . . . . . . . . . . 6".'~'83"2"'"--~ ............. "2";Ii.................
............ --~ -~';,'~"" ~ -'~.q~, i 0.6~ i 0.6"*% I 0.410 0.07 ~.:14 0.086~ : :1~ ..........
.......... " - - ~ ; , ~ ' _ - - - ~ - % : ~ ' ~ F - ,-T-E6~'~ ! o.:174 ; 0.0:1 ~.~ 00704 ~ Ol,
" .::"~ -::~;:i:: ~. ~ :~~................ o . ~ i : - - . ~ : ~ ........ o..,~, ........ ~ , , . . . . . . . . . 1 ~ , ................ q o , - , , ...............::::...-7~:,-.~:::.
................-~'0....... 0.:z 0.0, 0.~s, i 0.40, i 0.,1 1.,, 0.07~0 i ,0,
.................... L._.~AS:i. _ _ ~ _ ~ 0 . 7 : 1 i O.'1"ll 0.%'1"-$ " 0.:151 Ooill ~.0~- 0.050'8 i$i'4" . . . . . . . '-
9 ~ A52 ~ 0 75 0.31 0.075 i 0.018~ i 0.58 1.00 0.058? i 1154
[: i ~ : : : i : ~ : ; ~ : ~ i ~ :-~ " ~:~v -~ ~: ~ - ."-~,~i-~--~~.i:::_--'--i:~ ........ ! ....... ~ : - ~ '~ ................. ~ i .................

-.............. ~ A558 T 0.'~'i"'--~---6":~""-T--'~:~'~'-T~:~i--T-~.07- s.~-- T---3?~iB'---T-----~...........i..
i :::"-'~-;~}'~"--T--'~'i~ ~ ~'~'-----'6:~'6~" . . ' ~ o . ~ 4 ~ 000 450 oWi'~" - - ' ~ i ........... i
" . . . . . . . . C'"-~',~'~'"--T--'~ "~'~ I E'6~'"--r-'~:i'~i~o:1 0.00 ~ 7~ o o~'~ ~ .........
l.......... " i " ~ 4 4 - ~ i ~ ................ o ~ ' t ~:isi .......... ~:fii T6:i~T ......... i:~ ................... 6:~is " "~ ................ ~ 6 ................. i
............... : A45 0.4~ 0.0~ ~ , o~7 ~ o 711 ~ o.oo ~ s.os d'~'~" ~ ~---~ ............
:-':-"~,~---~ "~~----~:~~-- "~-.6ii ..-7-E., ~ ~ 01.,,...... ; 0 0 , ~ ~ - . - - ~ - - - ~ - ~ ............
~. ......: ' A , , 'T-- --o , , ............... ~ ~ , ............ ~ o , ~ ~ - ~ i ~ ~ - i ~ . . . . . . ~-,o ....................~ : , ~ , , ......... ~................. -~, .................
i..... :::-:::-~~-:::::::~.:~:<:-:T::_-o:~i::::--:U~ooi~ii~ - ~ ~:.,:~:~ ~.a O 2401 ~ 41 :
..........................
.............
i .............................................~......................................J _ J . . . . . . . . ~ . . . . . . L ...... ' ==========================================
: ........ ...............
A and 8 are constants in Iha kinetic equations, C - AtR. where C is tJlo commdon Io88 in mils (25.4 pro), and t is lima
in years. Rsq is the square (:4 the regression coefficient.
11 -year loss is calculated from C - N 8. The 11 -yr rate is cak:~laled from d C / d l . ABIB-1. The lime to 10-rail (250-pro)
Ioso is calculated from t - (~O/A) 1/B.
92 A T M O S P H E R I C C O R R O S I O N
Effects of Silicon and Nickel on Corrosion of A588 Weatherin~ Steel
The effects of silicon and nickel content on the corrosion

p e r f o r m a n c e o f A 5 8 8 w e a t h e r i n g s t e e l at t h e f o u r a t m o s p h e r i c t e s t s i t e s
a r e s h o w n in F i g u r e s 2 t o 4. These results show that both elements have
g e n e r a l l y f a v o r a b l e e f f e c t s in r e d u c i n g t h e a m o u n t o f c o r r o s i o n . In
order to quantify these beneficial effects, linear regression analyses
were performed to generate relationships between corrosion performance
a n d c o m p o s i t i o n as f o l l o w s
Y = a + b(%Si) + c(%Ni). (5)
w h e r e a, b, a n d c a r e c o n s t a n t s , a n d Y 1 is t h e l l - y e a r c o r r o s i o n loss,
Y 2 is t h e l l - y e a r c o r r o s i o n rate, a n d Y3 is t h e t i m e t o 1 0 - m i l (250 pm)
c o r r o s i o n loss. T h e s e v a l u e s a r e s u m m a r i z e d in T a b l e 4.
TABLE 4--Reoression coefficients and calculated effects of 0.~ %

increases in s i l i c o n a n d nickel
Sits ~ n i Y1 ~ Y2 ! Y3 i%C~For + 0 1 ~Y, Si ~% C ~ i For +0.1.:% Ni

Coefficents 11-y,r Loss z 11-y.r R a t s = Time to l O - r n i l loss= loss Rats i Time ; Loss i Rats ! Time
mils ~. mp...v .,yr i i i ; .;. 'i.
M o u n ~ ! n . t O l ~ . ........ .b ......... L . . . : . O . : 7 5 . . . . . . i . . . . . . : . . 0 . : 0 . . 4 . . . . . . . i .......... 12..?.6.: 0...6.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,....................................

. ~ C . -0.76 - -0.04 825.68 . . . . . . . . . . . . . . . . . . . . . . . . . ~... . .~
0,94
...................................................... ~.i . . . . . . . .0. ...8. .6. . . . . . !i. . . . . . . . . . . . . . . 0. . .. .7. .8. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2:::::~:~::::::~:.:~::~.~::::~::.2::~.~:~j~:~:~:~:::~:~::~:::::::.~:.1.:~.(:::~:::::..::~i:i:~:~:::~:~:::i:~::~12.~;5~i.~::~::~:i~:~t~:~:~.~..~:~z~
..... R..o.o~.~....~ . . . . . . . . . .~. . . . . . . . . . L . . . . . : . o . : ~ T ........... :..0.:.0.!.... 4 . . . ' I ~ ~. 9 9 ........................................ :. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .c. . . . . . . . . . . . . . . . . . . .-.0. . . .4. .9. . . . . . . . . . . . . . . . . -. .0. . . .0. 3. . . . . . . . . . .!. . . . . . . . . . .3. .0. .4. .6. . . . .8. .4. . . . . . . . . . . . . . :~. . . . . . . . . . . . . . . ~~ . . . . . . . . . . . . . . . . .~ :. - . .". . . . . . . . . . .
i ~ ~ 0.86 i 0.87 i 0.88 ................ i ............... i ................ i . . . . . . . . . . . . . . . . . ~,. . . . . . . . . . . . . . =~. . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . t ........ " ; ........ t ' " " ~ ~ 8 - 6 T ~ .................. :U~"6~ ............. : ~ ' ~ ' ' I : 6 ~ - Y ~ ~ T ! : ; s 1 6 3
....... R. u...~. . . . . . . . . . . . . . . . b . . . . . . . . . . . . . . . :!0.8. . . . . . . . . . . . . . :..o..o..s. . . . . . . . . . . . . . . . . . . . V . . 4 8 . . 9 9 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
c ~ -1 0 5 i -0 05 i 1 9 8 5 91 -~ ~. ~.
..................... t ~ - - : - ( s ~~ .................... ~:~ ............................................................................. ~. . . . . . . . . . . . . . ~. . . . . . . . . . . . . .
..................... f ....................................... - ........................................................................................................... ...............................................
a ! 781 i 059 688 -702 -10.83 15.05 -5.63 i -9.9 ! 10.0
...... . u . ~ . . ~ . . . . . . ~ ......... .k).. . . . . . . . . i . . . . . . : ~ . . _ 9 7 . . . . . . . . . . . . . :..o.:~.o. . . . . . . . . . . . . . . . . . . . ~,.!.:S_7_ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9. . . . . . . . . . . . . . . . :.3..;.19 . -0,96 . 27.88 .................. ~. . . . . . . . . . . . . . . . =. . . . . . . . . . . . . . . . . ~. . . . . . . . .
~ i 0.94 0,96 0.91 . . . . . . . . . . . . . . . . . . . . . . . . .
:~'&r;;~; ] [ . . . . . . :'~:::~'~'" ":s:~iY" ""Ti:~'"":'~:~'~ .... -5.7 ~5.4
a, b, and c are coefficients in the equations Y= a + b(%Si) + c(%Ni),

where Y1 is the ll-year loss, Y2 is the ll-year rate, and Y3 is the time
to 10-mil (250 ~m) loss. Rsq is the square of the regression
coefficient. % changes a r e calculated from the above equation for
increases in Si or Ni by 0.1% in an A588 steel with an initial
composition of %Cu = 0.34, %Ni = 0.30, %Cr =0.56, %Si = 0.3, and %P =
0.009
S , , , , , 10 ,
4 MOUNTAINTOP
SITE MOUNTAINTOP SITE
l L O W Ni A 5 8 8
! LOW Ni A588
o.ss% sl - ~ ) @ 0.15% SJ -..-'. ~

9 SI
O_~ I w f i i I i J , , , , I
O
0 2 4 6 8 10 3 10
ID(POSURE "TIME.yqerl z
EXPOSURETIME. ymmI
m
z
u
i I I 10 0
z
4
!
'1 !
R(X)F'~P SITE
E
LOW Ni A588 L O W NI A 5 8 8 >
C~
CO
@
o.ts% si : . m
- 0.49% >
@.41~ $J
0.77 % 8i i
1 m
z
o i i i i i , i , I o9
-t
o 2 4 @ 8 lO 12 3 10 m
EXPOSURET1ME.m ~ E I'~E. ~ m
r-
FIG. 2 - - C o r r o s i o n p e r f o r m a n c e of low-nickel A 5 8 8 B w e a t h e r i n g
steels. L e f t - l i n e a r plots. R i g h t - l o g a r i t h m i c plots 9 (D
CO
10
i I I I I
RURALSITE >
RURALSITE ! L O W Ni A 5 8 8
! 4 L O W Ni A588 O
O9
~3 O -- 0.15% Si -- -0
..,0 +_-:...,.. o,,, o "1-
0.1S% @i m
~o
0 . ~ ,~
@.-
i 2 I, o
0
I ~0
~o
.. I 0
0 w
~ I I I I I 3 10
Go
6z
o 2 4 P 8 1o 12 I~POSURE TIME. ]team
~ E TIME. )lem
10 L- , , , , ,
10
MARINE SITE
O
| e~ MaRINESffE .I,o L O W Ni A 5 8 8 o.ss,/, sl . - .a
! 9" 0.49% Si . O
sl
/,.-d
1
2
J
O T I ~ i i , ;
0 2 4 8 8 10 12 3 10
E~I,O6URE ~ )l,m EXPOSURE TIME.
FIG. 2 - - C o r r o s i o n p e r f o r m a n c e of low-nickel A 5 8 8 B w e a t h e r i n g
steels (continued). L e f t - l i n e a r plots. R i g h t - l o g a r i t h m i c plots.
I I I I ;
10
MOUNTAINTOP SITE
4
MEDIUM Ni A588 MOUNTAINTOP SITE
! MEDIUM NI A588
o 3
0.15% Sl 0,15% Si ..--_ @

2 t ~ 0.4;'% S* .0.47% Sl 9
l~. ~_.~..---"-f~ "~ o.7a%, sl
1 ~ ~ 0.73%, SI
-4
O -J ~ t I t , t m m J , i , I O
0 2 4 6 8 10
lO Z
EXPOSURETIME. years EXPOSURETIME, years Oo
m
Z
E~
10 0
z
4 R(X)FTOP SITE
| ROOFTOP SITE -4
MEDIUM Ni A588 | MEDIUM Ni A588 >
o-i
co
co
0.15% $1 0.15% S! _,11 m

0.47% SI 0.47% S! -4
1
//~,,~r 0.73 % SI
t ~..,.r,~-.r,""~'" 0.73% Si 1"
m
I1
z
0 w
I f I I I
i i h m I
o 2 4 6 8 10 12 -.-I
10 m
EXPOSURETIME. yews m
EXPOSURETIME.yNm i--
FIG. 3 - - C o r r o s i o n p e r f o r m a n c e of m e d i u m - n i c k e l A588B weathering

steels. L e f t - l i n e a r plots. Right-logarithmic plots. O"I
5 i i ; I I I 10
4 I RURAL SITE
RURAL SITE
t MEDIUM Ni A588 t MEDIUM Ni A588
O
00
-o
.= ! 0,,% s, _ T
0.15% SI -'. :~
Ud ........ _ .... ~. :.: ~..-. ! o 4 ~ . si m
0.73% SI ~.,. , 0.73% Si
0
0
Oa" n : I i f 0
J , = , , , , I co
0 2 4 6 8 10 2 3 10 0
Z
EXPOSURETIME. EXPOSURETIME.years
10 , , , , , 10
MARINE SITE - ~ aO
1~ 8 MARINE SITE MEDIUM Ni A588 O.lS% si ,- " (3
s o.47% si
I 6 MEDIUM NI A588 o.ls% si " ~ - : :- ;i ; " 0.73% s,
t3
9 j
~ 2 1
O - , , . . . . I
0 2 4 6 8 10 12 3 10
EXPOSURETIME,ymml EXPOSURETIME. years
FIG. 3 - - C o r r o s i o n p e r f o r m a n c e o f m e d i u m - n i c k e l A 5 8 8 B w e a t h e r i n g
steels (continued). Left-linear plots. Right-logarithmic plots.
5 , , 10 . . . . . t
4 MOUNTAINTOP SWE MOUNTAINTOP SITE

HIGH NI A588
| HIGH NI A588
3
o.,2% s, . - ~
_ --0" - 0 . 4 9 % 5i
2 r- o . 1 2 % S!
~ - . . [ :-~ "-T ----
. . .""
. O9 ' 0.75% Sl
| ~ o.4g~, sl ....--a
0_~.- , , i i i , , , , i i i I
O
0 2 4 6 8 10 3 10
EXPOSURE llME. y~am Z
E X P O S U R E TIME. r~
m
Z
5 , , , , , 10
0
Z
>
4 ROOFTOP SITE ROOFTOP SRE
| --I
HIGH Ni A588 HIGH Ni A588 E
ol
0 . 1 2 % Si ; m
0 . 1 2 % SI >
~-. -. r. --, .--- :" "-' ~ r ' ; ~ s,Sl -t
/ ~ ~ ~ L 0.49%
0.75 % ~1
SI -1-
1 m
z
I I i i ; , , T
0 w
o 2 4 6 8 10 12 3 10 --I
m
EXPOSURE TIME. yura EXPOSURE TIME. yearn m
r-
FIG. 4 - - C o r r o s i o n performance of high-nickel A 5 8 8 B w e a t h e r i n g

~D
steels. Left-linear plots. R i g h t - l o g a r i t h m i c plots. -4
(D
CO
I i I I I 10
RURAL SITE RURAL SITE

| 4 HIGH NI A588 I HIGH Ni A588 O
gd3 O9
"U
-I"
m
2 F _/~.~.. o.12% $1
0.49% SI . . . - - 0.49% Sl 0
O ............ G 0.75"/,SI 0
0
0 i i t i I * l I I i , I
0 2 4 6 8 10 12 3 I0 Z
EXPOSURETIME,ymn EXPOSURE TIME.
10
10
8 MARINE SITE MARINE SITE . .o

| HIGH Ni A588 ! HIGH Ni A588 0.12% s= .-
~D O ."." 0.49% Si
0.12% SI - " .- 0.75% SI
.,- .ll
~ 0.7S% SI
0 -- ' , I I
0 2 4 6 8 10 12
EXPoSuRETIME.yurl 10
EXPOSURETIME.yum
FIG. 4--Corrosion performance of high-nickel A588B weathering

steels (continued). Left-linear plots. Right-logarithmic plots.
A l s o shown in Table 4 are the p e r c e n t a g e changes in p e r f o r m a n c e for each

0.1% of either s i l i c o n or nickel added to A588 steel w i t h an initial
c o m p o s i t i o n of: 0.34%Cu, 0.30%Ni, 0.56%Cr, 0.3%Si, a n d 0.009%P. In the
c a s e of silicon, the a v e r a g e values for the four e n v i r o n m e n t s s h o w that
each 0.1% of a d d e d s i l i c o n leads to a 4% d e c r e a s e in c o r r o s i o n loss
after ii years, a 6% d e c r e a s e in c o r r o s i o n rate after ii years, and a
12% increase in the time to reach a 10-mil (250~m) p e n e t r a t i o n . In the
case of Ni, e a c h 0.1% increase produces a 4% d e c r e a s e in c o r r o s i o n loss
after ii years, a 7% decrease in c o r r o s i o n rate a f t e r ii years, a n d a
15% increase in the time to reach a 10-mil (250~m) p e n e t r a t i o n .
Effects of S i l i c o n and Nickel on the GI01 C o r r o s i o n Index
A c c o r d i n g to A S T M GI01 (Method 2) [I0], an e s t i m a t e of the

r e l a t i v e c o r r o s i o n r e s i s t a n c e of low alloy steels is g i v e n by the
c o r r o s i o n index, CI, as c a l c u l a t e d from the f o l l o w i n g equation:
CI = 26.01(%Cu) + 3.88(%Ni) + 1.20(%Cr) + 1.49(%Si) + 17.28(%P)
- 7.29(%Cu) (%Ni) - 9.10 (%Ni) (%P) - 33.39(%Cu) 2. (6)
F r o m this equation, the CI of the A588 steel w i t h the c o m p o s i t i o n given

in the p r e c e d i n g s e c t i o n is 6.65. C a l c u l a t i o n s w i t h E q u a t i o n 1 also
indicate that the CI of that composition increases by 2% each 0.1%
i n c r e a s e in either s i l i c o n or nickel.
CONCLUS IONS
E l e v e n - y e a r c o r r o s i o n tests of a series of A588 l o w - a l l o y

w e a t h e r i n g steels in industrial, rural, and m a r i n e environments, and
c a l c u l a t i o n s b a s e d on A S T M GI01 (Method i) s h o w b e n e f i c i a l e f f e c t s of
i n c r e a s e s in silicon and nickel as follows:
o For silicon, on average, each 0.1% increase r e s u l t s in a 4% d e c r e a s e

in c o r r o s i o n loss after Ii years, a 6% d e c r e a s e in c o r r o s i o n rate after
ii years, and a 12% increase in the time to r e a c h a 10-mil (250~m)
penetration.
o For nickel, on average, each 0.1% increase r e s u l t s in a 4% d e c r e a s e

in c o r r o s i o n loss a f t e r Ii years, a 7% d e c r e a s e in c o r r o s i o n rate after
ii years, and a 15% increase in the time to reach a 10-mil (250~m)
penetration.
By w a y of comparison, M e t h o d 2 of A S T M GI01 p r e d i c t s a 2% increase in

the c o r r o s i o n index for each 0.1% increase in s i l i c o n or nickel.
1 O0 ATMOSPHERIC CORROSION
ACKNOWLEDGMENTS
The author is grateful to J. C. Zoccola, E. H. Gehman, and E. J.

McInerney, retired former coworkers at Bethlehem Steel Corporation's
Research Department, for their roles in initiating and monitoring the
long-term atmospheric corrosion tests.
REFERENCES
[1] Shastry, C. R., Friel, J. J., and Townsend, H. E., in Dearadation

of Materials in the Atmosphere. ASTM STP 965, S. W. Dean and T. S.
Lee, Eds., American Society for Testing and Materials,
Philadelphia, 1988, pp 5-15.
[2] Albrecht, P., and Naeemi, A. H., Performance of Weatherina Steel
in Bridaes. National COoDerative ~iahwav Research Proaram RePort
272, Transportation Research Board, Washington, DC, 1984.
[3] Uncoated Weatherina Steel Structures. US Department of
Transportation Technical Advisory T5140.22, Federal Highway
Administration, Washington, DC, 1989.
[4] ASTM A588/A588M - 88a. Standard Specification for Hiah-Strenath
Low-Alloy Structural Steel with 50KSI (345 MPa) Minimum Yield
Point to 4 in.(100 mm) Thick. Annual Book of ASTM Standards, Vol.
01.04, American Society for Testing and Materials, Philadelphia,
1990, p 175.
[5] Copson, H. R., Proceedings ASTM, 45, 1948, p 554.
[6] Larabee, C. P., and Coburn, S. K., Proceedinas of the First
International Conaress on Metallic Corrosion. Butterworths, London
1962, pp 276-285.
[7] N A D P / N T P Annual Data Summary. Precipitation Chemistry in the
United States.1989, National Atmospheric Deposition Program,
Colorado State University, Fort Collins, Colorado 1990.
[8] ASTM GI-90. Standard Practice for PreDarina. Cleanina. and
Evaluatinu Corrosion Test SDecimens, Annual Book of ASTM
Standards, Vol. 03.02, American Society for Testing and Materials,
Philadelphia, 1990, p 39.
[9] Horton, J. B., The Composition. Structure. and Growth of
AtmosDheric Rusts on V a r i Q ~ Steels, PhD Dissertation, Lehigh
University, Bethlehem, Pa., 1964.
[I0] ASTM GI01-89. Standar4 Gui~@ for Estimatina the Atmospheric
Corrosion Resistance of Low-Alloy Steels, Annual Book of ASTM
Standards, Vol. 03.02, American Society for Testing and Materials,
Philadelphia, 1990, p 388.
[II] Townsend, H. E. and Zoccola, J. C., in Atmospheric ~QrrosiQD of
Metals. ASTM STP 767, Dean, S. W. and Rhea, E. C., Eds., American
Society for Testing and Materials, Philadelphia, 1982, pp 45-59.
S e y m o u r K. C o b u r n I, M. E d w a r d K o m p 2, a n d S t a n l e y C. L o r e 3
A T M O S P H E R I C C O R R O S I O N R A T E S OF W E A T H E R I N G S T E E L S AT T E S T S I T E S IN THE
E A S T E R N U N I T E D S T A T E S - E F F E C T OF E N V I R O N M E N T A N D T E S T - P A N E L O R I E N T A T I O N
REFERENCE: Coburn, S. K., Komp, H. E., and Lore, S. C., " A t m o s p h e r i c

C o r r o s i o n R a t e s of W e a t h e r i n g S t e e l s at T e s t S i t e s i n the E a s t e r n U n i t e d
S t a t e s - E f f e c t of E n v i r o n m e n t and T e s t - P a n e l O r i e n t a t i o n , " A t m o s p h e r i c
CQrrosion, A $ T M STp 1259, W. W. K i r k and H e r b e r t H. Lawson, Eds., A m e r i c a n
S o c i e t y for T e s t i n g and Materials, P h i l a d e l p h i a , 1995o
ABSTRACT: To o b t a i n l o n g - t e r m a t m o s p h e r i c c o r r o s i o n d a t a for w e a t h e r i n g
s t e e l s s u c h as A S T M A 242 T y p e 1 (USS C O R - T E N A) a n d A S T M A 588 Gr. A
(USS C O R - T E N E), an e x p o s u r e p r o g r a m w a s i n i t i a t e d in w h i c h test p a n e l s
w e r e e x p o s e d for u p to s i x t e e n y e a r s at t h r e e c o r r o s i o n test s i t e s in
the e a s t e r n U n i t e d States. A u n i q u e f e a t u r e of this p r o g r a m w a s that
test p a n e l s w e r e e x p o s e d in four d i f f e r e n t o r i e n t a t i o n s (30~ 30~
90~ 90~ at e a c h site. The r e s u l t s c o n f i r m e d the s u p e r i o r r e s i s t a n c e
of the w e a t h e r i n g s t e e l s as c o m p a r e d to that of c o p p e r - b e a r i n g steel a n d
c a r b o n steel u n d e r v i r t u a l l y all the test conditions, w i t h the A 242
steel b e i n g the m o s t c o r r o s i o n resistant. Overall, the r u r a l t e s t site
(Potter County, PA), w h i c h is in line w i t h the p r e v a i l i n g w i n d s c a r r y i n g
a c i d - r a i n c o n s t i t u e n t s f r o m the m i d d l e w e s t e r n U n i t e d States, w a s a b o u t
t w i c e as c o r r o s i v e to t h e s e s t e e l s as was the u r b a n - i n d u s t r i a l site
(Kearny, NJ), w h e r e a s the m o d e r a t e - m a r i n e site (Kure Beach, NC, 250 m)
w a s a b o u t t e n t i m e s as c o r r o s i v e as w a s the u r b a n - i n d u s t r i a l site. with
r e s p e c t to the e f f e c t of test p a n e l orientation, the s o u t h - f a c i n g p a n e l s
t e n d e d to s h o w l o w e r c o r r o s i o n rates t h a n d i d the n o r t h - f a c i n g p a n e l s at
all the test sites. Also, in m o s t cases, the i n c l i n e d (30 ~) p a n e l s
s h o w e d l o w e r rates t h a n d i d the v e r t i c a l (90 ~) panels.
KEYWORDS: a t m o s p h e r i c corrosion, w e a t h e r i n g steel, A S T M A242, A S T M A 5 8 8 ,

C O R - T E N A, C O R - T E N B, c o p p e r - b e a r i n g steel, c a r b o n steel.
ipresident, C o r r o s i o n Consultants, Inc., P. O. B o x 81085,

Pittsburgh, P A 15217.
2Consultant, 129 W e s t m i n s t e r Drive, M o n r o e v i l l e , P A 15146.
3Director, C O R - T E N M a r k e t i n g a n d T e c h n i c a l Services, U S X E n g i n e e r s
a n d C o n s u l t a n t s Inc., 600 G r a n t Street, Pittsburgh, P A 15219-4776.
101
C oDownloaded/printed
p y r i g h ~ 1 9 9 5 b y Aby
STM International www.astm.org
In the e a r l y 1970's, U S X C o r p o r a t i o n a n d several of its U S S COR-

T E N steel l i c e n s e e s i n i t i a t e d an a t m o s p h e r i c e x p o s u r e p r o g r a m to d e m o n -
s t r a t e the p e r f o r m a n c e of w e a t h e r i n g steels. In this p r o g r a m d u p l i c a t e
test p a n e l s of the w e a t h e r i n g steels A S T M A 242 T y p e 1 (USS C O R - T E N A)
a n d A S T M A 588 Gr. A (USS C O R - T E N B), a l o n g w i t h t h o s e of c o p p e r - b e a r i n g
steel a n d c a r b o n steel, w e r e e x p o s e d for up to s i x t e e n y e a r s in u r b a n -
industrial, rural, a n d m o d e r a t e - m a r i n e e n v i r o n m e n t s in e i g h t countries.
A sununary of the w o r l d w i d e r e s u l t s of this p r o g r a m has b e e n p r e s e n t e d
p r e v i o u s l y [i]- The p r e s e n t p a p e r p r o v i d e s a m o r e d e t a i l e d a n a l y s i s of
the r e s u l t s at test sites in the e a s t e r n U n i t e d States. A unique
f e a t u r e of this p r o g r a m was that test p a n e l s w e r e e x p o s e d in four dif-
ferent o r i e n t a t i o n s at e a c h test site.
MATERIALS AND EXPERIMENTAL METHOD
Steel Compositions
The c o m p o s i t i o n s of the four steels t e s t e d are s h o w n in T a b l e 1.

T h e A S T M A 588 Gr. A steel u s e d is of the o r i g i n a l (pre-1978)
c o m p o s i t i o n for C O R - T E N B; the p r e s e n t c o m p o s i t i o n c o n t a i n s g r e a t e r
a m o u n t s of n i c k e l a n d s i l i c o n and is m o r e c o r r o s i o n resistant.
T A B L E 1 - - C o m p o s i t i o n of test panels, p e r c e n t .
Steel Type C Mn P S Si Cu Ni Cr V
Carbon 0.046 0.38 0,012 0.022 0.016 0.014 0.012 0.025 <0.01
Copper-bearing 0.042 0.35 0.002 0.012 0.004 0.26 0.014 0.014 <0.01
ASTM A242 0.ii 0.31 0.092 0.020 0.42 0.30 0.31 0.82 <0.01
(COR-TEN A)
ASTM A588 Gr.A 0.13 1.03 0.006 0.019 0.25 0.33 0.015 0.56 0.038
(COR-TEN B*)
*Pre-1978 c o m p o s i t i o n
Test P r o c e d u r e
P r o c e d u r e s u s e d for test p a n e l p r e p a r a t i o n , c l e a n i n g a n d e v a l u a -
t i o n h a v e b e e n d e t a i l e d e a r l i e r [!]. Briefly, t e n 4 - i n c h (I0 cm) b y 6-
inch (15 cm) b y I / 8 - i n c h (3 mm) p a n e l s of e a c h steel w e r e p i c k l e d to
r e m o v e m i l l scale and e x p o s e d at e a c h test site at 30 ~ to the h o r i z o n t a l
f a c i n g s o u t h a n d f a c i n g north, a n d at 90 ~ to t h e h o r i z o n t a l f a c i n g s o u t h
a n d f a c i n g north. A p h o t o g r a p h of one of the test racks u s e d is s h o w n
in F i g u r e i. O n l y one s u r f a c e of the p a n e l s w a s exposed; the o t h e r
s u r f a c e a n d the edges w e r e p r o t e c t e d w i t h a d u r a b l e p a i n t coating.
D u p l i c a t e test p a n e l s w e r e r e m o v e d a f t e r one, two, four, e i g h t a n d
s i x t e e n y e a r s exposure. The p a n e l s w e r e t h e n c l e a n e d a n d the m a s s loss
determined. A v e r a g e p e n e t r a t i o n a n d c o r r o s i o n rates w e r e c a l c u l a t e d
b a s e d o n the m a s s loss. The d a t a w e r e a l s o a n a l y z e d u s i n g a l o g - l o g
l i n e a r r e g r e s s i o n technique, p e r A S T M S t a n d a r d G u i d e for E s t i m a t i n g the
A t m o s p h e r i c C o r r o s i o n R e s i s t a n c e of L o w - A l l o y Steels (GI01). R e s u l t s of
the r e g r e s s i o n a n a l y s i s a l l o w p r e d i c t i o n of l o n g - t e r m c o r r o s i o n loss.
COBURN ET AL./WEATHERING STEELS AT EASTERN U,S. SITES 103
FIG. 1 - - A t m o s p h e r i c test rack at rural site in the U n i t e d States.
Exposure Locations
Test sites i n c l u d e d the u r b a n - i n d u s t r i a l a t m o s p h e r e of Kearny, N e w

Jersey; the m o d e r a t e - m a r i n e a t m o s p h e r e of the 2 5 0 - m e t e r (800-foot) lot
at K u r e Beach, N o r t h Carolina; and the rural a t m o s p h e r e of P o t t e r
County, P e n n s y l v a n i a .
The u r b a n - i n d u s t r i a l e x p o s u r e site at Kearny, N e w Jersey, lies in
the i n d u s t r i a l r e g i o n s u r r o u n d i n g N e w a r k Bay. The site is a p p r o x i m a t e l y
two m i l e s (three km) n o r t h e a s t of the N e w a r k A i r p o r t a n d five m i l e s
(eight km) w e s t of l o w e r M a n h a t t a n Island, N e w Y o r k City. The c l o s e s t
i n d u s t r i a l i n s t a l l a t i o n is an o i l - b u r n i n g e l e c t r i c a l g e n e r a t i n g s t a t i o n
of the P u b l i c S e r v i c e C o r p o r a t i o n of N e w Jersey. The s t a c k s of t h i s
g e n e r a t i n g s t a t i o n are a p p r o x i m a t e l y 750 y a r d s (690 m) f r o m the test
site. D u r i n g the last 15 to 20 years, m a n y of the s u r r o u n d i n g indus-
t r i a l p l a n t s h a v e i n s t a l l e d s c r u b b e r s to c l e a n t h e i r e x h a u s t g a s e s a n d
s u b s t a n t i a l r e d u c t i o n s in the c o r r o s i v i t y of the e n v i r o n m e n t h a v e b e e n
noted. T h i s e f f e c t w i l l be d i s c u s s e d f o l l o w i n g the p r e s e n t a t i o n of t h e
results.
T h e m o d e r a t e - m a r i n e e x p o s u r e site at the 2 5 0 - m e t e r lot at K u r e
Beach, N o r t h Carolina, is on a n a r r o w p e n i n s u l a b e t w e e n the C a p e F e a r
R i v e r a n d the A t l a n t i c Ocean. The p r e v a i l i n g w i n d is f r o m the l a n d to
the sea, but sea b r e e z e s a n d o c c a s i o n a l storms b r i n g salt s p r a y to the
test lot. B a s e d on 30 y e a r s of w e t - c a n d l e testing, p e r s o n n e l at t h e
L a Q u e C e n t e r for C o r r o s i o n T e c h n o l o g y (owner of the test site) h a v e
e s t a b l i s h e d that the c h l o r i d e d e p o s i t i o n rate at this site r a n g e s f r o m
80 to 180 m g / m 2 / d a y , and a v e r a g e s 127 m g / m 2 / d a y .
T h e rural test site in P o t t e r County, P e n n s y l v a n i a , is l o c a t e d in
a s p a r s e l y p o p u l a t e d a r e a a p p r o x i m a t e l y five m i l e s (eight km) n o r t h e a s t
of the small t o w n of Port Allegheny. T h e r e are no local s o u r c e s of
atmospheric contaminants. However, d u r i n g the p a s t 15 to 20 years,

breezes f r o m the i n d u s t r i a l m i d w e s t e r n states h a v e p a s s e d o v e r the
r e g i o n and i n f l u e n c e d the e n v i r o n m e n t somewhat. This e f f e c t w i l l b e
d i s c u s s e d f o l l o w i n g the p r e s e n t a t i o n of the results.
RESULTS
E f f e c t of Steel TVDe
The a v e r a g e p e n e t r a t i o n s (per side), in ~m, b a s e d on the m a s s loss

of e a c h s a m p l e are g i v e n in the Appendix, a l o n g w i t h p e n e t r a t i o n vs.
t i m e c u r v e s for the t h r e e test sites. T h e c a l c u l a t e d c o r r o s i o n rates
for t h e 8 - t o - 1 6 y e a r p e r i o d are g i v e n in T a b l e 2. The a v e r a g e c o r r o s i o n
r a t e s for e a c h steel are p r e s e n t e d g r a p h i c a l l y in F i g u r e 2. (Note that,
for the s i x t e e n - y e a r c a r b o n - s t e e l s a m p l e s e x p o s e d at the m o d e r a t e - m a r i n e
location, p e n e t r a t i o n s c o u l d not be c a l c u l a t e d b e c a u s e of s e v e r e edge
a t t a c k of the samples. Therefore, rates b a s e d on the 4-to-8 y e a r p e r i o d
w e r e used.)
T A B L E 2 - - C o r r o s i o n rates, 8-to-16 y e a r period, e x c e p t as noted.
A S T M A 242 A S T M A 588 Copper-bearing C a r b o n Steel

Type 1 Gr. A Steel
Orient. ~m/yr mils/yr ~m/yr mils/yr ~m/yr mils/yr ~m/yr mils/yr
U r b a n - i n d u s t r i a l site - Kearny, N J
30~ 1.5 0.06 1.6 0.06 2.8 0.11 3.0 0.12
30~ 1.3 0.05 2.3 0.09 3.9 0.15 3.1 0.12
90~ 1.4 0.06 3.3 0.13 3.2 0.13 3.1 0.12
90~ 1.9 0.07 2.7 0.ii 4.2 0.16 3.6 0.14
AVG 1.5 0.06 2.5 0.10 3.5 0.14 3.2 0.12
R u r a l site - P o t t e r CountT, P A
30~ 3.3 0.13 3.4 0.13 6.4 0.25 6.1 0.24
30~ 3.1 0.12 4.6 0.18 6.5 0.26 6.6 0.26
90~ 1.4 0.06 3.7 0.15 6.5 0.26 8.4 0.33
90~ 2.2 0.09 5.2 0.20 8.2 0.32 7.8 0.31
AVG 2.5 0.10 4.2 0.16 6.9 0.27 7.2 0.28
M o d e r a t e - m a r i n e site - K u r e Beach. NC. 250 m lot

30~ 6.1 0.24 10.3 0.41 17.7 0.70 48.1" 1.89"
30~ 7.8 0.31 12.4 0.49 23.3 0.92 47.0* 1.85"
90~ 9.3 0.37 10.4 0.41 18.8 0.74 17.8" 0.70*
90~ 11.9 0.47 16.7 0.66 36.8 1.45 122.1" 4.81"
AVG 8.8 0.35 12.4 0.49 24.2 0.95 58.8* 2.31"
* S e v e r e edge a t t a c k on 1 6 - y e a r c a r b o n steel panels; u s e d 4 - t o - 8 y e a r

d a t a to c a l c u l a t e rates.
In all cases, the A 242 steel s h o w e d the l o w e s t a v e r a g e c o r r o s i o n

rate, r a n g i n g f r o m 1.5 to 8.8 ~ m / y e a r (0.06 to 0.35 m i l s / y e a r ) . The
A 588 steel s h o w e d the next lowest a v e r a g e rates, r a n g i n g f r o m 2.5 to
12.4 ~ m / y e a r (0.i0 to 0.49 m i l s / y e a r ) . R a t e s for c o p p e r - b e a r i n g steel
a n d c a r b o n steel r a n g e d f r o m 3.2 to 58.8 ~ m (0.12 to 2.3 m i l s / y e a r ) .
T h e d i f f e r e n c e s in a v e r a g e rates b e t w e e n c o p p e r - b e a r i n g steel a n d c a r b o n
COBURN ET AL./WEATHERING STEELS AT EASTERN U.S. SITES 105
To 58.8 ~n/yr
~m/yr
30
25
20 9 INDUSTRIAL
15 [] R U R A L
10 [] M A R I N E
A 242 A 588 COPPER- CARBON

STEEL STEEL BEARING STEEL
STEEL
FIG. 2 - - A v e r a g e c o r r o s i o n rates, 8-to-16 y e a r p e r i o d e x c e p t

as noted.
steel w e r e not s i g n i f i c a n t at the u r b a n - i n d u s t r i a l a n d r u r a l test sites,

w h e r e a s at the m o d e r a t e - m a r i n e site, c o p p e r - b e a r i n g steel w a s
a p p r e c i a b l y m o r e resistant.
R e s u l t s of the l o g - l o g l i n e a r r e g r e s s i o n a n a l y s i s of the d a t a for

the e n t i r e test p e r i o d are p r e s e n t e d in T a b l e 3. B a s e d o n t h e s e data,
e s t i m a t e d l o s s e s in f i f t y y e a r s w e r e c a l c u l a t e d a n d are s h o w n in T a b l e
4. T h e A 242 steel s h o w e d a v e r a g e e s t i m a t e d losses r a n g i n g f r o m 57 to
268 ~ m (2.2 to 10.5 mils). The A 588 steel s h o w e d the n e x t l o w e s t
a v e r a g e e s t i m a t e d losses, r a n g i n g f r o m i01 to 411 ~ m (4.0 t o 16.2 mils).
A v e r a g e e s t i m a t e d losses for c o p p e r - b e a r i n g steel a n d c a r b o n steel
r a n g e d f r o m 130 to 2523 ~ m (5.2 to 99.3 mils). Again, d i f f e r e n c e s be-
t w e e n c o p p e r - b e a r i n g steel a n d c a r b o n steel do not a p p e a r to be
s i g n i f i c a n t at the u r b a n - i n d u s t r i a l or rural sites, w h e r e a s at t h e
m o d e r a t e - m a r i n e site, c o p p e r - b e a r i n g steel s h o w e d a m u c h l o w e r a v e r a g e
e s t i m a t e d loss in f i f t y y e a r s (824 vs. 2523 ~m).
E f f e c t of L o c a t i o n a n d O r i e n t a t i o n
T h e a v e r a g e c o r r o s i o n rates for all steel types for t h e 8 - t o - 1 6

y e a r p e r i o d are s u m m a r i z e d w i t h r e s p e c t to e x p o s u r e site a n d o r i e n t a t i o n
in T a b l e 5. At all test sites, the a v e r a g e r a t e s of the s a m p l e s e x p o s e d
f a c i n g s o u t h w e r e l o w e r t h a n t h o s e f a c i n g north, p r o b a b l y b e c a u s e d i r e c t
s o l a r r a d i a t i o n f r o m the south r e s u l t e d in r e d u c e d t i m e of w e t n e s s for
t h e s o u t h - f a c i n g samples. Also, in m o s t cases, the i n c l i n e d (30 ~)
s a m p l e s s h o w e d l o w e r rates t h a n d i d the v e r t i c a l samples. These results
are c o n s i s t e n t w i t h t h o s e r e p o r t e d b y L a r r a b e e [~] a n d a l s o b y L a Q u e [3]
w i t h r e s p e c t to v e r t i c a l v e r s u s i n c l i n e d samples. An exception occurred
at t h e m o d e r a t e - m a r i n e site, w h e r e for the s a m p l e s f a c i n g s o u t h the
v e r t i c a l s a m p l e s s h o w e d a l o w e r a v e r a g e r a t e t h a n d i d the i n c l i n e d
T a b l e 3 - - L o u - l o a l i n e a r r e u r e s s i o n c o n s t a n t s for p e n e t r a t i o n data.
C a l c u l a t e d p e r A S T M G i01.
1 6 - y e a r d a t a e x c e p t as noted.
C = At B
Log C = Log A + B Log t
C = Corrosion penetration, ~m
A a n d B are c o n s t a n t s
Urban- Rural Moderate-

Industrial Marine
Steel Type Orient. A B A B A B
A S T M A 242 30~ 20.05 0.208 18.65 0.386 26.62 0.515

30~ 21.45 0.249 21.28 0.524 29.66 0.581
90~ 22.02 0.217 20.54 0.409 25.22 0.550
90~ 21.45 0.312 24.82 0.504 32.21 0.622
ASTM A 588 30~ 24.24 0.268 22.02 0.523 34.43 0.587

30~ 26.46 0.349 24.16 0.611 38.13 0.614
90~ 29.17 0.304 23.91 0.543 34.18 0.608
90~ 28.68 0.398 26.13 0.626 37.63 0.668
Copper- 30~ 24.49 0.350 22.10 0.658 38.62 0,718

bearing 30~ 26.62 0.421 21.69 0.691 41.25 0.756
90~ 24.98 0.410 23.01 0.656 38.62 0.764
90~ 24.08 0.491 24.08 0.731 43.06 0.827
Carbon 30~ 30.40 0.350 25.80 0.632 46.92* 0.900*

30~ 34.51 0.378 27.20 0.644 52.67* 0.938*
90~ 28.84 0.369 28.10 0.623 43.80* 0.876*
90~ 28.60 0.432 27.69 0.691 54.89* 1.158"
* B a s e d o n 8 - y e a r data.
samples. However, this e x c e p t i o n w a s due e n t i r e l y to the a n o m a l o u s l y

l o w r a t e f o r t h e 90~ c a r b o n - s t e e l s a m p l e (Table 2).
Overall, it a p p e a r s that the rural site is about t w i c e as c o r r o -
s i v e as the u r b a n - i n d u s t r i a l s i t e , a n d that the m o d e r a t e - m a r i n e site is
a b o u t ten t i m e s as c o r r o s i v e as the u r b a n - i n d u s t r i a l site. The results
for the w e a t h e r i n g s t e e l s e x p o s e d at the rural a n d m o d e r a t e - m a r i n e sites
w e r e c o n s i s t e n t w i t h t h o s e p u b l i s h e d p r e v i o u s l y b y Shastry, et al.[4].
However, the c o r r o s i o n rates at the u r b a n - i n d u s t r i a l site w e r e l o w e r
b e c a u s e of t h e r e a s o n s d i s c u s s e d below.
It is k n o w n that the K e a r n y u r b a n - i n d u s t r i a l site has b e e n
d e c r e a s i n g in c o r r o s i v i t y o v e r the years, p r o b a b l y b e c a u s e of a d e c r e a s e
in SO 2 c o n t e n t in the area. Thus, w h a t a p p e a r to b e a n o m a l o u s m a s s
l o s s e s for the s a m p l e s e x p o s e d in rural P o t t e r C o u n t y a n d i n d u s t r i a l
K e a r n y are m o r e a c o n s e q u e n c e of two a c t i o n s t a k e n in the U n i t e d S t a t e s
in the i n t e r e s t of c o n t r o l l i n g the "acid rain" p r o b l e m s o c c u r r i n g in t h e
n o r t h e a s t e r n p a r t of the c o u n t r y a n d the s o u t h e a s t e r n c o r n e r of Canada.
T h e first a c t i o n w a s to r e l i e v e local p o l l u t i o n a r o u n d p o w e r p l a n t s in
t h e m i d d l e w e s t e r n states b y b u i l d i n g v e r y tall e x h a u s t s t a c k s as h i g h
as 240 to 365 m (800 to 1200 ft) [5]. The p u r p o s e w a s to d i s p e r s e a n d
d i l u t e s u l f u r o x i d e gases. To e v e r y o n e ' s s u r p r i s e a n d d i s a p p o i n t m e n t ,
the g a s e s w e r e c a u g h t u p in the n a t u r a l w e s t - t o - e a s t p r e v a i l i n g w i n d s a n d
c r o s s e d n o r t h e r n P e n n s y l v a n i a , e n c o m p a s s i n g P o t t e r County, i n t o u p p e r
N e w Y o r k S t a t e a n d i n t o C a n a d a [6]. T h e r e s u l t of t h i s p a s s a g e of the
COBURN ET AL./WEATHERING STEELS AT EASTERN U.S. SITES 107
Table 4--Estimated 50-year corrosion penetrations.

B a s e d o n r e g r e s s i o n a n a l y s i s of 1 6 - y e a r d a t a e x c e p t as noted.
Urban- Rural Moderate-

Industrial Marine
Steel Type Orient. ~m mils ~m mils ~m mils
A S T M A 242 30~ 45 1.8 84 3.3 200 7.9

30~ 57 2.2 165 6.5 288 11.3
90~ 51 2.0 102 4.0 217 8.5
90~ 73 2.9 178 7.0 367 14.4
AVG 57 2.2 132 5.2 268 10.5
A S T M A 588 30~ 69 2.7 170 6.7 342 13.5

30~ 104 4.1 264 10.4 421 16.6
90~ 96 3.8 200 7.9 369 14.5
90~N 136 5.4 302 11.9 513 20.5
AVG I01 4.0 234 9.2 411 16.2
Copper- 30~ 96 3.8 290 11.4 641 25.2

bearing 30~ 138 5.4 324 12.8 794 31.3
90~ 124 4.9 300 11.8 767 30.2
90~ 164 6.5 420 16.5 1094 43.1
AVG 130 5.2 334 13.1 824 32.4
Carbon 30~ 120 4.7 306 12.0 1586" 62.4*

30~ 151 5.9 338 13.3 2066* 81.3"
90~ 122 4.8 322 12.7 1348" 53.1"
90~ 155 6.1 413 16.2 5092* 200.5*
AVG 137 5.4 345 13.6 2523* 99.3*
* B a s e d o n 8 - y e a r data.
T a b l e 5 - - A v e r a q e c o r r o s i o n rates, all steel tYPes.

8-to-16 y e a r p e r i o d e x c e p t as noted.
Urban-Industrial Rural Moderate-Marine*

Orientation ~m/yr mils/yr ~m/yr mils/yr ~m/yr mils/yr
30~ 2.2 0.09 4.8 0.19 20.6 0.81

90~ 2.8 0.11 5.0 0.20 14.4 0.56
30~ 2.7 0.11 5.2 0.20 22.6 0.89

90~ 3.1 0.12 5.9 0.23 46.9 1.85
AVG 2.7 0.11 5.2 0.20 26.0 1.03
* 4 - t o - 8 y e a r d a t a u s e d for c a r b o n steel at the m o d e r a t e - m a r i n e site.
a c i d r a i n w a s to p r o f o u n d l y i n f l u e n c e the p e r f o r m a n c e of the s a m p l e s in
r u r a l P o t t e r County. T h i s o c c u r r e d d e s p i t e the s a m p l e s b e i n g p a r t i a l l y
s h e l t e r e d b y some m o u n t a i n s in the distance.
In contrast, the s a m p l e s e x p o s e d in K e a r n y w e r e not in the p a t h of
t h e s e p a r t i c u l a r a g g r e s s i v e b r e e z e s b u t w e r e i n f l u e n c e d b y the fact that
all of the m a j o r i n d u s t r i a l p l a n t s h a d to u t i l i z e l o w s u l p h u r fuels
a n d i n s t a l l s c r u b b e r s on t h e i r e x h a u s t stacks. This r e d u c t i o n in
p o l l u t i o n l e v e l s b e g a n s l o w l y in the late 1960's and, b y t o d a y ' s
m e a s u r e m e n t s , the e n v i r o n m e n t is r e l a t i v e l y mild. Another factor

l e a d i n g to a r e d u c t i o n in a g g r e s s i v e n e s s of this site is the fact that
it is l o c a t e d in a w i d e - o p e n a r e a w h e r e c o n s t a n t b r e e z e s blow, t h u s the
t i m e - o f - w e t n e s s of the s a m p l e s is m u c h less t h a n it is in P o t t e r County.
O n e final o b s e r v a t i o n c o n c e r n i n g K e a r n y is that, m a n y y e a r s ago,
c o r r o s i o n of s t e e l s at the 2 5 0 - m e t e r lot at K u r e Beach, NC, w a s
c o m p a r a b l e to that at N e w a r k - K e a r n y . F r o m the p r e s e n t study, the
c o r r o s i v e n e s s of the K e a r n y site is o n e - t e n t h that of the K u r e B e a c h
site.
Appearance
In all cases, the w e a t h e r i n g - s t e e l p a n e l s s h o w e d a m o r e u n i f o r m

a p p e a r a n c e w i t h less f l a k i n g of c o r r o s i o n p r o d u c t s t h a n d i d the c o p p e r -
b e a r i n g steel a n d c a r b o n steel panels. At the u r b a n - i n d u s t r i a l site,
the w e a t h e r i n g - s t e e l p a n e l s d e v e l o p e d a b l u e - g r a y patina, as o p p o s e d to
a b r o w n i s h c o l o r at the o t h e r test sites. In m o s t cases, the i n c l i n e d
(30 ~) s a m p l e s s h o w e d a s m o o t h e r s u r f a c e t h a n d i d the v e r t i c a l samples.
Also, e x c e p t for the m o d e r a t e - m a r i n e site, s a m p l e s e x p o s e d f a c i n g s o u t h
a p p e a r e d s o m e w h a t s m o o t h e r t h a n t h o s e f a c i n g north.
CONCLUSIONS
The r e s u l t s of the s i x t e e n - y e a r e x p o s u r e test at the u r b a n -

industrial, rural, a n d m o d e r a t e - m a r i n e sites in the U n i t e d S t a t e s can be
s u n m ~ r i z e d as follows:
i. In all cases, A S T M A 242 steel (USS C O R - T E N A) s h o w e d the

l o w e s t a v e r a g e c o r r o s i o n rates for the 8-to-16 y e a r period, w i t h r a t e s
r a n g i n g f r o m 1.5 to 8.8 ~ m / y e a r (0.06 to 0.35 m i l s / y e a r ) .
2. A S T M A 588 steel (USS C O R - T E N B) s h o w e d the next l o w e s t a v e r a g e
c o r r o s i o n rates, r a n g i n g f r o m 2.5 to 12.4 ~ m / y e a r (0.i0 to 0.49
mils/year).
3. A v e r a g e c o r r o s i o n rates for c o p p e r - b e a r i n g steel a n d c a r b o n
steel r a n g e d f r o m 3.2 to 58.8 ~ m / y e a r (0.12 to 2.3 m i l s / y e a r ) . In the
u r b a n - i n d u s t r i a l a n d rural atmospheres, t h e r e w a s no s i g n i f i c a n t
d i f f e r e n c e in a v e r a g e rates for t h e s e two steels. However, in the
m o d e r a t e - m a r i n e environment, c o p p e r - b e a r i n g s t e e l w a s a p p r e c i a b l y m o r e
c o r r o s i o n r e s i s t a n t t h a n w a s c a r b o n steel.
4. B a s e d on a v e r a g e c o r r o s i o n rates for all t y p e s of steel tested,
t h e rural test site was about t w i c e as c o r r o s i v e as the u r b a n - i n d u s t r i a l
s i t e a n d the m o d e r a t e - m a r i n e site w a s about t e n t i m e s as c o r r o s i v e as
t h e u r b a n - i n d u s t r i a l site. However, the u r b a n - i n d u s t r i a l s i t e u s e d
(Kearny, NJ) w a s less c o r r o s i v e t h a n in p r e v i o u s t e s t s b e c a u s e of
e n v i r o n m e n t a l changes.
5. C o r r o s i o n rates w e r e g e n e r a l l y l o w e r for p a n e l s e x p o s e d f a c i n g
south, as o p p o s e d to north, a n d for p a n e l s e x p o s e d at 30 ~ to t h e
h o r i z o n t a l , as o p p o s e d to vertical.
6. In all cases, the w e a t h e r i n g - s t e e l p a n e l s s h o w e d a m o r e
u n i f o r m a p p e a r a n c e t h a n that of the c o p p e r - b e a r i n g steel or c a r b o n steel
panels.
COBURN ET AL./WEATHERING STEELS AT EASTERN U.S, SITES 109
REFERENCES
[!] Komp, M. E., Coburn, S. K., and Lore, S. C., "Worldwide Data on the
A t m o s p h e r i c C o r r o s i o n R e s i s t a n c e of W e a t h e r i n g Steels," Pro-
ceedinus of the 12th International C o r r o s i o n Conqress, Vol.2, N A C E
International, Houston, 1993, pp. 509-528.
[2] Larrabee, C. P., "Corrosion R e s i s t a n c e of H i g h - S t r e n g t h L o w - A l l o y

Steels as I n f l u e n c e d by C o m p o s i t i o n and E n v i r o n m e n t , " Corrosion,
Vol. 9, No. 8, August 1953.
[3] LaQue, F. L., "Corrosion Testing," M a r b u r g Lecture, P r o c e e d i n u s of

the ASTM, Vol. 51, A m e r i c a n Society for T e s t i n g and Materials,
Philadelphia, 1951.
[4] Shastry, C. R., Friel, J. J., and Townsend, H. E., " S i x t e e n - Y e a r

A t m o s p h e r i c C o r r o s i o n P e r f o r m a n c e of W e a t h e r i n g Steels in Marine,
Rural, and Industrial Environments," D e g r a d a t i o n of Metals in the
Atmosphere, A S T M STP 965, S. W. Dean and T. S. Lee, Eds., A m e r i c a n
S o c i e t y for T e s t i n g and Materials, Philadelphia, 1988, pp. 5-15.
[5] Special Report, "The B u i l d i n g of Tall (And Not So Tall) Stacks,"

E n v i r o n m e n t a l Science & Technoloq7, Vol. 9, June 1975, pp. 522-
527.
[6] Likens, G. E., Wright, R. F., Galloway, J. N., and Butler, T. J.,
"Acid Rain," Scientic American, Vol. 241, O c t o b e r 1979, pp. 43-51.
-.&
TABLE A--Averaue corrosion penetration, um (calculated from mass loss). _~
O
A242 A588 C o p p e r - b e a r i n ~ Steel C a r b o n Steel
Years 30 S 30 N 90 S 90 N 30 S 30 N 90 S 90 N 30 S 30 N 90 S 90 N 30 S 30N 90 S 90 N
U R B A N - I N D U S T R I A L S I T E - KEARNY, N J
0.5 18.1 18.1 19.7 17.3 21.4 19.7 28.8 20.5 20.5 19.7 18.9 19.7 23.8 32.0 23.0 21.4
0.5 17.3 18.9 17.3 17.3 18.1 18.9 19.7 22.2 17.3 18.9 18.9 16.4 23.0 25.5 22.2 23.8 o
1 19.7 20.5 22.2 21.4 24.7 23.0 32.9 26.3 25.5 26.3 24.7 23.0 28.8 34.5 29.6 25.5 CO
1 21.4 21.4 23.8 21.4 23.8 29.6 26.3 27.9 23.8 26.3 23.8 21.4 32.9 33.7 28.8 27.1 -r
2 23.0 27.1 26.3 27.9 33.7 41.9 36.2 42.7 36.2 41.1 37.0 37.8 43.5 50.1 38.6 40.3 m
2 22.2 24.7 26.3 26.3 28.8 37.8 34.5 38.6 31.2 36.2 32.0 32.0 36.2 43.5 34.5 37.0 ~D
4 27.1 30.4 28.8 32.9 37.0 44.4 47.7 55.1 41.1 50.1 46.0 47.7 51.8 58.3 50.9 54.2
4 27.9 30.4 29.6 34.5 33.7 43.5 46.0 53.4 37.8 47.7 44.4 50.1 49.3 58.3 46.8 53.4 0
8 27.1 35.3 32.0 38,6 40.3 51,8 47.7 64.1 47.7 58.3 56.7 64.9 60.0 75.6 60.0 69.8 0
8 27.1 32.9 31.2 37.8 38.6 50.1 48.5 61.6 48.5 56.7 52.6 62.4 57.5 72.3 58.3 66.6 ~D
~D
16 38.6 46.8 41.9 50.9 55.1 67.4 87.9 83.8 73.1 88.7 82.2 96.1 78.9 i00 80.5 97.8 0
16 40.3 42.7 43.5 55.1 50.1 71.5 60.8 84.6 68.2 88.7 78.9 97.8 87.1 97.8 87.1 96.1 GO
R U R A L SITE - P O T T E R COUNTY, PA 5
0.5 12.3 13.1 14.0 14.8 14.0 14.8 14.0 16.4 13.1 12.3 14.8 14.0 15.6 17.3 16.4 16.4 Z
0.5 14.0 14.0 12.3 16.4 14.8 14.0 15.6 15.6 13.1 13.1 13.1 14.8 16.4 15.6 16.4 17.3
1 20.5 21.4 22.2 23.8 20.5 24.7 24.7 23.8 22.2 21.4 23.0 20.5 23.8 24.7 26.3 26.3
1 18.1 20.5 20.5 25.5 21.4 23.8 23.8 26.3 21.4 20.5 22.2 22.2 26.3 31.2 26.3 24.7
2 26.3 32.9 31.2 39.4 36.2 41.1 39.4 44.4 38.6 39.4 38.6 45.2 44.4 43.5 43.5 48.5
2 25.5 35.3 31.2 39.4 35.3 41.9 37.8 45.2 38.6 38.6 40.3 46.8 42.7 45.2 42.7 49.3
4 31.2 46.8 41.1 55.9 50.9 60.8 56.7 66.6 59.2 61.6 59.2 71.5 64.9 72.3 66.6 78.1 H
4 33.7 46.8 43.5 56.7 50.9 60.0 55.1 67.4 57.5 60.8 61.6 71.5 64.9 69.8 68.2 78.1
8 32.9 63.3 46.0 71.5 60.8 85.5 71.5 96.1 80.5 88.7 85.5 104 95.3 102 i03 118
8 34.5 59.2 46.0 71.5 62.4 85.5 70.7 96.1 83.0 87.9 87.1 104 93.7 97.8 88.7 113
16 46.8 83.0 64.9 76.4 87.9 113 104 138 135 140 141 170 145 153 162 167
16 73.1 89.6 49.3 102 89.6 131 97.8 138 131 141 135 --- 141 --- 164 188
MODERATE MARINE SITE - K U R E BEACH, NC
0.5 18.9 20.5 18.1 22.2 24.7 25.5 25.5 27.1 25.5 27.1 24.7 27.1 26.3 29.6 24.7 31.2
0.5 19.7 19.7 19.7 21.4 23.8 27.9 22.2 25.5 23.0 25.5 23.0 26.3 27.9 29.6 23.8 29.6
1 27.1 27.9 24.7 32.0 35.3 35.3 32.9 35.3 40.3 41.9 37.8 44.4 40.3 50.1 41.9 48.5
1 28.8 31.2 25.5 36.2 32.9 36.2 34.5 37.0 36.2 39.4 36.2 44.4 47.7 48.5 38.6 48.5
2 35.3 46.0 36.2 49.3 50.1 57.5 50.1 63.3 63.3 68.2 64.1 69.0 91.2 92.9 88.7 97.0
2 38.6 44.4 37.0 45.2 51.8 65.7 50.1 55.9 63.3 67.4 64.1 72.3 86.3 98.6 78.9 104
4 51.8 63.3 49.3 66.6 71.5 82.2 75.6 83.0 103 106 115 119 142 211 229 230
4 53.4 66.6 53.4 72.3 73.1 80.5 77.2 83.0 104 108 113 120 150 182 202 275
8 73.1 90.4 68.2 113 113 129 117 146 159 186 183 219 380 417 288 674
8 76.4 98.6 75.6 107 108 130 115 140 162 190 181 218 297 352 285 808
16 126 150 147 205 194 224 199 288 305 371 333 550 467 * * *
. - - - * *
16 121 164 146 205 192 234 199 265 299 378 332 476
*Severe edge attack
~m rr
nils I~m mils
I 4 100 4
75 . . . . . . . . . . . 4 . . . . . . . . . . . . . . . . . . . . . . . . . t.................................~ ~ ~ ~5
i f i ~u Ste~l '
50 ................ i i ' iA i (3
)- 50
0
O0
C
I 25 Z
m
>
0 0
) 2 4 6 8 0 12 14 16 0 2 4 6 8 10 12 14 16 m
Years Years ". -rt

m
z
~m mils Mm mils
I00 , 4 tO0 , : , 4
-4
= m
] m
i r-
75 ................. i .................... i ........... ......... i3 75
L
--t
50 ..................... i..................... ~ ...... I ................[ 50 3o

-4
"11
11
z
25 25 z
i , --t
o o 13
D 2 4 6 8 10 12 14 16 0 2 4 6 8 10 12 14 16
Years Years
YIG. A l - - A v e r a g e corrosion penetration vs. time curves, urban-industrial site, Kearny, NJ.
jim mils i.~m mils
25O i 10 25O i ,, ~ ~ jl0
/
2OO ...................~................................................................. 8 200 >

........................ ~....................................i .....................'.........................................t 8 -%
150 6 150 O
(n
"U
-1-
100 ...... ~ ...... ~ ......... } .................... , ................. :.....................~.................. 4 100 m
33
N
50 50 0
.~. . . ; ........ j ~ _ _ i A 242-JJ 2 0
="i :, I j I
0 0 0
0
2 4 6 8 10 12 14 16 0 2 4 6 8 10 12 14 16 9
Z
Years Years
#m mils }lm mils

250 ~ 10 25O 10
2OO
=
~~176 I ................................................................ i ................................................................
150 ....................................... ~.....................i .....................!.....................~........................................... i. . . . . . . 6 150
100 4 100 ' ~ ~ 4
5O 2 50
0 i, i i i 0
0 9 0
0 2 4 6 8 10 12 14 16 2 4 6 8 10 12 14 16
Years Yeam
FIG. A 2 - - A v e r a g e corrosion penetration vs. time curves, rural site, P o t t e r County, PA.
p,m mils ~m mils
800 8OO 132
i ! ! 32 I )
600 24 600 24
i i i '
1 O
400 16 400 16
O
i i i a ~ I . . . . . . . . . . . . . . .............. i ....... i . . . . . . . . . . ~0
C
:D
.................................i ..................! ............. Z
200 200 8
Ill
-I
i I r-
~ T "i ~i "i i i 0
0
2 4 6 8 10 12 4 16 0 2 4 6 8 10 12 14 16
m
Years Years
-T
m
z
~m mils ~m mils
8OO 800 ~ ) .-t
i i 32 m
i 32 m
L ! r-
600 600 .............. ) ) ....................... 24

-.-t
L ) m
400 j,'E .1~ - ! .................. i ........ 1 6 ....... i .................. i ................. i .................. 16

400 i ) ) --t
m
z
4 . i
200 ~..................... i................ ~ 8
200 ..................
[ .................i ....................i .............
, c
0 --t
0 ~- ~ ' . . . . 0 ' 0 m
0 2 4 6 8 10 12 14 16 0 2 4 6 8 10 12 14 16
Years Years
--L
--L
FIG. A3--Average corrosion penetration vs. time curves, moderate-marine site, Kure Beach, NC, (250 m) O3
Dagmar Knotkova I and Jaroslava Vlckova 1
ATMOSPHERIC CORROSION OF BOLTED LAP JOINTS MADE

OF WEATHERING STEEL
REFERENCE: Knotkova, D. and Vlckova, J., "Atmospheric

Corrosion of Bolted Lap Joints Made of Weathering Steel,"
Atmospheric Corrosion, W. W. Kirk and Herbert H. Lawson,
Eds., American Society for Testing and Materials,
Philadelphia, 1995.
ABSTRACT: For certain types of steel structures the

application of w e a t h e r i n g steels is e s p e c i a l l y suitable.
These are electrical transmission towers, masts, b r i d g e s
and other structures, used in outdoor exposure, where
brown color is appreciated and no m a i n t e n a n c e is
necessary.
Proposals for the use of weathering steels for various

types of steel structures are based mainly on the results
of field corrosion tests (outdoor and under sheds) in
which a significantly higher corrosion resistence of
weathering steels as compared to that of plain carbon
structural steel, has been proved in the atmospheres of
low or m e d i u m aggressivness.
At bolted joints of certain design exposed to a more

corrosive environment, significant defects were found in
the crevices which cause even deformation of the joints.
After d i s m a n t l i n g and pickling, these phenomena were
quantified. Recommendations were prepared to minimize
these c o r r o s i o n effects, and also possibilities were
considered of increasing the lifetime of structures
already affected by crevice corrosion.
KEYWORDS: w e a t h e r i n g steel, atmospheric corrosion, test

site result, steel structure, transmission tower, bolted
joint, crevice corrosion, ultrasound measurement, residual
thickness.
i. Senior research scientist, research scientist

respectively, National Institute for Protection of
Material (SVUOM), U Mestanskeho pivovaru 4,
114
Copyrightm1995by
KNOTKOVA AND VLCKOVA ON BOLTED LAP JOINTS 115
INTRODUCTION
Corrosion resistance of low-alloy w e a t h e r i n g steels was

the object of various site testing experiments as well as
of tests with samples exposed on existing structures
(i, 2, 3).
All these tests resulted in a clear conclusion that in

low to medium corrosivity atmospheres, w e a t h e r i n g steels
are distinctly more resistant than plain carbon structural
steels. The tests results have been p u b l i s h e d and were
then used as background for specifying the guiding
corrosion values in ISO 9224 (Table i).
A part of SVUOM on site tests included separate

evaluations of the upper and lower sample surfaces and
also at the influences of orientation (to S, N, W, E). The
tests showed that reduced rinsing by rain of the evaluated
surfaces as well as poorer drying conditions raised the
corrosion rate of weathering steel to some extent, but
also increased corrosion resistance (if compared with
plain carbon structural steel) (4).
Technical conclusions and recommendations were

formulated after a complex evaluation of site tests
(outdoor and under sheds), of tests with simple structural
components, and utilization of many years of investigations of
different existing structures manufactured with weathering
steel (1,4).
Table 1 - Guiding corrosion values for corrosion rates of

carbon steel and weathering steel according to
ISO 9224
corrosion rate (~m/a)

steel corrosivity
category for the first steady state
i0 y e a r s
1 <O.5 < 0.i

carbon 2 0.5 - 5 0.i - 0.5
3 5 - 12 1.5 - 6
4 12 - 30 6 - 20
5 30 - i00 20 - 90
1 < 0.i < 0.I

weathering 2 0.1 - 2 0.I - 1
3 2 - 8 1 - 5
4 8 - 15 5 - i0
5 15 - 80 i0 - 80
NOTE:
i. C a t e g o r i e s of corrosivity according to ISO 9223.
2. C l a s s i f i c a t i o n of p o l l u t i o n b y S O 2 a c c o r d i n g
ISO 9223
Deposition rate of SO 2 Concentration of SO 2

P P Category
(mg.~d2d-I) (~g~m-3)
Pd < i0 Pc < 12 P0
i0 < P d < 35 12 < P c < 40 P1
35 < P d < 80 40 < P c < 90 P2
80 < P d < 200 90 < P c < 250 P3
RESULTS OF ATMOSPHERIC CORROSION TESTS: CATEGORY

OF LOCATIONS 1 AND 2
In order to describe the corrosion behaviour of

low-alloy weathering steel on large and voluminous
structures with various surface orientations and shielding
d e g r e e (bridges, f a c a d e covers, etc.) r e s u l t s of o p e n air
exposure tests (category i) a n d l o u v e r box exposures 1
( c a t e g o r y 2) w e r e used. T h e s e r e s u l t s a l l o w c a l c u l a t i o n of
quantitative d a t a on corrosion attack at both t y p e s of
atmospheric exposure. The corrosion kinetics and
mechanisms in joints of the structural elements however
are m u c h m o r e c o m p l i c a t e d and h e n c e t h e e v a l u a t i o n is m o r e
difficult as will be shown below. It is therefore
necessary to f i n d data from site tests (both exposure
categories) as well as examples of quantitatively
evaluated corrosion damage on selected strl~ctural
elements.
Long term c o r r o s i o n t e s t s of w e a t h e r i n g s t e e l s on the

testing s i t e s of eastern countries were organized from
1974 to 1986. T h e r e s u l t s for the C z e c h w e a t h e r i n g steel
A T M O F I X 2 in o p e n e x p o s u r e c o n d i t i o n s and in t h e l o u v e r box
are illustrated by F i g u r e s 1 and 2. T h e m e a n v a l u e s of
e n v i r o n m e n t a l c h a r a c t e r i s t i c s d u r i n g the e x p o s u r e t i m e are
in T a b l e 2.
T h e site t e s t s of A T M O F I X at e x p o s u r e c a t e g o r i e s 1 and 2
are p a r t of the p r e s e n t extensive international testing
program (UN E C E International Cooperative P r o g r a m m e on
E f f e c t s of P o l l u t i o n on M a t e r i a l s I n c l u d i n g H i s t o r i c and
Cultural Monuments).
Four-year exposure results on C z e c h t e s t i n g s i t e s and

other selected sites are s u m m a r i z e d in T a b l e s 3 to 5.
Category 2 exposure was not f o u n d in louver boxes but
u n d e r s p e c i a l shelter.
1 mode of e x p o s u r e in s h e l t e r shed
2 C h e m i c a l c o m p o s i t i o n of A T M O F I X steel:
C max. 0.12 %, M n 0.30 % - 0.80 %, Si 0.25 % - 0.70 %,
P 0.07 % - 0.15 %, S 0.040 %, Cr 0.50 % - 1.20 %,
Ni 0 . 3 0 % - 0.60%, Cu 0.30% - 0.55%, A1 min. 0.01%.
Figure I - Corrosion os ATMOFIX 52A in open air

and in l o u v e r box
1600~
1400-
1200-
1000-
E
r
0 800-
s
0
o
600-
400-
200-
0-~ L
0 20 40 60 80 100 120 140 160

time of exposure (months)
X Zven.open I Zven.louvre ~K Murm.open

[] Murm.louvre - I - Letn.open ~ Letn.louvre
K N O T K O V A A N D V L C K O V A ON B O L T E D L A P J O I N T S 119
Figure 2 - Corrosion os carbon steel in open air

and in l o u v e r box
1800-
1600-
1400-
1200-
E 1000-
c
O
2 800-
0
0
600- ........ i.
400-
200-
0 20 40 60 80 100 120 140 160

time of exposure (months)
X Zven.open ,L Zven.louvre ;K Murm.open

[] Murm.louvre - I I - Letn.open -~-Letn.louvre
Table 2 - Mean values of climatic parameters and

concentrations of pollution for exposure period
1975 - 1986
Mean value
Test site
RH Tamp SO C1
(%) (~ ( m g . m 2 2 d -I) (mg.m-2d -I)
open atmosphere
Zvenigorod 81 3.90 26.1

Murmansk 82 0.70 1.2 11.2
Letnany 78 8.70 82.6
louver box
Zvenigorod 81 3.50 ii.0

Murmansk 81 0.09 0.8 2.3
Letnany 74 8.00 39.4
Table 3 - Mean values of climatic parameters and

concentrations of pollutions for 4 years of
exposure
Type of Test site Tamp RH TOW S0 { NO CI-

atmosphere (%) (%) (hours) (~g.~-3) (~g.m23) (mg.l-l)
rural KasperskeHory 6.7 77 3232 18.8 11,4 1.05
urban Prague - Letnanny 9.5 75 2834 65.1 35.5 2.66
industrial Kopisty 9.4 73 2228 81.1 37.2 2.02
rural Gar~isch-Partenkirchen 7.5 82 3346 7.6 13.3 0,20
urban R0~e 16.5 65 1790 33.3 68.4
industrial Ste~ville 12.1 61 1088 59.4 44.9 0.59
~arine Clatteringsshaws L0ch 9.2 96 4.1 4.0 7.64
KNOTKOVAANDVLCKOVA ON BOLTEDLAPJOINTS 121
Table 4 - Mass l o s s e s of weathering steel (g.m -2) a f t e r

I, 2 a n d 4 y e a r s of e x p o s u r e
T y p e of Test site Time of Mass l o s s e s ( g . m -2)

atmosphere exposure
o p e n ex. shelter
rural Kasperske Hory 150 96

236 180
324 292
urban Prague - 250 190

Letnanny 361 365
402 531
industrial Kopisty 304 227

427 476
437 860
rural Garmisch- 112 58

Partenkirchen 162 115
180 143
urban Rome 154 60

204 106
211 131
industrial Steubenville 213 106

280
306 267
marine Clatteringsshaw 1 190 86

Loch 2 267 223
4 377 408
Table 5 - Calculated differential corrosion rate

( g . m - 2 y e a r -I) of w e a t h e r i n g steel for t h e p e r i o d
0 - 2 y e a r s (a) and 2 - 4 y e a r s (b)
Type of e x p o s u r e
T y p e of T e s t site
atmosphere open shelter
a b a b
rural Kasperske Hory 118.0 37.3 90.0 56.2
urban Prague - Letnanny 180.5 27.3 182.5 80.0
industrial Kopisty 213.4 11.5 238.0 186.0
rural Garmisch-
Partenkirchen 81.0 17.3 57.5 15.3
urban Rome 102.0 11.0 53.0 14.2
industrial Steubenville 140.0 1.3 134.0
marine Clatteringsshaws
Loch 133.3 53.0 112.0 85.5
CORROSION ATTACK OF STEEL STRUCTURES
For c e r t a i n types of steel s t r u c t u r e s the a p p l i c a t i o n

of weathering steels is e s p e c i a l l y suitable. T h e s e are
electrical transmission towers, masts, b r i d g e s and o t h e r
structures, u s e d in outdoor exposure, where brown color
and no m a i n t e n a n c e is a p p r e c i a t e d . E l e c t r i c a l t r a n s m i s s i o n
t o w e r s are the t y p i c a l example. In the C z e c h R e p u b l i c in
the p a s t 20 y e a r s a n u m b e r of t h e s e t o w e r s w e r e erected.
Corrosion attack of ATMOFIX 52A power transmission

towers was systematically evaluated (5) for a long period
with respect to
- corrosivity of the locations or area

- microclimatic effects of the nearby surroundings
- space orientation of the tower element above the base
height
- corrosion of the joining material (bolts and washers)
- special corrosion phenomenon, effects at important
structural elements.
The most important element affecting corrosion is

bolted joints. The worse corrosion conditions in bolted
joints are characterized by accumulation of water during
condensation and rain periods. Water then penetrates into
the joint together with corrosive components of the
atmosphere. Drying is hindered as well as elution of
corrosive rust components so that the periodic scaling of
the upper rust layer does not take place.
It was the goal of the investigation to quantify these

effects as the basis of the following evaluation of these
corrosion effects on the static properties of the
structures. Selected dismantled elements of towers after
different exposure periods were evaluated. Table 6
contains the specification of the evaluated elements.
Evaluation of corrosion attack
- photodocumentation of elements, samples and contact

surfaces before and after dismantling
- evaluation of rust inside the crevice
metallographic analysis of rust layer
phase analysis of rust
determination of corrosion stimulating components in
rust
measurement of residual thickness after rust
- removal by
pickling in Clark's solution
- corrosion attack of joining elements by
visual evaluation
measurement of bolt shank diameter after removing rust
in Clark's solution
metallographic evaluation of local attack (pit depths)
124 ATMOSPHERIOCORROSION
Table 6 - Specification of evaluated elements
Exposure
No Tower type Corrosivity time Element Specification
of locality (years)
two bolts joint angle iron/cover plate

1 400 kVsingle 3- 4 6 A angle iron 80 x 80 x 6 mm
transmission bolts M 20
line
one line (4 bolts) joint angle iron/cover plate
angle iron I00 x i00 x 8 mm
bolts M 16 probably diffusion chromized
two line (4 bolts) point angle iron/cover plate

angle iron 160 x 160 x 12 mm
bolts M 24 probably galvanized
two line joint with several bolts

2 400 kV double 4- 5 i0 angle iron/cover plate
transmission angle iron 150 x 150 x i0 mm
line cover plates 160 x 8 mm, 120 x 8 mm
bolts M 16
more complicated spatial element (plate with

angle irons)
plates 320 x 320 x i0 mm, 360 x 360 x 8 mm,
angle irons 80 x 80 x 7 n, 60 x 60 x 6 mm
bolts M 20
one line joint with several bolts angle iron/

3 110 kV 3 12 A cover plate
distribution nominal thickness 6 ~, width 70 mm
tower bolts M 16, spacing of holes 100 and 150 mm
one line joint with several bolts angle iron/

cover plate
nominal thickness 6 mm, width I00 mm
bolts M 20, spacing of holes i00 and 150 mm
NOTE: Number in bolts specification indicate diameter of

male thread in mm
Results
Rust layer evaluation
Inside the crevice, the rust layer thickness and

a p p e a r a n c e is n o t uniform. H i g h e s t thicknesses are found
near the edges w h e r e the layer can be d i s t i n g u i s h e d .
T o w a r d s t h e b o l t hole, t h e r u s t l a y e r t h i c k n e s s d e c r e a c e s .
The rust is m o r e c o h e r e n t in close p r o x i m i t y of the bolts
w h e r e almost no rust is found. L i g h t e s t colors a p p e a r on the
steel surface; the rust inside shows a dark color.
Qualitative phase analysis revealed a- and y - F e O O H ~

a-FeOOH prevailing i n s i d e the layer. On its s u r f a c e the
a m o u n t s of b o t h p h a s e s are a l m o s t equal. No s p e c i f i c p h a s e
f e a t u r e s of r u s t in the c r e v i c e w e r e found.
Results of the chemical analysis of r u s t i n s i d e and

o u t s i d e of the joint i n c l u d i n g d e t e r m i n a t i o n of s u l f a t e and
c h l o r i d e c o n t e n t s and their s o l u b l e parts are shown in T a b l e
7.
Table 7 - Content of c o r r o s i o n s t i m u l a n t s in rust from

crevice of e l e m e n t 2A (see T a b l e 6)
content (%)
Layer
CI- S042-
total soluble total soluble
outer 0.07 0.011 0.73 0.04
inner 0.06 0.007 0.45 0.07
The a m o u n t s of c o r r o s i o n s t i m u l a t i n g c o m p o n e n t s are not

v e r y high. It can be c o n c l u d e d t h a t s t i m u l a n t s do n o t g e t
a c c u m u l a t e d in the r u s t layer and t h a t l i m i t e d a c c e s s of
the outer e n v i r o n m e n t lowers their c o n t e n t in the russ The
outer, l i g h t - c o l o r e d layer shows a s o m e h o w h i g h e r c o n t e n t of
stimulants, but even this is lower than e x p e c t e d b a s e d on the
appearance. The p r e v a i l i n g p a r t of the s t i m u l a n t s in b o n d e d
in i n s o l u b l e form.
Metallographic analyses show a different t y p e of r u s t

inside the c r e v i c e t h a n t h a t of the r u s t outside. I n s i d e
the c r e v i c e the rust seems more c o m p a c t t h a n o u t s i d e on
the o p e n surface. The r u s t g r o w s f r o m the steel surface
and l a t e r the r u s t l a y e r b e c o m e s fused. The compactness
and visual uniformity of r u s t i n s i d e the crevice gives
evidence about the p r o c e s s s t a b i l i z a t i o n and the l i m i t e d
e f f e c t of o u t s i d e c o n d i t i o n s .
Measurement of E l e m e n t R e s i d u a l Thickness
Detailed a r e a l t h i c k n e s s m e a s u r e m e n t s and c i r c u m f e r e n c e
m e a s u r e m e n t s of the b o l t h o l e s w e r e p e r f o r m e d . T h e r e s u l t s
w e r e e v a l u a t e d f o r s e l e c t e d areas, d i r e c t i o n s and lines on
t h e joint surfaces. These complex r e s u l t s are s u m m a r i z e d
in T a b l e s 8, 9, a n d i0.
Table 8 - Mean relative corrosion losses of joints

- e l e m e n t s IA, B, C
corrosion loss r e l a t e d to n o m i n a l
t h i c k n e s s (~m)
Element joint s u r f a c e
free s u r f a c e
one side b o t h side
crevice crevice
i A residual thickness exceed nominal

value
1 B 180 20
1 C 300 500 200
KNOTKOVAANDVLCKOVAON 8OLTEDLAPJOINTS 127
Table 9 - Relative corrosion losses of element 2A, 2B
I
Elementl Measured area Corrosion loss
(~m)
free area i00 - 300

2 A 1 cm from crevice edge 50 - 465
in the bolt axis line 260 - 345
circumference of bolt holes 215 - 300
free corner of cover plate 435 - 503
fre~ area 350 - 500

2 B 1 cm from crevice edge 115 - 575
in the bolt axis line 155 - 360
circumference of bolt holes i0 - 260
free corner of cover plate 175 - 260
NOTE: Measured with SOMET thickness gauge
Table i0 - Mean remaining thicknesses of areas in the

crevice defined by spacing of bolt holes
Spacing Thickness (mm) Thickness

Element of holes loss 3
(mm) xI s2 (mm)
3 A 150 5.30 0.316 0.57

5.33 0.247 0.54
i00 5.75 0.167 0.12

5.73 0.108 0.14
5.73 0.210 0.14
3 B 150 5.14 0.255 0.73

5.09 0.213 0.78
i00 5.46 0.412 0.41

5.33 0.350 0.54
5.41 0.260 0.46
1 mean
2 standard deviation
3 relative to mean thickness of area under bolt
heads and nuts ( 5.87 mm)
NOTE: Measured with ultrasonic gauge Krautkramer DM 3.
The r e s i d u a l t h i c k n e s s d i s t r i b u t i o n s are i l l u s t r a t e d b y
Figs. 3 and 4. The r e m a i n i n g t h i c k n e s s distribution along and
n e a r the joint b o u n d a r y angle i r o n / c o v e r plate for e l e m e n t s IB
and IB (Table 6) is shown in T a b l e ii.
It is n o t p o s s i b l e to d e f i n e the real c o r r o s i o n losses

as no initial thickness data are available. These
corrosion losses s h o u l d be u n d e r s t o o d as r e l a t i v e data
c o v e r i n g l o s s e s of b o t h s u r f a c e s and r e l a t e to the n o m i n a l
t h i c k n e s s e s of the elements. In the case of e l e m e n t s 3A
and 3B the losses r e l a t e to the m e a n t h i c k n e s s e s of the
s u r f a c e b e l o w the b o l t h e a d s a n d nuts.
A r e v i e w of the r e l a t i v e corrosion losses allows the

f o l l o w i n g deductions:
- Most intense corrosion occurs along the e d g e s of the

joints and at such places w h e r e the c r e v i c e is less
t i g h t in c o n n e c t i o n w i t h the p o s i t i o n and d i s t a n c e of
the bolts. H e r e the r e l a t i v e losses e x c e e d the n o m i n a l
production tolerances.
- In the b o l t axis-line the a t t a c k is d i s t i n c t l y lower.
- No or u n s u b s t a n t i a l attack is f o u n d on the c i r c u m f e r e n c e
of b o l t holes.
- The s u r f a c e r o u g h n e s s and p i t s on the s u r f a c e i n s i d e the

crevice is d i s t i n c t l y lower than on fully exposed
surfaces.
Figure 3 - Renoinin9 thickness distribution in both side
crevice of elenent 2A (ongie iron 150 x 150 x ]0 nn)
I
I0,0 9,8 I0,I 9,7 9,H 9,8 9,8 9,8 9,4 9,6 9,8 10,7 Z
~s 0
~K
9,8 9,8 lO,O 9,9 9,8 IO, 1 9,8 10,2 lO,O 9,8 10,2 10,5 0<
~g,gg
10,2 10,2
lO, l g,6 10,4

z
I0,0 10,0 I0,2 I0,0I~,2 ~LO,) tO,4 10,3 lO,O L~,I "~10,! o
~ ]0,]2
r-
0
IO,l lO,l 10,2 10,3 ~I0, I [0, 1 10,2 10,3 -10,2 g,7 g,g lO, i
1(],2 ~10,11 0<
:10,3
I0,0 lO,l ( ~~LO,3 I0,I I0,0 10,I~ ~~I0,2 10,1 IO,O 9,7 9,6 10,2 0
w 10,04 z
0
9,8 9,g "-10,2 10,0 I0,0 10,1 -LO, I 9,6 9,6 9,4 g,4 10,0 r-
~g,87 mE~
9,6 g,6 9,8 g,8 9,7 9,7 g,6 g,5 g,5 g,4 g,7 10,4 r-
eg,54
2
~9,90 ~9,90 ~10,10 ~10,00 elO,O0 o10,00 ~10,00 ~9,90 ~9,90 e9,67 ~9,75 e10,33 ---I
,--L
DO
(D
Figure 4 - Renoining thickness d i s t r i b u t i o n in one side Oo
0
crevice of elenent 2B (ongle iron ]8 x 80 x 7 nn)
'-4
5,85 ,~ G, I0 ~ 6,35 a 6,05 a 6, lO
0
oo
-13
-r
oG,CG m
" sG,O5
~ ~, t~ t,.o ~o o
9
6,0f""~,g G,3 ._.i_.&4 s6,20 ;lJ
,,, t,o.,, ),., t =,o f 0
s G, L::5
0
z
,a 5,00
05,95 06,07 06,23 B 6,13

one side crevice
o6,20 o 6,05 ~6,10 o5,g5 .s5,05
~6,43
t'" t 5.0 t 7.` t~'
~" s6,86
~, }~ t~ t"'
~6,13
t~ to., t~ t5.o
~6,s
~G,C5
+,,, ~6,o t,,0 t~,o
~'6,17 06,23 .s6,57 - 05,03
free surfQce
KNOTKOVAANDVLCKOVAON BOLTEDLAPJOINTS 131
Table Ii - Distribution of r e m a i n i n g thicknesses on joint

b o u n d a r y - e l e m e n t s IB, iC
remaining thickness (mm)
crevice area free area
0.5 cm from at boundary at boundary 0.5 cm from

boundary line boundary
element 1 B
7.73 7.65 8.13 7.98

7.53 7.42 7.78 7.80
7.50 7.53 7.85 7.78
7.59 7.37 7.77 8.00
7.66 7.65 8.04 8.19
7.84 7.79 8.16 8.04
mean 7.64 7.57 7.95 7.96

s- 0.128 0.158 0.176 0.154
0.35 0.43 0.05 0.04
element 1 C
11.65 11.54 11.80 11.89

11.65 11.72 11.82 11.75
11.30 11.63 11.78 11.85
11.60 11.25 11.85 11.80
11.23 11.50 11.78 11.84
11.53 11.39 11.89 11.79
11.30 11.67 11.84 11.75
11.50 11.46 11.90 11.85
11.33 11.53 11.88 11.85
11.40 11.53 11.87 11.90
mean 11.45 11.52 11.84 11.83

s- 0.157 0.137 0.044 0.053
0.55 0.48 0.16 0.17
Corrosion Attack of Joining Elements
Joining elements always are the weak point of t o w e r

structures. Visual examination showed different severities
and character of corrosion attack. Results of bolt
evaluation for elements IA, B, and C ( s e e T a b l e 6) a r e
s h o w n in T a b l e 12. R e s u l t s o f bolt shank measurement are
s h o w n i n T a b l e 13, a n d r e s u l t s o f m e t a l l o g r a p h i c pit depth
measurements o n b o l t s a n d w a s h e r s a r e s h o w n in T a b l e 14.
Table 13 - B o l t shank diameters
nominal degree shank diameter (mm)

element dimensiontolerance of
(mm) attack ~ean min. mx. sx
slight 15.80 15.76 15.87 0.03

IB M 16 - 0.70 middle 15.79 15.74 15.84 0.03
severe 15.80 15.72 15.87 0.04
slight 23.88 23.87 23.91 0.01

iC M 24 - 0.84 middle 23.87 23.73 23.98 0.05
severe 23.83 23.72 23.99 0.08
Table 14 - M e t a l l o g r a p h i c evaluation of pitting attack of

b o l t s - e l e m e n t 2A
corrosion max. pit depth (~m)

element attack
bolt washer
slight 135 140

2 A middle 220 150
severe 335 215
Table 12 - Visual evaluation of bolts elements IA, B, C
(description of elements - see Table 6)
element type of joint heads and boil shank thread

z
rough, continuous discontinuous rough rust layer, part covered by rust unsignifioant O
two bolts rust layer, pits one side deformation (depressions) attack, out of cover O<
one row joint expressive different attack intensity Lhread covered by nuLs without
M 16 bolts local attack - stems only slightly corroded, significant only sligh aLLack; z
o
probably chromized (pits) most of surface with no attack outside cover significant <
- stems with higher attack corrosion attack at some screws
voluziness rust, pits, only small parLial Lhread partially leveled O
part of surface without attack <
- interne corrosion on stem, rough O
rust, local attack by pits z
0
two roy joint medium rough, nonuniform, at some points incoherent, by nuL cowered part of thread with
rough rust, some bolts with pits whiLe corrosion producL and rust m
H 24 bolts uniform, adherent o
probably galvanized rust layer, some spoLs, Lhread outside cover n e a r r-
bolt ends without stem - heavy corrosion attack 'u
attack
z
-.-I
==A
co
co
CONCLUSION
The major l o c a t i o n of corrosion failures of steel

structures made from w e a t h e r i n g steels are c r e v i c e s at
b o l t joints. The d e g r e e of a t t a c k d e p e n d s on the kind and
q u a l i t y on the joint, c o r r o s i v i t y of the environment, the
p o s i t i o n of the joint w i t h r e s p e c t to the tower, and, of
course, on e x p o s u r e time.
The n o m i n a l t o l e r a n c e s of the e v a l u a t e d e l e m e n t s were,

viewing their thickness, f r o m • 0.75 to • 1.25 mm. The
inside and outside mean relative corrosion losses
e x p r e s s e d as differences between nominal t h i c k n e s s value
and r e s i d u a l v a l u e w e r e from about 0.i0 to 0.80 mm.
The c o r r o s i o n loss grows in the d i r e c t i o n of the joint

b o u n d a r y line to the t r a n s v e r s e axises b e t w e e n the line
between two bolt holes. Highest corrosion attack is
observed at p o i n t s with both these c h a r a c t e r i s t i c s . At
such points some of the c o r r o s i o n losses e x c e e d the minus
tolerance values. Minimum corrosion losses are found
around the b o l t hole circumferences, that is where at
places w e r e the joint is tightest. C o r r o s i o n losses and
joints are in g e n e r a l h i g h e r than those of open surfaces,
but not by range of order of magnitude.
Inside the crevice rust does not show protective '

properties. The rust layer t h i c k n e s s d e c r e a s e s from the
joint b o u n d a r y t o w a r d s the b o l t hole. The rust layers are
compact and do not c o n t a i n h i g h e r a m o u n t s of stimulants.
The c o m p a c t n e s s of the layer d i s t i n c t l y grows in d i r e c t i o n
into the joint.
R o u g h n e s s of s u r f a c e and pits in the c r e v i c e are less if

c o m p a r e d w i t h fully e x p o s e d surfaces.
Corrosion attack of joining parts (bolts, nuts, and

washers) depends on the material, c o r r o s i v i t y conditions,
and exposure time. No problems in the strength of
the bolts have b e e n i n d i c a t e d by the evaluation.
Elimination of crevice corrosion seems to be a complex

problem with no simple or easy long-term solution. Viewing
the volume of the rust in the crevice and its properties
its hydrophobic treatment is practically impossible and
cannot be efficient. Barrier coatings will not easily
penetrate the crevice, and their parts covering the
crevice will decompose and lose protective capacity.
Sanatation of crevice corrosion attack should become
a topic of new research activities, but such methods
should be only be used for selected structures with
extreme corrosion attack.
New towers and structures made of weathering steel

should be designed with bolted joints that fully comply
with the optimum recommended distances for bolt holes (6,
7), the necessary rigidity and planeness of the contact
surfaces. The contact surfaces should be painted or
otherwise coated but in complete accordance to actual
standards a n d other recommendations. Another requirement
is checking the bolt joints during and after assembly
REFERENCES:
i. J.Gulmann, D.Knotkova, V.Kucera, P.Swartling, J.Vlckova,

Weathering steels in building - cases of corrosion
damage and their prevention (booklet), Swedish
Corrosion Institute, National Institute for Protection
of Material, Stockholm, 1985
2. H.E.Townsend, J.C. Zoccola, Eight-year atmospheric

corrosion performance of weathering steel in
industrial, rural and marine environments, in
Atmospheric corrosion of metals, S.W. Dean, E.C. Rhea,
Eds., ASTM STP 767, American Society for Testing and
Materials, Philadelphia, 1982, p. 45
3. M. McKenzie, The corrosion of weathering steel under

real and simulated bridge decs, TRRL Research
Report 233, Transport and Research Laboratory,
Crownthorne, Berkshire, U.K., 1990
4. D.Knotkova, J.Vlckova, J.Honzak, Atmospheric corrosion

of weathering steels in Atmospheric corrosion of
metals, S. W. Dean, E. C. Rhea, Eds., ASTM STP 767,
American Society for Testing and Materials,
Philadelphia, 1982, p. 7
5. P r o t o c o l s from inspections of weathering steel

structures, National Institute for Protection of
Material, Prague, 1972 - 1992
6. R . L . B r o c k e n b r o u g h and R.T.Schmitt, C o n s i d e r a t i o n s in
the P e r f o r m a n c e of Bare H i g h - s t r e n g h t L o w - a l l o y Steel
Transmission Towers, paper No C 15 041 - 9, IEEE,
J a n u a r y 1975
7. R . L . B r o c k e n b r o u g h and W . P . G a l l a g h e r , E f f e c t of C l a m p i n g
P r e s s u r e and J o i n t G e o m e t r y on C o r r o s i o n Induced Bowing
a n d D i s t o r t i o n of B o l t e d J o i n t s in W e a t h e r i n g Steel,
J. Construct. Steel Research, 5, 1985, p. 213-238
Joaquin Simancas, I Karen L. Scrivener, 2 and
Manuel M o r c i l l o I
A STUDY OF RUST MORPHOLOGY, CONTAMINATION AND POROSITY BY

BACKSCATTERED ELECTRON IMAGING
REFERENCE: Simancas, J., Scrivener, K. L., and Morcillo,

M., "A Study of R u s t Morphology, C o n t a m i n a t i o n and Porosity
by B a c k s c a t t e r e d Electron Imaging," A t m o s p h e r i c Corrosion,
A S T M STP 1239, W. W. Kirk and H e r b e r t H. Lawson, Eds.,
A m e r i c a n Society for T e s t i n g and Materials, Philadelphia,
1995.
ABSTRACT: A t m o s p h e r i c corrosion is a complex process

involving m a n y variables including metal, a t m o s p h e r i c
environment, and exposure conditions. Once the c o r r o s i o n
process has been initiated and a continuous film of
c o r r o s i o n products covering the whole surface of steel has
been established, the kinetics of the c o r r o s i o n process
will be controlled by (a) the thickness of c o r r o s i o n
p r o d u c t layer, (b) their m o r p h o l o g y (degree of
compactness, crack network, etc.), and (c) the nature and
d i s t r i b u t i o n of the different phases. This w o r k explores
the p o t e n t i a l of b a c k s c a t t e r e d electron (BSE) imaging as a
tool for the study of atmospheric corrosion. The
s e n s i t i v i t y of the b a c k s c a t t e r e d signal to small
d i f f e r e n c e s in average atomic number and v a r i a t i o n s in
microporosity, allows study of the d i s c o n t i n u o u s nature of
the a t m o s p h e r i c corrosion process and the d i s t r i b u t i o n of
c o n t a m i n a n t s in the corrosion product layers. Q u a n t i t a t i v e
image analysis of BSE images has also been used to
c h a r a c t e r i z e the compactness of rust layers.
i Research fellow and Professor of research,

respectively, Department of C o r r o s i o n and Protection,
Centro N a c i o n a l de I n v e s t i g a c i o n e s Metalurgicas, Avda.
G r e g o r i o del Amo, 8, 28040-Madrid, Spain.
2 Lecturer, Department of Materials, Imperial
College, Prince Consort Road, London SW7 2BP, England.
137
Copyrigh~1995by
KEYWORDS: a t m o s p h e r i c corrosion, mild steel, l o n g - t e r m

exposures, b a c k s c a t t e r e d e l e c t r o n (BSE), image analysis,
energy d i s p e r s i v e X-ray a n a l y s i s (EDS)
A t m o s p h e r i c c o r r o s i o n is e l e c t r o c h e m i c a l in nature,
and the p r o c e s s is the sum of the c o r r o s i o n that takes
place each time a film of e l e c t r o l y t e (rain, dew, etc.)
forms on the metal. The factors that d e t e r m i n e the rate
of the c o r r o s i o n p r o c e s s are as follows: (a) the time of
w e t n e s s (TOW) of m e t a l l i c surface, (b) a t m o s p h e r i c
c o n t a m i n a n t s (SO2, NOx, a e r o s o l s of sea water, etc.), and
(c) the c o n d i t i o n s of exposure (open air, s h e l t e r e d
exposures, etc.) [!-~].
U n d e r the film of e l e c t r o l y t e m o s t of the metal

e x p o s e d to the a t m o s p h e r e corrodes. The a n o d i c p r o c e s s of
iron o x i d a t i o n is b a l a n c e d by the c a t h o d i c p r o c e s s of oxygen
reduction:
89 + H20 + 2e ~ 2 OH
This p r o c e s s is c o n t r o l l e d by the diffusion of oxygen

t h r o u g h the film of electrolyte.
Once the c o r r o s i o n process has been i n i t i a t e d and a

c o n t i n u o u s film of c o r r o s i o n p r o d u c t s c o v e r i n g the w h o l e
surface of steel has been established, the k i n e t i c s of the
c o r r o s i o n p r o c e s s will be c o n t r o l l e d by (a) the t h i c k n e s s of
the c o r r o s i o n p r o d u c t s layer, (b) t h e i r m o r p h o l o g y (degree
of compactness, cracks network, etc.), and (c) the nature
and d i s t r i b u t i o n of the d i f f e r e n t phases. T h e s e will in
turn be a f f e c t e d by the p r e s e n c e of salt contaminants,
mainly chlorides and sulfates, resulting from the
i n t e r a c t i o n of the metal with air pollutants.
M a n y authors [l-L] have found that the a t m o s p h e r i c

c o r r o s i o n p r o c e s s obeys an e x p o n e n t i a l e x p r e s s i o n of the
type M = a.t b, where M is the loss of metal, t is the time of
exposure, and a and b are constants. B e n a r i e and Lipfert
[!] s u g g e s t the e x p o n e n t b as an index of the p r e s e n c e and
of the p h y s i c o - c h e m i c a l b e h a v i o r of the c o r r o s i o n p r o d u c t
layer, including the reactions of this layer with
e n v i r o n m e t a l factors. For b = 0.5 it is the special case of
an ideal d i f f u s i o n - c o n t r o l l e d m e c h a n i s m w h e n all c o r r o s i o n
p r o d u c t s remain on the surface as an u n p e r t u r b e d layer.
However, if the d i f f u s i o n c o e f f i c i e n t d e c r e a s e s w i t h time,
then b will have a lower value than 0.5. A l t e r n a t i v e l y , if
the d i f f u s i o n p r o c e s s is a c c e l e r a t e d by removal of the
layer, the e x p o n e n t b will be h i g h e r than 0.5, a t t a i n i n g
the limiting value of 1.0.
SIMANCAS ET AL. ON BACKSCATIERED ELECTRON IMAGING 139
The p h e n o m e n o n of a t m o s p h e r i c c o r r o s i o n has been the

s u b j e c t of m u c h r e s e a r c h r e s u l t i n g in the c o m p i l a t i o n of
s u b s t a n t i a l amounts of information. M u c h of this i n f o r m a t i o n
has been d e r i v e d from o p e n - a i r field studies in a v a r i e t y of
e n v i r o n m e n t s (e.g. rural and urban). Empirical expressions
have been d e v e l o p e d from t h e s e c o r r o s i o n data to e v a l u a t e
the effect a t m o s p h e r i c c o n t a m i n a n t s have on the c o r r o s i o n
process. Q u e s t i o n s still remain r e g a r d i n g the m e c h a n i s m s of
a t m o s p h e r i c corrosion. For example, little is k n o w n about
the effect of the m i c r o s t r u c t u r e of the c o r r o s i o n p r o d u c t
layer on the c o r r o s i o n process. The aim of the p r e s e n t work
is to i n v e s t i g a t e the p o t e n t i a l of BSE imaging in the
scanning electron microscope (SEM) for studying the
m i c r o s t r u c t u r e of the c o r r o s i o n layers.
The study was c a r r i e d out on s p e c i m e n s (100x40 mm) of

m i l d steel exposed for long p e r i o d s of time in d i f f e r e n t
S p a n i s h atmospheres: E1 Escorial (rural), M a d r i d (urban),
Bilbao (industrial), and Barcelona (marine). These
s p e c i m e n s belong to a large a t m o s p h e r i c c o r r o s i o n p r o j e c t
i n i t i a t e d in 1976 [6].
Once r e m o v e d from the test stations, s p e c i m e n s (15x10

mm) w e r e p r e p a r e d for m i c r o s c o p y as follows. R e p r e s e n t a t i v e
s p e c i m e n s w e r e cut using a d i a m o n d w i r e saw so as to cause
the m i n i m u m d i s t u r b a n c e p o s s i b l e to the fragile rust layer.
The s p e c i m e n s w e r e m o u n t e d on edge in e p o x y r e s i n and
p o l i s h e d so that the steel s u b s t r a t e and c o r r o s i o n layers
could be v i e w e d in cross section. The s p e c i m e n s were then
p o l i s h e d to a 88 ~m d i a m o n d finish, c o a t e d w i t h carbon and
e x a m i n e d in a J E O L 35 CF SEM, e q u i p p e d w i t h a solid state
b a c k s c a t t e r e d e l e c t r o n d e t e c t o r and a Link A N i0000 energy
d i s p e r s i v e X-ray (EDS) a n a l y s i s system. The SEM was also
i n t e r f a c e d to a K o n t r o n IBAS image analyses. The images
c o l l e c t e d on the image a n a l y s e s w e r e d i g i t i s e d into a 512 x
512 pixel array and 256 grey levels [Z].
Each specimen has a layer of c o r r o s i o n p r o d u c t on each

side of the original metal, c o r r e s p o n d i n g to the surface
w h i c h faces the sky and to that facing the g r o u n d d u r i n g
exposure. BSE images and some X-ray dot maps w e r e taken at
various magnifications. To o b t a i n a m e a s u r e of the amount
of cracks and pores that the layers contained, 20 images
w e r e r e c o r d e d at a m a g n i f i c a t i o n of x1500. To e s t i m a t e the
a v e r a g e c o n c e n t r a t i o n of S and Cl in the p r o d u c t layers the
X - r a y s p e c t r u m was o b t a i n e d from 20 r e g i o n s a b o u t 50x50 ~m
for 200 seconds.
Discontinuous Nature of A t m o s p h e r i c Corrosion Process
At the outer edge of the product layers (skyward side)

a series of striations were usually observed as shown in
Figure i. A l t e r n a t i n g light and dark bands were o b s e r v e d at
the outer edges of the corrosion layers (skyward side) of
all specimens regardless of test atmosphere.
Due to the electrochemical nature of the m e c h a n i s m of

m e t a l l i c c o r r o s i o n in the atmosphere, the c o r r o s i o n process
is d i s c o n t i n u o u s and it takes place each time e l e c t r o l y t i c
layers form on the metal or on the c o r r o s i o n products,
either from p r e c i p i t a t i o n (rain, snow, fog) or c o n d e n s a t i o n
(dew). The cyclic process of w e t t i n g and drying of corrosion
p r o d u c t s in the atmosphere with contaminants b u i l d i n g up in
layers during the drying cycles perhaps could explain those
observed striations.
So, the bands might be associated with the

s e g r e g a t i o n of the contaminant salts, but since each band is
less than 0.5 ~m thick it was impossible to d e t e r m i n e any
compositional variations by X-ray microanalysis. The
d i f f e r e n c e s in grey level could also result from differences
in m i c r o p o r o s i t y or c r y s t a l l i n i t y between the layers.
On other side, the number of striations is much

smaller than the number of w e t t i n g and drying cycles the
specimens have experienced; for example, the one-year old
specimen from Escorial exhibited about i0 layers, whilst in
the 13-year old specimens this has only increased to 20 or
30 (Figure la).
Below the striated surface region the c o r r o s i o n

p r o d u c t s appear more homogeneous. In the specimens exposed
in rural and urban atmospheres (Figures la and ib) the
r e g i o n below the layers is fairly porous, but otherwise
appears to be very uniform. In the specimens exposed in
m o r e aggressive environments (Figure le) there is a complex
a r r a n g e m e n t of light and dark areas. It would appear that
cracks have formed within the light (more dense and older)
regions and that these cracks have subsequently been
infilled with less dense, darker product (e.g. arrowed in
Figure le).
It is usually considered that the c o r r o s i o n products

are formed at the interface between the metal and the
corrosion layer. The m i c r o g r a p h s could indicate that
perhaps this is not exclusively the case. Light and dark
bands continue to form on the outer edge of the corrosion
layer and corrosion product appears to form within cracks.
In addition, some dark areas within the p r o d u c t layer,
SIMANCAS ET AL. ON BACKSCA'I-FERED ELECTRON IMAGING 141
FIG. l--Backscattered images of the outermost surface

layers of corrosion products (skyward side) on the
steel exposed during 13 years in the atmosphere.
a) Escorial (rural atmosphere), b and d) Madrid
(urban atmosphere), c) Bilbao (industrial
atmosphere) and e) Barcelona (marine atmosphere).
o r i g i n a l l y t h o u g h t to be pores, w e r e found by EDS analysis

to be s i l i c a t e minerals. These w o u l d have been d e p o s i t e d on
the outer surface of the c o r r o s i o n p r o d u c t layer as dust but
a p p e a r w i t h i n the c o r r o s i o n p r o d u c t s layer what p e r h a p s
p r o v i d e a further e v i d e n c e that c o r r o s i o n products, at least
partially, are not always formed at the corrosion
p r o d u c t / m e t a l interface.
The P r e s e n c e of Salt Contamination within the Atmospheric

Corrosion Product
T h e r e has been m u c h r e s e a r c h and m a n y p u b l i c a t i o n s

about the importance of atmospheric contaminants,
particularly SO 2 and CI, on the p r o c e s s of a t m o s p h e r i c
c o r r o s i o n of m e t a l l i c materials. Data h a v e been p u b l i s h e d
[2, 8-9] r e g a r d i n g the d e p e n d e n c e of c o r r o s i o n rate on the
c o n c e n t r a t i o n s of c o n t a m i n a n t s in the a t m o s p h e r e s u r r o u n d i n g
the test stations, but little has been r e p o r t e d on the
c o n c e n t r a t i o n s of c o n t a m i n a n t s in the c o r r o s i o n p r o d u c t s
themselves. This reflects the d i f f i c u l t y in d e t e r m i n i n g
this k i n d of data. Due to the low c o n c e n t r a t i o n by mass of
c o r r o s i o n p r o d u c t s the p r e s e n c e of c h l o r i d e and s u l f a t e in
rust can pass u n n o t i c e d w i t h m a n y types of analysis, e.g.
XRD, IR, M6ssbauer, etc.
The SEM can c o n t r i b u t e important i n f o r m a t i o n in this

regard, in p a r t i c u l a r about the d i s t r i b u t i o n of c o n t a m i n a n t s
in the corrosion product layers and their respective
concentrations. Ross and C a l a g h a n [i0] have shown by SEM
the seasonal m i g r a t i o n of bands and nests of sulfur w i t h i n
the rust layer. Initially, in the p e r i o d s of m a x i m u m
a c t i v i t y of the sulfate ion, sulfur p r e f e r a b l y locates in
bands at the s t e e l / r u s t interface.
In our case, bands rich in chlorine have also been

o b s e r v e d at the s t e e l / r u s t interface in rust layers formed
during 13 years in the m a r i n e atmosphere in B a r c e l o n a
(Figure 2).
For p o s s i b l e q u a n t i f i c a t i o n of c o n t a m i n a n t s in the
rust layer, the EDS can c o n t r i b u t e at least relative
i n f o r m a t i o n and s e m i q u a n t i t a t i v e data. T a b l e 1 shows the
w e i g h t p e r c e n t a g e of S and Cl o b t a i n e d by EDS in v a r i o u s
rust layers formed during 13 years in the different
atmospheres. This table also lists the s o l u b l e s u l f a t e and
c h l o r i d e c o n c e n t r a t i o n s o b t a i n e d by chemical a n a l y s i s of
w a t e r e x t r a c t s p e r f o r m e d on similar specimens, s u b j e c t e d to
leaching in b o i l i n g deaerated distilled water for 30
minutes, in a c c o r d a n c e w i t h the p r o c e d u r e d e s c r i b e d by M a y n e
[11].
The c o n t a m i n a n t s contents s u p p l i e d by the w a t e r
extracts c o r r e s p o n d to the entire c o r r o s i o n p r o d u c t s layer
SIMANCAS ET AL. ON BACKSCATTERED ELECTRON IMAGING 143
FIG. 2--Backscattered i m a g e and t h e c o r r e s p o n d i n g

C1 X - r a y d o t m a p of a r u s t l a y e r f o r m e d on
s t e e l a f t e r 13 y e a r s of e x p o s u r e in the
m a r i n e a t m o s p h e r e of B a r c e l o n a .
w h e r e a s the i n f o r m a t i o n obtained f r o m EDS r e f e r s to an

a v e r a g e spot, 50 ~m thick, on the layer. T h e r e f o r e to a s s e s s
T A B L E 1 - - R e s u l t s of m e a s u r e m e n t s of c o n t a m i n a n t s in the r u s t
by EDS and by c h e m i c a l a n a l y s i s of w a t e r extracts after
l e a c h i n q in d i s t i l l e d w a t e r .
Test Thickness wt % (by EDS) Soluble salts, m g / ~

site of the
rust, ~m
sulfur chlorine sulfates chlorides
Escorial 59.5 0.66 0.06 562 723

Madrid 93.0 0.74 0.41 974 1117
Bilbao 124.5 0.85 0.07 1410 756
Barcelona iii.0 0.78 1.03 1203 2237
the c o n t a m i n a n t s c o n t e n t s by t h i s t e c h n i q u e the i n f o r m a t i o n
s u p p l i e d by EDS m u s t t a k e i n t o a c c o u n t t h e t o t a l t h i c k n e s s
of the r u s t layer. Figure 3 indicates the correlation
b e t w e e n the % c o n c e n t r a t i o n by EDS x r u s t l a y e r t h i c k n e s s
vs. c o n c e n t r a t i o n f r o m l e a c h i n g data.
Diffusion Properties of the Atmospheric Corrosion Product

Layers.
For a long t i m e it has b e e n k n o w n t h a t u n d e r c e r t a i n

conditions, weathering steel have better resistance to
atmospheric c o r r o s i o n t h a n p l a i n steel. O n e of t h e r e a s o n s
t h a t has b e e n p r o p o s e d for t h i s b e h a v i o r is t h e f o r m a t i o n of
m o r e c o m p a c t l a y e r s of c o r r o s i o n p r o d u c t s [12]. It is a l s o
k n o w n t h a t the r u s t l a y e r s m a y u n d e r g o p r o c e s s e s s u c h as
a g g l o m e r a t i o n , f i l l i n g up of pores, r e c r z s t a l l i z a t i o n , etc.,
w i t h i n c r e a s i n g time. T h e s e p r o c e s s e s l e a d to m o r e c o m p a c t
l a y e r s t h a t i m p e d e t h e d i f f u s i o n of r e a c t a n t s [!]. M o r c i l l o
et al. in a r e c e n t p a p e r p a r t i a l l y a t t r i b u t e t h e s i g n i f i c a n t
d e c r e a s e in the c o r r o s i o n r a t e of s t e e l a f t e r 4 to 5 y e a r s
in E s c o r i a l and M a d r i d to the f o r m a t i o n of v e r y c o m p a c t
l a y e r s of r u s t at t h e s e t e s t s i t e s [13]. It is of i n t e r e s t
to q u a n t i f y in s o m e w a y the c o m p a c t n e s s of the r u s t layers.
To i n v e s t i g a t e the p o s s i b i l i t y of d o i n g t h i s f r o m B S E
images, s e c t i o n s w e r e p r e p a r e d f r o m m i l d s t e e l t e s t p a n e l s
e x p o s e d to the a t m o s p h e r e at the M a d r i d s i t e for i, 2, 3.5,
E 120
O
t~ Bilbao arcelona
u~ 100
O9
C
- Barcelono >
z
._u 80
I o
>
o9
m
m 60
/Madridi
F
O
z
x / 9 Sulphur (33
m 40 3>
O~adrid 0 Chlorine c)
D o9
LI.I c)
>
>, 20
m
m
I ~ El Escor,iol I l o
_; 0 m
r--
~ 0 500 1000 1500 2000 2500 ('D
r~
.-I
:D
mg/m2by chemical analysis 0
z
>
FIG. 3--Correlation between sulfur and chlorine z

contents in t h e r u s t m e a s u r e d by EDS and by
chemical analysis of water extracts
after leaching in d i s t i l l e d water.
6.5, 13, and 16 years. BSE images were r e c o r d e d from these

samples, and the percentage areas of pores and cracks in the
rust layer m e a s u r e d by image analysis. Figures 4 and 5 (left
side) show m i c r o g r a p h s of sections for d i f f e r e n t times of
a t m o s p h e r i c exposure, and the c o r r e s p o n d i n g views (Figures
4 and 5, right side) of the cracks and pores.
Figure 6 shows the variation, w i t h the exposure time,

of the p e r c e n t a g e area c o r r e s p o n d i n g to cracks and pores. It
is observed that there is an increase in the c o m p a c t n e s s of
rust layers with the time, which corresponds to a decrease
in the corrosion rate (Figure 7) [14].
CONCLUSIONS
i.- Scanning electron m i c r o s c o p y has shown to be a useful

t e c h n i q u e for studying atmospheric c o r r o s i o n of metals.
2.- B a c k s c a t t e r e d electron (BSE) imaging has shown evidences

about the d i s c o n t i n u o u s nature of the a t m o s p h e r i c
corrosion process and supplied information about the
d i s t r i b u t i o n of contaminants (S and Cl) w i t h i n the
c o r r o s i o n product layers.
3.- S e m i - q u a n t i t a t i v e information about the c o n c e n t r a t i o n of

both contaminants can be obtained by means energy
d i s p e r s i v e X-ray analysis.
4.- The decrease in the corrosion rate of steel observed

during long-term w e a t h e r i n g in certain a t m o s p h e r e s
appears to be associated with a r e d u c t i o n in the
p o r o s i t y of the rust layer. This feature can be
q u a n t i f i e d by BSE and image analysis.
ACKNOWLEDGEMENTS
The authors acknowledge the support of the Ramsay Memorial

Fellowships Trust and the Spanish Scientific Research
Council (CSIC), for the visit of J. Simancas to Imperial
College during which the work p r e s e n t e d here was carried
out. They also thank S. Flores for the d e t e r m i n a t i o n s of
soluble contaminants within the corrosion products.
REFERENCES
[!] Barton, K. and Bartonova, Z., "0ber den

b e s c h l e u n i g e n d e n Einflub von S c h w e f e l d i o x i d und
Wasser anf die A t m o s p h ~ r i s e h e K o r r o s i o n von
V e r r o s t e t e n Eisen", W e r k s t o f f e und Korrosion, Vol.
3, 20, 1969, p 216.
SIMANCAS ET AL. ON BACKSCAFFERED ELECTRON IMAGING 147
FIG. 4 - - B a c k s c a t t e r e d m i c r o g r a p h s (left) and the

c o r r e s p o n d i n g views showing the cracks and
pores (right) by image analysis Images
c o r r e s p o n d i n g to rust layers formed at the
Madrid test station after 1 (top) and 16 years
of (bottom) atmospheric exposure, respectively.
FIG. 5--Backscattered micrographs (left) and the

corresponding views showing the cracks and
pores (right) after image analysis Images
corresponding to rust layers formed at the
Madrid test station after 2 (top) and 6.5 years
(bottom) of atmospheric exposure, respectively.
SIMANCAS ET A L ON 8ACKSCATTERED ELECTRON IMAGING 149
~ ~o
7 6
r,o
~ 2
n
0 I 1 ! I i i I t
2 4 6 8 10 12 14 16
Exposure time ( y e a r s )
FIG. 6 - - P e r c e n t a g e of c r a c k s and p o r e s in rust layers

f o r m e d in the M a d r i d a t m o s p h e r e vs. e x p o s u r e time,
5O
>, 40
'3o
,,,,,,
e - B
I,, , 1 ............. I ..... | i m
2 4 6 8 10 12 14 16
TIME OF EXPO5URE, y e a r s
FIG. 7 - - C o r r o s i o n rate of p l a i n steel in the M a d r i d

a t m o s p h e r e vs. e x p o s u r e time.
[2] Kucera, V. and Mattsson, E., "Atmospheric Corrosion"

in Corrosion mechanisms, Mansfeld, F. Ed., Marcel
Dekker, Inc., New York, 1987, pp 211-284.
[3] Benarie, M. and Lipfert, F.L., "A General Corrosion

Function in Terms of Atmospheric Pollutant
Concentrations and Rain pH", Atmospheric Environment,
Vol. 20, No. i0, 1986, pp 1947-1958.
[4] Pourbaix, M., "The Linear Bilogarithmic Law for

Atmospheric Corrosion", in Atmospheric corrosion,
W.H.Ailor,Ed., John Wiley and Sons, New York, 1982,
p 107.
[5] Feliu, S., Morcillo, M., and Feliu, Jr., S., "The
Prediction of Atmospheric Corrosion from
Meteorological and Pollution Parameters -II, Long-
Term Forecasts". Corrosion Science, Vol. 34, No. 3,
1993, pp 415-422.
[6] Feliu, S. and Morcillo, M., "Atmospheric Corrosion

Testing in Spain" in Atmospheric corrosion,
W.H.Ailor,Ed., John Wiley and Sons, New York, 1982,
p 913.
[Z] Scrivener, K. L. and Pratt, P. L., Proceedinqs First

International RILEM Congress, Vol. i, J.C. Maso,Ed.,
Chapman and Hall, London, 1987, p 61.
[8] Haagenrud, S., Henriksen, J.F. and Gram, F., "Dose-

response Functions and Corrosion Mapping for a Small
Geographical Area", Report, Norwegian Institute for
Air Research, Lillestrom, 1986.
[9] Feliu, S., Morcillo, M. and Feliu, Jr., S., "The

Prediction of Atmospheric Corrosion from
Meteorological and Pollution Parameters-I, Annual
Corrosion", Corrosion Science, Vol. 34, No. 3, 1993,
pp 403-414.
[i0] Ross, T. K. and Callaghan, B. G., "The

Seasonal Distribution of Ferrous Sulphate Formed
During the Atmospheric Rusting of Mild Steel",
Corrosion Science, Vol. 6, 1966, pp 337-343.
[ii] Mayne, J. E. O., , "The Problem of Painting

Rusty Steel, Journal of Applied Chemistry, 9,
1959, p 673.
[12] Schmitt, R. J. and Gallagher, W. P., "Unpainted High

Strength Low Alloy Steel", Materials Protection,
Vol. 8, No. 12, 1969, p 70.
SIMANCAS ET AL. ON BACKSCATTERED ELECTRON IMAGING 151
[13] Morcillo, M., Feliu, S. and Simancas, J., "Deviation

from b i l o g a r i t h m i c law for atmospheric c o r r o s i o n of
steel", British Corrosion Journal, Vol. 28, No. i,
1993, p 50.
[14] Morcillo, M., Simancas, J. and Feliu, S.: "Long-Term

A t m o s p h e r i c Corrosion in Spain. Results After 13-16
Years of Exposure", A t m o s p h e r i c Corrosion, ASTM STP
1239, W. W. Kirk and Herbert H. Lawson, Eds.,
A m e r i c a n Society for Testing and Materials,
Philadelphia, 1994.
Ashok Sabata I, Gary S. Drigel I, and Terry L. Cooper 2
CORROSION EVALUATION OF AUTOMOTIVE TRIM MATERIAL
REFERENCE: Sabata, A., Drigel, G. S., and Cooper, T. L., "Corrosion

Evaluation of Automotive Trim Material," Atmospheric Corrosion, ASTM
STP 1239, W. w. Kirk and Herbert H. Lawson, Eds., American Society
ABSTRACT: Bright annealed ferritic stainless steel is used as automotive

trim material. A 20% Cr ferritic stainless steel gave adequate corrosion
protection in chloride atmospheres. Both 17% Cr materials, 434 and 436,
need a Cr flash for good corrosion protection. Electrochemical
techniques such as Electrochemical Impedance Spectroscopy (EIS) and
Cyclic polarization curves were used to evaluate the corrosion
performance. The corroded samples were analyzed with Time-of-flight Mass
Spectrometer (TOFSIMS) and Scanning Electron Microscope (SEM). The 20%
Cr ferritic stainless steel performed better than the 17% Cr materials
in all the tests. Some differences in the corrosion products were
observed between the accelerated tests and outdoor exposures.
KEYWORDS: corrosion, atmosphere, electrochemistry, ferritic stainless

steel, TOFSIMS, EIS
INTRODUCTION
Ferritic stainless steels are commonly used for automotive trim

applications because of their bright appearance and lower cost. These
materials, however, do not give adequate corrosion protection in many
situations. The requirement for improved corrosion resistance is mainly
due to deicing salts on roads and SO 2 and NO x emissions. A Cr-flash on
stainless is, therefore, very often used to improve the corrosion
performance of the common ferritic alloys. Also, new alloys with high Cr
(20%) and small amounts of Cu (0.5%) have been developed to give
superior corrosion performance [1,2]. The corrosion properties of these
materials have been reported to be very good. A pitting potential of
IResearch Engineer and Senior Staff Engineer, respectively, Armco

Research and Technology, 705 Curtis Street, Middletown, OH 45044-3999.
2Development Metallurgist, Coshocton Stainless Division, Armco
Inc. 17400 State Route 16, Coshocton, OH 43812.
152
Copyrightm1995by
Downloaded/printed byASTM International www.astm.org
SABATA ET AL. ON AUTOMOTIVE TRIM MATERIAL 153
around +500 mV (vs SCE) at 20~ in 0.SM NaCI (~ 3wt-%) solution has been
reported [2].
Extensive trailer tests have been conducted on many automotive
t r i m materials by General Motors (GM). Some of these data have been
reported by the SAE Stainless and Bright Trim subcommittee and, also, by
GM's Inland Fisher Guide Division [1,4]. The conclusions from these
studies suggest that type 434 stainless does not give sufficient p i t t i n g
corrosion performance. However, a chrome flash coated 434 stainless was
found to pass the trailer test.
In this paper, the corrosion resistance of type 434 and type 436
stainless steel will be compared to a high Cr ferritic stainless
(designated as 436LM in this paper). The materials were e v a l u a t e d in
accelerated corrosion tests and also in outdoor exposures.
E l e c t r o c h e m i c a l tests were carried Out to get an u n d e r s t a n d i n g of
the corrosion mechanisms. Analytical techniques such as Scanning
Electron M i c r o s c o p y (SEM), Energy Dispersive X-ray Analysis (EDX) and
Time-of-Flight Secondary Ion Mass Spectrometry (TOFSIMS) were used to
study the corrosion productS.
Test Materials and SamDle Preparation
Stainless steels of the compositions shown in Table 1 were used in

this study.
Table 1--Stainless steel base metal compositions (in wt.-%)
Material C N S Cr Ni Mo Cu Si Nb
434 .05 .08 .001 16.4 .40 1.04 .04 .5 .2

436 .03 .07 .003 16.4 .20 .90 .06 .5 .5
436LM .02 .05 .002 20.8 .34 .98 .5 .5 .6
All the materials went through bright annealing followed by p i c k l i n g and

a final temper pass. The samples were d e g r e a s e d before corrosion
testing. The electrochemical measurements were made after the samples
were alkaline cleaned followed by ultrasonic water cleaning.
Corrosion Tests
There are numerous accelerated corrosion tests that can be

p e r f o r m e d to evaluate a material's performance. Here, a wide spectrum of
tests were conducted with rust formation as the primary p a r a m e t e r for
evaluation. Duplicate samples per substrate were run in all tests. The
tests could be broadly categorized as: i) outdoor atmospheric tests; and
ii) laboratory tests. The outdoor tests include exposure at Kure Beach,
North Carolina, and in Middletown, Ohio. A brief description of the
tests follows:
CASS T e s t - - T h i s test was run as p e r A S T M B368 specifications. The

samples (size 200 x 100mm) are e x p o s e d to a s o d i u m c h l o r i d e - c o p p e r
c h l o r i d e s o l u t i o n fog at 50~ for 16 hrs.
DiD & D r y T e s t - - T h i s test was run as per GM 4359-P specifications.
The test includes i m m e r s i o n of 50 • 50mm samples in NaCI s o l u t i o n
f o l l o w e d by drying. Samples were run for i00 cycles.
Salt Foa T e s t - - H e r e 100 x 150mm samples were e x p o s e d to 3.5 wt.-%
NaCI fog for 480 hours. The t e s t i n g was done as per A S T M BII7.
Moist SO~ T e s t - - S a m p l e s of 100 x 1 5 0 m m size are e x p o s e d to SO 2 at
40~ for 24 hours. The t e s t i n g p r o c e d u r e was as per A S T M G87.
P i t t i n a C o r r o s i o n T e s t - - T h i s test was c a r r i e d out as p e r A S T M G48,
M e t h o d A, to d e t e r m i n e the relative p i t t i n g r e s i s t a n c e of s t a i n l e s s
steel. The samples of 50 x 2 5 m m were i m m e r s e d in about 6 wt.-% ferric
c h l o r i d e s o l u t i o n for 24 hours at 22~
Electrochemical Testina--Cyclic potentiodynamic polarization
curves were o b t a i n e d as per A S T M G61. The m e a s u r e m e n t s w e r e c a r r i e d out
in a cell w i t h a p l a t i n u m c o u n t e r e l e c t r o d e and a A g / A g C I r e f e r e n c e
electrode. Samples of 100mm 2 area were m o u n t e d in the e l e c t r o c h e m i c a l
cell. All tests were c a r r i e d out in a fully d e a e r a t e d 3.5% NaCI
solution. The scan rate was 0.17mV/sec. The samples were a l k a l i n e
c l e a n e d and then c l e a n e d u l t r a s o n i c a l l y in d e i o n i z e d water. Samples were
e x p o s e d to the NaCI s o l u t i o n for 30sec at +975mV. This t r e a t m e n t gave
r e p r o d u c i b l e p i t t i n g c o r r o s i o n p o t e n t i a l s as it r e m o v e d p o s s i b l e
c o n t a m i n a t i o n from the surface.
G a l v a n o s t a t i c e x p e r i m e n t s were also c a r r i e d out to c o n f i r m the
c y c l i c p o l a r i z a t i o n results. A constant current of 0 . 5 A / m m 2 is a p p l i e d
to the sample for 2 m i n u t e s in a d e a e r a t e d 3.5 wt.-% NaCI solution.
E l e c t r o c h e m i c a l impedance s p e c t r o s c o p y was also u s e d to e v a l u a t e the
samples in an a e r a t e d 3.5 wt-% N&CI solution. The area of the sample was
3200mm2 .
O u t d o o r E x D o s u r e - - P a n e l s (size i00 x 150mm) were e x p o s e d in a
m a r i n e a t m o s p h e r e at Kure Beach, N o r t h Carolina, at 25m a n d 2 5 0 m from
the sea. Some panels were also e x p o s e d in a m i l d l y u r b a n c l i m a t e at
Middletown, Ohio.
~ - - T h i s is a c y c l i c c o r r o s i o n test, w h e r e each cycle
(24 hours) c o n s i s t s of e x p o s u r e to salt, f o l l o w e d by d r y i n g and then
e x p o s u r e to humidity.
Analytical TechniQues
As the c o r r o s i o n p r o t e c t i o n is d e p e n d e n t on the oxide film

composition, sample surfaces were a n a l y s e d u s i n g T O F S I M S w h i c h is v e r y
s e n s i t i v e (ppm level) to all elements. A u g e r E l e c t r o n S p e c t r o s c o p y (AES)
was u s e d to collect depth p r o f i l e s and d e t e r m i n e the t h i c k n e s s and
c o m p o s i t i o n of the oxide film.
T O F S I M S a n a l y s i s was p e r f o r m e d on a Kratos P r i s m instrument. A
p u l s e d 2 5 k V l i q u i d m e t a l ion source of m o n o i s o t o p i c 69Ga+ ions was used.
P o s i t i v e a n d n e g a t i v e spectra were o b t a i n e d at a total i n t e g r a t e d ion
dose of not m o r e than i0 II i o n s / c m 2. The l i q u i d m e t a l gun was also u s e d
for m a p p i n g of ions, with a 2000 A lateral resolution.
EIS m e a s u r e m e n t s were done u s i n g a P A R m o d e l 5301 L o c k - i n
A m p l i f i e r w i t h a m o d e l 5315 two channel preamplifier. D i s c r e t e single
f r e q u e n c y m e a s u r e m e n t s were m a d e in the 5 to 100 kHz range w i t h AC
amplitude of 5 mV. Over the frequency range of 0.01 Hz to 11.31 Hz, a

m u l t i - s i n e technique employing a fast fourier t r a n s f o r m was used. This
was done in two parts of 10 data cycles each and i0 mV AC amplitude. A
3.5 wt.-% NaCI solution was used for the EIS measurements. The
m e a s u r e m e n t s were made at the open circuit potential at 25~ with air
gently bubbling through the solution.
Secondary electron images were obtained using a JEOL 840A Scanning
electron m i c r o s c o p e operated at 15 kV. The elemental maps were collected
using a Kevex Energy Dispersive Analyzer.
RESULTS
In this section, the results from the various corrosion tests will
be presented. Also, the results from the various analytical techniques
will be described.
Electrochemical Tests
To determine the relative s u s c e p t i b i l i t y to localized corrosion

(pitting) in a chloride environment, cyclic p o t e n t i o d y n a m i c polarization
m e a s u r e m e n t s were made. The m e a s u r e d pitting corrosion potential is
reported in Table 2.
Table 2 - - P i t t i n Q corrosion potential in d e a e r a t e d NaCI solution
Sample Pitting potential

(mY vs Ag/AgCl)*
434 +350
436 +400
434 + Cr flash +ii00
436LM +1250
* an average of three m e a s u r e m e n t s
C h a r a c t e r i s t i c cyclic polarization curves for 436 and 436LM are shown in

Figure i. The curve for stainless steel type 436 shows that in the
p a s s i v a t i o n region the current increased s p o r a d i c a l l y and then
repassivated. The sporadic rise in the current is p r o b a b l y due to the
formation of pits. The actual pitting potential is therefore much lower
than that reported in Table 2. The differences from the cyclic
p o l a r i z a t i o n tests is probably due to the difference in the 436 and 434
chemistries. 436 has a higher Nb content as compared to 434.
Figure 2 compares the potential versus time curves for the four
m a t e r i a l s in the g a l v a n o s t a t i c experiments. The plot shows that 436LM
and 434, with the Cr flash, provide better corrosion p r o t e c t i o n in a
NaCI environment. This was confirmed by e x a m i n a t i o n of the corroded area
under the optical microscope. Optical micrographs in Figure 3 at 50X
0.7.~
0.6t
5f
0.3(
LM
0.1.~
1 I i m, , ~ I II A ~ & II I I II 9 , 1 . . . . *
C'
0.01 1 100 I0~0C
1.7r , 9 ,, 9 , .i , , , ,, ," , , ,t
436LM
1,5(
>~
/
c_ 1.2!
.s
1.00
LU
0,75
9 , 9 ,. , , J il 9 . . . . .
0.50 , , *, , , II ,
10.2 le~ 10t 1o'
C u r r e n t d e n s i t y ( i J V c m 2)
Figure 1--Cyclic polarization curve for 436 and 436LM measured in

deaerated 3.5 wt.-% NaCI solution.
m a g n i f i c a t i o n show the high d e n s i t y of pits in 434. SIMS m a p p i n g of the

pit s h o w e d Fe in the pit and d e p l e t i o n of Cr (Figure 4). A high pit
d e n s i t y was also o b s e r v e d for 436 but v e r y little p i t t i n g was seen on
436LM a n d 434 w i t h Cr flash.
Results from EIS have been s u m m a r i z e d in Table 3. The EIS data
were m o d e l e d u s i n g s o f t w a r e d e v e l o p e d by B o u k a m p [~]. A simple
e q u i v a l e n t circuit was a s s u m e d c o n s i s t i n g of the c a p a c i t a n c e of the
oxide film, and the p o l a r i z a t i o n r e s i s t a n c e Rp. The i m p e d a n c e of 436LM
to c o r r o s i o n is c l e a r l y higher then 434 or 436. The film c a p a c i t a n c e
also suggests that the oxide film on 436LM is more dielectric.
Salt S D r a v (Foa) Test and SO~ Test
434 m a t e r i a l d i d not show any red rust in e i t h e r tests. In the SO 2

test however, 434 m a t e r i a l e x h i b i t e d a w h i t e d i s c o l o r a t i o n w h i c h on
e x a m i n a t i o n u n d e r an o p t i c a l m i c r o s c o p e s h o w e d that the surface was
etched.
436 m a t e r i a l in the salt fog test s h o w e d some red rust formation
and severe c o r r o s i o n in the SO 2 test (Figure 5). AS for 434, a s i m i l a r
e t c h i n g p r o c e s s takes place as in 436 in the initial stages of exposure,
but here, the removal of the surface exposes inclusions. The low sulfur
content suggests that these are not sulfide inclusions. SIMS m a p p i n g of
the inclusions s h o w e d the inclusions to be Nb based. 436LM and 434 with
Cr flash d i d not form any red rust in e i t h e r the salt fog test or in the
SO 2 test.
CASS Test and D i n & D r v Test
All the m a t e r i a l s p a s s e d b o t h tests. The dip & dry test was

c o n d u c t e d for 100 cycles. Stainless steel type 430, w h i c h does not
Table 3 - - I m p e d a n c e of the samples after d i f f e r e n t e x p o s u r e times in NaCI

solution
Sample Ecorr , m V Rp, ~ Cfilm, F
434- A f t e r lhour -161 17,066 6.0 x 10 -4

434- A f t e r iday -254 2,474 6.2 x 10 -4
434- A f t e r 3days -291 3,122 6.8 x 10 -4
436- A f t e r lhour -150 9,967 8.6 x 10 -4
436- A f t e r iday -230 1,200 1.3 x 10 -3
436LM- A f t e r lhour +23 100,000 2.5 x 10 -4
436LM- A f t e r iday -225 62,489 3.3 x 10 -4
436LM- A f t e r 3days -320 51,063 3.4 x 10 -4
N o t e - All n u m b e r s are for 3 2 c m 2 e x p o s e d area
i
.~ I.- 43e
I .... '3"I
>
0 o.5~i- ~,,'\
._r
9 ~ \ / ,.
o) . \ ".. I \.
UJ
f
0 25 50 75 100
""
L
1.75 p
0
>
._C 1.5r
OI
<.
o)
<:
UJ
1.0r
, i , , i , i i i i i 9 | 9 .
025
25 5O 75 I00
Time (sec.)
F i g u r e 2 - - P l o t of p o t e n t i a l v e r s u s t i m e on a p p l i c a t i o n of a c o n s t a n t
c u r r e n t d e n s i t y o f 5 m A / c m 2 in a d e a e r a t e d 3.5 w t . - % N a C I s o l u t i o n .
Figure 3--Optical micrographs of 434 material before and after exposure

to corrosion conditions in Figure: (a) before, and (b) after exposure
(Magnification- 50X: ~ - - ~ 2 0 0 D m )
Figure 4--SIMS mapping of a pit on 436 material after exposure to NaCI

solution: (a) Cr + (+52 amu), and (b) Fe + (+56 amu).(Magnification- 270X:
~--'--~100~m)
Figure 5--Photographs showing corrosion on samples after exposure to 24

hours of SO 2 test; (a) 434, and (b) 436 stainless steel.
have any MO is known to fail the dip & dry test.
FeCII Dittina test
The FeCI 3 p i t t i n g corrosion test is supposed to simulate the

solution w i t h i n a pit. Samples were immersed in FeCI 3 solution for 24
hours at 22~ This test is normally either run at 50~ or 22~ The
test was found to be very severe for ferritic grade stainless m a t e r i a l s
when the solution temperature was 50~ The weight loss in the test was
m e a s u r e d and is reported in Table 3.
Table 3 : Weight loss in the FeCI 3 test
Material Weight loss, gm % weight loss
434 3.4166 65.9

436 3.5603 68.9
436LM 0.2503 5.0
434+Cr flash 0.169 3.3
Outdoor exposure
Panels were e x p o s e d at Kure Beach, a marine atmosphere, and at

Middletown, a m i l d l y urban atmosphere. Figure 6 shcws photographs after
exposure for 4 months at Kure Beach. Panels were e x p o s e d at 25m from the
sea and 250m from the sea. 434 and 436 material clearly show fairly
severe corrosion at the 25m site. 436LM panels do not show significant
corrosion at the 25m site and very little corrosion at the 250m site.
There are some d e p o s i t s / c o r r o s i o n product on all panels which was wiped
off using a paper towel in the top half of the panels. After 4 months
exposure, the panels at M i d d l e t o w n did not show any corrosion.
P r e l i m i n a r y results from the Ford Arizona Proving G r o u n d test show that
434 fails in 5-30 cycles, whereas, no corrosion was observed on 436LM
after 30 cycles.
Analyses were carried out using SIMS and EPMA to determine the
composition of the corrosion product. Figure 7 shows the SIMS maps of
Fe + (+56 amu), Cr + (+52 amu), A1 + (+27 amu) and K + (+39 amu). The
corroded region also showed CI- and O- peaks. The EPMA results are shown
in Figure 8.
Discussion
AES depth profiles (not shown) of all the materials give an oxide
thickness of 50 A. The oxide composition is a mixture of SiO x and
FeOx.CrOy. The corrosion of the four materials investigated here is
dependent on the Cr and Nb content of the steel. The superior corrosion
behavior of 436LM in all the tests is due to the high c h r o m i u m content.
Higher c h r o m i u m in the substrate enriches the oxide film with c h r o m i u m
oxide, which is known to provide superior corrosion performance.
In the lab tests , 434 showed much better corrosion p e r f o r m a n c e as
compared to 436 especially in the SO 2 test. It also was slightly better
in the salt fog test. The major difference between 434 and 436 is that
434 has a p p r o x i m a t e l y 0.25 wt.-% Nb and 436 has a p p r o x i m a t e l y 0.5 wt.-%
Nb. Nb is added to stabilize the carbon and nitrogen in solid solution
by formation of carbides and nitrides. These, however, seem to affect
the corrosion behavior. In the moist SO 2 test, the low pH environment
leads to the etching of the panels and removal of the surface layers,
thus, exposing the carbide or nitride inclusions. These inclusions act
as sites of local corrosion cells and result in the formation of rust.
436 m a t e r i a l has a high concentration of these inclusions as compared to
434, therefore, the corrosion is more severe in 436. Further work is
being carried Out to confirm this hypothesis. Though 436LM has 0.6wt.-%
Nb, the high chromium content prevents the initial etching of the
surface. 434 with Cr flash has very good corrosion resistance as the Cr
flash layer not only acts as a barrier, but c h r o m i u m is known to be
resistant to chloride attack.
E l e c t r o c h e m i c a l tests clearly indicated that 436LM has a higher
p i t t i n g corrosion potential. Not much difference is seen in Epit between
434 and 436. The EIS data shows differences between 434 and 436 which
can be interpreted as follows. Local b r e a k d o w n of films lead to
initiation of pits or corroding sites which is represented by the
p o l a r i z a t i o n resistance. The capacitance is indicative of the protective
(or dielectric) property of the oxide film. Rp for 434 is higher than
Figure 6--Photographs of samples exposed at Kure Beach, North Carolina.

The top half of the panels were wiped to remove superficial corrosion.
Figure 7--SIMS m a p p i n g of a corroded area in 436LM after 4 months

exposure at Kure Beach (25m lot).(Magnification- 1 8 0 X : ~ - ~ I 0 0 ~ m)
Figure 7--(continued) Magnification- 250X: ~----~100~m
F i g u r e 8--(a) S e c o n d a r y e l e c t r o n m i c r o g r a p h of 436LM sample after

e x p o s u r e at 2 5 m from sea in Kure B e a c h for 4 months. EDX m a p of the
c o r r o d e d area shows (b) oxygen.
for 436 and Cfilm is lower for 434.

In outdoor exposures, not much difference in the corrosion
p e r f o r m a n c e was observed between 434 and 436. Also, some differences in
the corrosion products were observed from o u t d o o r exposure as compared
to the accelerated indoor tests. The corrosion products in most indoor
tests form iron oxide, whereas, on exposure at Kure Beach, it is a
mixture of oxides and chlorides of Fe, AI, Na, K and Mg. The origin of
A1 and Mg is probably from the sea water.
Further research is underway to develop a suitable a c c e l e r a t e d

corrosion test.
CONCLUSIONS
The following conclusions can be made from this corrosion evaluation:
i. 436LM, without Cr flash coating, gives adequate corrosion protection

in chloride atmospheres.
2. In the laboratory tests 434 p e r f o r m e d better then 436. This was due
to a higher Nb content in 436 which resulted in a higher amount of
carbides and nitrides.
3. 434 and 436 need a Cr flash for good corrosion protection.
4. Though the accelerated tests had different corrosion products as
compared to the outdoor tests the ranking of materials was the same
in both types of exposure.
REFERENCES
[i] Tarutani, Y., Kudo, T. and Moroishi, T., "Effects of N i o b i u m and

Copper Addition on Corrosion Behavior of Ferritic Stainless
Steels," Proceedinas of International Conference on Stainless
Steels, ISIJ, Chiba, 1991.
[2] Akiyama, S., Kiya, S., Goshokubo, K., Yokoyama, K., Hirahara, K.
and Hoshi, H., "Development of an Improved Corrosion Resistant
Ferritic Stainless Steel "NAR-FC3"," Nippon Stainless Technical
Report 12, 1986.
[3] Baboian R. and Gorman W., "Corrosion Mechanisms in Bright Stainless

Steel Trim Systems," Proceedinas of the 6th Automotive Corrosion
and Prevention Con~grence~ Dearborn, 1993, pp 45-51.
[4] Black H. L. and Lherbier L. W., "A Statistical Evaluation of

Atmospheric, In-Service, and A c c e l e r a t e d Corrosion of Stainless
Steel Automotive Trim Material," Metal Corrosion in the Atmosphere,
ASTM STP 435, 1968, pp 3-32.
[5] Geenen F. M., De Wit J. H. W. and van Westing E. P. M., "An

Impedance Spectroscopy study of the degradation m e c h a n i s m for a
model epoxy coating on m i l d steel," Proaress in Oruanic Coatinas,
vol. 18, 1990, pp 299-312.
George A. KingI and David J. O'Brien 2
THE INFLUENCE O F MARINE ENVIRONMENTS ON METALS AND FABRICATED

COATED METAL PRODUCTS, FREELY EXPOSED AND PARTIALLY SHELTERED
REFERENCE: King, G. A. and O'Brien, D. J., "The Influence of Marine

Environments on Metals and Fabricated Coated Metal Products, Freely
Exposed and Partially Sheltered, N Atmospheric Corrosion, ASTM
STp 1239, W. W. Kirk and Herbert H. Lawson, Eds., American Society
ABSTRACT: Corrosivity surveys have demonstrated that in Australia marine environments

represent by far the main corrosion hazard to metals and coated metal products. Also field inspection
of some commercial product has revealed cases of very significant early corrosion in unwashed
areas. Existing published data on the relative performance of metals and prepainted coated metals,
especially as fabricated building products, is inadequate to meet the needs of those faced with
decisions regarding product selection. A ten-year industrially funded project has been initiated to
address this by studying the comparative performance of generic classes of metal products and
alternative finishes, and this paper presents some interim results. Twenty-two commercial products
based on galvanised steel, 5% and 55% aluminium-zinccoated steel, stainless steels and aluminium,
were obtained from five countries, some prepainted with acrylic, polyester, silicon-modified poly-
ester (SMP), or polyvinyldifluoride (PVF2) topcoats, and two with a polyvinylflouride (PVF) or
polyvinylchloride (PVC) film laminate. All have been fabricated into 'bent' specimens, the test
piece designed to simulate the types of distress metal products encounter during manufacture and
building. Initial microcracking at bends and Erichsen domes was recorded photographically. A
complex aluminium extrusion in four finishes was also exposed and measurements of initial colour
and gloss were made for all specimens. Materials exposed for mass loss measurements include
'mild' steel, low-alloy copper-steel, zinc, 5% and 55% aluminium-zinccoated steel, and 'wire-on-
bolt' assemblies. Specimens are exposed at three marine sites (severe, moderate and mild) both
in the open and under a shelter designed to permit deposition of salt and particulates but prevent
rainwashing. A glass canopy roof enables some UV degradation of the organic coatings. After
one year the shelters have produced a remarkable deterioration of the coated steel products at the
severe and moderate sites, the sheltered corrosion rates being up to seven times those in the open.
Of the three coatings, the 55% aluminium-zinc consistently has the lowest corrosion rate which
on average is about one-third that of zinc. Strong relationships have been established between the
corrosion rates and the measured levels of airborne chloride.
KEYWORDS: atmospheric corrosion, corrosivity, marine environment, prepainted coated

product, formed testpiece, microcracldng, semi-sheltered exposure, 'mild' steel, zinc, aluminium-
zinc alloy, aluminium extrusion.
1Senior Research Scientist, Commonwealth Scientific and Industrial Research Organisation

(CSIRO), Division of Building Construction & Engineering (DBCE), PO Box 56, Higbett, Victoria
3190, Australia.
2Technical Officer, CSIRO DBCE, PO Box 56, Highett, Victoria 3190, Australia.
167
Copyright9 1995
Downloaded/printed byby ASTM International www.astm.org
INTRODUCTION
The rationale for this project had its beginnings with an inspection of corroded metal members,
roofing and cladding at four schools on a marine peninsula to the south-east of Melbourne, Australia
(see Fig. 1), in December 1986. The following observations reflect both the situations where
products were performing inadequately and the special problems faced in marine environments.
The locations are near semi-enclosed salt-water bays as opposed to ocean surf beaches.
Location 1 - Mt Eliza, 300 m from the sea, building age 7.5 years:
9 Severe corrosion on the underside of galvanised steel roofs over walkways with widespread
white corrosion products, 'red rusting' on profile leading edges facing the sea and occasional
perforation.
9 Scanning electron microscopy/energy dispersive spectrometry (SEM/EDS) analysis of red rust
showed the chloride content to be greater than 4%.
9 A younger section of 55% aluminium-zinc coated steel roofing (age 4+ years) in a less exposed
situation was generally in good condition.
9 Galvanised stanchions supporting the roofs were in good condition, but 'mild' steel gussets welded
to these and then painted were very severely corroded.
9 Prepalnted coated steel 'weatherboard' cladding (metallic coating type unknown) was corroding
badly on the profile nose especially in 'unwashed' areas, and red rust spotting was occurring.
9 In contrast to the above, anodised aluminium windows (reported to have no regular
maintenance washing) and aluminium sunshades, including their undersides, were in good
condition.
Melbourne
Port Philli
"~'~Bay P14~ 3t
Bass Strait
3r Board
FIInders
Bass Strut
Fig. 1--Map of the Port Ptdllip region, Victoria, Australia, showing locations of
four schools on the Momington Peninsula. The enlargement of area 5 shows
locations of marine exposure sites for present study.
KING AND O'BRIEN ON MARINE ENVIRONMENTS 169
Location 2 - Hastings, 1.8 km from the sea, building age 8-12 years:
9 Similar problems with covered walkways, corrosion being most extensive on the south-facing
profile leading edges (i.e. away from the sun).
9 Galvanised box gutters had corroded and laad been replaced due to the problem of run-off from
the inert prepalnted roofing, well documented by the Sheet & Coil Products Division of the
Broken Hill Proprietary Company Limited (BLIP Steel) [1.]. When rain falls on a large area of
roof it is collected and directed in concentrated streams into smaller areas such as gutters and
spouting. Metal coatings in the roofing system are most at risk here. BHP have shown with a
series of run--offexperiments that corrosion is most likely to occur when water falls on roofs
which do not modify the corrosive properties of the rain. They have termed such a roof an 'inert
catchment', typical examples being glazed terracotta tiles, glass-reinforced polyester (fibreglass),
alumihium and 55% aluminium-zinc (bare and painted). In contrast, unglazed cement tiles and
unpainted zinc-coated steel tend to neutralise the acids and chlorides in rainwater, rendering it
less reactive.
Location 3 - Cranbourue, 14 km from the sea, building age 7 years:

9 A classic example of gutter failure due to inert run-off was encountered.
Location 4 - Carrum, 1.2 km from the sea, building age 20 years:

9 The chloride content of red rust exceeded 5%.
9 Corrosion was worst in areas sheltered from morning sun.
9 Electrogalvanised steel louvre windows had totally corroded to red rust, a good example of an
inappropriate choice of coating for an application which should have been hot-dipped.
Additionally, increasing numbers of enquiries were being received at CSIRO regarding appropriate
materials for roofing, cladding and other building elements such as windows, especially for marine
environments. Decisions relating to product selection are faced by designers, builders and build-
ing owners, and they require information on the comparative performance of generic classes of
materials or alternative finishes, to facilitate the optimum selection for desired performance at
known cost. A long-term project was initiated in part to address this need.
Studies using formed specimens and sheltered exposures have been carried out in other countries.
A major project at British Steel [2] was drawn to the authors' attention. The researchers noted that
previous conventional atmospheric testing had not taken account of design features, and that the
published methods for assessing defects assumed that they occurred uniformly across a surface.
The project used nine commercial coil-coated products based on hot-dipped AI, Zn and 55% AI-Zn,
five sites, and specimens as formed panels and box structures, the latter evaluating eaves effects
and direction of exposure. New Zealand work [3] has used SMP-coated galvanised steel with
bends over formers of 2-20T diameters, and exposed specimens at severe marine and rural marine
sites for five years. The results were compared with those from accelerated salt-spray tests.
Norwegian studies [4_]used 'K'-shaped specimens of 20 commercial materials, and the results
were evaluated visually and by gloss and colour measurement. The effects of partial shelter have
been variously studied. In Spain, mild steel, zinc, copper and aluminium have been exposed inside
louvered boxes and in the open for eight years, with only aluminium showing increased corrosion
when sheltered [5.]. Researchers at the US Bureau of Mines [6] point out that sheltering devices
designed to isolate samples from specific environmental inputs can exaggerate the influence of
other inputs. Their polycarbonate enclosing shelter excluded rain washing but also reduced the dew
cycle, increased daytime temperatures, and cut out all UV radiation compared to normal ambient
conditions. They found that all the sheltered corrosion rates were significantly less than those for
bold exposure. Other US work [2] with rows of vertical specimens covered to varying degrees by
a steep roof but otherwise open, found some corrosion rates increased up to threefold.
EXPERIMENTAL
Selection of Exoosure Siles
Considering the large number of specimens required for this project and their consequent value
and time invested, the security of the exposure sites was the overriding priority in site selection.
A BHP technical bulletin [ ~ defines a very sevexe marine environment as being within 100 m of
rough active surf, moderate marine from 500-1000 m, and benign as being >1000 m from rough
surf. This is confirmed by the results of a recent corrosivity survey conducted in the Greater
Newcastle region of NSW on Australia's east coast [9]. Specimens of a standard low-alloy copper-
bearing steel, of similar composition to those used in previous surveys in Australia and New
Zealand, were exposed for nearly two years at 150 sites. The area covexed by the survey (1000 km2)
featured a very wide range of atmospheric environments, from rural to extremely severe marine
and severe industrial. The variation in corrosivity approaching the coastline was shown to be
hyperbolic in nature, and a new technique for hyperbolic interpolation in mapping was developed
together with a computer-generated contour map of corrosivity, which showed variations of more
than an order of magnitude across the area surveyed. The two-year rates at the beachfront sites
were the highest ever measured in Australia, and approached 200 ktm/y but fell quite sharply with
distance from the ocean, reaching about 30 lam/y I km inland. A similar patton has been observed
for the Victor Harbour region of the state of South Australia, but with corrosivity about 150 Iam/y
at the ocean front [9]. Consequently this project required ideally a pair of adjacent and very secure
sites, one at a surf beachfront and the second 1 km inland.
The requirements for suitable sites were achieved at Hinders (see location 5 to the south-east of
Melbourne, Fig. 1), with the severe marine site being within the grounds of the Royal Australian
Navy West Head Gunnery Range, and a moderate to mild marine/rural site at the enclosure for the
Mornington Peninsula Water Board, 1100 m from Western Port Bay and 1300 m from the ocean
(Bass Strait). Both sites were very elevated and with open aspects. A third site was also used
within the grounds of CSIRO (at Highett, a suburb of Melbourne 18 km NW of location 4), some
2.9 km east of Port Phillip Bay which is almost land-enclosed but covers a large area approxim-
ately 60 x 35 kin. It is generally regarded as being a 'body of water' that can be subject to quite
rough conditions. The ocean and surf beaches are about 45 km SW and prevailing winds are
sometimes from the SSW and 'over the Bay'. This site could be described as mild marine/urban.
The general climate of the region could be described as temperate (to warm-temperate) with
uniform rainfall. At Cape Schanck Lighthouse (Lat 38~ Long 144~ 12 km west of
Flinders, extensive climate records are available; a brief summary is given in Table 1.
Selection of M~terials for the Exoosure Program
This project is to run for 10 years and is being jointly sponsored by the International Lead Zinc
Research Organisation Inc. (II_.ZRO), BHP Coated Products Division (Research and Technology),
and Comalco Aluminium Ltd. Specimens representative of three main classes of metal products
used in building, cladding and roofing are exposed in this study, viz.:
1. zinc, galvanised steel and 5% aluminium-zinc coated steel ('Galfan'), including prepainted products;
2. steel and 55% aluminium-zinc coated steel (known as 'Galvalume' in the USA and 'Zincalume'
in Australasia), including prepainted products; and
3. aluminium, including prepalnted products, and anodised and powder-coated extrusions.
Products for folded or 'bent' 8pecimcns--A total of 22 products for the folded or bent
specimens were obtained from the USA, Japan, Germany, New Zealand and Australia. Details of
the product descriptions are given in Table 2. The bent and the extruded specimens are to be
exposed for periods of 2, 5 and 10 years.
Extruded aluminium specimens--The section shown in Fig. 2 was chosen to be a good

representation of a typical section used in the marketplace. The extrusions were mounted in a
similar manner to the bent specimens using two-part polypropylene mounting spacers and 14 g x
90 ram, 304 grade stainless steel self-drilling wood screws. Figure 2 shows the orientation in which
all samples of the extrusion were mounted, with no part contacting the timbea"rails of the exposure
racks or the mounting screws. The extrusions were supplied precut in 350 mm lengths, with five
different coating types:
El - natural anodising of 25 Ilm thickness to Australian Standard AS 1231-1985, 'Alumihium and
Alurninium Alloys-Anodized Coatings for Architectural Applications';
E3 - polyester powder coating (chromate pretreatment), colour Pottery;
E4 - PVDF powder coating (chromate pretreatment, epoxy primer), colour off-white;
E5 - polyester powder coating (chromate pretreatment), colour Horizon Blue; and
E6 - PVDF wet coat (chromate prea-eatment), colour Malt.
Materials for measurement of corrosion rates--The atmospheric corrosion rate will be
measured at each site using the following materials, exposed (in duplicate) for periods of 1, 2, 5
and 10 years both in the open and under shelter.
Standard copper steel. The composition (%) was as follows and very similar to previous batches:
C 0.20, P 0.014, Mn 0.58, Si 0.040, S 0.019, Ni 0.28, Cr 0.12, Mo 0.004, Cu 0.23, sol AI < 0.003,
Sn 0.003. This low-alloy steel was developed by the British Iron and Steel Research Association
(BISRA) [.L0_]to use as a standard for calibrating atmospheric corrosion test sites. The small addition
of copper renders the corrosivity of the alloy relatively insensitive to small variations in composition,
and batch to batch variations can be ignored in accounting for measured differences in corrosivity.
Specimens 100 x 50 x 3.14 mm are exposed by mounting vertically through central holes. They
were pretreated by degreasing and pickling in hot 5% hydrochloric acid (80~ followed by
thorough washing and flash drying.
TABLE l--Climate data for Cape Schanck Lighthouse near exposure sites at Flinders
(location 5, Fig. 1).
January (summer) July (winter) Year
9 am mean temperatures (~ and mean relative humidity (%)

Dry-bulb 17.4 9.5 13.8
Wet-bulb 15.0 8.3 11.8
Dew point 13 7 10
Humidity 76 84 78
3 pm mean temperatures (~ and mean relative humidity (%)
Dry-bulb 19.0 11.4 15.5
Wet-bulb 16.0 9.6 12.9
Dew-point 14 8 11
Humidity 72 78 73
Daily maximum temperature (~C)
Mean 21.4 12.2 17.0
Daily minimum temperature (~C)
Mean 14.0 7.5 11.0
Rainfall (ram)
Mean 40 78 750
Raindays (no.)
Mean 8 18 161
TABLE 2--Details of products used for bent specimens.
Code Country Product details and description Thick-
of heSS
origin Name Substrate Alloy coating Paint system (nun) >
Type Mass (g/m 2) Pretreat Primer Topcoat
O
o~
"D
I1 USA low C steel 'G-allan' 275 Zn phos 5 [am epoxy 20 ~ SMP 0,62 -1-
I2 Japan low C steel galvanised 272 unpainted 0.90
m
I3 Japan low C steel 'Galfan' 272 unpainted 0.88 -11
14 Japan low C steel galvanised 272 n.a. 5 I.un epoxy 12 larn polyester 0.90
I5 Japan low C steel 'Galfan' 272 n.a. 5 lain epoxy 12 I.tmpolyester 0.87 o
I6 NZ Colorsteel FL steel NZS3441 galvanised 275 Za phos 5 Irmaacrylic 33 pm PVF 0.71 0
laminate -n
-11
17 NZ Colorstee15000 steel NZS3441 galvanised 275 7_a phos 5 lain epoxy 20 lain SMP 0.63 0
18 Germany Pladur low C steel galvanised 275 chromate 5 pan epoxy 20 lain PVDF/ 0.65 6o
(0.1%C,0.2c/d2u) acrylic 70/30 5
19 Germany Pladur low C steel 'Galfan' 255 chromate 5 l.tm epoxy 20 gun PVDF/ 0.69 z
(0.1%C,0.2%Cu) acrylic 70/30
BI Aust. Zincalume low C steel 'Zincalume' 150 unpainted 0.48
B2 Aust. 316 stainless unpainted 0.95
B3 Aust 430 stainless unpainted 0.46
B4 Aust. 304 stainless chromate 5 lam chrome 20 ~ PVDF 0.72
epoxy Kynar 500
B5 Aust. Colorbond XRW low C steel 'Zincahmae' 150 chromate (as B4) 20 lain polyester 0.65
B6 Aust Colorbond XPD low C steel 'Zincaltune' 150 chromate (as 134) (as B4) 0.67
B7 Anst. Colorbond XSE low C steel 'Zincalume' 150 chromate 25 lain 'Hibild' (as B4) 0.68
B8 Aust. Marviplate low C steel galvanised 275 chromate none 200 pm PVC 1.32
laminate
CI USA 3004 aluminium none 'dean only' 2 coat PVDF 0.82
alloy acrylic
C2 USA (as C1) chromate none 24 lain acrylic 1.25
C3 USA (as C1) chromate none 18 pm tar.thane 0.52 &
X link polyestea" 0.81
C4 USA (as CI) chromate none 20 gm polyester 1.22
C5 USA (as CI) chromate none 30 [am PVDF 0.95
Notes: PVDF = polyvinyldifluoride (also referred to as PVb2); SMP = silicon modified polyester; Zn phos = zinc phosphate.
Coating mass is for total both sides. Final column is measured thickness after back surfaces painted for extra protection.
For products I8, 19 the Cu content of the steel substrate can be up to 0.2%.
The 'Galfan' coating is 5% AI-Zn, the 'Zincalume' coating is 55% AI-Zn.
Aust. refers to Australia.
14g x 90 mm self
drilling wood screw
in 304 stainlesssteel %
" ~ ' I / )v ~ 7 ~ ~ 66r~w32o~mailof
2 part polypropylene N 7-'/7" ._ \

mounting spacer ~ / 45~ I Racksat 45~to ground
Fig. 2--Cross-section of aluminium extrusion showing mounting detail.
The other materials are of specimen size 150 • 100 mm and are mounted on the exposure racks in
the conventional way using porcelain insulating bobbins.
Mild steel. This is to Australian Standard AS 1204 nominally 200 grade, of composition (%):
C 0.16, Si 0.038, Mn 0.909, P 0.026, S 0.016, Cr 0.027, Cu 0.017, Mo 0.014, Ni 0.021, and is
from lhe same batch as thal used in a survey in south-east Melbourne [11]. Pretreatment was as
for the copper steel.
Zinc. Rolled zinc strip (1 mm thickness) was supplied by La Salle Rolling Mills Inc., La Salle,
Illinois. The alloy used was LSRM-2400 with residual composition (%) Pb 0.07 max, Cd 0.005
max, Fe 0.010 max, Cu 0.15-0.25, "H 0.05 max, Mn 0.01 max. Residual rolling oil was removed
by washing in trichlorethane followed by ethanol.
'Galfan'. Steel coated with a zinc-5% aluminium-mischmetal alloy (135 g/m 2 on each side), known
by the tradename 'Galfan', was supplied by Nisshin Steel (Japan). Both 'Galfan' and 'Zincalume'
were exposed as received (i.e. no precleaning was carried out). The initial coating thicknesses on
the 'Galfan' and 'Zincalume' were not directly measured.
'Zincalume'. 55% aluminium-zinc coated steel with a coating mass of 150 g/m 2 total both sides
was supplied by BHP Coated Products (Research and Technology). The Australian produced product
is known by the tradename 'Zincalume'; it is very similar to 'Galvalume' produced in the USA.
'ATCORR' units. Atmospheric coffosion (ATCORR) wire-on-bolt units vex), similar to classification
of industrial and marine atmospheres (CLIMAT) testers [12] are also exposed and renewed
qualterly. They will prove useful in monitoring any changes in levels of corrosivity with time.
The technique exploits the phenomenon of galvanic corrosion. The specimens consist of 1 m lengths
of high-purity aluminium wire wound tightly into the threads of nylon, steel and copper bolts
mounted vertically on a perspex block. The aluminium wire used by CSIRO is electrical conduct-
ivity grade (99.6% purity and similar to type 1350), 0.81 mm in diameter. After drawing, it was
annealed and vapour degreased in trichlorethylene. CLIMAT testers have conventionally been
manufactured using plastic or aluminium screws and washers fitted into holes in the bolts to secure
the ends of the length of wire. An improved method developed at CSIRO involves simply bending
7-8 mm 'tags' at the ends of the wire and securing these to the bolt with silicone rubber 'O rings'.
Processing of Mass Loss Specimens after Recovery
Blanks were included in the chemical cleaning operations of all materials except the ATCORR
ahiminium wires where tests have shown that the blank losses are approaching zero and certainly
not significant.
Steel specimens--Loose corrosion products were gently scraped from the specimens and
saved for subsequent analysis of pollutants (principally chloride). The specimens were then cleaned
in Clarke's solution according to BISRA [1_.03.
Zinc and 5% aluminium-zinc--Both materials were cleaned in 20% chromic acid at

75-80~ For these and for 55% AI-Zn usually two cleaning cycles were carried out, the selected
mass loss (corrected for the blank) being that for which the total blank loss as a percentage of the
corrected specimens mass loss was minimised.
55% aluminium-zinr specimens were cleaned in a solution of 10% chromic 5%

phosphoric acid also at 75-80~
'ATCORR' aluminium wires--Corrosion products were removed by boiling in a solution

containing 35 ml of phosphoric acid and 20 g of chromic acid per lille according to ASTM Standard
B 137-45 (1979) for 'Measurement of Weight of Coating on Anodically Coated Aluminium'.
Desi2n and Manufacture of Bent Soecimens
The folded or bent specimens made from the coated and prepainted/coated sheet products have
been designed to simulate the various types of distress metal products are subjected to during the
processes of fabrication and building. The specimen and its features is shown in Fig. 3.
Bend over mandrel of

variable radius;
-3 mm dia. to -20 mm dia. Cover plate with Bends
2 Enchsen Domes / I\
-5mmhigh&deep St/ 3:\
t
..........~...i!~.i.i~!.,!
~ ~/--~ mm
Cut-out Scribes to alloy layer & Fasteners for fixing Mounting
base metal cover plate hole
Fig. 3--Features of bent specimen.
Blanks of dimensions 540 x 95 mm were made by guillotining the samples supplied. Considering
the large number of specimens to be made, a die was made to press out the specimen blanks. This
die was placed in a standard type cast-iron die set and mounted in a 20 ton press. The surfaces of
the specimens were protected during pressing and bending by paper liners cut to size. The specimen
blanks were pressed in two operations with the cover plate (for the Erichsen domes) attached to
the main body.of the specimen. The back of the specimen was labelled in these two areas and the
cover plate then guillotined off. After the Erichsen domes were pressed into the cover plate, the
two parts of the specimen were matched.
Incorooration of bends into the specimgn--A variety of features are incorporated into the
specimens. The right end of the specimen (see Fig. 3) is based on a test panel specified in an
Australian Standard 2728-1984, 'Prepainted and Organic Film/Metal Laminate Products -
Performance Requirements for Interior/Exterior Applications in Buildings'. Two bends were
placed in the specimens using mandrels of diameter 3t and 5t, where t is the thickness of the
product. Zero t bends were also included in the specimens (top right edge) for all products (except
C2 and C4) where this did not result in fracture. The bends or folds were carried out using a
standard sheet metal folder with a replaceable top clamping bar machined to the required radius on
the leading edge. The radii of these mandrels were measured using a Mitutoyo Profile Projector.
There were 22 products at 20 different thicknesses. An examination of the range of thicknesses of
the products showed that a total of nine mandrels would enable 3t and 5t bends to be put into all
products with acceptable variations from the theoretical mandrel radii required. The maximum
variation on the 3t bend is about +10%, and on the 5t bend about - 9 to +6%. The mean variations
are very close to zero. The variations will be taken into account when comparing the extent of
microcracking in the products and their corrosion performance at the 3t and 5t bends.
At the left end of the specimen is a bend made using a conical mandrel test apparatus (Sheen
Instruments Ltd, UK) conforming to ASTM D522-88, 'Standard Test Methods for Mandrel Bend
Test of Attached Organic Coatings' 1988, BS 3900-E11 and ISO 6860. The tapered steel mandrel
has a length of 203 mm and a diameter varying from 38 mm down to 3 mm. The specimen blanks
with a width of 95 mm were clamped at the narrow end of this mandrel and the diameter of the
resulting bend varies from about 3-20 ram.
Incorooralion of drawn domes into thr ~;pecimen--The US National Coil Coaters Association
specifies a reverse drawn dome be included in test panels for exterior exposure [13.]; this feature
has been included in the specimens, a die being made in accordance with British Standards
Institute 3900: Part E4 'Cupping Test' (1976). The cover plates were clamped flat against the die
and drawn domes produced using an indenter fitted to a horizontal spindle on a Cincinnati milling
machine. Initial experiments determined the depth of indentation that could be produced without
fracture occurring. This was found to be generally 5 ram, and adopted as the consistent standard,
except for the thicker aluminium products which could tolerate only 2.5 ram. The cover plates will
also result in 'crevice corrosion' occurring between them and the main body of the bent specimens.
Other features in the specimr specimens include a large circular cut-out (diameter
31 mm), and two inscribed lines made using a workshop scribing tool, one being through the
paint coating to the alloy coating layer, and the other through to the base metal. The guillotined
edges of the specimens were not protected in any way prior to exposure. However the back surfaces
of most products were painted with two coats of a high-build water-based anticorrosive primer for
steel prior to guillotining. The stainless steel and aiumihium products were not painted. The pur-
pose of the painting is to provide additional protection to the backs of the specimens and prevent
them from falling by corroding through from the underside. In practice, with products fixed to
structures, this scenario is largely avoided whereas it is a real possibility with specimens mounted
on exposure racks.
Fastenings Used to Assemble and Mo0n[ the Bent Soecimens
Attachment of cover nlates featuring Ericksen domes--The aluminlum specimens were

assembled using 'Bulbtite' 7000 series aluminium rivets, with ethylene polymer diammine
monomer (EPDM) seal assemblies under the head. The coated steel specimens were assembled
using 8 gauge x 12 mm spoon point (S point) screws. They had a hex head with EPDM seal
assembly and were obtained especially hot-dipped galvanised for this project. The stainless
'Colorbond' was initially assembled using the same screws, but these have been replaced with
304 grade stainless S point stitch screws.
Attachment of cover olates on the 3 ! 6 and 430 slainless oroducts--Product B2 (316) was
analysed (by spectographic means) and the composition (%) is as follows: C 0.049, Si 0.667, Mn
1.24, P 0.048, S 0.016, Cr 18.00, Ni 11.76, Mo 2.03, Cu 0.208, V 0.068, "1"I0.027, Nb 0.027,
Fe 65.85. Needle-point screws used for product B3 would not penetrate the material and the cover
plates were consequently fixed using cadmium plated 410 grade stainless screws of composition
(%): Si 0.44, Cr 12.26, Ni 0.00, Cu 0.08, S 0.36, Fe 86.85 (determined using SEM/EDS). Product
B3 (430) had a (spectrographic) composition (%) as follows: C 0.048, Si 0.42, Mn 0.44, P 0.045,
S 0.0047, Cr 17.07, Ni 0.12, Mo 0.011, Cu 0.050, V 0.081,1i 0.003, Nb 0.034, Fe 81.07. The cover
plates were fixed to the main body of the specimens using needle-point self-drilling 302 HQ grade
stainless screws of composition (%): Si 0.98, Cr 17.85, Ni 8.93, Cu 3.57, S 0.14, Fe 68.55 (SEM/EDS).
Mountin~ of bent soecimens onto ex_oosure racks--Special insulating mounting spacers

were designed to fix both the bent and extruded specimens (see Fig. 2) to the timber exposure
racks such that no bimetallic reaction could occur with the mounting screws. The spacers come
in two halves (male and female) and were turned from 19 mm polypropylene rod. They are fixed
to the timber racks using 304 stainless steel, cadmium-plated 14 gauge x 50 mm self-drilling
wood screws with EPDM seals. The mounting spacers perform another function in that they keep
the specimens approximately 14 mm above the timber rail of the exposure rack, ensuring no
'heat sink' effect occurs.
Microscoov of Bent Soecimens
Each of the coated/painted bent specimens was examined at low magnification using a Wild Leitz
Macroscope model M420 fitted with a 1:5 Macrozoom objective, giving a continuously adjustable
primary magnification of 6.3-32X and a working distance of 100 mm. It was fitted with a Wild
MPS 46/52 Photoautomat for automatic exposure and a 35 mm film magazine. Most of the photo-
graphs of microcracking were taken at a viewing magnification of 40X (magnification on film
12.8X), each specimen being examined and photographed in the same sequence, viz. ft, 3t, 5t
bends, 3 mm and 20 mm bends from the conical mandrel, scribe to alloy coating and scribe to
metal substrate, and finally the upward Erichsen dome and the indented dome. Three of the
products, i.e. the unpainted stainless steels and the PVC laminated steel, showed litlle damage
and these products were not photographed. With 9 photographs required for each specimen, over
3000 photographs of the bent specimens were taken.
Measurement of Colour and Gloss on Bgn[ ~n~l Extru0r Soecimens
Measurement of both colour and gloss was conducted after the specimens had been mounted on
the exposure racks. Colour was measured in five different notations simultaneously using a
Minolta CR200 chroma meter. These notations are L* a* b*, Yxy, Munseil, L.C.H. and a density
difference measurement Dx Dy Dz. The chroma meter was calibrated after every 30 measure-
ments. Gloss was measured using a Labotron/BYK 60' Pocket Gloss meter, the instrument being
calibrated after every 10 measurements.
Construction of Exposure Racks and Shelters
Details of the stands for the exposure racks and the structure to carry a glass roof over some are
shown in elevation in Fig. 4. A plan view of the area occupied by the racks and the glass roof is
shown in Fig. 5. All dimensions are in milUmetres. The large area of the roof in relation to the area
of the racks is to ensure reasonable uniformity of the sheltered micro-environment. To assist further
in this regard, the timber racks under the roof are interchanged at regular intervals. Both considcr-
ations are important, as one aim of the study is to assess the relative performance of different
classes of materials where they are not cleaned naturally by rain washing.
The roof structures are designed for a wind pressure of 1.52 kPa, terrain category 1. The racks and
shelters are oriented to face true north, both set at an angle of 45 ~ to the ground. The structural
steelwork at the Higher site was painted, initially with an etch ptimcr followed by two coats of a
chlorinated tubber topcoat. The steelwork at the Hinders sites was hot-dipped galvanised to
Australian Standard 1650-1981 'Galvanized Coatings'. All steelwork was fixed to concrete slabs
using stainless steel belts. The roof joists were 130 x 35 mm oregon timber and were painted
with an undercoat and two coats of a quality acrylic exterior gloss paint. All fastenings used were
galvanised.
Careful consideration was given to the selection of the best material for the roofs of the shelters. In
terms of only simulating typical unwashed areas, such as under eaves or covered waikways, a non-
Iransparent material would have been best. However, it was also desirable to gain some information
on the influence of UV radiation especially on the organic coatings. Ultraviolet radiation is con-
sidered to be that with wavelengths below 380 rim, UVa being from 380 to about 313 rim, and UVb
below 313 tun. Clear float glass (1/4" thick) transmits a much greater percentage of UVa radiation
than polycarbonate (the other roof option). Laminated glass could not be used as it has virtually
zero transmission of wavelengths below 380 nm. It was decided to use 5 mm toughened glass
for the roofs of the shelters, the toughening process having little effect on the transmission of UV.
The glass was fixed to the roof joists using aiuminium glazing bars with a mill finish. A silicone
sealant ~was used for waterproofing. The exposure racks were of 66 x 32 dressed kiln-dried (KD)
hardwood; fasteners were hot-dipped galvanised and painting was as for the roof joists.
/ .\~/ \% W /
TI' II ~. U
Fig. 4--Elevation detail of exposure racks and shelters.
,',','-'-'-" ! ,,'.-,-.',',
," .",",",". . , . , ,
i ....
2":'~'~'~"
i:i:i:i:i:il
T
g
o
""'"
..... ".....
, , , , , . ,. ,. ,. . . :::::::::::: iiii i;i!i;i~
.....
r590~
7740
Fig. 5--Plan view of exposure racks and sheltered area.
Exoosure of racks/soecimens on site--The timber racks were stored indoors and as specimens
were photographed and measurements made on them, they were progressively mounted on the
racks, with no deterioration occurring until all racks were simultaneously attached to the stands
already in place at each site. The exposure phase of the project at CSIRO (Highett) was begun on
21 May 1991. Eight exposure racks were tlansported to the Flinders sites by enclosed truck, and
installed on 23 May 1991.
Measurement of Almosoheric Chloride
The wet-candle technique for the measurement of airborne chloride has been set up according to
International Standards Organisation (ISO) standard 9225 'Corrosion of Metals and Alloys -
Corrosivity of Atmospheres - Measurement of Pollution' (1992), both in the open and under the
shelter at each of the three sites. The first data was obtained for the month of April 1992 and the
salt candles were changed at monthly intervals thereafter. The changeover date was not always at
the beginning/end of each month, the intervals varying from a minimum of 24 days to a maximum
of 41 days with a mean interval of 31 days (standard deviation 6 days). The calculation of chioride
deposition rate takes the interval into account and expresses the result as a daily rate.
Measurement of Climatic Parameters. TCmperi~tore and Relative Humidity
Measurements will be made continuously at all three sites of temperature, relative humidity, and
time-of-wetness both inside a standard meteorological screen (Stevenson screen - 'open' conditions)
and under the shelters. Some preliminary data has been obtained for the Navy Base only, and is
reported here. Temperature was measured using a National semiconductor LM 335 which has a
range o f - 5 5 to +150~ with a reported accuracy of only +3~ (at 25~ Humidity was measured
using a Humitter Integrated Humidity Transmitter (by Valsala Sensor Systems) with a range of
10-90% RH and accuracy of better than +_5% RH at +20~
Observations on 'Bent' Specimens
A detailed record of observations was made after one year's exposure for both the sheltered and
open Slx~imens at the severe marine site (Site 1 Navy Base), and for the sheltered specimens only
at the moderate marine site (Site 2 Water Board); the specimens in the open at the Water Board
and the specimens at CS1RO were generally in very good condition. The most noteworthy defects
on the specimens at the severe marine site (Navy Base) alter intervals of 6, 7.75 and 12.8 months
are summarised.
Observations at 6 months--A remarkable deterioration for most of the steel-based products

started to become apparent in the severe marine sheltered environment al~er about 4-5 months.
This deterioration was first noticed on the stainless steel specimens. At 6 months the 430 grade
stainless steel was covered in loosely adherent red rust on and around the cover plates and their 300
series stainless fastenings, and around the main specimen mounts. These are, of course, ideal sites
for crevice corrosion. The 300 series cover plate fasteners are not corroding. Two points must be
emphasised, viz. 430 grade stainless is not recommended for outdoor exposure, and the specimens
made from the stainless products B2 and B3 were not treated in a passivating bath after their
manufacture using machinery made of non-stainiess steel. 'Iron pick-up' has contributed to the
corrosion, especially on the cut edges. The specimens of 316 stainless (B2) were in much better
condition, but conversely the 410 grade cover plate fasteners that had been supplied for them
were totally corroded to red rust; an excellent example of poor materials selection and bimetallic
effect. At the moderate marine site, the sheltered specimens were showing similar although less
pronounced effects.
The galvanised (12), 5% Al-Zn (13) and 55% AI-Zn (BI) products were all heavily encrusted with
white corrosion products, but one area of the general surface of a specimen of B 1 had progressed
to very significant red rust. A few spots of rust were also visible on the 55% AI-Zn mass loss
specimens. The ahiminium bent specimens, notably C4, were showing white corrosion products
only at cut edges and in the scribes.
Observations at 7.75 months--At the severe marine site in the open, the galvanised steel (I2)
bent specimens had substantial white corrosion products on their general surfaces and red rusting
starting in one ~t bend. The 5% Al-Zn specimens (13) had less corrosion product and no sign of~t
rusting, and the 55% Al-Zn specimens (BI) had the least corrosion product and also no Ot rusting.
Under the shelter, the galvanised specimens had heavy deposits of white corrosion products, with
one specimen having red rusting starting on its general surface and established on the Ot bend. One
5% Al-Zn specimen (I3) had traces of red rust on its general surface but all Ot bends were clear. The
55% Al-Zn product (B 1) was now showing extensive red rusting on two specimens but interest-
ingly not on the ~t bends. The specimens of galvanised steel with the PVF laminate (I6) were
outperforming the painted galvanised specimens, both in the open and under shelter and especially
on the ~t bend, reflecting the enhanced formability of the PVF laminate.
Observations at 12.8 months--Severe marine site under the shelter. Very marked deterioration
had occurred on virtually all of the steel-based products. The unpainted products I2, I3 and BI were
covered in white corrosion products with I3 (5% Al-Zn) probably the least of the three. All three
products showed red rusting. On the cut edges and the ~t bends product I2 (galvanised) showed the
most rusting, one ~t bend being actually perforated. Product I3 (5% Al-Zn) was overall showing
the least red rusting of the three products, but its r bends although better than I2 had more rust
than the ~t bends of product B 1 (55% Al-Zn). However considering the general surfaces of the
specimens, product B 1 was by far the worst of the three in terms of general rusting. At this stage
product I3 (5% Al-Zn) was overall probably performing the best of the three unpainted products,
but all were performing badly.
Four of the products have 20 pm SMP or polyester topcoats. Three are based on steel and have a
5 Inn epoxy or chrome epoxy primer (I1, I7, B5). The fourth has an aluminium substrate and no
primer (C4). Product B5 was in better condition than 17 and both were substantially better than I1.
The aluminium product (C4) was perhaps in slightly better condition than B5 but the aluminium
rivets were showing substantially less corrosion product than the bex head galvanised fasteners.
The steel products with topcoats based on PVDF were not performing well. Significant blistering
of the paint films and peeling at the cut edges (edge creep) had ocemred. Product I6, the PVF
laminate, although showing red rusting on cut edges whereas products B6 and B7 had not, was in
overall better condition due to the blistering in the latter products.
Severe marine site in the open. Whereas under the shelter product B 1 (55% AI-Zn) had rusting
on its general surface, no trace of rusting was observed on the general surfaces of the specimens
(including the unwashed surfaces) in the opera A l s o n o rusting was present on the cut edges or the
~t bends. In contrast, product I2 (galvanised) had red rusting on the ~t bends and on the unwashed
surfaces adjacent to the ~t bends. Product 13 (5% AI-Zn) was dearly outperforming I2 with red
rusting on only one of the ~t bends but was not performing as well as product B1.
Mea~rements of Airborne Chloride
Data for the levels of airborne chloride is available only for the second year of this exposure
program, viz. April 1992 through March 1993. The means of the data for this period will however
be used at this stage to characterise the sites according to atmospheric chloride level, and the
first-year corrosion rate data is plotted against them.
The mean levels for each of the sites (for the 12 periods) together with their standard deviations
are as follows: Navy Base (open) 112 (41), Navy Base (sheltered) 42 (29), Water Board (open) 27
(13), Water Board (sheltered) 12 (6), CSIRO (open) 4 (1), CSIRO (sheltered) 3 (1); all mg/m2.d.
"o
,,o[
The means of the data are plotted in Fig. 6 against distance from the ocean together with fitted
hyperbolic models. The values in the open categorise the Navy Base in class $2, the Water Board
I I I I - I
%
120
E
O3
U.tO'=
g~
Oo
0 ,
Wt'~
ZO~
<-~ 60
Open exposure
Ta.
F-'~
gg
z<
i.
0 1 2 3
DISTANCE FROM THE OCEAN
OR PORT PHILLIP BAY (kin)
Fig. 6--Mean site levels of airborne chloride with fitted hyperbolic models
versus distance from the ocean.
in class S 1, and CSIRO at the bottom end of class S 1 according to ISO Standard 9223 'Corrosion
of Metals and A l l o y s - Corrosivity of Atmospheres -Classification' (1992). The ratio of chloride
levels in the open to the sheltered conditions is about 3 for the Navy Base, 2.3 for the Water Board,
and 1.5 for CSIRO the mild marine site. The chloride levels for the Navy Base and Water Board
are significantly less than those for the 25 m and 250 m (80 ft and 800 ft) lots at Kure Beach NC,
being 417 and 106 mg/m2d (LaQue Center for Corrosion Technology, Inc., pers. comm.).
A good association exists between chloride deposited in the open and under the shelter at CSIRO
and the Water Board (mild and moderate marine sites) with Spearman Rank Correlation
Coefficients of 0.87 and 0.85 respectively. However the relationship is poor for the Navy Base
(severe marine) with a coefficient of 0.43. The chloride deposition level under the shelter at the
Navy Base is reasonably constant from about 25-45 mg/m2.d independent of the level in the open.
There is however one high reading under the shelter (129) and it cannot be concluded at this stage
that the shelter presents a limit to the level of chloride deposition that can occur.
One-year Mass Loss Soecimens - Corrosion Rate Data
Mild steel and standard low-alloy copper-steel--The mean cleaning blank losses for these
materials expressed as percentages of the specimen corrected mass losses are 4.2% and 1.3% for the
mild steel and copper steel respectively. The densities of the mild steel and copper steel used for the
conversion of corrosion rates in g/m2.year to Bm/year are 7778 and 7769 kg/m 3 respectively. Table
3 gives the individual results for the duplicate specimens of the steels for the first years exposure.
TABLE 3--First-year corrosion rates of 'mild' steel and low-alloy copper-steel.
Site Aspect One-year corrosion rates (lam/year)
Mild steel Copper steel
Navy Base Open 31.8 30.3

(severe marine) Open 29.9 29.7
Sheltered 34.6 37.4
Sheltered 36.2 39.8
Water Board Open 22.5 20.1
(moderate-mild Open 21.3 19.4
marine/rural) Sheltered 17.9 21.3
Sheltered 20.5 23.6
CSIRO Open 11.2 9.9
(mild marine/ Open 11.2 10.0
urban) Sheltered 8.9 8.3
Sheltered 7.8 9.0
The means of the duplicates are plotted in Fig. 7 together with data from a corrosivity survey in
south-east Melbourne in 1983 (conducted in the vicinity of location 4 in Fig. 1) [11]. The mild
steel used in the present study is of the same batch as that used 10 years ago but the copper-steel is
from a different batch. A linear regression of the 1983 data forced through the origin has a slope of
1.12 (with R 2 = 0.965). A similar regression of the present data yields a slope of 1.06 (R 2 = 0.989)
for the open exposures, and a slope of 0.90 (R 2 = 0.995) for the sheltered exposures. The agreement
of the present open data with that obtained 10 years ago is remarkable, confirming the batchwise
reproducibility of the copper-steel corrosion rates and validating its use as a standard calibrating
material. It is interesting to note that whereas in the open the mild steel corrodes at a slightly
higher rate than the copper steel, under the shelter the order is reversed. More data is required to
40 I I I
o 2 yr exposures at a grid of 68 sites
in S.E. Melbourne (1983 - 85)
0 Present study 0/~,

Open exposures
30 9 Present study
Sheltered e x p o s i 7
uJ
1--
03
,/"
a
20
LL
0
LU
I--
<
nr"
Z
n'-
cr
/' 9
o /
o /
/
/
/
,/ I I I
0 10 20 30 40
CORROSION RATE OF LOW ALLOY COPPER STEEL (pro/year)
Fig. 7--Corrosion rate of mild steel versus corrosion rate of standard low-alloy
copper-steel for present study and previous corrosivity survey in south-east Melbourne.
confirm if this effect is significant. The corrosion rates of both steels are plotted against the site
mean levels of airborne chloride (measured over the second year of exposure) in Fig. 8, and it is
apparent that the level of chloride has a markedly greater effect for sheltered specimens than for
those freely exposed.
Zinc. 5% aluminium-zinc and 55% alumini~m-zinc--The mean cleaning blank losses for
zinc and 5% aluminium-zinc expressed as percentages of the specimen corrected mass losses are
0.004% and 0.12% respectively. Because of the very low mass losses of the 55% aluminium-zinc
specimens at the Water Board and CSIRO sites, the blank corrections represent a significant con-
tribution to these results. The mean percentage blank losses for the 55% aluminium-zinc specimens
are 1.3% at the Navy Base, 9.8% at the Water Board, and 24.6% at CSIRO. Density figures of 7140
and 6600 kg/m 3 have been used for the zinc and 5% aluminium-zinc specimens respectively to
convert the corrosion rates from gm/m2.year to lam/year. The figure used for the density of 55%
aluminium-zinc to calculate corrosion rates was determined from analyses supplied by BHP
Coated Products Division for the overall composition of the 55% aluminium-zinc alloy layer, and
was 3814.5 kg/m 3. The use of this figure instead of that for the zinc-rich phase which initially
corrodes from the aluminium-zinc matrix is overestimating the corrosion rate of the 55% aluminium-
zinc at CSIRO and the Water Board, and perhaps also at the Navy Base in the open. However, at the
Navy Base under the shelter this is unlikely to be the case as the coating class used (AZI50) has
a coating thickness of approximately 20 IJ-mper side and the corrosion rate is seen to be 10.2 Ixm/y.
Both the 55% aluminium-zinc and 5% aluminium-zinc mass loss specimens had just started to
show signs of red rusting after one year under these conditions.
Table 4 gives the individual results for the duplicate specimens of zinc, 5% aluminium-zinc and
55% aluminium-zinc for the first year's exposure.
40 i i i i |
/ / / L o w alloycoppersteel
'Mild steel'
'Mild steel',..z3
SHELTERED
30 EXPOSURE 1 ~ . ~ / , ~ ''~
/ ~.
LU
t---
// ..... -- "~,,/~ow alloy
/// . EXP~).~RE copper I
},;y
n"
Z
0
Ii
o
uJ
>- 10 I ~
0 I I I I I
20 40 60 80 100 120
MEAN MONTHLYAIRBORNECHLORIDE (mg/m2.d)
(for periodApril 1992 - March1993)
Fig. 8--Corrosion rates of mild steel and low-alloy copper-steel
versus site mean level of airborne chloride.
TABLE 4--First-year corrosion rates of zinc, 5% aluminium-zinc and 55% aluminium-zinc.

Site Aspect One-year corrosion rates (I.tm/year)
Zinc 5% aluminium-zinc 55% aluminium-zinc
Navy Base Open 6.94 3.22 1.47
Open 5.49 3.27 1.36
Sheltered 14.36 13.65 9.55
Sheltered 15.95 12.70 10.77
Water Board Open 1.91 0.43 0.35
Open 1.85 0.43 0.34
Sheltered 3.76 1.29 0.58
Sheltered 4.12 1.09 0.65
CSIRO Open 0.99 0.30 0.23
Open 0.96 0.27 0.25
Sheltered 0.90 0.70 0.41
Sheltered 0.96 0.73 0.41
The means of these duplicate results are plotted in Figs 9-13. The comparative corrosion rates in
the open and under the shelters at each of the I/tree sites are shown in the form of bar charts in
Figs 9, 10 and 11, for zinc, 5% aluminium-zinc and 55% aluminlum-zinc respectively. The
remarkable influence of the shelters increasing the corrosion rate of all three materials (the only
exception being zinc at CSIRO the mild marine site) is clearly apparent. The ratios for the
sheltered to open corrosion rates are given in Table 5.
16
sheltered
(marine environment)
I I~(marine environment)
12
Ill
z 8 Fig. 9--Comparative one-year corrosion

o_ rates o f zinc e x p o s e d in the open and
orr under the shelters.
n,"
0
rr
,,, 4
NAVY WATER CSIRO

BASE BOARD (mild)
(severe) (moderate)
16
~] sheltered (marine environment)
I J open (marine environment)
~. 12
E
UJ
Z
Fig. 10--Comparative one-year
_o 8 corrosion rates o f 5% aluminium-zinc
oI I e x p o s e d in the open and under the
shelters.
0
n-
'"
>.- 4
NAVY WATER CSIRO

BASE BOARD
(severe) (moderate) (mild)
16
sheltered (marine environment)
I I open (marine environment)
12
E
UJ
Z Fig. 11--Comparative one-year

o_ 8
corrosion rates of 55% aluminium-zinc
0 /// exposed in the open and under the
///
/// shelters.
///
O
or
/1/
r//
m 4 / / /
/ / /
/ / /
/ / /
/ i /
//.,-
/ / /
/ / /
///
f / /
z / /
/ / /
/// I i 1777A I
NAVY WATER CSIRO
BASE BOARD
Exposed in the open (marine environment)

Zinc /--'-]
5% AI-Zn
55% AI-Zn
6
o
UJ

rc 4
Z
corrosion rates of zinc, 5% aluminium-
o_ zinc and 55% aluminium-zinc exposed
U)
O in the open.
i,L
n,-
n"
oo
2
NAVY WATER CSlRO

BASE BOARD
16
Exposed under shelter
(marine environment)
Zinc [ Z ]
5% AI-Zn
55% AI-Zn
12
:>,,
?
W
F-
if-
z 8 corrosion rates of zinc, 5% aluminium-
o_
O3 zinc and 55% aluminium-zinc exposed
o
II under the shelters.
n-
O
o
,. 4
>-
NAVY
BASE
(severe)
I
LWATER I
BOARD
(moderate)
CSIRO
(mild)
TABLE 5--Ratio of sheltered to open corrosion rates.

Site Zinc 5% aluminium-zinc 55% aluminium-zinc
Navy Base (severe marine) 2.44 4.06 7.18

Water Board (moderate marine) 2.10 2.77 1.78
CSIRO (mild marine) 0.95 2.51 1.71
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Mean ratio for 3 sites 1.83 3.11 3.56
The trends in the ratios are quite consistent, all showing increases with severity of site, airborne
chloride in the open, and the ratio of chloride in the open to that under the shelters. It is the authors'
belief that the explanation for this behaviour is the deposition of salt and formation of corrosion
products on the unwashed sheltered surfaces, thereby reducing the critical relative humidity at
which the surface can be considered 'wet' from the point of view of corrosion. The very marked
increase in corrosion of the 55% aluminium-zinc at the severe marine site could possibly be due
to the formation in situ of a very hygroscopic compound such as aluminium chloride; this will be
looked into further.
The comparative corrosion rates of the three materials based on zinc used for coating steel are
shown in bar-chart form in Figs 12 and 13 for open and sheltered exposures respectively.
In the open at the severe marine site, the corrosion rate of 5% aluminium-zinc is half that of zinc,
and the corrosion rate of 55% aluminium-zinc is less than one-quarter that of zinc. At the moderate
and mild marine sites, the rates for 5% aluminium-zinc and 55% aluminium-zinc are much closer
and range from one-third to one-fifth that of zinc. Under the shelters the performance of the three
materials is much closer at the severe marine and mild marine sites (particularly the former), but
there are marked differences at the moderate marine site with the corrosion rate of 55% aluminium-
zinc being less than one-sixth that of zinc.
The mean corrosion rates of all three materials are plotted against the site mean levels of airborne
chloride (measured over the second year of exposure) in Fig. 14 and, as for the steels (but to a
much greater degree), the level of airborne chloride has a marke(gy greater effect for sheltered
specimens than for those freely exposed. The 'curves' in Fig. 14 show no sign at all of plateauing
as is somewhat the case in Fig. 8. The ranking of the three matexials in terms of corrosion rate
versus alrhome chloride is the same for both open and sheltered exposures with 55% aluminlum-
zinc deafly performing the best; this can be contrasted with the comments made under Observations
at I2.8 months.
The remarkably higher corrosion under the shelters is obvious with increased corrosion rates at an
airborne chloride level of 40 mg/m2.d of about 6 for zinc, 9 for 5% aluminium-zinc and 20 for 55%
aluminium-zinc. It appears that this type of shelter can provide a means of markedly increasing the
corrosion rate of some materials notably the zinc-based alloys and stainless steels under outdoor
exposure in marine environments. The options for this as a new type of testing facility are to be
explored further.
ATCORR (CLIMAT) wire-on-bolt indices--The ATCORR wire-on-bolt indices for the
first year of exposure are given in Table 6 and it is clear that with the exception of Autumn 1992,
corrosivity is reasonably constant with season. The aluminium/copper (AVCu) and aluminium/iron
(Al/Fe) indices are not reflecting the enhanced corrosivity of the plate mass loss specimens under
the shelters. The ahiminium/nylon (AI/Nyion) index which is defined by the inventors of the
CLIMAT devices to be the measure of the general corrosivity of an atmosphere is however
reflecting this enhanced corrosivity. As the AVFe index is reputed to be the best measure of the
relative level of marine corrosivity, it must be noted the Ai/Fe indices obtained to date bear no
relation to the plate corrosion rates.
16 I l I 1
SHELTERED EXPOSURE
t Zinc
/ / / 5 % AI -Zn
12
LU
I,--
<
n,-'
/I
//'/"
o A,-Z.
Z
Q Fig. 14--Corrosion rates of
m 8 zinc, 5% aluminium-zinc, and
oer" OPEN EXPOSURE 55% aluminium-zinc versus
n-
O
o
/ Zinc site mean level of airborne
chloride.
I i
<
W ;/
~ 4
55% AI -Zn
0 ~
0 20 40 60 80 100 120
MEAN MONTHLYAIRBORNECHLORIDE (mg/m2 .d)
TABLE 6--'ATCORR' indices for first four exposure periods

(May-Aug '91 winter, Sept-Nov '91 spring, Dec '91-Feb '92 summer, Mar-May 92 autumn)
(results for different periods normalised to 91.3 days).
Period AI/Cu AI/Fe AI/Ny AFCu AFFe AI/Ny
Site 1. Navy Base open Site 1. Navy Base sheltered

Winter 10.40 11.82 Lost 12.55 9.95 1.45
Spring 11.18 10.51 0.40 10.07 7.82 1.28
Summer 9.30 9.63 0.36 14.94 I 1.04 0.73
Autumn 7.31 6.94 0.26 5.25 3.84 0.65
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Mean 9.55 9.73 0.34 10.70 8.16 1.03
Site 2. Water Board open Site 2. Water Board sheltered

Winter 8.12 7.75 0.09 3.33 3.18 0.32
Spring 8.00 7.56 0.26 2.48 3.00 0.75
Summer 6.80 6.77 0.25 4.07 3.27 0.30
Autumn 6.27 5.74 0.18 1.48 1.46 0.37
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Mean 7.30 6.96 0.20 2.84 2.73 0.44
Site 3. CSIRO open Site 3. CSIRO sheltered

Winter 2.33 1.69 0.04 0.33 0.19 0.05
Spring 2.56 2.28 0.14 0.23 0.29 0.09
Summer 2.70 1.23 0.04 0.16 0.21 0.05
Autumn 1.55 1.38 0.04 0.10 0.13 0.06
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Mean 2.29 1.65 0.07 0.21 0.21 0.06
In Figs 15 and 16 the first-year corrosion rates for zinc, 5% aluminium-zinc and 55% aluminium-
zinc are plotted against the mean nylon ATCORR index (CLIMAT AI Atmospheric Corrosivity
Index) for the open and sheltered exposures respectively. The data appears consistent and the
results are promising. This data will be compared with results from exposures in other periods
and from other sites to see if any fundamental relationships exist.
Data on Temoerature and Relative Humidity in the Open Comoared to Under the Shelters
At this time data is available for only a very limited period for the Navy Base only. Measurements
were made at 30-minute intervals and the data recorded on a Datataker model DT500. The daily
mean results for 6 days in May of 1993 are presented in Table 7. Considering that the temperature
measurements are subject to an error of +3~ and the humidity measurements an error of +__5%,
the data so far does not enable any conclusion to be drawn as to whether there is any significant
difference between climatic conditions in the open and under the shelter. On these very preliminary
results it would appear that such a difference if it exists is minimal. It can be postulated that the
markedly higher corrosion under the shelters is due to the presence of deposited salt and corrosion
products (not removed by rain washing) dramatically increasing the 'time-of-wetness' at the
specimen metal surfaces.
I I
OPEN EXPOSURE
Zinc
I--
IT" Fig. 15--One-year open
z exposure corrosion rates of
zinc, 5% aluminium-zinc and
onr -Zn 55% a l u m i n i u m - z i n c versus site
ft. m e a n nylon A T C O R R (wire-
o
on.- on-bolt) index for open
exposure (normalised to 3
uJ months).
y // 55% AI -Zn
0 9==T===-=-'-~i
0.0 0.1 0.2 0.3 0.4
MEAN NYLON ATCORR INDEX FOR 1st YEAR
(CLIMAT AI Atmospheric Corrosivity Index)
16 I I I I
SHELTERED EXPOSURE Zinc
12
=k
Iii
<
tr Fig. 16--One-year sheltered
z
o~/o/AI
/ -Zn
_o exposure corrosion rates of
Or) zinc, 5% aluminium-zinc and
o 55% aluminium-zinc versus site
0 / 9 mean, nylon ATCORR (wire-
o on-bolt) index for sheltered
i1: II // exposure (normalised to 3
months).
I / ii/ /
,/
I;
0 L
0.0 0.2 0.4 0.6 0.8 1.0 1.2
MEAN NYLON ATCORR INDEX FOR 1st YEAR
(CLIMAT AI Atmospheric Corrosivity Index)
TABLE 7--Mean daily temperature and relative humidity in the open

and under the shelter at the Navy Base (standard deviation in parenthesis).
Date 1993 Mean temperature (~
Open Sheltered Difference Difference

(Stevenson screen) (open-sheltered) significant?
19 May 14.3 (1.7) 14.1 (1.8) 0.2 No

20 May I 1.8 (1.0) 11.6 (1.2) 0.2 No
21 May 12.4 (1.2) 11.1 (1.1) 1.3 Yes
22 May 14.0 (1.3) 12.4 (1.9 1.6 yes
23 May 14.0 (t.8) 12.1 (1.1) 1.9 Yes
24 May 12.3 (1.9) 11.7 (1.5) 0.6 No
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . , . . . . . . . . . . . . . . . . . . . . . .
19-24 May inc. 13.1 (1.7) 12.0 (1.7) 1.1 Yes
Date 1993 Mean relative humidity (%)
Open Sheltered Difference Difference

(Stevenson screen) (open-sheltered) significant?
19 May 64 (14) 67 (15) -3 No

20 May 81 (4) 85 (4) --4 Yes
21 May 78 (8) 81 (7) -3 Yes
22 May 73 (4) 76 (6) -3 Yes
23 May 65 (8) 68 (10) -3 No
24 May 74 (5) 78 (5) -4 Yes
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
19-24 May inc. 74 (8) 77 (9) -3 Yes
CONCLUSIONS
After one year of an exposure program, it has been found that corrosion rates of steel-based coated
products exposed under a special shelter designed to simulate unwashed areas are remarkably higher
than those of equivalent products in the open. At a severe marine site under the shelter, for the
unpainted coated products, the 5% A1-Zn product is overall probably performing best in terms of
appearance, but all are showing very significant corrosion. However in the open the 55% AI-Zn
product is outperforming the 5% AI-Zn product and clearly outperforming the galvanised product
which is starting to show red rusting. For the mass loss/corrosion rate specimens, the ratio of the
sheltered to open corrosion rates is about 1.8 for zinc, 3.1 for 5% AI-Zn, and 3.6 for 55% A1-Zn.
However in comparing the three materials, the 55% AI-Zn always has the lowest corrosion rate
which for both open and sheltered conditions is on average about one-third that for zinc and about
two-thirds that for 5% AI-Zn. Considering only open exposures, the corrosion rate of the 55%
AI-Zn is on average less than one-quarter of that for zinc and about 70% of that for 5% A1-Zn.
The relationship between the corrosivities of mild steel and a standard low-alloy copper-bearing
steel have been shown to be in excellent agreement with results obtained previously. Strong
relationships have been shown between the corrosion rates of all plate materials and measurements
of airborne chloride according to ISO 9225.
Virtually all the painted coated steel products under the shelter at the severe marine site are showing
very severe deterioration after two years, with significant red rusting in many cases. Blistering
and edge creep of the PVDF paint topcoats is particularly noticeable; rids is now being observed
on some of the specimens exposed in the open throwing doubt on the durability of this type of
paint system in a severe marine environment in Australia.
At the severe marine site under the shelter, the products based on aluminium are showing the least
corrosion, and the aluminium cover plate rivets are outperforming their equivalent galvanised
fasteners. At the moderate marine and mild marine sites, all products (with the exception of one
stainless steel) exposed in the open are performing satisfactorily to date.
FUTURE WORK
9 A methodology for semi-quantitative assessment of the recovered two-year 'bent' specimens

will be developed and implemented.
9 Two-year mass loss specimens will be processed and the results correlated with the one-year
results.
9 Systems will be installed for the continuous measurement of temperature, relative humidity and
'time-of-wetness' at all sites.
9 Initial microcracking at the bends and features of all the 'bent' specimens will be characterised
and quantified using image analysis of the photographic records, and the results correlated with
product performance.
ACKNOWLEDGMENTS
This extensive project would not be possible without the assistance of many people and organlsations.
The authors would like to thank firstly BHE Comalco and ILZRO for financial support. Special
thanks are also due to the RAN HMAS Cerberus and Lt Cmdr Peter Rawlings, and the Momington
Peninsula and District Water Board's Messrs Peter Eaton and Peter Palmer for their permission and
kind assistance in establishing the exposure racks within their grounds.The authors would also like
to thank John Kennedy, Mike DiLeva and Ron Simcock of BHP; Phil Maxwell, Neil Isles and
Phil Gigliotti of Comalco; Drs Dodd Cart (retd), J. Cole and E Goodwin of ILZRO for organising
samples and much general assistance. Others who provided samples are Dr Yusuke Hirose of
Nisshin Steel, Dr B. Meuthen and Dr IC Netzke of Hoesch Stahl, Mr D. Patterson and Mr E De
Paul of Weirton Steel, Mr J. Butler and Mr D. Martin ofLa Salle Rolling Mills, and Mr R. Naidu
of New Zealand Steel. Thanks are also due to John Hare, Keith Day and Jim Martyn of W.A.
Deutshcr (Buildex Division) for the supply of fasteners for the project, AZDA for hot-dip galvan-
ising of the steelwork, and Mike Dennett for measuring same, and Paul Taylor of Taubmans for an
anticorrosive primer. Finally the authors would like to thank CSIRO colleagues, notably Guiseppe
Biviano, for the engineering design of the shelters, Marie Scott for the figures, Mary Cope for the
word processing, and Cathy Bowditch for editing and layout of this paper.
REFERENCES
[1] BHE Technical Bulletin TB-15 "Recommended Steel Gutter Systems," John Lysaght
(Australia) Ltd, Rev. 2, May 1992.
[2] Johnson, IC, and Marsh, E., "A Study of Relationsldps Betweer. Design of Precoated Steel
Cladding and its Environmental Behaviour in Service," Commission of the European
Communities Report EUR 10715EN, 1987.
[3] Brown, H.M., MacGregor, I.D., and Maclsaac, L.A., Construction and Building Materials,
Vol. 5, No. 3, 1991, pp. 123-126.
[4_] Atteras, L., and Haagenrud, S., "Atmospheric Corrosion," ed. W.H. Ailor, pub. Wiley, 1991,
pp. 873-891.
[~ Morcilio, M., and Feliu, S., British Corrosion Journal, Vol. 19, Nol. 3, 1984, pp. 143--145.
[fi] Carter, J.P., Lindstrom, PJ., Flinn, D.R., and Cramef, S.D., NACE Corrosion 87, Paper No.
414, 1987.
[2] Larrabee, C.P., Corrosion, VoL 9, 1953, 259-271.
[fd BLIP,Technical Bulletin TB-I "Steel Roofing and Walling Products Selection Guide," John
Lysaght (Australia) Ltd, Rev. 2, March 1992.
[9_] King, G.A., and Carberry, B., "Atmospheric Corrosivity of the Greater Newcastle Region,"
CSIRO DBCE Technical Report 92/1, 1992.
LL0.] BISRA, "Method of Conducting Tests on Reference Specimens at Atmospheric Corrosion
Sites," British Iron and Steel Research Association, UIL Memorandum 5.M.55, 1955.
[J_l.] King, GA, Corrosion Australasia, Vol. 13, No. 1, 1988, pp. 5-14.
[12.] Doyle, D.P, and Wright, T.E., "Atmospheric Corrosion," ed. W.H. Allot, pub. Wiley, 1982,
pp. 227-243.
LL3_] National Coil Coaters Association, Technical Bulletin III-9 "Guidelines for Conducting
Exterior Exposure Tests," 1972.
Metals and Alloys
Manuel Morcillo, l Joaquin Simancas, l and Sebastian Feliu I
LONG-TERMATMOSPHERIC CORROSION IN SPAIN: RESULTS AFTER 13-16

YEARS OF EXPOSURE AND COMPARISON WITH WORLDWIDE DATA
REFERENCE: Morcillo, M., Simancas, J., and Fe]iu, S., "I~ng-

Term A t m o s p h e r i c C o r r o s i o n in Spain: Results after ]3-16
Years of Exposure and Comparison w i t h W o r l d w i d e Data,"
Atmospheric Corrosion, ASTM STP 1239, W. W. Kirk and Herbert
H. Lawson, Eds., American Society for Testing and Materials,
Philadelphia, 1995.
ABSTRACT: A v a i l a b l e information on atmospheric corrosion over

long periods of time (10-20 years or longer) is u n f o r t u n a t e l y
very scanty despite its great usefulness; in fact, only from
such type of data can reliable long-term a t m o s p h e r i c corrosion
predictions be made. This paper reports the results obtained
after 13-16 years of field exposure tests at various Spanish
test sites including several types of atmosphere: rural (El
Escorial), urban (Madrid, Zaragoza), industrial (Bilbao), and
marine (Barcelona, Cadiz, Cabo Negro, Alicante). Panels of
l o w - c a r b o n steel, zinc, copper, and aluminum were removed from
open-air racks after 1-6, 8, i0, 13, and 16 years of exposure,
and their weight losses used to determine the corrosion rate.
L o n g - t e r m corrosion data were found to conform to a general
equation, C = At", where A and C are the corrosion losses
after one and t years of exposure, respectively, and n is
a constant. Only mild steel in scarcely aggressive atmospheres
of central Spain was found to fit a more complex equation.
The results are compared with those found throughout the
world, which were compiled in a c o m p r e h e n s i v e literature
survey. Finally, an attempt was made at c o r r e l a t i n g exponent
n with the type of atmosphere for each metal studied.
KEYWORDS: atmospheric corrosion, low-carbon steel, copper,

zinc, aluminum, rural environment, urban environment,
industrial environment, marine environment, regression
analysis, long-term predictions
l Professor of research, research fellow, and p r o f e s s o r of

research(retired), respectively, Centro Nacional de
Investigaciones Metalurgicas, Avda. G r e g o r i o del Amo nQ 8,
28040-Madrid, Spain.
195
Copyrightm1995by
T h e i n f o r m a t i o n r e q u i r e d to p r e d i c t l o n g - t e r m a t m o s p h e r i c
c o r r o s i o n of m e t a l s is of g r e a t i n t e r e s t to e n g i n e e r s (on
a c c o u n t of its r e l a t i o n s h i p to s t r u c t u r e s d u r a b i l i t y ) , as w e l l
as to e c o n o m i s t s (it a l l o w s e s t i m a t i o n c o s t s d e r i v e d f r o m
m a t e r i a l s d e t e r i o r a t i o n ) , and s c i e n t i s t s (it m a y be of h e l p to
i n c r e a s e a v a i l a b l e k n o w l e d g e of the e f f e c t of e n v i r o n m e n t a l
v a r i a b l e s on c o r r o s i o n k i n e t i c s ) .
T h e a b o v e a p p l i c a t i o n s , h o w e v e r , c a l l for a t m o s p h e r i c
corrosion data acquired over long exposure periods (10-20
y e a r s or l o n g e r ) ; s u c h data, u n f o r t u n a t e l y , a r e v e r y scanty.
T h i s p a p e r is a i m e d at e x p a n d i n g s u c h i n f o r m a t i o n . It
r e p o r t s the r e s u l t s o b t a i n e d in a S p a n i s h t e s t s t a t i o n n e t w o r k
o v e r 1 3 - 1 6 y e a r s of a t m o s p h e r i c e x p o s u r e . A n a n a l y s i s of a
l a r g e n u m b e r of r e p o r t e d d a t a o b t a i n e d a f t e r a t m o s p h e r i c
e x p o s u r e for I0 or m o r e y e a r s in s i m i l a r s t u d i e s c a r r i e d out
in o t h e r c o u n t r i e s is a l s o p r o v i d e d .
The s t u d y was s t a r t e d in 1976 and i n v o l v e d the e x p o s u r e

of c a r b o n steel, zinc, c o p p e r , and a l u m i n u m to t h e a t m o s p h e r e
for v a r i o u s l e n g t h s of time. The c o m p o s i t i o n of the m a t e r i a l s
u s e d is s h o w n in T a b l e i.
TABLE i-- C h e m i c a l composition (wt%) of m a t e r i a l s used.
Low-carbon steel
C P Si Mn S Cr Ni Mo Cu Fe
0.44 <0.22 <0.05 0.40 0.018 <0.I <0.i <0.i <0.05 Balance
Zinc
Pb Fe Cu Cd Sn Zn
0.36 0.015 0.0007 0.007 <0.001 Balance
Copper
Fe A1 Sn Pb Zn Cu
0.02 0.i 0.i 0.01 0.002 Balance
Aluminum
Fe Si Mn Zn Mg Cu A1
0.48 0.175 0.02 0.024 0.014 0.006 Balance
MORCILLO ET AL. ON ATMOSPHERIC CORROSION IN SPAIN 197
T h e t e s t s t a t i o n s n e t w o r k c o m p r i s e d s e v e r a l t y p e s of
atmospheres, viz., rural (El Escorial), urban (Madrid,
Z a r a g o z a ) , i n d u s t r i a l (Bilbao), and m a r i n e ( B a r c e l o n a , Cadiz,
C a b o N e g r o and A l i c a n t e w i t h t w o s i t e s l o c a t e d 30 and i00 m,
r e s p e c t i v e l y , f r o m the ocean). All the s t a t i o n s w e r e e q u i p p e d
w i t h t e m p e r a t u r e and h u m i d i t y r e c o r d e r s , r a i n g a u g e s , and the
i n s t r u m e n t a t i o n n e e d e d to m e a s u r e a t m o s p h e r i c p o l l u t i o n in
t e r m s of S02 and c h l o r i d e ion.
T h e p a n e l s u s e d w e r e i00 x 40 m m and 2 m m t h i c k w i t h the
e x c e p t i o n of t h o s e e m p l o y e d at the h i g h l y m a r i n e e n v i r o n m e n t
of t h e C a b o N e g r o s t a t i o n , w h i c h w e r e 250 x 125 m m a n d 3 m m
t h i c k . T h e p a n e l s w e r e e x p o s e d in t r i p l i c a t e on r a c k s in the
o p e n air at an a n g l e of 45 ~ w i t h the h o r i z o n t a l p l a n e . T h e SO 2
a c t i v i t y at the t e s t s i t e s w a s d e t e r m i n e d by t h e l e a d p e r o x i d e
c a n d l e m e t h o d [!]. In a d d i t i o n , c h l o r i d e l e v e l s in the m a r i n e
a t m o s p h e r e s w e r e m e a s u r e d by the H a c h e m e t h o d [2]. T h e t i m e of
wetness (TOW) for e a c h a t m o s p h e r e w a s e s t i m a t e d f r o m the
n u m b e r of h o u r s d u r i n g w h i c h the r e l a t i v e h u m i d i t y w a s e q u a l
to or g r e a t e r t h a n 85% a n d t h e t e m p e r a t u r e e x c e e d e d 0~ Table
2 s u m m a r i z e s the e n v i r o n m e n t a l c h a r a c t e r i s t i c s of the t e s t
sites.
TABLE 2-- T e s t sites. E n v i r o n m e n t a l c h a r a c t e r i s t i c s of t h e

surroundinq atmospheres.
Test site TOW, SO: deposition Cldeposition

thousands rate, mg/m:.d rate, mg/mZ.d
of h/year
E1Escorial (EE) 3.9 9 ...

Madrid (MA) 2.1 54 ...
Zaragoza (ZA) 2.1 46
Bilbao (BI) 3.4 94 "55
Barcelona (BR) 3.2 58 27
Cadiz (CA) 4.1 36 29
Cabo Negro (CN) 5.2 24 150
Alicante, 30m(Al) 5.1 106 126
Alicante, 100m(A2) 4.3 15 31
Metallic corrosion was determined from the weight

changes measured after corrosion products were removed from
t h e e x p o s e d p a n e l s by c h e m i c a l c l e a n i n g [!]. T h e c o r r o s i o n
r a t e for the last two s p e c i m e n b a t c h e s w a s d e t e r m i n e d by the
ISO s e q u e n t i a l c l e a n i n g c y c l e p r o c e d u r e [4].
W h i l e t h e s t u d y w a s i n i t i a l l y s c h e d u l e d to l a s t i0 y e a r s
w i t h a n n u a l r e m o v a l of s p e c i m e n s , the last b a t c h e s w e r e
r e m o v e d at a l a t e r t i m e s in o r d e r to e x p a n d the t e s t p e r i o d
a n d o b t a i n i n f o r m a t i o n for l o n g e r e x p o s u r e times.
S p e c i m e n b a t c h e s w e r e r e m o v e d a f t e r i, 2, 3, 4, 5, 6, 8,
i0, 13, a n d 16 y e a r s of e x p o s u r e . U n f o r t u n a t e l y , t e s t s h a d to
be e n d e d b e f o r e 16 y e a r s at s o m e s t a t i o n s for d i v e r s e r e a s o n s .
The r e s u l t s o b t a i n e d a f t e r i, 6, and 8 years of e x p o s u r e have

been p u b l i s h e d e l s e w h e r e [5T7].
RESULTS
This p a p e r r e p o r t s the r e s u l t s o b t a i n e d at the S p a n i s h test

s t a t i o n s n e t w o r k after 13-16 years of a t m o s p h e r i c exposure. In
order to e x p a n d the data p o p u l a t i o n a v a i l a b l e for discussion,
we also c a r r i e d out a c o m p r e h e n s i v e l i t e r a t u r e s u r v e y in
s e a r c h for c o r r o s i o n d a t a o b t a i n e d for e x p o s u r e s of i0 years
or longer [5-25]. T a b l e 3 lists the c o u n t r i e s w h e r e the
s t u d i e s c o n c e r n e d w e r e p e r f o r m e d and c o r r e s p o n d i n g references.
T A B L E 3-- R e f e r e n c e s used to o b t a i n i n f o r m a t i o n on l o n q - t e r m
a t m o s p h e r i c c o r r o s i o n and c o u n t r i e s for w h i c h i n f o r m a t i o n
was r e p o r t e d
Country References
Czechoslovakia 9
Germany 15
Panama 17,18
Russia 8
Spain 5-7
Sweden 25
U.S.A. 10-14,16,19-24
DISCUSSION
A t m o s p h e r i c c o r r o s i o n is known to d e v e l o p according to an
e x p o n e n t i a l f u n c t i o n of the f o l l o w i n g type:
C :At" (1)
where A and C are the c o r r o s i o n losses after one and t

years of exposure, r e s p e c t i v e l y , and n is a constant.
As a result, c o r r o s i o n p e n e t r a t i o n data are u s u a l l y fitted to
a p o w e r m o d e l i n v o l v i n g l o g a r i t h m i c t r a n s f o r m a t i o n of both the
e x p o s u r e t i m e and c o r r o s i o n p e n e t r a t i o n [7,14,26,27]. This
power f u n c t i o n (also c a l l e d b i l o g a r i t h m i c law) is s e e m i n g l y of
g e n e r a l use for p r e d i c t i n g c o r r o s i o n b e h a v i o r of m e t a l l i c
m a t e r i a l s e v e n after a long e x p o s u r e time.
Some authors [28-30] however use a mixed linear-
- e x p o n e n t i a l e q u a t i o n a c c o r d i n g to w h i c h a plot of c o r r o s i o n
a g a i n s t t i m e w o u l d c o n s i s t of an initial p a r a b o l i c p o r t i o n
f o l l o w e d by a s t r a i g h t line. This model was the basis of the
r e c e n t l y d e v e l o p e d ISO 9224 s t a n d a r d [31], w h i c h allows long-
term a t m o s p h e r i c c o r r o s i o n to be p r e d i c t e d for the v a r i o u s
categories of atmospheric corrosiveness according to ISO 9223

standard [32].
Recently, McCuen and Albrecht [30] c o m p a r e d both models
o n t h e b a s i s o f d a t a of a t m o s p h e r i c corrosion of weathering
steels reported in t h e United States and concluded that
experimental data fitted the power-linear model better than
the power model. Accordingly, the former provides more
accurate predictions of long-term atmospheric corrosion.
In t h i s w o r k w e s t u d i e d t h e g o o d n e s s of the power model
(Eq I) o n t h e b a s i s of a l l t h e i n f o r m a t i o n compiled for the
four materials surveyed: low-carbon steel, zinc, copper, and
aluminum. We chose to use this model rather than the
power-linear m o d e l o n a c c o u n t of i t s g r e a t e r simplicity. In
fact, only exponent n and corrosion a f t e r t h e f i r s t y e a r of
exposure A need be known. Determining n in t e r m s o f t h e t y p e
of atmosphere concerned was the primary aim of this work.
According to Benarie and Lipfert [27], eq 1 suggests a
diffusional process that determines the atmospheric corrosion
rate. Such a rate depends on the diffusional properties of t h e
corrosion products layer existing between the metal base and
the atmospheric environment. A t n = 0.5, a t m o s p h e r i c corrosion
takes place via an ideal mechanism controlled by diffusion of
t h e r e a c t a n t in c o n t a c t w i t h t h e m e t a l s u r f a c e . B e l o w n = 0.5,
diffusion decreases with time through decreased layer
porosity, agglomeration, filling up of pores, etc. O n t h e
other hand, if t h e d i f f u s i o n process is a c c e l e r a t e d as a
result of the complete or partial removal of the corrosion
layer through erosion, dissolution, scaling, cracking, etc.,
t h e n e x p o n e n t n e x c e e d s 0.5.
Therefore, n could be used as an indicator for the
physico-chemical behaviour of the corrosion layer and hence
for its interactions with the atmospheric environment. The
value of n would thus depend both on the metal concerned, the
local atmosphere and the exposure conditions.
TABLE 4-- Slopes In) a n d c o r r e l a t i o n coefficients (p) of

loq-log plots in F i g s . 1-4.
Test site Low-carbon steel Zinc Copper Aluminium

n p n p n p n p
E1 Escorial (EE) * 0 58 o. 97 0.37 0.97 0.68 0.96

Madrid (MA) * 0 83 o. 99 0.53 0.98 0.79 0.99
Zaragoza (ZA) * 0 96 1.00 0.64 0.99 0.81 1.00
Bilbao (BI) 0.77 1.00 0 96 o. 99 0.63 0.99 0.76 0.97
Barcelona (BR) 0.70 1.00 1 12 I. oo 0.50 0.98 1.03 0.99
Cadiz (CA) 0.63 1.00 0 76 0.99 0.36 0.95 0.81 1.00
Cabo Negro (CN) 0.86 0.96 0 78 o. 97 0.45 0.99 0.63 0.98
Alicante,30m (AI) 0.78 0.98 0 99 o. 96 0.40 0.98 1.04 0.99
Alicante,lO0m(A2) 0.62 0.99 0 88 o. 99 0.51 0.99 0.75 0.99
* corrosion data do not fit well equation I.
-~ |
E 600~-
,~:'-/.00~
E200 t
iooI
0 ~
~IOOF . . k,j'
g loa
B0~ f'~.- -
~ 8o
6o
2 /.0I ~
o 20 , , , , ' '
2C 2 /. 6 10 1/. 20
o
I0
8 800
6 t ~ 1 t a =
600
2 4 6 10 1/. 20
E 400
:a.
E200 " 200

Z
o
,,100 100
='80 o 80
_o 60 ~: 6o
o /.0
U
ac
o
u 2(1 20
10 I i i i L [ 10 I i i i L i
2 /. 6 1 0 14 20 2 /. 6 10 1/. 20
TIME, years T I M E years
FIG. 1 -- L o g - l o g plots of c o r r o s i o n of m i l d steel

v e r s u s e x p o s u r e time for d i f f e r e n t test
sites in Spain.
In order to d e t e r m i n e how the c o r r o s i o n data obtained

at the S p a n i s h t e s t stations n e t w o r k fitted eq 1 we set up
the log-log plots shown in figs. 1-4. In log-log
c o o r d i n a t e s these figures show the v a r i a t i o n of corrosion
in m i l d steel, zinc, copper, and a l u m i n u m d u r i n g the 13-16
years of e x p o s u r e to the d i f f e r e n t S p a n i s h atmospheres.
Table 4 lists the c o r r e l a t i o n c o e f f i c i e n t s (@) and slopes
(n) of the graphs.
Let us analyze i n d i v i d u a l l y for each metal the results
o b t a i n e d with an o v e r v i e w including the results reported
for other c o u n t r i e s as well.
Mild Steel
The c o r r o s i o n data for m i l d steel (Fig. i) e x p o s e d at the
M a d r i d (MA), E1 Escorial (EE) and Zaragoza (ZA) stations do
not fit eq i. A f t e r 4-5 years of exposure, d u r i n g which the
b i l o g a r i t h m i c law was s t r i c t l y obeyed, the r e s u l t s started
to d e v i a t e from this b e h a v i o r and fitted a n o t h e r straight
line w i t h a smaller slope than the first. The log-log
graphs obtained for the r e s u l t s obtained at the above test
stations fit an e q u a t i o n of the f o l l o w i n g type
C = Alp",-",.,
t (2)
where A and C d e n o t e c o r r o s i o n after one and t years,

respectively, tp is the length of the first e x p o s u r e period
(of slope nl) , and n 2 is the slope for the second exposure
period.
This b e h a v i o r can be ascribed to the joint effect of
the low local a t m o s p h e r i c a g g r e s s i v e n e s s and the o c c u r r e n c e
of short w e t t i n g - d r y i n g cycles leading to the f o r m a t i o n of
h i g h l y compact and p r o t e c t i v e c o r r o s i o n p r o d u c t s layers
[33].
J u d g i n g by the high c o r r e l a t i o n c o e f f i c i e n t s (Table 4)
o b t a i n e d (close to unity), the results for the rest of the
test stations seem to c o n f o r m to eq i, w i t h n = 0.6-0.8.
It is i n t e r e s t i n g to analyze l o n g - t e r m a t m o s p h e r i c
c o r r o s i o n data for l o w - c a r b o n steel at d i f f e r e n t places
w o r l d w i d e in order to fit them to the e x p o n e n t i a l function
r e p r e s e n t e d by eq i. T a b l e 5 lists for each test station
the first year corrosion A, the slope n and the
c o r r e l a t i o n c o e f f i c i e n t of the fitting p. It is worth
e m p h a s i z i n g the high c o r r e l a t i o n c o e f f i c i e n t s o b t a i n e d as
a rule for the log-log plots.
The test stations w e r e grouped a c c o r d i n g to the local
type of atmosphere. R u r a l - u r b a n a t m o s p h e r e s and industrial
atmospheres, both w i t h o u t marine component, were d i s t i n -
g u i s h e d a c c o r d i n g to ISO 9223: the former w e r e c l a s s i f i e d
as CI-C3 (A < 51 ~m) and the latter as C4 and C5 (A > 51
~m). W h i l e exponent n was highly d i s p e r s e w i t h i n each
group, a trend was o b s e r v e d in these l o n g - t e r m tests to
slopes b e t w e e n 0.3 and 0.7 for rural, urban, and industrial
atmospheres, and s i g n i f i c a n t l y greater slopes (0.6-0.9) for
m a r i n e atmospheres, w h e t h e r or not they w e r e close to the
shoreline. This confirms the high s i g n i f i c a n c e of the
variable "marine atmosphere quality" (which does not
d i s t i n g u i s h between the various chloride levels but refers
e x c l u s i v e l y to the m a r i n e character) in e x p o n e n t n observed
in a recent s t a t i s t i c a l study [34].
Zinc
The c o r r o s i o n data for zinc obtained in all the Spanish

stations fitted r e a s o n a b l y a linear log-log plot (Fig. 2)
w i t h c o r r e l a t i o n c o e f f i c i e n t s close to u n i t y (Table 4).
With the e x c e p t i o n of the E1 Escorial (EE) and Barcelona
(BR) stations, w h e r e n was 0.58 and 1.12, respectively, the
exponent n was found to be 0.8-1.0 (Table 4). Thus,
a t m o s p h e r i c c o r r o s i o n in zinc often c o n f o r m s to a roughly
TABLE 5-- Lonq-term atmospheric corrosion data for low-carbon

steel obtained throuqhout the world. For each test site the
maximum exposure time, the first year corrosion (A), and the
slope (n) a n d the correlation coefficient (p) obtained by
applyinq Eq 1 are qiven.
Type of Test site Ref. Max. exp. First year n p

atmosphere time, years corros.(A),
~m
EL Escorial 13 8 0.55 0.96

Madrid 16 45 0.23 0.87
Rural and Urban Zaragoza 13 33 0.48 0.97
atmospheres without Zvenigorod 8 10 18 0.73 0.98
marine component. Batumi 8 I0 27 0.48 1.00
First year corrosion Moscow 8 10 31 0.29 0.96
corresponding to Praha Letnany 9 16 34 0.62 0.98
CI-C3 corrosivity Kaperske Hory 9 9 27 0.49 0.99
categories in ISO Kurbanovo 9 15 47 0.38 1.00
9223 [32] State College 10 12 45 0.41 1.00
Cinder Dump 19 10 36 0.76 ...
O[pe 15 10 25 0.37 0.99
MuLheim 15 10 37 0.44 1.00
Bilbao 16 71 0.75 1.00

I n d u s t r i a l atmos- Usti 9 15 86 0.68 1.00
pheres without marine Kopisty 9 10 114 0.38 1.00
component. First East Chicago I I0 12 68 0.33 1.00
year corrosion East Chicago 2 11 30 65 0.39 1.00
corresponding to Pittsburgh 12 10 70 0.67 1.00
C4-C5 corrosivity Bayonne 13 18 74 0.45 1.00
categories in Bethlehem 1 12 10 75 0.32 1.00
ISO 9223 [32] Bethlehem 2 19 65 0.47 ...
Kearny I 10 i2' 81 0.34 1.00
Kearny 2 14 20 119 0.26 1.00
Colun~bus 19 53 0.52 ...
Duisburg 15 i6" 109 0.62 0.99
A l i c a n t e , 30m 5 94 0.81 0.98

Aticante, lOOm 16 28 0.64 1.00
Cabo Negro 1 5 52 0.86 0.96
Cabo Negro 2 10 38 0.81 0.99
Marine atmospheres. Cadiz 10 40 0.63 1.00
First year corrosion Barcelona 13 51 0.70 1.00
corresponding to Kure Beach, 24m 10 12 141 0.65 1.00
CI-C5 corrosivity Kure Beach, 240m I 16 30 28 0.85 1.00
categories in ISO Kure Beach, 240m 2 19 ... 31 0.76 ...
9223 [32] Point Reyes I0 12 96 0.98 1.00
Miraf[ores 17,18 16 34 0.75 1.00
Cristoba[ 17,18 16 68 0.62 0.99
Cuxhaven 15 I0 46 0.37 1.00
100 9 9 9 " e ( ~
~ 100
80 (~ IO0 80
60 8O 60
4O 9 60 o
E E 40 0
:% E40 A r-
t-
N 20 O
@ 20 m
Z N 20 Z
O 0 >
g p-
I0
o 8 9 ~'10 o
o 8 z
ne 6 o 8' n- 6' >
n-
o 4 ne 6
u 12) ' O I. 0
U O0
u 4 "0
-i-
2 q ra
2
2
0
1, I onl
I I I I l 1 I I i i i ~a
0.61 , i , ' ' J 0.8
2 4 6 10 14 20 2 4 6 10 14 20 2 4 6 10 14 20 o6O
TIME. years TIME, years TIME. years o
z
Y~
O9
FIG. 2 -- L o g - l o g plots of c o r r o s i o n of zinc v e r s u s exposure "0
time for d i f f e r e n t test sites in Spain. _>
Z
rO
0
TABLE 6-- Long-term atmospheric corrosion data for zinc

obtained throuqhout the world. For each test site thp
maximum exposure time, the first year corrosion (A)
and the slope (n) a n d the correlation coefficient {p)
obtained by applyinq Eq 1 are qiven.
Type of Test site Ref. Max. exp. First year n p

~ue
E{ Escoriai 13 0.94 0.58 0.99

Madrid 16 1.4 0.85 1.00
Zaragoza 13 1.2 0.96 1.00
Rural and urban Zvenigorod 8 10 2.0 0.61 0.98
atmospheres without Bat~i 8 10 1.2 0.93 1,00
marine component. Moscow 8 10 1.6 0.94 1.00
F i r s t year corrosion Praha Letnany 9 18 1.9 1.12 1.00
corresponding to Kaporske Hory 9 10 1.2 0.82 0.98
CI-C3 corrosivity Hurbanovo 9 15 1.2 1.04 0.98
categories in ISO State College I 20 20 ... 1.13 1.00
9223 [32] State College 2 21,22 20 1.4 0.91 1.00
Industrial atmos- Bilbao 16 5.3 0.96 1.00

pheres without Usti 9 18 4.6 1.02 1.00
marine component. Kopisty 9 10 4.5 0.92 0.97
First year corrosion Kearny 20 20 1.02 0.99
corresponding to New York 21,22 20 5~i 1.04 1.00
C4-C5 corrosivity Sandy Hook 21,22 20 2.2 0.91 1.00
categories in ISO
9223 [32]
Aticanta, 30m 16 5.9 1.01 0.95

A l i c a n t e , lOOm 16 1.0 0.95 0.99
Cabo Negro 10 9.3 0.Z8 0.99
Marine atmospheres. Cadiz 10 1.7 0.76 1.00
First year corrosion Barcelona 13 2.3 1.17 1.00
corresponding to Kure Beach, 24m I 20 20 ... 0.80 0.98
C1-C5 c o r r o s i v i t y Kure Beach, 24m 2 23 10 ... 0.81 ...
categories in ISO Kure Beach, 240m 23 10 ... 0.50 1.00
9223 [32] Point Reyes 20 20 ... 0.62 0.96
Miraftores 17,18 16 1.4 0.83 0.98
Cristobal 17,18 16 5.8 0.72 1.00
linear law (C = At), as f r e q u e n t l y reported in the

l i t e r a t u r e [22,35-37].
This behavior is also apparent from information
o b t a i n e d in l o n g - t e r m tests t h r o u g h o u t the w o r l d (Table 6)
and is c o n s i s t e n t w i t h the results obtained in a p r e v i o u s
study [34].
The slopes o b t a i n e d were close to unity i r r e s p e c t i v e of the
type of a t m o s p h e r e concerned; yet they w e r e somewhat
s m a l l e r for the marine a t m o s p h e r e s (average, 0.8). This
d e v i a n t behavior of the m a r i n e a t m o s p h e r e s could be related
to the f o r m a t i o n of insoluble c o r r o s i o n products, zinc
h y d r o x y c h l o r i d e (Zns(OH)8C ~ . Hz0 ) in severe, p u r e l y m a r i n e
atmospheres [38], and s o d i u m zinc c h l o r o h y d r o x y s u l p h a t e
(NaZn4CI(OH)6SO4"6H20) in those marine a t m o s p h e r e s w i t h an
i n d u s t r i a l or u r b a n c o m p o n e n t [39], which may exert some
p r o t e c t i v e effect, rather than the highly soluble c o r r o s i o n
products formed under u r b a n and industrial atmospheres
[40] .
Copper
The c o r r o s i o n data o b t a i n e d for this metal at the S p a n i s h

test stations also fitted eq 1 r e a s o n a b l y well (Fig. 3)
w i t h n values b e t w e e n 0.4 and 0.6 (Table 4). The c o r r o s i o n
rate for copper d e c r e a s e d g r a d u a l l y with time, p r o b a b l y
through the formation of a protective layer. Cross-
s e c t i o n a l scanning e l e c t r o n m i c r o g r a p h s of the c o r r o s i o n
layer have r e v e a l e d it to be of such a highly p o r o u s nature
that it allows the g r o w t h of an a d d i t i o n a l p a s s i v a t i n g
layer on it [41].
T a b l e 7 also shows the i n f o r m a t i o n c o m p i l e d from the

l i t e r a t u r e survey about l o n g - t e r m studies t h r o u g h o u t the
world classified according to the type of a t m o s p h e r e
s u r r o u n d i n g the test site. The average n values are 0.5-0.7
and tend to be smaller for industrial and marine
a t m o s p h e r e s than for rural and urban atmospheres. As w i t h
zinc, this seems to be related to the formation of
insoluble corrosion products (basic copper sulfates and
chlorides) under the latter types of a t m o s p h e r e [40].
Aluminum
T h e c o r r o s i o n data for this metal obtained at the Spanish

test stations (Fig. 4) also fitted eq 1 quite well, with
n v a l u e s in the range 0.6-1.0 (Table 4).
Available literature on long-term atmospheric
c o r r o s i o n of a l u m i n i u m is even more scanty than for the
other three m a t e r i a l s studied. In fact, our l i t e r a t u r e scan
p r o v i d e d i n f o r m a t i o n for only three stations in the former
USSR [8] and another two in Panama [17,18], all of w h i c h
gave low c o r r e l a t i o n c o e f f i c i e n t s for the c o r r o s i o n v s time
log-log plots. This p r e c l u d e d the analysis p e r f o r m e d for
the o t h e r three materials.
TABLE 7-- Lonq-term atmospheric corrosion data for

copper obtained throuqhout the world. For each test
site the maximum exposure time, the first year
corrosion (A) a n d t h e s l o p e (n), and the correlation
coefficient (p) o b t a i n e d by applyinq Eq 1 are qiven.
Type of Test s i t e Ref. Max. exp. F i r s t year n P

~m
El Escoriat 13 1.0 0.37 0.97

Madrid 16 1.4 0.53 0.99
Rural and urban Zaragoza 13 1.1 0.64 0.99
atmospheres without Zvenigorod 8 10 1.1 0.8/, 1.00
marine component. Batumi 8 10 0.9 0.92 1.00
F i r s t year corrosion Moscow 8 10 0.8 0.81 1.00
corresponding to KaperskeHory 9 8 1.5 0.59 1.00
CI-C4 corrosivity Praha Letnany 9 18 1.3 0.90 0.99
categories in ISO Hurbanovo 9 15 2.2 0.74 0.98
9223 [32] State College I 24 10 ... 0.52 1.00
State College 2 23 20 ... 0.76 0.99
Erken 25 16 1.2 0.67 0.97
Stockholm 25 16 ... 0.93 0.99
Industrial atmos- Bilbao 16 4.3 0.61 0.99

pheres without Usti 9 18 4.7 0.61 1.00
marine coercxment. Kopiaty 9 10 6.3 0.58 1.00
First year corrosion Kearny 24 20 ... 0.83 1.00
corresponding to C5
corrosivity category
in ISO 9223 [32]
~licante, 30m 16 &.1 0.38 0.98

Alicante, 100m 16 1.7 0.49 0.99
Marine atmospheres. Cabo Negro 10 5.3 0.45 0.99
F i r s t year corrosion Cadiz 10 2.4 0.36 0.96
corresponding to Barcelona 13 2.9 0.50 O. 98
CI-C5 c o r r o s i v i t y Kure Beach, 240m 24 20 1.8 0.79 0.99
categories in ISO Miraflores 17,18 16 2.0 0.43 1.00
9223 [32] Cristobal 17,18 16 4.1 0.59 1.00
Bohus Malmon 25 16 1.3 0.73 0.99
E20L
, .9
E
J10 -E
='
z 8 z 8
o 6
o z,
n,-
n,,"
e
i i L i i i I i 1 i i i
2 ,~ 6 10 ll. 20 2 4 G 10 14 20
2O E 20
='10 u10
Z
u 8 o 8
oz6, N 6
~ /.
0
IZ
0
o 2 ~ 2
U
1 I i L ~ a i
2 4 6 10 1~ 2 0 2 I. 6 101Z. 20
TIME, yeors T I M E years
FIG. 3 -- L o g - l o g plots of c o r r o s i o n of copper

v e r s u s e x p o s u r e time for d i f f e r e n t t e s t
sites in Spain.
Prediction of L o n q - T e r m Atmospheric Corrosion
As s h o w n above, the e x p o n e n t i a l e q u a t i o n C = At" is v a l i d

for the d i f f e r e n t m e t a l s and t y p e s of a t m o s p h e r e s t u d i e d
and can be r e l i a b l y u s e d to e s t i m a t e l o n g - t e r m a t m o s p h e r i c
c o r r o s i o n by o b t a i n i n g a p p r o p r i a t e A and n v a l u e s .
B a s e d on the r e s u l t s o b t a i n e d in t h i s work, l o n g - t e r m
a t m o s p h e r i c c o r r o s i o n p r e d i c t i o n s s h o u l d r e l y on the A and
n v a l u e s s h o w n in T a b l e 8 (a s u m m a r y of T a b l e s 5-7) for
e a c h t y p e of a t m o s p h e r e . As n o t e d e a r l i e r , a l u m i n u m was
excluded from the discussion owing to the scanty

i n f o r m a t i o n a v a i l a b l e for this metal.
W i t h the s a m e p u r p o s e , the ISO 9224 s t a n d a r d [31]
recently established some g u i d i n g values for long-term
p r e d i c t i o n s for the four m e t a l s in t e r m s of the a t m o s p h e r i c
c o r r o s i v e n e s s c a t e g o r i e s d e f i n e d in the ISO 9223 s t a n d a r d
[32]. The ISO 9224 standard, which is based on the
power-linear model, distinguishes two parts in the
v a r i a t i o n of a t m o s p h e r i c c o r r o s i o n w i t h t h e e x p o s u r e time:
an i n i t i a l p o r t i o n for the f i r s t i0 y e a r s of e x p o s u r e w i t h
an a v e r a g e c o r r o s i o n r a t e range, and a second, s u b s e q u e n t
p o r t i o n w i t h a s t e a d y - s t a t e c o r r o s i o n r a t e range.
6oo!
I
2000 | 2o0r
80V/
1000
8O0 | 60~/
600
2 4 6 I0 14 20
400
~E
-a 200
200~-
s 100
---: 80,
'~ 60
Z
~,oo~"
=
I
2 ~
I L
6 ,'oIi~o
o AO'
.| O
O
|
o 20
20 n~
n~ 4 O
o U
o 10 I0
8 8
6
2J- / . 2!
1 1
1 2 & 6 I0 14 20 2 4 6 10 14 20
TIME, y e a r s TIME, y e a r s
FIG. 4 -- L o g - l o g of c o r r o s i o n of a l u m i n i u m v e r s u s
e x p o s u r e time for d i f f f e r e n t test s i t e s in
Spain.
TABLE 8-- Predictions for long-term atmospheric corrosion of low-carbon steel~ O
zinc, and copper. The ranqe of the exponent n in Eg 1 for each type of O
atmosphere and ISO corrosivity category [32] are shown.
O
m
>
Rural-Urban atmospheres Industrial atmospheres Marine atmospheres .f-
(without marine component) ( w i t h o u t marine c o m p o n e n t ) O

z
>
ISO corrosivity R a n g e of ISO c o r r o s i v i t y R a n g e of ISO c o r r o s i v i t y R a n g e of
Material category n in Eq 1 category n in Eq i category n in Eq 1 O
60
-i-
m
Low-carbon
steel C1 - C3 0.3-0.7 C4 - C5 0.3-0.7 Cl - C5 0.6-0.9
Zinc C1 - C3 0.8-1.0 C4 - C5 0.9-1.0 C1 - C5 0.7-0.9 0
0-n
Copper C1 - C4 0.5-0.9 C5 0.6-0.8 C1 - C5 0.4-0.6
0
6o
m
O
z
6o
>
~O
O
T A B L E 9-- C o m p a r i s o n s b e t w e e n the real l o n q - t e r m {more

than i0 years) a t m o s p h e r i c c o r r o s i o n data and the v a l u e s
e s t i m a t e d a c c o r d i n q to ISO 9224 c r i t e r i a [31] and by
a p p l y i n q the p o w e r law (Eq i) and n r a n g e in T a b l e 8.
Low-carbon steel corrosion, ~m
T i m e of Experimental ISO 9224 criteria Power law

Test exposure, data
site years range Satisfactory range Satisfactory
prediction prediction
E1 E s c o r i a l 13 32.7 5.3- 54.5 yes 17- 48 yes

Madrid 16 90.0 59 - 156 yes 1 0 3 - 313 no
Zaragoza 13 119.0 5 4 . 5 - 138 yes 71- 199 yes
Praha Letnany 16 205 59 - 156 no 78- 237 yes
Hurbanovo 15 131 5 7 . 5 - 150 yes 1 0 6 - 313 yes
Bilbao 16 534 156 - 420 no 162- 491 no
Usti 15 540 400 -1450 yes 4 3 7 - 987 yes
East Chicago 30 244 240 - 700 yes 1 8 0 - 703 yes
Bayonne 18.1 278 169 - 462 yes 1 7 6 - 562 yes
Kearny 12 154 340 -1180 no 3 6 0 - 758 no
Alicante, lOOm 16 173 59 - 156 no 64- 194 yes
Barcelona 13 315 138 - 360 yes ii0- 306 no
K u r e Beach, 2 4 m 12 776 340 -1180 yes 626-1320 yes
K u r e Beach, 2 4 0 m 30 502 65 - 180 no 78- 303 no
Point Reyes 12 1028 340 -1180 yes 426- 899 no
Miraflores 16 279 59 - 156 no 78- 237 no
Cristobal 16 393 156 - 420 yes 156- 474 yes
Zinc corrosion,
E1 E s c o r i a l 13 4.5 6.5- 26 no 7.3- 12.2 no

Madrid 16 16.5 8.0- 32 yes 13.2- 23.0 yes
Zaragoza 13 15.2 6.5- 26 yes 9.2- 15.3 yes
Praha Letnany 18 49.0 9.0- 36 no 19.2- 34.2 no
Hurbanovo 15 24.0 7.5- 30 yes 9.6- 16.5 no
State College 20 22.6 i0 - 40 yes 15.4- 28.0 yes
Bilbao 16 70.6 64 - 160 yes 36.6- 63.7 no
Ueti 18 88.0 72 - 180 yes 34.8- 62.0 no
New York 20 114.8 80 - 200 yes 41.5- 75.6 no
Sandy Hook 20 37.0 40 - 80 no 32.6- 44 yes
Alicante, 100m 16 14.7 8.0- 32 yes 9.2- 16.0 yes
Miraflores 16 13.7 8.0- 32 yes 12.9- 22.4 yes
Cristobal 16 41.7 64 - 160 no 40.4- 83.5 yes
Copper corrosion,
E1 E s c o r i a l 13 2.6 1.3- 18 yes 3.7- 10.5 no

Madrid 16 5.4 1.3- 18 yes 4.1- 11.5 yes
Zaragoza 13 5.9 21 48 no 5.7- 17.2 yes
Praha Letnany 18 18.2 1.8- 23 yes 5.5- 17.5 no
Bilbao 16 24.4 48 80 no 22.6- 39.4 yes
Usti 18 30.4 54 90 no 26.6- 47.5 yes
Alicante, 30m 16 11.9 48 80 no 21.6- 37.6 no
Alicante, 100m 16 6.1 21 48 no 7.0- 21.1 no
Barcelona 13 10.6 39 65 no 13.4- 22.3 no
Miraflores 16 6.9 21 48 no 8.0- 24.3 no
Cristobal 16 20.1 48 80 no 21.6- 37.7 no
It may be of interest to d e t e r m i n e the accuracy of the

e s t i m a t i o n s made by using the potential law (Eq i) and the
values given in Table 8 on the one hand and the criteria
e s t a b l i s h e d in the ISO 9224 standard on the other. It
should be noted that both types of e s t i m a t i o n s require the
e x p e r i m e n t a l c o r r o s i o n value for the first year of exposure
to be known since it is included as a m u l t i p l i c a t i v e factor
in the potential law and is used to define the c a t e g o r y of
the a t m o s p h e r e in the ISO 9224 standard.
Table 9 lists the d i f f e r e n t e s t i m a t i o n s and results
obtained. It gives the m i n i m u m and m a x i m u m c o r r o s i o n values
o b t a i n e d by d u p l i c a t e calculations using the IS0 9224
g u i d i n g values and the guiding values of e x p o n e n t n in
Table 8, respectively, in each instance. It is worth
noting the g e n e r a l l y high imprecision of the p r e d i c t i o n s
p r o v i d e d b y both methods. It is thus quite d i f f i c u l t to
choose either e s t i m a t i o n method. P a r t i c u l a r l y with zinc and
copper, the power law seemingly provides smaller
d i f f e r e n c e s between the m a x i m u m and minimum values in the
c o r r e s p o n d i n g estimations.
CONCLUSIONS
L o n g - t e r m a t m o s p h e r i c c o r r o s i o n data (I0 years or

longer) for low-carbon steel, zinc, copper, and a l u m i n u m
o b t a i n e d in Spain and at d i f f e r e n t places w o r l d w i d e fit
r e a s o n a b l y well a law of type C = At n, where A and C
are c o r r o s i o n losses after one and t years of exposure,
respectively, and n is a constant. Values of A and n
ranges for long-term a t m o s p h e r i c c o r r o s i o n e s t i m a t i o n s and
d e p e n d i n g on the type of a t m o s p h e r e are given.
This paper compares the long-term e x p e r i m e n t a l data
with the values e s t i m a t e d according to the above law and
ISO 9224 criteria. A high imprecision of the p r e d i c t i o n s
p r o v i d e d by both methods is obtained. However, p a r t i c u l a r l y
w i t h zinc and copper, the power law s e e m i n g l y provides
smaller d i f f e r e n c e s between the m a x i m u m and m i n i m u m values
in the c o r r e s p o n d i n g estimates.
ACKNOWLEDGMENT
The authors a c k n o w l e d g e to the following c o m p a n i e s for

the facilities allowed and the help provided to carry out
this study: Astilleros Espa~oles, Compa~la Telef6nica
Nacional de Espa~a, ENDASA, ENSIDESA, Institutos de
Investigaciones P e s q u e r a s of Barcelona and Cadiz, and
U n i v e r s i d a d de Zaragoza. They are also indebted to Liboria
Mariaca (Mexico) for her c o o p e r a t i o n in the r e g r e s s i o n
analysis of the c o r r o s i o n data.
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[25] Mattsson, E. and Holm, R. " A t m o s p h e r i c corrosion of

copper and its alloys" in "Atmospheric corrosion" Ed.
W.H. Ailor, Wiley-Interscience, New York, 1982, pp
365-382.
[263 Feliu, S. and Morcillo, M., "Corrosion y Proteccion

de los metales en la atmosfera", Bellaterra,
Barcelona, 1982.
[27] Benarie, M. and Lipfert, F.L., Atmospheric

Environment, Vol. 20, 1986, p 1947.
[28] Mikhailovski, Y.N. et al., Zaschita Metallov, Vol.

16, No. 4, 1980, pp 396-413.
[29] Holler, P. and Knotkova, D., "Determination of the

corrosivity of atmosphere. Methods and results".
Internal Report, State Research Institute for
Protection of Materials (SVUOM). Czechoslovakia.
[30] McCuen, R.H. and Albrecht, P., "Composite modeling of

atmospheric corrosion penetration data" in
"Application of accelerated corrosion tests to
service life prediction of materials", Eds. G.
Cragnolino and N. Sridhar, American Society for

Corrosivity of atmospheres. Guiding values for the
corrosivity categories". International Standards
Organization, Geneve, 1991.

Corrosivity of atmospheres. C l a s s i f i c a t i o n " ,
International Standards Organization, Geneve, 1991.
[33] Morcillo, M., Feliu, S., and Simancas, J., British

Corrosion Jorunal, Vol. 28, No. i, 1993, pp 50-52.
[34] Feliu, S., Morcillo, M., and Feliu Jr., S., Corrosion
Science, Vol. 34, No. 3, 1993, pp 415-422.
[35] Guttman, H., in "Metal corrosion in the atmosphere",

ASTM STP 435, Philadelphia, 1967, p 223.
[36] Barton, K., Proceedinqs 9th International Conference

on Hot Dip Galvanizinq, DUsseldorf, 1970.
[37] Haynie, F.H. and Upham, J.B., Materials Protection

and Performance, Vol. 9, No. 8, 1970, p 35.
[38] Morcillo, M., Ruiz, J.L., and Gonzalez, M.,

Werkstoffe und Korrosion, Vol. 40, 1989, pp 668-673.
[39] Odnevall, I. and Leygraf, C., Corrosion Science, Vol.

34, No. 8, 1993, p 1231.
[40] Kucera, V. and Mattsson, E., "Atmospheric corrosion"

in "Corrosion mechanisms", Ed. F. Mansfeld, Marcel
Dekker, New York, 1987, pp 211-284.
[41] Franey, J.P. and Davis, M.E., Corrosion Science, Vol.

27, No. 7, 1987, p 659.
Inger Odnevall 1 and Christofer Leygraf 1
REACTION SEQUENCES IN ATMOSPHERIC CORROSION OF ZINC
REFERENCE: Odnevall, I. and Leygraf, C., "Reaction Sequences in

A t m o s p h e r i c C o r r o s i o n of Zinc," A~mo~pherir Corrosion, A S T M STP
i~39, W. W. Kirk and Herbert H. Lawson, Eds., A m e r i c a n Society for
ABSTRACT: Frequent phase identifications of a large number of zinc

panels exposed to different atmospheric conditions, both in national an
international exposure programs, have revealed a variety of corrosion
products. In order to extract basic information about the atmospheric
corrosion processes involved, emphasis has been placed on more precise
characterization of corrosion products, from the initial stages to full
developed end products. Extensive field exposures under rain sheltered
conditions have been performed in rural, urban, industrial and marine
atmospheres. These programs have included different methods for surface
and bulk analysis of corrosion products, as well as measurements of
deposition rates for gases and aerosols, and measurements of climatic
parameters. Depending on atmospheric conditions, the complex growth of
corrosion products seems to result in end products containing at least
one of the structurally related phases: Zns(CO3)2(OH)6, Zns(OH)sCI2.H20,
Zn4SO4(OH)6-4H20, Zn4CI2(OH)4SO4-5H20 and NaZn4CI(OH) 6SO4-6H20.
This presentation discusses actual reaction sequences in the formation
of the above-mentioned corrosion products in terms of structural
chemistry and deposition rates for atmospheric constituents. SeverAl of
the reaction sequences seem to depend on actual deposition rates for
sulfur dioxide (SO2) and chloride (Cl-)in the atmosphere.
KEYWORDS: atmospheric corrosion, zinc, field exposure, dry deposition,

corrosion products, crystal structure, reaction sequences, X-ray
Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy with
X-ray microanalysis (SEM/EDS)
INTRODUCTION
Although zinc is a common metal exposed to different outdoor

atmospheres, especially in galvanized steel applications, very few phas(
identifications of corrosion products have been made on zinc and
galvanized steel panels exposed to atmospheric conditions. Corrosion
effects have mainly been described in terms of mass losses after
extended exposure periods. This is surprising in view of the strong
influence of corrosion products upon corrosion kinetics.
iDr. and Professor, respectively, Department of Materials Science

and Engineering, Division of Corrosion Science, Royal Institute of
Technology, S-100 44 Stockholm, Sweden
215
CDownloaded/printed
o p y r i g h ~ 1 9 9 5 b yby A S T M International www.astm.org
Recent phase identifications, by the authors, on a large number of

zinc panels exposed to different atmospheric environments have disclosed
a variety of corrosion products on zinc. Table 1 is an attempt to
summarize the phase identifications reported in the literature by the
authors and by others. Some of the phases are known to appear naturally
as minerals [~]. A few of them tend to appear as end products. Lack of
adequate environmental data is the most probable reason why it has been
difficult, so far, to connect the appearance of the end products with
any particular type of environment.
TABLE 1--Phase characterizations from field exposures.

Numbers (2-21) indicate references.
Corrosion products Type of atmosphere

rural urban marine industrial
ZnO 2 3,4,5,8,9 4,5
Zn(OH) 2 6, 9, i0, 8,9, i0 6, 9 9
19
Zn5 (CO3) 2 (OH) 6 6,7,9,10 8,9,10,11 2,4,5,6,7 4,9,12
ii, 14, 15 8, 13,21 21
19,21
ZnSO 4.nH20 6,8 6,8,16 4, 6 4,6,8,
17
Zn 4S04 (OH) 6. nH20 6,8,9, 6,8,9,20 6,9 6,8,9
14, 15
Zn 5 (OH) 8CI 2 "H20 9 3,4,5,8, 6,8
9,12,13
NaZn4CI(OH) 6SO4.6H20 18 18 8, 13,17
Zn4CI2(OH)4SO4.5H20 18 18,20 18,20
FIELD EXPOSURE PROGRAM
In order to study the formation of end products in more detail,

insight into the initial corrosion behavior and the subsequent growth of
corrosion products is essential. For this reason, a large field exposure
program of rain sheltered zinc panels was implemented in four different
atmospheres characterized by different end products; rural
(Zn5(CO3)2(OH) 6 and Zn4SO4(OH)6-4H20), Aspvreten, Sweden [15]; urban
(Zn4SO4(OH) 6.nH20 and Zn4CI2(OH)4SO4.SH20), S6dra N~mndhuset, Sweden
[20]; industrial (Zn4CI2(OH)4SO4-5H20), Borregaard, Norway [20]; and
marine (Zn5(OH)sCI2-H20, NaZn4CI(OH) 6SO4.6H20), Bohus-Malm6n, Sweden
[13]. The corrosion behavior is the result of several processes that
involve atmospheric chemistry, meteorology and surface chemistry, as
well as physical chemistry and electrochemistry. Environmental species,
such as sulfur dioxide and chloride, influence the c o r r o s i o n processes
on zinc by favoring different reaction sequences [4,12,17,22-25, among
others]. The formation of end products is elucidated in Fig. I, where
the environmental characteristics of each test site in the field
exposure program are schematically displayed. The mean amount of dry
deposited sulfate is plotted vs. the mean amount of dry deposited
chloride. Dry deposition measurements were made using passive filters
impregnated with triethanol amine and analyzed by means of ion
chromatography. Deposition includes deposited gases and aerosols without
any significant contribution of heavier or larger particles.
Type of atmosphere and end products, as displayed in the figure, show
that the formation of the final corrosion products seems to be dependent
on the ratio between amounts of deposited sulfate and chloride.
ODNEVALL AND LEYGRAF ON ATMOSPHERIC CORROSION OF ZINC 217
S042- [mgSm-2d -I]
0 0,5 1 1,5 2 2,5

01 I 9 I I I I
RURAL
0,2"
zn 5 (c%) 2 (OH) 6 URBAN
0,4"
Zn4SO 4 (OH) 6"nH20 Zn4SO 4 (OH) 6 "nH20
0,6'
Zn4Cl 2(OH)4SO4-nH20
<) 0,8'
1
i 1,2"
O 1,4"
1,6"
%
1,8"
INDUSTRIAL
2
MARINE Zn4CI2 (OH)4SO4"5H2 O
Zn5(OH)8CI2-H20
NaZn4CI(OH)6SO4-6H20
FIG. 1--Environmental characteristics of the four test sites in the

field exposure program. The mean amount of dry deposited sulfate [mgSm-
2d i] is plotted v s . the mean amount of dry deposited chloride [mgClm-2d -
i] during the exposure periods. The dashed line corresponds to a sulfate
to chloride ratio of one.
To elucidate reaction sequences in the formation of end products,

it is essential to p e r f o r m a corrosion study ranging from initial stages
to fully developed corrosion products. This can be achieved by combining
surface and bulk analytical techniques with environmental and
depositional measurements. This multianalytical approach can be used to
study different reaction sequences not only on zinc but also on other
metals exposed to different atmospheres. The essential features of the
field exposure p r o g r a m are schematically displayed in Fig. 2. Pure zinc
panels were exposed under rain sheltered conditions for i, 2, 3, 5, 14,
30 and 90 days. Air quality, rain chemistry and dry deposition were
studied simultaneously. Corrosion product characterizations were made by
means of surface sensitive methods as well as bulk sensitive methods
[14]. X-ray Photoelectron Spectroscopy (XPS) was used for qualitative
and quantitative analysis of thin films, Ion Chromatography (IC) for
analysis of water soluble anions and Scanning Electron Microscopy with
X-ray microanalysis (SEM/EDS) for morphology studies and for qualitative
and quantitative compositional analysis. Crystalline phases w e r e
identified by means of X-Ray powder Diffraction (XRD). Experimental
setup of the different methods is described elsewhere [ ~ , 1 5 ] .
In order to refine a few reaction sequences, the rural atmosphere
was also used for artificial studies. Chloride (0.25 mgm 2d-l) was added
manually to exposed, sheltered, zinc panels in order to simulate
different reaction sequences. The sodium chloride solution was applied
on the surfaces using a shaker. The added solution was sufficiently
small and the holes in the shaker tiny enough to allow small droplets to
form without dripping off the surface. To be certain how large the
chloride deposition really was, the shakers were rinsed and analyzed on
remaining chloride ions.
Through this multianalytical approach, a more comprehensive
picture of the corrosion processes from the initial stages to fully
developed corrosion products was obtained.
I Environment a i I
characterization
I ~. ~. I I~o~.,o~, % I Irain
chemistrYl
Surface I
characterization
Surface chemical composition
Water extract chemical composition
I
I SEM/EDS ~ Morphology and bulk chemical
composition
~Crystalline phase identification

FIG. 2--Schematic presentation of the field exposure
and analysis programs.
CRYSTAL STRUCTURE OF CORROSION PRODUCTS
In the following section, information about the crystal structure

of corrosion products is presented. The data have been obtained from the
literature as well as from the present project. Information on the
structural chemistry of corrosion products facilitates the understanding
of different atmospheric corrosion se~Jences.
Zinc oxides and hydroxides - The initial corrosion product that

forms instantaneously on zinc in dry air and room temperature is ZnO,
Zincite. Zincite has a hexagonal cell structure with a=3.25 A and c=5.21
[26].
In humid air, zinc hydroxides are possible constituents of the
corrosion products. There are several forms of zinc hydroxides but only
one has been detected by the authors, namely s 2 , Wulfingite. This
form is also the only one known to occur naturally as a mineral. The
structure is built up from tetrahedrally coordinated zinc atoms forming
a three-dimensional network with hydroxyl ions. The cell structure is
orthorhombic with a:8.49 ~, b=5.16 A and c:4.92 ~ [27].
Zinc hvdroxvcarbona~es - A common phase in benign environments is

Zns(CO3)2(OH) 6 (Hydrozincite). Hydrozincite has a monoclinic cell
structure w i t h a=13.58 A, b=6.28 A, c=5.41 A and ~=95.6 ~ The phase has
a layered-type structure with sheets consisting of both octahedrally and
tetrahedrally coordinated zinc atoms. The sheets are held together by
carbonate ions in a three-dimensional network [28].
Zinc sulfates and hvdroxvsul~ates - Water soluble zinc sulfates

are common as corrosion products in environments with high sulfur
dioxide levels. The most frequently observed zinc sulfate, ZnSO4.H20
(Gunningite), has a monoclinic cell structure with a=7.51 A, b=7.59 A,
c=6.94 A and 9=116.25 ~ [29]. Sulfates with 4 and 6 water molecules have
also been detected. ZnSO4.4H20 (Boyleite) is monoclinic w i t h a=5.95 ~,
b=13.60 ~, c=7.95 A and 9=90.4 ~ [30 ]. ZnSO4.6H20 , too, has a monoclinic
cell structure with a=9.98 ~, b=7.25 A, c=24.28 ~ and ~=98.45 ~ [ 31].
Zinc hydroxysulfates w i t h different number of water molecules are
observed in sulfur dioxide containing environments. The most frequently
observed zinc hydroxysulfate is the phase w i t h four water molecules, but
corrosion products with three and five water molecules also exist [15].
Zn4SO4(OH)6.4H20 has a triclinic cell structure with a=8.36 A, b=8.37 ~,
c=20.68 A, ~=90.06 ~ ~ =89.93 ~ and y=120.11 ~ The tri- and pentahydrates
have similar cell dimensions. They all have layered structures w i t h
octahedrally and tetrahedrally coordinated zinc atoms. Sulfate groups
connect on either side of the sheets through corner sharing. The neutral
sheets are held together by strong hydrogen bonding between the
coordinated and free water molecules and the basal oxygen atoms of the
sulfate groups [32,33].
Zinc hvdroxvchlorides - In the presence of chlorides,

Zns(OH)sCI2-H20 (Simonkolleite) can form, notably in marine and traffic
environments. The cell structure is hexagonal with a=6.34 A and c=23.64
A. The phase consists of sheets with octahedrally and tetrahedrally
coordinated zinc atoms. The electrically neutral sheets are held
together by weak O-H-'-CI bonds [34,35].
Zinc chlorohvdroxvsulfates - Another common phase in marine and

traffic environments is NaZn4CI(OH) 6SO4.6H20. The structure of this phase
has been determined in cooperation with the Department of Structural
Chemistry, the University of Stockholm, Sweden. The phase is hexagonal
with a unit cell of a=8.3691 A and c=13.047 ~. It has a layered
structure with octahedrally and tetrahedrally coordinated zinc atoms in
the negatively charged sheets. Sulfate groups are coordinated with the
octahedral sheet through corner sharing via one oxygen atom. Between the
layers, sodium atoms are coordinated with three sulfate oxygen and three
crystal water molecules [18].
Another chlorosulfate, Zn4CI2(OH)4SO4-5H20 , occurs in industrial
and urban atmospheres. The unit cell is monoclinic w i t h a=i0.92 A,
b=4.1365 A, c=7.1671 A and 9=102.621 ~ . Because of crystallographical
difficulties, no structure determination has yet been made [18].
The structural resemblance between the end products (zinc

hydroxycarbonate, zinc hydroxychloride, zinc hydroxysulfate and sodium
zinc chlorohydroxysulfate) is illustrated in Fig. 3a-d. All of them have
layered structures with sheets of Zn(II) in octahedral and tetrahedral
coordination, the main difference being the content and bonding between
the sheets. The structural resemblance may facilitate the transformation
from one phase into another, given the proper environmental conditions.
Layered structures are common in basic salts of divalent cations
containing hydroxyl groups and other anions, such as carbonate and
sulfate [36]. Similarities with respect to both corrosion behavior and
structural chemistry have been observed between zinc and nickel [37].
On nickel, crystalline and amorphous nickel hydroxysulfates seem to

dominate in rural, urban and industrial atmospheres.
FIG. 3--Crystal structures of (a) zinc hydroxycarbonate, (b) zinc

hydroxychloride, (c) zinc hydroxysul~ate and (d) sodium zinc
chlorohvdroxvsulfate.
REACTION PATH SEQUENCES ON ZINC
Depending on the actual deposition of atmospheric constituents a

variety of different reaction paths are possible. According to the HSAB
(Hard and Soft Acid-Base) principle [38], zinc(II) is an intermediate
acid. This means that it is capable of coordinating with a number of
different bases. The most important bases seem to be chloride and
sulfate (cf Fig. I). Fig. 4 illustrates corrosion sequences observed on
sheltered zinc panels. The solid arrows correspond to corrosion
sequences identified in the field exposure program, and the dashed
arrows correspond to structurally possible reaction paths.
Zn (OH) 2
Zn 5 (CO3) 2 (OH)6
~|
Zn 5 (OH) 8C12 -H20 Z n 4 S O 4 (OH) 6 "nH20
J
|
NaZn4C1 (OH) 6SO4 9 6H20 Zn4C12 (OH) 4SO4 - 5tt20
FIG. 4--Reaction sequences on zinc. N u m b e r e d circles indicate different

steps in r e a c t i o n sequences d e s c r i b e d in the text.
In the following paragraphs an attempt is m a d e to d e s c r i b e each

step in the p r o p o s e d r e a c t i o n p a t h sequences w i t h data from the field
exposure program.
A useful m e t h o d of d e t e c t i n g different corrosion p r o d u c t s is by
m e a n s of SEM/EDS. A p r e r e q u i s i t e is that the thickness of the corrosion
layer is sufficient, in the m i c r o m e t e r range. XPS is an alternative
technique for a n a l y z i n g thinner layers. A q u a n t i t a t i v e X - r a y m i c r o
a n a l y t i c a l p r o c e d u r e has been d e v e l o p e d to study the g r o w t h and
t r a n s f o r m a t i o n from one phase in the corrosion p r o d u c t s to other
phases[13]. In o r d e r to illustrate e a c h step in the r e a c t i o n sequence,
we have chosen to present the data in ternary d i a g r a m s o b t a i n e d from
EDS. The only exception is the first step, for w h i c h no EDS data were
a v a i l a b l e owing to difficulties in d e t e c t i n g thin films. In this case,
data from XPS are p r e s e n t e d directly.
A p o s i t i o n in one of the corners of the ternary d i a g r a m corresponds to
an area w i t h a c o m p o s i t i o n c o r r e s p o n d i n g to i:0:0 of the element
displayed. Since EDS is a b u l k analytical method, a n d since the films
m a y be thinner than the information d e p t h (on the order of one
micrometer), the amount of zinc m a y in some cases be o v e r e s t i m a t e d and,
hence, the oxygen content too small.
R e a c t i o n sequence no. i: Zn(OH) 2 to Zns(CO3)2(OH) 6
E x p o s u r e of a p u r e zinc surface in a moist atmosphere, i.e. rain,

dew, will result in the formation of zinc hydroxide. In contact w i t h
carbon dioxide the hydroxide reacts and forms zinc hydroxycarbonate.
This is a common o b s e r v a t i o n d e s c r i b e d by several authors [1,11,19,39].
The formation of the carbonate layer is a r a p i d process, in w h i c h a thin
layer is formed w i t h i n m i n u t e s or hours. This is i l l u s t r a t e d by means of
XPS. The rate of formation was studied indoors after panel grinding in
w a t e r (Fig. 5). A continuous g r o w t h can be o b s e r v e d b e t w e e n 5 minutes
and 6 days in a b e n i g n environment, w h i c h points to a more or less
instantaneous formation of a carbonate d u r i n g and a f t e r sample
preparation [13].
The formation of zinc h y d r o x y c a r b o n a t e was also o b s e r v e d on
s h e l t e r e d zinc panels in the rural atmosphere. Q u a n t i t a t i v e analysis, by
m e a n s of XPS, on panels after i, 3, 5 and 14 days of s h e l t e r e d exposure
r e v e a l e d no significant divergence from the theoretical c o m p o s i t i o n of
zinc h y d r o x y c a r b o n a t e [15].
900
850
800
750
700
650
600
D 550
500
450
400 I I I I I I I
1 2 3 4 5 6 7
log t [min]
FIG. 5--Carbonate g r o w t h indoors studied by means of XPS.
Depending on the environmental characteristics, zinc h y d r o x y c a r b o n a t e

either continues to g r o w or, if e x p o s e d to p o l l u t e d atmospheres, m a y
accumulate different anions and eventually t r a n s f o r m into other
corrosion products.
Reaction sequence no. 2: Zns(CO3)2(OH) 6 to Zn5(OH)sCI2.H20
If chlorides are present in the atmosphere as h y d r o g e n chloride

(HCI), sodium chloride (NaCI) or other chlorine containing species, a
condition favoring zinc h y d r o x y c h l o r i d e formation is attained. This is
the case in m a r i n e atmospheres, where the main source of chlorides is
sea w a t e r aerosols, and in traffic environments w i t h deicing salts.
Chlorides can easily deposit on the wet zinc or g a l v a n i z e d steel surface
and accelerate the corrosion process. In the m a r i n e atmosphere, small
islands of zinc h y d r o x y c h l o r i d e appear on the surface w i t h i n 24 hours,
as shown by m e a n s of SEM/EDS (Fig. 6) and X R D [13]. Since the thickness
of the carbonate layer is in the nanometer range, it cannot u n d e r
present conditions be d e t e c t e d by means of SEM/EDS.
FIG. 6--Island of zinc h y d r o x y c h l o r i d e after 24 hours of sheltered

exposure in the m a r i n e atmosphere.
In order to allow the layer of zinc hydroxycarbonate to grow, and

to investigate the reaction sequence in more detail, the rural
atmosphere was chosen for more detailed studies because of its
negligible chloride deposition rate and benign atmosphere. The left
ternary diagram in Fig. 7 shows the compositional variations between
investigated areas of zinc, chlorine and oxygen content after two weeks
of exposure and no chloride deposition. The composition of the corrosion
layer is now comparable to the composition of zinc hydroxycarbonate.
Some of the individual data points are shifted toward the zinc corner
because the information depth achieved with EDS reaches below the
thickness of the corrosion layer. For the purpose of stimulating the
formation of zinc hydroxychloride, chlorides were deposited manually
after two weeks of exposure in the rural atmosphere. After another two
weeks of exposure, areas consisting of zinc hydroxychloride were
observed, together with areas of zinc hydroxycarbonate as well as
intermediate stages between the two phases (right ternary diagram in
Fig. 7). Due to the structural similarities, chloride ions can replace
carbonate ions in the lattice of zinc hydroxycarbonate and eventually
form zinc hydroxychloride. Zinc hydroxychloride may however also be
formed in addition to already existing zinc hydroxycarbonate.
Zn Zn
Compos i t ion / ~
of individual / \
cl ~)2 6 \o c] 8c12 ~ \o
FIG. 7--Ternary diagrams displaying compositional variations of zinc,

chlorine and oxygen content (in atomic per cent) by means of EDS studies
of individual areas after 14 days of natural exposure (left) and another
14 days of artificial exposure (right) in the rural atmosphere.
Reaction sequence no. 3: Zns(CO3)2(OH) 6 to Zn4SO4(OH)6.nH20
This reaction path is possible if sulfur containing species

dominate the atmosphere and thereby the deposition process. This is the
case in the rural atmosphere. To illustrate the reaction sequence, we
have chosen to present data from 14 and 30 days of sheltered exposure.
The compositional variations of zinc, sulfur and oxygen content in
analyzed areas are given in ternary diagrams (Fig. 8). The diagrams
illustrate that the corrosion products most probably consist of zinc
hydroxycarbonate after 14 days of sheltered exposure (Fig. 8, left).
After 30 days the situation is different (Fig. 8, right). In addition to
the carbonate layer (not displayed in the figure), areas with platelets
are located all over the surface. The composition of the platelets
coincides with the theoretical composition of zinc hydroxysulfate. Since
zinc hydroxysulfate can exist with different amounts of water, the
theoretical position is drawn as an area.
The incorporation of sulfur is gradual, which indicates that the
supply and incorporation of sulfate ions in the corrosion products
probably is a rate determining step.
Zn Zn
~
/
Compositon
\ of individual
s/ \o s o

sulfur and oxygen content (in atomic per cent) by means of EDS studies
of individual areas on sheltered panels, exposed for 14 days (left) and
30 days (right) in the rural atmosphere.
Reaction seauence no. 4: Zns(OH)8CI2-H20 to NaZn4CI(OH) 6SO4-6H20
If the environmental conditions cause deposition of both chlorides

and sulfates and the ratio between the two species is larger than one,
the prerequisite for this reaction sequence is obtained. The results
from the marine atmosphere are used to illustrate the phenomena. Fig. 9
displays the zinc, chlorine and oxygen content of islands on sheltered
panels after 1 and 30 days of exposure. The diagrams show that the
composition of the islands (cf Fig. 6) after 1 day of exposure
corresponds quantitatively to the theoretical composition of zinc
hydroxychloride (Fig. 9, left). A few data are shifted toward the zinc
corner because the islands are very thin and the information depth
reaches deeper than the thickness of the islands. After 30 days of
exposure, the composition of some of the individual islands agrees with
the theoretical composition of sodium zinc chlorohydroxysulfate (Fig. 9,
right). There are also islands that are composed of zinc hydroxychloride
as well as islands with intermediate compositions.
Zn Zn
Composition
oK individua / \

chlorine and oxygen content (in atomic per cent) by means of EDS studies
of individual islands after 1 day (left) and 30 days (right) in the
marine atmosphere.
The rate of formation of sodium zinc chlorohydroxysulfate is

dependent on the supply of both sulfate and sodium ions. The origin of
sulfate ions is mainly sodium sulfate (Na2SO4) from a nearby oil
combustion plant [13]. Most sodium and chlorine originate from sea water
aerosols. The field exposure study in the marine environment has
provided evidence that sulfates incorporate between the sheets of zinc
hydroxychloride before the incorporation of sodium takes place.
Reaction sequence no. 5 : Z n 4 S O 4 ( O H ) 6 - n H 2 0 to Zn4CI2(OH)4SO4.5H20
This reaction sequence is possible if the ratio between deposited

chloride and sulfate is less than one. This is the case in the urban
atmosphere in the field exposure program. Data of oxygen, chlorine and
sulfur in individual areas after 5 days and 30 days of sheltered
exposure are used to illustrate this reaction sequence (Fig. 10).
O
O
(OH) 6 "
C1 S Cl/ \
FIG. 10--Ternary diagrams displaying compositional variations of oxygen,

chlorine and sulfur content (in atomic per cent) by means of EDS studies
of individual areas after 5 days (left) and 30 days (right) in the urban
atmosphere.
After five days of sheltered exposure, the composition of the

locally distributed corrosion products corresponds to the theoretical
composition of zinc hydroxysulfate (Fig. i0, left). The position of zinc
hydroxysulfate is drawn as an area because of differences in water
content (i, 3, 4 or 5 water molecules). In a few areas, some
incorporation of chlorine is observed. After 30 days of exposure (Fig.
i0, right) the surface is more or less covered with islands of thin
platelets. These areas are still in quantitative agreement with the
theoretical composition of zinc hydroxysulfate. Other islands, locally
distributed over the corroded surface, are also observed. The
quantitative composition of these islands corresponds to zinc
chlorohydroxysulfate. This position is also drawn as an area, since the
number of water molecules can change in the vacuum chamber.
Since the individual positions of the atoms in the cell structure
of zinc chlorohydroxysulfate are not structurally determined, it is
difficult to speculate on the structural formation in the reaction
sequence. Clearly, sulfate from sulfur dioxide and other sulfur
containing species in the atmosphere dominate while forming zinc
hydroxysulfate. Due to a certain chloride deposition (cf Fig. i),
chloride ions accumulate in the lattice of zinc hydroxysulfate and form
zinc chlorohydroxysulfate. The formation is dependent, for one thing, on
the deposition rate of chloride species.
Reaction seauenGe no. $: Zns(OH)8CI2-H20 to Zn4CI2(OH)4SO4-5H2 O
Isolated observations of this reaction sequence have been made

b o t h in the urban and the industrial atmosphere. In order to refine the
sequence, the rural atmosphere was used for artificial studies. Zinc
panels were exposed for 2, 4 and 8 weeks under sheltered conditions.
Chlorides were manually deposited for the purpose of forming zinc
hydroxychloride. After two weeks of exposure, islands of this phase
could be observed on the surface (Fig. ii, left).
Composition O
0 of individual
Cl S C1
FIG. ll--Ternary diagrams displaying compositional variations of oxygen,

chlorine and sulfur content (in atomic per cent) by means of EDS studies
of individual areas after 14 days of artificial exposure (left) and
another 28 days of natural exposure (right) in the rural atmosphere.
After these first two weeks, no more chlorides were added and only
natural sulfate deposition was present. This resulted in the formation
of zinc chlorohydroxysulfate after another four weeks of exposure (Fig.
ii, right). The results suggest that zinc hydroxychlorides may form, if
there is significant initial deposition of chlorides in an otherwise
sulfur containing atmosphere. This phase can function as a nucleus in
the formation of zinc chlorohydroxysulfate, which is an indication that
the sequence is possible although the sequence based on zinc
hydroxysulfate (described above) seems to dominate.
~eactioD seauence no. 7 : Z n 4 S O 4 ( O H ) 6 . n H 2 0 to NaZn4CI(OH) 6SO4-6H20
This sequence has not been observed, either in natural or simulated

atmospheres. However, the structural similarities described above
indicate that if the environmental circumstances are advantageous the
transformation would be possible.
SUMMARY
By means of a multianalytical approach, which includes

environmental, depositional and surface characterizations of exposed
zinc panels, a picture of the corrosion processes has been obtained,
which ranges from initial stages to fully developed end products.
Different reaction sequences can be outlined depending on the initial
ratio between dry deposited chloride and sulfate. Fig. 12 describes
schematically the different reaction sequences in terms of the ratio of
sulfate and chloride species on sheltered exposed zinc panels.
Zn (OH) 2
...... . :::::.:::::::::::::::.
Zns
% -
~,. ~
Zn 5 (OH)8C12 .H20 Zn4SO 4 (OH) 6 "nH20
D"
X 9 ~<V _, =
N a Z n 4 C I (OH) 6SO4 -6H20 Zn4Cl 2 (OH) 4S04 95H20
FIG. 12--Schematic description of atmospheric corrosion sequences on

exposed, sheltered, zinc panels.
In the marine atmosphere, where the ratio between chloride and

sulfate is larger than one, a reaction sequence with three different
steps can be identified. The sequence includes the formation of zinc
hydroxycarbonate as the initial step, zinc hydroxychloride as the
intermediate step, and sodium zinc chlorohydroxysulfate as the final
step. If sulfate deposition is negligible, zinc hydroxychloride becomes
the end product.
If the ratio between chloride and sulfate is less than one, other
reaction sequences are possible. In the rural atmosphere, with minor
chloride deposition, the sequence involves two steps; the formation of
zinc hydroxycarbonate followed by the subsequent, and sometimes
parallel, growth of zinc hydroxysulfate. In the urban atmosphere,
characterized by larger amounts of deposited sulfate than of deposited
chloride, the zinc hydroxysulfate is observed. This phase can accumulate
chloride ions and eventually form zinc chlorohydroxysulfate. This
sequence does also take place in the highly aggressive industrial
atmosphere with high deposition rates for both sulfates and chloride,
resulting in rapid formation of zinc chlorohydroxysulfate.
ACKNOWLEDGMENT
We gratefully acknowledge the kind assistance and skilled

competence of Prof. P.-E. Werner and Ms M. Westdahl, University of
Stockholm, Sweden for advice on structural chemistry, and Dr. J.
Henriksen, Norwegian Institute of Air Research, Lillest6m, Norway for
depositional data. This w o r k forms part of a project with financial
support from the Swedish Steel company, SSAB, Borl&nge, the Swedish
National Board for Industrial and Technical Development, NUTEK,
Stockholm and the Swedish Corrosion Institute, Stockholm.
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No. 4, April 1989, pp 193C-203C.
[~] Beccaria, A.M., Corrosion, Vol. 46, No. ii, 1990, pp 906-912.
[!] Morcillo, M., Ruiz, J.L. and Gonzalez Matilla, M., Werkstoffe und
Korrosion, Vol. 40, 1989, pp 668-673.
[4] Friel, J.J., Corrosion, Voi.42, No. 7, 1986, pp 422-426.
[~] Granese, S.L., Rosales, B.M. and Fernandez, A., Bulletin of

ElectrQchemistrv, Vol. 7, No. 2, February 1991, pp 67-72.
[~] Biestek, T., Drys, M., Sokolov, N., Knotkova, D., Ramishvili, R.,
Kozhukharov, V. and Zeidel, M., Protgction of Metals, Vol. 19,
1983, pp 612-615.
[~] Morral, F.R., Transactions o[ the American Electrochemical Societv,

Vol. 77, 1940, pp 279-288.
[~] Odnevall, I., unpublished data
[2] Biestek, T., "Atmospheric Corrosion", Ailor, W.H., Ed., John Wiley
and Sons, New York, 1982, pp 631-643.
[i0] Flinn, D.R, Cramer, S.D., Carter, J.P., Hurwitz, D.M. and Linstrom,
P.J., ACS Symposium Series 318, "Materials Degradation Caused by
Acid Rain", 1986, pp 119-151.
[ii] Cramer,S., Carter, J.P, Linstrom, P.J and Flinn, D.R., "Degradation
of Metals in the Atmosphere", ASTM STP 965, Dean, S.W. and Lee,
T.S., Eds., American Society for Testing and Materials,
[12] Granese, S.L. and Rosales, B.M., Revista Iberoamericana de

Corrosion v Protection, Vol. 17, No. 3, 1986, pp 197-204.
[13] Odnevall, I. and Leygraf, C., Corrosion Science, Vol. 34, No. 8,
1993, pp 1213-1229.
[14] Odnevall, I. and Leygraf, C., Journal of the Electrochemical

Society, Vol. 138, No. 7, July 1991, pp 1923-928.
1994, pp 1077-1092.
[16] Yiping, Z., Zhenyao, W. and Fengqiu, Z., Journal of Environmental

Sciences (China), Vol. 3, No. 2, 1991, pp 53-60.
[17] Bonner, P.E., Proceedinas of the Fourth International Conaress of

Metallic Corrosion Amsterdam, 1969, pp 751-759.
[18] Odnevall, I. and Westdahl, M., Corrosion Science, Vol. 34, No. 8,
1993, pp 1231-1242.
[19] Bird, C.E. and Strauss, F.J., Materials Performance, Vol. 15, No.
ii, 1976, pp 27-29.
1994, pp 1551-1568.
[21] Townsend, H.E. and Zoccola, J.C., Materials Performance, Vol. 18,
No. i0, 1979, pp 13-20.
[22] Kucera, V., Haagenrud, S., Atteraas, L. and Gullman, J.,

"Degradation of Metals in the Atmosphere", ASTM STP 965, Dean, S.W.
and Lee, T.S., Eds., American Society of Testing and Materials,
[23] Walton, J.R., Johnson, J.B. and Wood, G.C., British Corrosion
Journal, Vol. 17, No. 2, 1982, pp 65-70.
[24] Guttman, H. and Sereda, P.J., "Metal Corrosion in the Atmosphere",

ASTM STP 435, American Society of Testing and Materials,
[25] Benarie, M. and Lipfert, F.L., Atmospheric Environment, Vol. 20,

No. i0, 1986, pp 1947-1958.
[26] Weber, L., Zeitschrift fur KristalloaraDhie, Vol. 58, 1923, pp 398-
403.
[27] Schmetzer, K., Schnorrer-K6hler, G. and Medenbach, 0., Neue~

Jahrbuch fur Mineraloaie. Monatshefte. Vol. 1985, No. 4, 1985, pp
145-154.
[28] Ghose, S., Acta Crvstalloarafica, Vol. 17, 1964, pp 1051-1057.
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Monatshefte, No. 7, 1991, pp 296-306.
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[31] Spiess, M. and Gruehn, Z., Zeitschrift fur den Anorqanische

Allqemeine Chemie, Vol. 456, 1979, p. 222
[32] Bear, I.J., Grey, I.E., Madsen, I.C., Newnham, I.E. and Rogers,
L.J., Acta Crystalloqrafica, Vol. B42, 1986, pp 32-39.
[33] Bear, I.J., Grey, I.E., Newnham, I.E. and Rogers, L.J., Australian
Journal of Chemistry, Vol. 40, 1987, pp 539-556.
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Vol. 115, 1961, pp 21-51.
[35] Allmann, R., Zeitschrift fur Kristalloaramhie, Vol. 126, 1968, pp

417-426.
[36] Oswald, H.R. and Asper, R., "Preparation and Crystal Growth of
Materials with Layered Strctures", Lieth, R.M.A, Ed., D. Reidel
Publishing Company, Dordrecht-Holland/Boston-U.S.A., 1977, p 71.
[37] Persson, D. and Leygraf, C., Journal of the Electrochemical

Societ V, Vol. 139, No. 8, August 1992, pp 2243-2249.
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STP 175, 1956, p 132.
X. Gregory Zhang I and Eugene M. Valeriote I
GALVANIC PROTECTION OF STEEL BY ZINC UNDER THIN LAYER ELECTROLYTES
REFERENCE: Zhang, X. G. and Valeriote, E. M., "Galvanic Protection

of Steel by Zinc Under Thin Layer Electrolytes," A~mospherir Corrosion,
ASTM STP i~39, W. W. Kirk and Herbert H. Lawson, Eds., American Society
ABSTRACT: The galvanic protection distance and protection area of

steel by zinc under thin layer electrolytes were determined based on
measurements of the potential and galvanic current distributions of a
zinc/steel couple. The protection distance was found to increase with
increasing conductivity and thickness of the electrolyte and with
decreasing surface area of the steel. The galvanic protection area was
found to proportionally increase with increasing area of the steel to a
certain value, then decrease with further increase in steel area. The
galvanic corrosion rate of zinc increased with the steel area up to a
certain size, then decreased slightly with a larger area. It decreased
sharply as the distance between zinc and steel increased.
KEYWORDS: Galvanic action, protection distance and area, steel, zinc,

thin layer electrolyte
INTRODUCTION
One important aspect of zinc coated steel is that it is mostly

used in atmospheric environments where corrosion occurs under a thin
layer of electrolyte during wettlng-drying cycles [i]. Experimental
results have shown that the corrosion rate of metals under a thin layer
electrolyte is very different from that in a bulk solution [2]. Under a
thin layer electrolyte in open air the corrosion process has been found
to be controlled by the diffusion of oxygen to the metal surface [3].
In atmospheric exposure tests, moreover, zinc corroded at considerably
different rates when it was coupled to different metals, indicating the
significance of the galvanic effect on the corrosion rate of zinc under
thin layer electrolytes [4]. It is important to systematically
determine the protection distance (distance between the galvanically
coupled zinc and steel); the extent of protection (the extent of steel
protected); and the galvanic corrosion rate.
Previously, the galvanic current and potential distributions of

zinc and steel electrically connected in a coplanar cell under a thin
layer of Na2SO 4 electrolyte were systematically studied [5]. It was
ICorrosion Research Specialist and Manager, Product Technology,

respectively, COMINCO Product Technology Centre, Sheridan Park,
Mississauga, ON, Canada LSK IB4
230
Copyrightm1995by
ZHANG AND VALERIOTE ON GALVANIC PROTECTION OF STEEL 231
found that, except for concentrated solutions and thick electrolyte

layers, the galvanic current over the zinc electrode was concentrated at
a narrow edge closest to the steel, resulting in a very steep spatial
current distribution. Over the steel electrode, except for a very thin
electrolyte layer or for a large scale electrode, the current density
was relatively constant. The potential was almost constant over the
zinc surface. It remained within 40 mV of the corrosion potential of
the zinc and changed little with the solution concentration, electrolyte
thickness or the size of the steel electrode. On the other hand, the
potential varied significantly over the steel surface, from a value
close to the zinc corrosion potential to the corrosion potential of the
steel, and sensitively changed with electrolyte concentration,
electrolyte thickness, area of the steel surface and the distance
between steel and zinc. While the width of the steel affected the
potential and the current distribution on the steel, the width of the
zinc had very little effect on either the potential or current
distribution over the steel and zinc surfaces.
Epoxy
z,~ I/s ,
Fig. i A schematic representation of the electrochemical cell

used for obtaining data on protection distance and galvanic
corrosion current; D is the distance between the zinc and the
steel electrode, L the length of the electrodes, W the width of
the steel electrode, and X the distance on the steel electrode
measured from the edge nearest to the zinc.
In order to determine the effect of the various parameters on the

protection distance, and the extent of protection, a specially designed
cell is used, The configuration and the definition of the parameters
are-schematically shown in Fig. i. By using cells with the zinc strip
at different distances from the steel, the effect of distance, D, on the
potential of the galvanically connected steel was characterized. By
using steel electrodes of different sizes, the effect of steel area on
the potential of galvanically connected steel was examined. The
dimension of the zinc electrode in the X direction was not controlled
since., as shown previously [5], the current on the zinc under a thin
layer electrolyte is concentrated in a very small region, within I mm of

the edge of the zinc closest to the steel, and the variation in the
width of zinc electrode wider than i mm has hardly any effect on the
potential or current distribution.
The zinc electrodes and the steel electrodes were made of thin
strips, moulded in epoxy. The purity of the zinc was 99.99% and the
steel was cold-rolled low-carbon steel. The epoxy cell containing the
zinc and steel electrodes was ground to #600 emery paper. The horizontal
top edges of the cell were bordered by a polyimide tape (0.06 mm in
thickness) to confine the electrolyte. The size of the electrodes was
considerably smaller than the area defined by the borders. NazSO 4
solutions of different concentrations, prepared with deionized water,
were used as electrolyte in the experiments. The thickness of the
electrolyte was determined using a pipette to deliver a pre-determined
volume, which was assumed to uniformly spread over the specimen surface.
To obtain the potential distribution, the local electrode

potential was measured relative to a saturated calomel reference
electrode (sce) using a high impedance voltmeter. The reference
electrode half cell included a Luggin capillary, which was filled with
the test solution and had a tip about 0.2 mm in diameter. The galvanic
current from each strip was measured using an ordinary ammeter (or a
potentiostat when IR drop was significant) placed in the circuit.
Further experimental details can be found in the previous paper [5].
Galvanic Protection Distance (Throwing Power)
Fig. 2 shows the potential at a position close (at X < i mm) to

the edge of the steel electrode, as a function of the distance between
the zinc and the steel (D) for different thicknesses of 0.001 M NazSO 4
solution. The potential increases as the distance between zinc and
steel increases and the change in the potential with distance is larger
for thinner electrolytes. The effect of electrolyte thickness, distance
and other parameters on the potential of the steel surface has been
described as the total ohmic potential drop caused by changing the
reaction surface area, reaction kinetics, length of the current path,
and resistivity of the electrolyte [5].
The c a t h o d i c p r o t e c t i o n o f s t e e l i s d e t e r m i n e d by t h e p o t e n t i a l of
the steel. Around the open-circuit corrosion potential steel will
corrode. If the steel is cathodically polarized to a certain potential
value by being galvanlcally connected to a piece of zinc, it will be
protected and corrosion will not occur. Based on the corrosion
behaviour of steel in aerated solutions, it can reasonably be assumed
that little corrosion will occur when the potential of the steel is more
negative than -700 mVs=| which is about 200 mV more negative than the
corrosion potential of the steel. This potential value is then used as
a criterion to estimate the galvanic protection distance of zinc for
steel.
-250 I [ : ~ O.17mm e O.~mm 9 O.~mm 9 1.36mm
-450
>
-650
- -7~ mV
o -850
-1,050
0 0.5 1 1.5 2 2.5 3 3.5 4 45
Distance (cm)
Fig. 2 The potential at X < I m m as a function of the distance

(D) between the zinc and the steel in 0.001 M Na2SO 4 solution for
different electrolyte thicknesses (t) for a steel width of i mm.
As illustrated in Fig. 2, taking the distance value, D, of each

curve at -700 mV, ce, the protection distances for the steel at X < I mm
under different thickness of electrolyte are obtained. For example, as
indicated in Fig. 2, the protection distance in 0.001 M NazSO 4 was about
4 mm for a 1 mm wide steel strip under a 0.17 mm electrolyte, and it was
about 47 m m under 1.36 mm thick electrolyte.
Using the same procedure, the protection distances for the steel
surface at different X values for different steel widths and solution
concentrations were obtained. Fig.3 (a) shows a three dimensional plot
of the protection distance for 0.001 M NazSO 4 solution. It is clearly
seen that the protection distance increases as the electrolyte thickens
or the steel strip narrows. Note that the protection distance changes
only slowly with width when the steel is wider than i0 mm, especially
for thinner electrolyte layers. The protection distance for the steel
surface at position X - 5 mm is shown in Fig. 3 (b). Compared to Fig. 3
(a), one can see that the protection distance for the steel surface at X
- 5 m m is much smaller than at X < i mm. When the steel strip becomes
wider and the electrolyte layer thickness becomes thinner, the galvanic
protection does not extend very far from the edge of the zinc-steel
boundary. For example, from Fig. 3 (b) it can be seen that there is no
protection for the steel surface at X - 5 mm for a steel electrode I0 mm
wide under an electrolyte thickness less than 0.3 mm. The protection
distance was found to greatly increase with increased concentration of
the electrolyte [5].
D D
T 80 mm 80 mm
X < 1 mm / X=Smm
O.O01MNa~O, ! 0.001MNatSO,
l~4tmm mm
t
W
(a) (b)
Fig. 3 Three dimensional plots of the galvanic p r o t e c t i o n

distance (D) for steel at two different p o s i t i o n s on the steel
surface in 0.001 M Na2SO 4 solution; (t - e l e c t r o l y t e thickness,
W = width of steel electrode)
Galvanic Protection A r e a
As seen above, w h e n a piece of steel is p l a c e d b e s i d e zinc, the

area of steel w h i c h is under galvanic p r o t e c t i o n depends on the
electrolyte thickness and the w i d t h of the steel at a g i v e n e l e t r o l y t e
concentration.
-400
-500
-600
>
g -700
i/ t
9 0.17 mm
c
-800 + 0.34 mm
protecdon width Y4 0 . 6 8 m m
-900
9 1.36 mm
-1,000
t i I
-1,100 '
0 2 4 6 8 10 12 14 16 18 20
X (ram)
Fig. 4 Potential d i s t r i b u t i o n on the surface of steel in 0.001 M

Na2SO4, 20 mm in w i d t h and in direct contact w i t h a zinc (D - 0),
as a function of X for four different e l e c t r o l y t e t h i c k n e s s e s (t).
This can be estimated considering the potential distribution across the

steel surface, as shown in Fig. 4, which presents the potential as a
function of X in 0.001 M Na2SO 4 for different electrolyte thicknesses
when the zinc and steel are in direct contact, that is, Dffi0. Similar to
the procedure for obtaining the protection distance, the protection area
under a given condition can be obtained by taking the X values
corresponding to -700 mVRc,, as the protection width X, and multiplying
by the length of the steel sample L. For example, in Fig.. 4, for a
steel sample of 20 mm in width under an electrolyte thickness of 0.34
mm, the X value corresponding to -700 mVs= , is about 3 mm and thus the
protection area so obtained is about 3xL mm 2.
Using the same procedure, the protection areas for different steel
widths were obtained and are shown in Fig. 5(a). The protection area
increases with increase in the electrolyte thickness. At a given
X (mrn) X (mm)
2o~ O.O01M NavqO,
20~
12~ 12~
W (mm) .' W (mm)

4~ 4~
(a) (b)
Fig. 5 Three dimensional plots of protection width X (the

galvanic protection area - X x L) as a function of the electrolyte
thickness (t), steel width (W), and the distance between the zinc
and steel (D); (a) D-0; (b) D-5 mm.
electrolyte thickness the protection area proportionally increases with

the width of the steel to a certain value, where it starts to decrease
with further increase in the width. After a relatively sharp drop, the
protection area becomes less sensitive to further increase of the width
of the steel sample. By projection of the ridge (in Fig. 5), at which
the protection width starts to decrease, onto the horizontal plane, one
obtains the range of conditions (marked with hatches) under which the
potential of the whole steel surface is more negative than -700 mVse e
and is, therefore, completely cathodically protected. The reason for
the decrease of the protection area at a certain steel width is due to
the increased ohmic potential drop in the direction perpendicular to the
contact line between the zinc and steel, because the current flow in the
electrolyte along that direction becomes larger owing to the larger
steel surface area (larger width) [5]. When the steel sample gets
sufficiently big, the cathodic reaction current on the far end of the
sample becomes very small. This is so because the potential there is
near the open-circuit potential of the steel, around -500 mVsc e, so that
there is very small change in the total current with addition of more
steel surface area at the far end from the zinc.
When the zinc and steel are not in direct contact and are
separated by a distance D, the protection area can be considerably
reduced, [see Fig. 5(b) as an example]. When the distance D is 5 mm,
except for steel widths less than I0 mm or electrolyte thicknesses
larger than 1 mm, the protection width is zero and no area of the steel
surface is under cathodic protection. On the other hand, it is
interesting to note that the hatched area in Fig. 5(b) is not much
smaller than that in Fig. 5(a), indicating that, for a small steel
surface, there is galvanic protection even when the zinc is located some
distance away.
30
t: ~E O.17mm $ 0.34ram ~< 0.68ram 9 1.36mm
25
2O
~10
i ] i i i i I i
0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
Distance (cm)
Fig. 6 The galvanic current as a function of the distance

between the zinc and the steel in 0.001 M NazSO 4 solution of
different electrolyte thicknesses for a steel width of 1 mm.
G a l v a n i c Corrosion of Zinc
Galvanic corrosion of zinc occurs when it is electrically

connected to steel in an electrolyte. The galvanic current is thus a
measure of the galvanic corrosion rate of the zinc. Fig. 6 shows the
galvanic current as a function of the distance between the zinc and
steel for a steel width of 1 mm and different electrolyte thicknesses.
The current changed slowly with distance for the thickest electrolyte,
while it changed more sharply with distance for thinner electrolytes.
It is interesting to note in Fig. 6 that the current was the highest for
the thinnest electrolyte when the zinc strip was very close to the
steel, i.e. 0.I mm, but it was the lowest when the zinc strip was at
distances greater than 1 cm. This phenomenon is due to different
processes which limit the galvanic current under different conditions.

When the electrolyte path is short, the ohmic resistance is relatively
small and the cathodic current on the steel is limited by the reduction
of oxygen [5]. When the distance increases, the ohmic resistance
becomes relatively large and the current becomes limited by the
resistance of the electrolyte.
120 ~A
D = 0.05mm
! D = 5 lalm
120 ~A
W
(a)
4tram
W
~ 4 m~
D = 40mmI120~A
l _
(c)
Fig. 7 Three dimensional plots of the galvanic corrosion current

of zinc in 0.001 M Na2SO 4 solution for different distances D
between the zinc and the steel.
Fig. 7 shows the galvanic current as a function of the width of

the steel strip (W), the thickness of the electrolyte (t), and the
distance between the zinc and steel electrodes (D) for 0.001 M Na2SO 4
solution. The galvanic current is high when the zinc is close to the
steel. It decreases as the distance between the zinc and the steel
becomes larger [compare Fig.7 (a), (b), (c)], and this is more
pronounced for thinner electrolyte layers than for thicker ones. As
discussed above, when the zinc is close to the steel, the cathodic
current on the steel is limited by diffusion of oxygen to the steel
surface. As the zinc becomes more distant from the steel, the galvanic
current becomes limited by the ohmic resistance of the solution,
resulting in a decrease of the total galvanic current.
The current increases sharply with steel strip width up to about

20 mm in the case of the conditions for Fig. 7(a). As the example shows,
when the width of the steel strip increases to a certain value, the
overall galvanic current actually decreases. This is a rather
interesting result. The peak current value occurs at about the same
steel width for different thicknesses of electrolyte. This happens
since an increase in the width of steel will increase the reaction area,
but at the same time will increase the ohmic resistance contribution
which will change the potential distribution. As reported previously
[5], when it is ohmic-resistance-controlled the cathodic current density
on steel can be much smaller than the limiting oxygen diffusion current
density. Thus, as the width of the steel gets greater, the current
density becomes smaller on the steel surface which is more distant from
the zinc/steel boundary. At a certain width, further increase in the
width of steel electrode will actually result in a decrease of the total
galvanic current.
The above is a systematic study of the effects of various

parameters on the galvanic protection of steel by zinc. It provides a
general understanding and quantitative estimate of the galvanic
protection of steel and the corrosion of zinc under a thin electrolyte
layer, such as occurs under atmospheric conditions. In real situations,
other factors, such as the accumulation of corrosion products and
formation of a passive layer, may also play roles which can greatly
change the overall reaction kinetics.
CONCLUSIONS
Based on experimental measurements of the potential and current

distributions for a zlnc/steel couple under thin Na2SO 4 electrolyte
layer, the protection distance and protection area for steel
galvanlcally connected to zinc were quantitatively determined for
various values of the parameters involved in the system. The protection
distance was found to increase with increasing conductivity of the
electrolyte and with decreasing surface area of the steel. The galvanic
protection area was found to proportionally increase with increasing
width of the steel to a certain value, then decrease with further
increase in the steel width. It increased with increasing electrolyte
thickness although less sensitively than with changes in steel surface
width. For small steel widths the whole steel surface could be
effectively under galvanic protection even when the zinc was at s o m e
distance. The galvanic corrosion rate of zinc increased with the area
of steel up to a certain size, then decreased slightly with a larger
area. It decreased sharply as the distance between zinc and steel
increased.
REFERENCES
[i] Guttman H., "Metal Corrosion in the Atmosphere", American Society

for Testing and Materials, STP435, 225 (1968).
[2] Rosenfel'd I.L., First Internatlonal Congress on Metallic
Corrosion, 243, London, April, (1961).
[3] Stratmann M. and Streckel H., Corrosion Science, 30, 697 (1990).
[4] Kucera V. and Mattsson E., in "Atmospheric Corrosion", Ed. Ailor
W.H., 561, John Wiley and Sons, New York, (1982).
[5] Zhang X.G. and Valerlote E.M., "Galvanic Protection of Steel and
Galvanic Corrosion of Zinc Under Thin Layer Electrolytes",
Corrosion Science, 30, 1957 (1993).
Eva J o h a n s s o n I and Jan G u l l m a n I'2
C O R R O S I O N S T U D Y OF C A R B O N STEEL A N D ZINC-
C O M P A R I S O N B E T W E E N FIELD E X P O S U R E A N D A C C E L E R A T E D TESTS
REFERENCE: Johansson, E. and Gullman, J., " C o r r o s i o n Study of C a r b o n

Steel and Z i n c - C o m p a r i s o n B e t w e e n F i e l d E x p o s u r e and A c c e l e r a t e d T e s t s , "
A t m o s p h e r i c CorrosiQn, A S T M STP 1239, W. W. K i r k and H e r b e r t H. Lawson,
Eds., A m e r i c a n S o c i e t y for T e s t i n g and Materials, Philadelphia, 1995.
A B S T R A C T z The results from a c c e l e r a t e d a t m o s p h e r i c c o r r o s i o n test

m e t h o d s do not g e n e r a l l y c o r r e s p o n d v e r y well to c o r r o s i o n b e h a v i o u r
u n d e r p r a c t i c a l conditions. The aim of the p r e s e n t i n v e s t i g a t i o n is
to increase the u n d e r s t a n d i n g of the influence of temperature,
w e t n e s s and sulfur d i o x i d e c o n c e n t r a t i o n in the air. Special
a t t e n t i o n is given to the extent to w h i c h results from a c c e l e r a t e d
tests d i f f e r from the results of o u t d o o r exposures..
C a r b o n steel and zinc h a v e b e e n e x p o s e d outdoors at four
d i f f e r e n t test sites and to c l i m a t e c h a m b e r test p r o c e d u r e s . The
study includes c o r r o s i o n a t t a c k m e a s u r e d as mass loss of test plates
and c o r r o s i o n p r o d u c t c h a r a c t e r i z a t i o n by x - r a y d i f f r a c t i o n .
The i n v e s t i g a t i o n shows that studying c o r r o s i o n w i t h r e g a r d to
b o t h mass loss and c o r r o s i o n products formed d u r i n g c l i m a t e c h a m b e r
e x p o s u r e s and field exposures, v a l u a b l e k n o w l e d g e is o b t a i n e d about
i m p r o v e m e n t s of a c c e l e r a t e d test methods.
KE~ORDS~ A t m o s p h e r i c corrosion, field exposure, a c c e l e r a t e d test,

c a r b o n steel, zinc, mass loss, c o r r o s i o n products.
There is a great d e m a n d for reliable, s h o r t - t e r m m e t h o d s for

c o r r o s i o n testing in the d e v e l o p m e n t of m a t e r i a l s and s t r u c t u r e s for
c o r r o s i v e environments, and a large number of s h o r t - t e r m m e t h o d s for
a t m o s p h e r i c c o r r o s i o n testing have b e e n d e v e l o p e d (1,2). It has b e e n
shown, however, that the results of these tests do not g e n e r a l l y
c o r r e s p o n d v e r y well to the b e h a v i o u r u n d e r p r a c t i c a l c o n d i t i o n s
(3,4). An important reason for this is that, in order to a c c e l e r a t e
the test, c o n d i t i o n s have b e e n c h o s e n w h i c h d e v i a t e s t r o n g l y from
s e r v i c e conditions, and the c o r r o s i o n m e c h a n i s m b e c o m e s d i f f e r e n t
from that w h i c h occurs in p r a c t i c e in a normal atmosphere.
The aim of this i n v e s t i g a t i o n is to increase the u n d e r s t a n d i n g
of the i n f l u e n c e of d i f f e r e n t factors on a t m o s p h e r i c c o r r o s i o n by
e x p e r i m e n t a t i o n , w i t h special a t t e n t i o n b e i n g g i v e n to the extent to
w h i c h results from a c c e l e r a t e d tests d i f f e r from the results of
o u t d o o r e x p o s u r e trials.
ISwedish C o r r o s i o n Institute, R o s l a g s v & g e n I01, B u i l d i n g 25,

S-I04 05 Stockholm, Sweden
2present address: The Central Board of N a t i o n a l A n t i q u i t i e s and the
National H i s t o r i c a l Museums, P.O. Box 5405, S-I14 84 Stockholm,
Sweden
240
Copyrightm1995by
Downloaded/printed byA S T M I n t e r n a t i o n a l www.astm.org
JOHANSSON AND GULLMAN ON CARBON STEEL AND ZINC 241
E X P E R I M E N T A L P R O C E D U R E
Materials
In t h i s i n v e s t i g a t i o n , t e s t p l a t e s of SS 1142 c a r b o n s t e e l a n d
of 9 9 . 9 9 % p u r e zinc w e r e u s e d w i t h d i m e n s i o n s of 150 x I00 m m 2 a n d
t h i c k n e s s e s of 0.8 a n d 1 m m r e s p e c t i v e l y .
Corrosion tests
The corrosion tests included four field exposures and two

series of e x p o s u r e s in a c l i m a t e c h a m b e r .
Field exposure
- Ryda; r u r a l a t m o s p h e r e
- Stockholm; urban atmosphere
- Borregaard; industrial atmosphere
- Bohus-Malm6n; marine atmosphere
T e s t p l a t e s w e r e e x p o s e d in b o t h o p e n a n d r a i n p r o t e c t e d
p o s i t i o n s . In t h e c a s e of t h e o p e n e x p o s u r e , t h e t e s t p l a t e s w e r e
e x p o s e d o n a s t a n d w i t h a n i n c l i n a t i o n of 45 ~ , f a c i n g south. In t h e
r a i n - p r o t e c t e d location, t h e t e s t p l a t e s w e r e e x p o s e d v e r t i c a l l y ,
h a n g i n g o n a r o d u n d e r a roof, p r o t e c t e d a g a i n s t d i r e c t s u n l i g h t a n d
precipitation. They were examined after one and three months and
a f t e r o n e a n d five y e a r s .
Climate chamber exDosu~
T h e t e s t s h a v e b e e n c a r r i e d out in a m o d i f i e d c o m m e r c i a l
c l i m a t e c h a m b e r . T h e p r i n c i p l e m o d i f i c a t i o n s a r e t h e i n t r o d u c t i o n of
a c o r r o s i o n r e s i s t a n t inner c h a m b e r a n d a fan w h i c h g i v e s r i s e to
t u r b u l e n t a i r f l o w a r o u n d t h e t e s t p l a t e s . T h e test p l a t e s w e r e
p l a c e d o n a r o u n d P l e x i g l a s s s h e l f w h i c h r o t a t e d at 1 r o t a t i o n / m i n .
T h i s w a y of e x p o s u r e h a s s h o w n to g i v e a v a r i a t i o n c o e f f i c i e n t for
p a r a l l e l t e s t p l a t e s of a m a g n i t u d e less t h a n 5 %.
T h e e x p o s u r e p r o g r a m s for t h e t w o test s e r i e s w e r e d e s i g n e d
m a i n l y a c c o r d i n g to t h e f o l l o w i n g b a s i c p r o g r a m :
Period Time, hours
Dry 2
Humid 18
Drying out 4
D u r i n g the d r y i n g period, t h e t e m p e r a t u r e w a s r a i s e d by 10~

O n e v e r y t h i r d day, s i m u l a t e d r a i n e v e n t s w e r e i n t r o d u c e d t o w a r d s the
e n d of t h e h u m i d p e r i o d . S u l f u r d i o x i d e w a s a d d e d d u r i n g t h e d r y a n d
h u m i d p e r i o d s , e x c e p t for the p e r i o d s w i t h rain.
The humid air mixed with sulfur dioxide entered through a pipe
in t h e b o t t o m p a r t of t h e chamber. T h e s u l f u r d i o x i d e c o n c e n t r a t i o n
in t h e c h a m b e r w a s d e t e r m i n e d w i t h a p u l s e d f l u o r e s c e n c e a n a l y z e r .
T h e a n a l y z e r s i g n a l c o n t r o l s t h e v a l v e t h a t r e g u l a t e s t h e s u p p l y of
t h e g a s c o n t a i n i n g 1% SO 2 in n i t r o g e n to the m a i n s t r e a m o f the air.
T h e c o n c e n t r a t i o n in t h e c h a m b e r w a s m a i n t a i n e d b e t w e e n 0.9 a n d 1.0
ppm during the exposures.
D u r i n g t h e r a i n periods, t h e r a i n s o l u t i o n w a s s p r e a d f r o m two
n o z z l e s f i t t e d in t h e c e i l i n g of t h e c l i m a t e c h a m b e r . T h e n o z z l e s
t o g e t h e r g a v e a f l o w of ca. 17 dm3/h, c o r r e s p o n d i n g to a p r e c i p i t a t i o n
of ca. 175 mm/h. I n i t i a l l y d e i o n i z e d w a t e r w a s used. A f t e r
d e v e l o p m e n t of s u i t a b l e e q u i p m e n t , s u l f a t e c o n t a i n i n g r a i n w i t h a
c h o s e n p H w a s used.
T h e t e s t s c o n t i n u e d for two to s i x weeks. D u r i n g the
e x p o s u r e s , t w o to s i x p a r a l l e l s a m p l e s w e r e used. T h e test p l a t e s
w e r e w i t h d r a w n at w e e k l y i n t e r v a l s . W h e n a set of test p l a t e s w a s
w i t h d r a w n , n e w p l a t e s w e r e i n s e r t e d in o r d e r to k e e p the s a m e
q u a n t i t y of test m a t e r i a l in t h e c h a m b e r d u r i n g t h e w h o l e e x p o s u r e
period.
Test series i: Influence of the r a i n p e r i o d
T h i s test s e r i e s c o n s i s t e d of e x p o s u r e s with three different

lengths of r a i n p e r i o d s .
Rain periods: 45 m i n e v e r y 3 r d day; 3 h every 3 r d day; 6 h every

3rd day
Rain solution: deionized water
Temperature: 40oC
Test series 2: Influence of the t e m n e r a t u r e
T h i s test series consisted of e x p o s u r e s at t h r e e d i f f e r e n t

temperatures.
Rain period: 3 h every 3rd day
Rain solution: Deionized water acidified with sulfuric acid and
a d j u s t e d to p H 4 b y small a d d i t i o n s of s o d i u m
h y d r o x i d e . T h e s o l u t i o n h a d a s u l f a t e c o n t e n t of
ca. 50 m g / l i t r e a n d a c o n d u c t i v i t y of ca. 170
~S/cm.
Temperature: 20~ 30~ and 40~
EVALUATION
Mass loss d e t e r m i n a t i o n
T h e c o r r o s i o n a t t a c k s of t h e test p l a t e s w e r e d e t e r m i n e d as
d i f f e r e n c e b e t w e e n t h e m a s s of t h e p l a t e s b e f o r e a n d a f t e r e x p o s u r e .
The corrosion products were removed by repeated pickling. The
c o n t r i b u t i o n t o m a s s loss f r o m a t t a c k o n the m e t a l b y p i c k l i n g a g e n t
w a s c o m p e n s a t e d b y e x t r a p o l a t i o n of the l i n e a r r e l a t i o n b e t w e e n m a s s
loss a n d p i c k l i n g t i m e to zero p i c k l i n g time. C a r b o n s t e e l w a s
p i c k l e d in C l a r k e ' s solution, (HCI i00 ml, Sb203 2 g, SnCI 2 5 g; see
A S T M s t a n d a r d G-I, A n n e x AI, s o l u t i o n C3.1) 6 x I0 min, a n d z i n c in 5
% b y v o l u m e a c e t i c a c i d solution, 4 x i0 min.
Analysis of c o r r o s i o n products
C o r r o s i o n p r o d u c t s f r o m c a r b o n steel a n d zinc w e r e i d e n t i f i e d
by the u s e of p o w d e r X - r a y d i f f r a c t i o n . G u i n i e r - H & g g c a m e r a s w i t h
CrK~I - or C U K ~ l - r a d i a t i o n w e r e used. T o e v a l u a t e t h e X - r a y
d i f f r a c t i o n p a t t e r n s , a "LS 18 f i l m s c a n n e r " w a s used. H i g h l y
p u r i f i e d s i l i c o n w a s u s e d for c a l i b r a t i o n .
In t h e c a s e of c a r b o n steel, t h e f o l l o w i n g lines w e r e r e g a r d e d
as the s t r o n g e s t c h a r a c t e r i s t i c line for e a c h phase: ~ - F e O O H d=4.18:
y - F e O O H d=6.26; Fe304 d = 2 . 9 5 ; FeSO4.4H20 d = 4 . 4 7 ; ~ - F e O O H d = 7 . 4 0 . T h e
r e l a t i v e q u a n t i t y of e a c h p h a s e w a s a s s u m e d to b e p r o p o r t i o n a l to t h e
i n t e n s i t y of t h e lines.
RESULTS
Environmental data
A comparison of the p r e c i p i t a t i o n at the d i f f e r e n t test sites,
as s h o w n in T A B L E I, i n d i c a t e s that o v e r the five y e a r p e r i o d the

p r e c i p i t a t i o n was 40% g r e a t e r in the i n d u s t r i a l a t m o s p h e r e (3862 mm)
t h a n in the u r b a n a t m o s p h e r e . T h e total a m o u n t of p r e c i p i t a t i o n is of
the s ~ n e m a g n i t u d e to that in the c l i m a t e c h a m b e r e x p o s u r e w h e r e the
r a i n q u a n t i t y d u r i n g a 4 - w e e k p e r i o d in the test w i t h 3 h e v e r y 3 r d
day a m o u n t e d to a b o u t 4800 mm. T h i s m e a n s that, w i t h r e g a r d to r a i n
quantity, four weeks' e x p o s u r e in a c l i m a t e c h a m b e r w i t h 3 h r a i n
e v e r y 3rd d a y a p p r o x i m a t e l y c o r r e s p o n d e d to five y e a r s in the
i n d u s t r i a l test of B o r r e g a a r d .
T h e m e a n v a l u e of pH of the rain, o v e r five y e a r s in the
rural, u r b a n a n d m a r i n e a t m o s p h e r e s was a p p r o x i m a t e l y the same, p H
4.3-4.4. In the i n d u s t r i a l a t m o s p h e r e , the m e a s u r e d p H of r a i n w a s
lower, a v e r a g e pH 3.9. T h e c o n d u c t i v i t y of the r a i n w a s h i g h e r in the
i n d u s t r i a l a t m o s p h e r e (77 ~S/cm) t h a n in the m a r i n e a n d u r b a n
a t m o s p h e r e s (55 a n d 48 DS/cm). T h e c o n d u c t i v i t y of the r a i n in test
s e r i e s 2 was c o n s i d e r a b l y higher, 170 DS/cm, t h a n that of o r d i n a r y
rain. T h i s w a s not, however, the c a s e in test s e r i e s 1 w h e r e
d e i o n i z e d w a t e r was used.
T h e a v e r a g e "time of wetness', d e f i n e d as the p e r i o d d u r i n g
w h i c h the r e l a t i v e h u m i d i t y e x c e e d s 80% a n d the t e m p e r a t u r e is h i g h e r
than 0~ d u r i n g the 5 - y e a r p e r i o d in the i n d u s t r i a l a t m o s p h e r e was
258 h o u r s p e r month. D u r i n g the c l i m a t e c h a m b e r e x p o s u r e w i t h 3 h
rain e v e r y 3 r d day, the "time of w e t n e s s " is a p p r o x i m a t e l y e q u a l to
the sum of the h u m i d p e r i o d a n d r a i n p e r i o d a n d a b o u t i h o u r of the
d r y i n g p e r i o d . T h e "time of w e t n e s s " is thus a b o u t 810 h o u r s / 6 w e e k s
w h i c h c o r r e s p o n d s to a b o u t 580 h o u r s / m o n t h . H e n c e the o u t d o o r test
p l a t e s w e r e e x p o s e d to "wet c o n d i t o n s " 36 % of the total t i m e a n d the
c h a m b e r p l a t e s for 80 %.
In sun~ary, all f a c t o r s i n c l u d e d in the c l i m a t e c h a m b e r test
w e r e m o r e s e v e r e t h a n ' i n the field test.
F i e l d test r e s u l t s
In the c a s e of c a r b o n steel, the c o r r o s i o n was g r e a t e r for

test p l a t e s e x p o s e d in an o p e n l o c a t i o n t h a n in a r a i n - p r o t e c t e d
l o c a t i o n at all f i e l d s t a t i o n s for short t e r m e x p o s u r e (3 m o n t h s ) ,
FIG i. This was a l s o t r u e for p e r i o d s as long as five y e a r s in
r e l a t i v e l y c l e a n a t m o s p h e r e s like R y d a and, to a c e r t a i n extent,
Vanadis. In the i n d u s t r i a l a n d m a r i n e a t m o s p h e r e s , a b o u t 40% g r e a t e r
m a s s losses w e r e r e c o r d e d a f t e r five y e a r s in the r a i n - p r o t e c t e d
l o c a t i o n s t h a n a f t e r o p e n exposure. T h i s shows that in e n v i r o n m e n t s
w i t h a large q u a n t i t y of a i r b o r n e c o n t a m i n a t i o n s u c h as c h l o r i d e a n d
s u l f u r dioxide, the f a v o r a b l e w a s h i n g e f f e c t of the rain, w h i c h g i v e s
a c o m p a r a t i v e l y lower r a t e of corrosion, p r e d o m i n a t e s at l o n g e r times
of exposure.
In less p o l l u t e d a t m o s p h e r e s , on the o t h e r hand, the w e t t i n g
e f f e c t of the r a i n by s u p p l y of e l e c t r o l y t e has a g r e a t e r r e l a t i v e
c o n t r i b u t i o n to the c o r r o s i o n than the c u m u l a t i o n of a i r b o r n e
c o n t ~ n i n a n t s . In all e n v i r o n m e n t s , the r a t e of c o r r o s i o n of c a r b o n
steel d e c r e a s e d w i t h time.
T h e X - r a y d i f f r a c t i o n a n a l y s i s of the c o r r o s i o n p r o d u c t s on
c a r b o n steel f r o m rural, u r b a n a n d i n d u s t r i a l a t m o s p h e r e s s h o w e d that
these contained p r i m a r i l y ~ - F e O O H a n d y-FeOOH, as s h o w n in T A B L E 2.
A f t e r the short e x p o s u r e times in an u r b a n a t m o s p h e r e (i month) a n d
an i n d u s t r i a l a t m o s p h e r e (3 m o n t h s ) , FeSO4.H20 w a s a l s o d e t e c t e d .
A f t e r the e x p o s u r e in the c h l o r i d e - c o n t a i n i n g m a r i n e a t m o s p h e r e ,
~ - F e O O H was a l s o found in the c o r r o s i o n p r o d u c t s on m a n y of the test
plates. T h e r a t i o ~ - F e O O H / y - F e O O H w a s in all c a s e s lower a f t e r o p e n
than a f t e r r a i n - p r o t e c t e d exposure.
In the S O 2 - c o n t a m i n a t e d i n d u s t r i a l a t m o s p h e r e , the r e l a t i v e
a m o u n t of ~ - F e O O H i n c r e a s e d w i t h time d u r i n g the o p e n exposure. In
TABLE i. A v e r a g e v a l u e s o v e r a 5 - y e a r p e r i o d of a n a l y s i s of a t m o s p h e r i c precipitation, time of h3
wetness, chloride deposition a n d g a s e o u s p o l l u t i o n at t h e d i f f e r e n t t e s t s i t e s . 4~
4~
Test site Rainwater CI- Time of SO2,

deposition, wetness, ~g/m 3 >
Total pH Conduc- S042- , Cl-, mg/m 2 , day h/year
amount, tivity,
mm ~S/cm mg/l mg/l O
O9
Rural 2411 4.3 36 3.6 0.6 3700 2.6 I
m
Urban 2687 4.4 48 5.7 1.5 - 3300 12.0 5
Industrial 3862 3.9 77 ii 5.9 - 3000 O
64 O
Marine 2777 4.3 55 5.1 6.4 439 3500 4.0 nl
O
CO
TABLE 2. Relative intensities of p h a s e s i d e n t i f i e d w i t h X - r a y diffraction in c o r r o s i o n products from 5
carbon steel exposed in f r e e a n d s h e l t e r e d p o s i t i o n s at t e s t s i t e s . Z
Test Exposure Free Sheltered

site time
FeOOH FeOOH
FeSO4.4H 2 ~/~ FeSO4-4H 2 ~/y
Y O Y O
Rural i year 41 I00 - 0.4 i00 46 2.2

5 years 26 i00 14 0.3 I00 76 1.3
Urban I month - 100 I00
3 months ii i00 - 0.i i00 97 1.0
1 year 47 100 - 0.5 100 23 4.4
5 years 47 i00 - 0.5 i00 32 3.2
Indus- 3 months 40 i00 - 0.4 93 i00 7 0.9
trial 1 year I00 96 1.0 I00 25 4.0
5 years I00 54 1.9 i00 24 4.1
Marine 3 months 43 100 0.4 62 i00 0.6
1 year 47 i00 19 0.2 93 I00 0.9
5 years 65 i00 I0 0.6 I00 34 21 2 2.9
t h e c a s e of t h e op,r~n e x p o s u r e s in rural a n d u r b a n a t m o s p h e r e s , y - F e O O H
was still the predominant phase after five years. The results
i n d i c a t e that t h e r a t e of t r a n s f o r m a t i o n of y - F e O O H t o ~ - F e O O H
i n c r e a s e s w i t h i n c r e a s i n g S O 2 - c o n t e n t a n d w h e n t h e surface is
p r o t e c t e d from washing.
In t h e c o r r o s i o n p r o d u c t s f r o m t h e e x p o s u r e in a m a r i n e
a t m o s p h e r e , ~ - F e O O H w a s d e t e c t e d a f t e r i y e a r ' s e x p o s u r e in a n o p e n
location. In the c a s e of test p l a t e s e x p o s e d in a r a i n - p r o t e c t e d
location, ~ - F e O O H w a s f o u n d in the c o r r o s i o n p r o d u c t s a f t e r 5 years'
exposure.
Mass loss, g/m 2
2000 [] 3 months
Open Sheltered
exposure exposure [] 1 year
9 5 years
1500 ............................
i000 ..........................
500 . . . . . . . . . . . . . . . . . . . . . .
F i g u r e I. M a s s l o s s e s for carbon steel plates in open and sheltered

field exposures.
T h e c o r r o s i o n of zinc w a s h i g h e r for o p e n e x p o s u r e t h a n in t h e
r a i n - p r o t e c t e d l o c a t i o n s in rural, u r b a n a n d i n d u s t r i a l a t m o s p h e r e s
d u r i n g all e x p o s u r e times, F I G 2. In t h e c h l o r i d e - c o n t a i n i n g m a r i n e
a t m o s p h e r e , o n the o t h e r hand, h i g h e r c o r r o s i o n w a s o b s e r v e d a l r e a d y
a f t e r 1 y e a r in a r a i n - p r o t e c t e d l o c a t i o n t h a n in t h e o p e n e x p o s u r e .
In the m a r i n e a t m o s p h e r e , the w a s h i n g a w a y b y r a i n of a g g r e s s i v e
c h l o r i d e s h a s a f a v o r a b l e i n f l u e n c e so that t h e c o r r o s i o n is reduced.
It m a y b e p o i n t e d out t h a t zinc c h l o r i d e is v e r y h y g r o s c o p i c , w h i c h
m a k e s it p o s s i b l e for zinc s u r f a c e s to r e m a i n m o i s t for a l o n g t i m e
in a r a i n - p r o t e c t e d location.
A f t e r 1 y e a r ' s o p e n e x p o s u r e , t h e m a s s loss of t h e z i n c w a s
t h e s a m e in t h e r u r a l a n d u r b a n a t m o s p h e r e s . A f t e r t h e 1 - y e a r
r a i n - p r o t e c t e d e x p o s u r e , on t h e o t h e r hand, t h e m a s s loss in a n u r b a n
a t m o s p h e r e was 2.5 t i m e s h i g h e r t h a n that in t h e r u r a l atmosphere.
The c o r r o s i o n rate for zinc was h i g h e r d u r i n g the first years of

e x p o s u r e in c o m p a r i s o n to the longer e x p o s u r e s at all the test sites.
The d i f f e r e n c e was highest in the rural site.
Zinc h y d r o x i d e c a r b o n a t e (Zns(CO3)2(OH)6) was i d e n t i f i e d only
in the rural and m a r i n e atmospheres, as shown in T A B L E 3. In the case
of the e x p o s u r e in a r a i n - p r o t e c t e d location in the rural and urban
a t m o s p h e r e s zinc h y d r o x i d e sulfate, Zn4(OH)6SO 4- nH20, was identified.
In c o r r o s i o n p r o d u c t s formed in b o t h r a i n - p r o t e c t e d and o p e n e x p o s u r e
in industrial atmosphere, Zn4CI2(OH)4SO4.5H20 was detected. A f t e r
e x p o s u r e in both an open and a r a i n - p r o t e c t e d location in the
c h l o r i d e - c o n t a i n i n g m a r i n e atmospheres, the c o r r o s i o n p r o d u c t s
c o n t a i n e d a s o d i u m h y d r o x i d e zinc s u l f a t e chloride,
(NaZn4CI(OH)6SO4.6H20) and Zns(OH)gCI2-H20 (5).
Mass 10ss, g/m 2
120
Open Sheltered ID 3 months
exposure exposure [] 1 year
i00
........... I ...................... I" 5 years
80 -t . . . . . . . . . . . B- . . . . . . . . . . . . . . . . . . .
60 -t . . . . . . . . . . .
40 -t . . . . . . . . . . .
20
0 . . . . . . . . . . . . . . .
F i g u r e 2. Mass losses for zinc plates in open and sheltered field

exposures.
Climate chamber exoosure results
The results of test series i, in w h i c h the i n f l u e n c e of the

length of the rain p e r i o d was studied, show that the c o r r o s i o n
i n c r e a s e d for zinc d u r i n g long rain p e r i o d s (FIGS 3 and 4). The rate
of c o r r o s i o n of the zinc was highest d u r i n g the first w e e k and
t h e r e a f t e r decreased. The rate of c o r r o s i o n of c a r b o n steel i n c r e a s e d
slightly until the second w e e k and t h e r e a f t e r d e c r e a s e d after 4
weeks. This p r o b a b l y depends on the fact that the c o r r o s i o n is
initiated locally and then spreads over the s u r f a c e in the early
stage, after w h i c h the layer of c o r r o s i o n p r o d u c t s b e g i n s to exert a
p r o t e c t i v e effect.
TABLE 3. C o r r o s i o n products o n zinc p a n e l s identified with X-ray diffraction analys~s.
Site Free/ 3 months 1 year 5 years

Sheltered
Rural Free Not analysed Zn5(CO3)2(OH) 6 Zn5(CO3)2(OH) 6 -I-

>
Sheltered Not analysed Zn4(OH)6SO4.nH20 Zn4(OH)6SO4.nH20 Z
GO
GO
0
Urban Free Zn4(OH)6SO4.nH20 Zn4(OH)6SO4-nH20 Zn4(OH)6SO4.nH20 Z
ZnO
Z
0
Sheltered Zn4(OH)6SO4.nH20 Zn4(OH)6SO4-nH20 Zn4(OH)6SO4.nH20 G-)
ZnSO4-H20 ZnSO4-H20 C
r-
r-
Industrial Free probably: >
Z
Zn4CI2(OH)4SO4-5H20
0
Z
Sheltered ZnSO4-H20 ZnSO4-H20 ZnSO4-H2 O 0
Zn4CI2(OH)4SO4.5H20 Zns(OH)sCI2-H20 Zn4CI2(OH)4SO4-5H20 >
"11
Zn4CI2(OH)4SO4.SH20
0
Z
Marine Free Zn5(CO3)2(OH) 6 Zns(CO3)2(OH)6 ZnO
NaZn4CI(OH)6SO4-6H20 NaZn4CI(OH)6SO4.6H20 N a Z n 4 C I (OH) 6SO 4 9 6H20 m
m
r-
Zn5(CO3)2(OH) 6 Zns(OH)sCI2-H20 N a Z n 4 C I (OH) 6SO 4 9 6H20 >
Sheltered NaZn4CI(OH)6SO4-6H20 NaZn4CI(OH)6SO4-6H20 z
N
O
4~
"4
Mass loss, g/m 2

5OO 0.75h/3rd day
- -m -
400 ............................ 3h/3rd day
6h/3rd day
300
200
i00
0
0 1 2 3 4 5 6 7
Exposure time, weeks
F i g u r e 3. M a s s losses for c a r b o n steel p l a t e s e x p o s e d in c l i m a t e c h a m b e r
at d i f f e r e n t t i m e of rain.
T h e m a s s loss in the c a s e of the c a r b o n s t e e l w a s b e t w e e n

1 5 0 - 2 0 0 g / m 2 a f t e r 2 weeks' exposure. T h i s c o r r e s p o n d s to 1 y e a r ' s
e x p o s u r e in an u r b a n a t m o s p h e r e . T h e m a s s loss of the zinc w a s
b e t w e e n 3.1 a n d 4.9 g / m 2 a f t e r 2 weeks, w h i c h c a n be c o m p a r e d w i t h 9.5
g / m 2 a f t e r 1 y e a r ' s o p e n exposure. W h e n the l e n g t h of the r a i n p e r i o d
w a s i n c r e a s e d by a f a c t o r of four (from 0.75 to 3 h), the m a s s loss
i n c r e a s e d a f t e r 2 w e e k s by 12% for c a r b o n steel a n d 29% for zinc.
L o n g e r wet times a p p e a r to h a v e a g r e a t e r i n f l u e n c e on the c o r r o s i o n
of zinc t h a n on the c o r r o s i o n of c a r b o n steel. T h e tests s h o w that 2
weeks' e x p o s u r e is p r o b a b l y too short. T h e e x p o s u r e t i m e s s h o u l d be
so long that the c o r r o s i o n p r o c e s s has e n t e r e d the s t e a d y state.
T h e a n a l y s i s of the c o r r o s i o n p r o d u c t s on c a r b o n steel s h o w e d
that in all t h r e e tests t h e s e c o n t a i n e d ~ - F e O O H , y - F e O O H a n d Fe304
(TABLE 4). T h e r e l a t i v e p r o p o r t i o n s of y - F e O O H a n d Fe304 i n c r e a s e d
w i t h i n c r e a s i n g l e n g t h of the r a i n p e r i o d s . T h e r a t i o ~ - F e O O H / y - F e O O H
w h i c h thus d e c r e a s e d d u r i n g a p r o l o n g e d r a i n period, w a s i0 w i t h 0.75
h r a i n e v e r y 3 r d day, 4 w i t h 3 h e v e r y 3 r d day a n d 2 w i t h 6 h e v e r y
3rd day. T h e r a t i o ~ - F e O O H / y - F e O O H o b s e r v e d for the tests w i t h 3 h
r a i n e v e r y 3rd day was of the s~ne m a g n i t u d e as that a f t e r the rain-
p r o t e c t e d e x p o s u r e for 1 and 5 y e a r s in u r b a n a n d i n d u s t r i a l
a t m o s p h e r e s . T h e r a t i o ~ - F e O O H / y - F e O O H for the t e s t i n g w i t h 6 h r a i n
e v e r y 3 r d day was c o m p a r a b l e to that a f t e r 1 a n d 5 years' o p e n
e x p o s u r e in an i n d u s t r i a l a t m o s p h e r e .
T h e a n a l y s e s of the c o r r o s i o n p r o d u c t s of the zinc s h o w e d that
it was o n l y a f t e r the test w i t h 3 h r a i n e v e r y 3 r d d a y that m o r e t h a n
t r a c e s of a c r y s t a l l i n e compound, ZnO, c o u l d b e f o u n d on t h e s u r f a c e
(TABLE 4). Zinc o x i d e w a s a l s o d e t e c t e d d u r i n g the short exposure, 3
m o n t h s in an o p e n l o c a t i o n in an u r b a n a t m o s p h e r e .
-r
TABLE 4. C o r r o s i o n p r o d u c t s i d e n t i f i e d w i t h X - r a y d i f f r a c t i o n a n a l y s e s o n c a r b o n s t e e l a n d zinc plates
e x p o s e d in c l i m a t e c h a m b e r . R e l a t i v e i n t e n s i t i e s of p h a s e s on c a r b o n s t e e l . Z
GO
Oo
0
Carbon steel Zinc Z
Exposure ~-FeOOH ~- Z
Fe304 ~/~ (D
time, FeOOH
weeks C
i'-
i'-
Test series 1
0.75 h/3rd day I00 I0 18 10 7 Z n ( O H ) 2 - 2 Z n S O 4 . H 2 0 (week t r a c e s ) >
3 h/3rd day Z
I00 23 36 4.3 ZnO; 7 Z n ( O H ) 2 . 2 Z n S O 4 . H 2 0 (week
6 h/3rd day i00 66 70 1.5 traces) 0
Z
>
Test series 2
20 ~ i00 54 Z n S O 4 9 4H20 0
30~ i00 12 28 8.3 Z
40 ~ i00 19 48 5.3 GO
m
m
>
Z
0
N
rO
Mass loss, g/m 2
6 0.75h/3rd day
- -m -
3h/3rd day
5 . . . . .~. "
.I 2 ~A . . . . . . . . . . . . . . . . . . . .
4 ---/ .... - ................. 6h/3rd day
3 --/---;'" .....................
2 / ,m'"
0
0 1 2 3 4 5 6 7
F i g u r e 4. M a s s l o s s e s f o r zinc plates exposed in climate ch~nber at
different t i m e of rain.
In ~ @ ~ t s e r i e s 2, t h e i n f l u e n c e o f t h e t e m p e r a t u r e on the
c o r r o s i o n of c a r b o n s t e e l a n d z i n c w a s s t u d i e d . T h e r a i n p e r i o d w a s
in t h i s s e r i e s 3 h e v e r y 3 r d d a y a n d t h e p H of t h e r a i n w a s 4. T h e
r e s u l t s of t h e m a s s l o s s d e t e r m i n a t i o n s on carbon steel showed no
g r e a t d i f f e r e n c e b e t w e e n t h e t h r e e t e s t s (FIG 5). A f t e r f o u r w e e k s
e x p o s u r e , t h e m a s s loss w a s 3 3 8 g / m 2 at 3 0 ~ a n d 3 8 1 g / m 2 a t 40~ The
zinc, o n t h e o t h e r hand, s h o w e d a m a r k e d l y g r e a t e r m a s s l o s s at 2 0 ~
t h a n at 3 0 ~ and 40~ (FIG 6 ) . T h e g r e a t d i f f e r e n c e in t h e m a s s l o s s
of z i n c is n o t c o m p l e t e l y u n d e r s t o o d . One influence could be that the
d r y i n g u p t i m e s a r e l o n g e r at t h e l o w e r t e m p e r a t u r e . From
measurements of f l o w r a t e s of SO 2 i n t o t h e c h a m b e r it h a s b e e n
o b s e r v e d t h a t imJch m o r e SO 2 w a s c o n s u m e d b y t h e z i n c s u r f a c e s d u r i n g
t h e e x p o s u r e at 20 ~ t h a n at t h e h i g h e r t e m p e r a t u r e s . One possible
explanation may be that protective corrosion products are formed more
e a s i l y o n z i n c at t h e h i g h e r t e m p e r a t u r e s . S u c h a l a y e r of c o r r o s i o n
products, if it e x i s t s m u s t , h o w e v e r , b e v e r y t h i n o r a m o r p h o u s since
it h a s n o t b e e n p o s s i b l e t o d e t e c t it b y X - r a y d i f f r a c t i o n .
The X-ray diffraction a n a l y s e s of t h e c o r r o s i o n p r o d u c t s f r o m
t h e c a r b o n s t e e l t e s t s s h o w e d n o y - F e O O H in t h e c a s e o f t h e
20~ in c o n t r a s t to t h e t w o o t h e r e x p o s u r e s . In t h e c a s e of
the 30~ and 40~ - e x p o s u r e s , t h e ~ y r a t i o w a s 8.3 a n d 5.3
respectively (TAB 4). T h e s e v a l u e s a r e s i m i l a r to t h o s e r e c o r d e d
after rain-protected e x p o s u r e in t h e u r b a n a n d i n d u s t r i a l
atmospheres.
In t h e c a s e of t h e zinc, it w a s o n l y at t h e l o w e s t t e m p e r a t u r e
t h a t a n y c o m p o u n d , Z n S O 4. 4H20, w a s d e t e c t e d in t h e c o r r o s i o n p r o d u c t s
(TAB 4). H e r e t h e c o r r o s i o n r a t e w a s at l e a s t f i v e t i m e s h i g h e r t h a n
at t h e o t h e r t e m p e r a t u r e s . The amount of corrosion products formed
after the last rain was large enough to be sampled for X-ray
diffraction a n a l y s i s . Z i n c s u l f a t e w a s a l s o d e t e c t e d in c o r r o s i o n
p r o d u c t s o n z i n c p l a t e s e x p o s e d in a r a i n - p r o t e c t e d l o c a t i o n in u r b a n
and industrial atmospheres.
Mass loss, g/m 2
500 20 ~
.4
- -I -
..~-
400 ................... it-" ............ 30 ~
40 OC
300 . . . . . . . . . . . . . .
/
z'_~"
. .1 .................. *
200 ........
100
0
0 1 2 3 4 5 6 7
F i g u r e 5. M a s s l o s s e s f o r c a r b o n steel plates exposed in c l i m a t e ch~nber
at d i f f e r e n t t e m p e r a t u r e s .
Mass loss, g/m a
50 20 ~
40 . . . . . . . . . . . . . . . . . . . . .1 . . . . . . . . . . . . . . .
30 ~
1 40 ~
30 . . . . . . . . . . . . . ~. . . . . . . . . . . . . . . . . . . . .
II"
20 . . . . . . . . . 9. . . . . . . . . . . . . . . . . . . . . . . . . .
I0 - - - ; . . . . . . . . . . . . f - ~ ..............
0 ~1~ I I I I I I
0 1 2 3 4 5 6

F i g u r e 6. M a s s l o s s e s f o r zinc plates exposed in climate chamber at
different temperatures.
DISCUSSION
CLIMATE CHAMBER EXPOSURE VERSUS FIELD EXPOSURE
General
During accelerated tests, it is o f i n t e r e s t t o n o t e w h i c h

acceleration f a c t o r for t h e d e t e r i o r a t i o n of d i f f e r e n t m a t e r i a l s a n d
c o a t i n g s is o b t a i n e d in r e l a t i o n to f i e l d e x p o s u r e s . During the
development of a n a c c e l e r a t e d t e s t m e t h o d , it w o u l d of c o u r s e b e
desirable if d i f f e r e n t m a t e r i a l s a n d c o a t i n g s a l l e x h i b i t e d t h e s a m e
value of the acceleration factor relating the accelerated t e s t i n g to
field exposure conditions. This may be impossible to attain, since
the corrosion mechanisms f o r d i f f e r e n t m a t e r i a l s a r e of d i f f e r e n t
kinds.
For an accelerated test to be relevant, i.e. if it is p o s s i b l e
t o u s e for p r e d i c t i n g h o w m a t e r i a l s w i l l c o r r o d e u n d e r u s e
conditions, it is a l s o n e c e s s a r y t h a t t h e c o r r o s i o n m e c h a n i s m s during
t h e t e s t p e r i o d a r e t h e s a m e as t h o s e u n d e r p r a c t i c a l u s e c o n d i t i o n s .
T h e c o r r o s i o n a t t a c k s of c a r b o n s t e e l a f t e r f o u r w e e k s o f
e x p o s u r e in t h e a c t u a l t e s t s a r e of t h e s a m e m a g n i t u d e as f i v e y e a r s '
f i e l d e x p o s u r e in t h e r u r a l a n d t h e u r b a n a t m o s p h e r e s T h i s is a l s o
a b o u t t h e s a m e as for o n e y e a r e x p o s u r e in t h e i n d u s t r i a l a t m o s p h e r e .
This corresponds to c o r r o s i v i t y c a t e g o r y C 3 - C 4 a c c o r d i n g to I S O
9223.(6)
In t h e c a s e of zinc, o n l y t h e e x p o s u r e at 2 0 ~ gives mass
l o s s e s of a m a g n i t u d e e q u a l to o r g r e a t e r t h a n t h a t o b s e r v e d a f t e r
o n e y e a r of o p e n e x p o s u r e in a n i n d u s t r i a l a t m o s p h e r e .
W h e n t h e r u s t l a y e r o n c a r b o n s t e e l is u n d e r d e v e l o p m e n t the
c o r r o s i o n r a t e is c o n t i n u o u s l y d e c r e a s i n g . W h e n a s t e a d y s t a t e of t h e
r u s t l a y e r is o b t a i n e d a c o n s t a n t c o r r o s i o n r a t e c a n b e e x p e c t e d . In
t e s t s e r i e s 2, t h i s s h o u l d o c c u r a f t e r e x p o s u r e t i m e s l o n g e r t h a n
f o u r w e e k s f o r c a r b o n s t e e l . F o r zinc, t h e s t e a d y s t a t e w a s a t t a i n e d
a l r e a d y a f t e r o n e t o t w o w e e k s . In f i e l d e x p o s u r e t h i s s t e a d y s t a t e
is u s u a l l y o b t a i n e d for c a r b o n s t e e l a f t e r s o m e y e a r s . F o r z i n c t h e
s t e a d y s t a t e c o r r o s i o n r a t e is u s u a l l y o b t a i n e d in a f e w m o n t h s .
Corrosion mechanisms
During the climate chamber exposure, the corrosion on carbon

s t e e l is v e r y s i m i l a r to t h a t d u r i n g t h e f i e l d e x p o s u r e s . A f t e r a n
introductory p e r i o d of a w e e k o r so w i t h a h i g h r a t e of c o r r o s i o n ,
the rate decreases. As w i t h o u t d o o r e x p o s u r e , t h e r u s t l a y e r t h a t h a s
been built up on the surface gives partial protection against
continued corrosion. The corrosion reactions on carbon steel are
f a v o r e d b y t h e a d d i t i o n of S O 2 w h i c h is a b s o r b e d a n d o x i d i z e d in t h e
r u s t l a y e r t o SO42- . S u l f a t e i o n s a r e d e p o s i t e d o n a n o d i c s u r f a c e s a n d
g i v e r i s e t o s o c a l l e d s u l f a t e n e s t s . T h i s w a s o b s e r v e d a q u a r t e r of
a century ago by Schwarz (7). S i n c e t h e c o r r o d e d m e t a l s u r f a c e
b e c o m e s wet, t h e s u l f a t e n e s t s b e c o m e a c t i v e c o r r o s i o n c e l l s t o g e t h e r
with intermediate cathodic surfaces. The anodic surfaces are
stabilized inside the sulfate nests, where the pH becomes low
c o m p a r e d w i t h that of t h e a d j a c e n t c a t h o d i c s u r f a c e s . T h e m a i n
c a t h o d i c r e a c t i o n is o x y g e n r e d u c t i o n :
89 02 + H20 + 2e- - 2OH-
T h i s c a u s e s a n i n c r e a s e in t h e p H w h i c h s t i m u l a t e s the
precipitation of s o l i d c o r r o s i o n p r o d u c t s . In a l i m i t e d o x y g e n
supply, the cathodic reduction becomes according to E v a n s (8):
8 FeOOH + F e 2§ + 2e- -- 3Fe304 + 4H20
A r e d u c e d o x y g e n s u p p l y is o b t a i n e d e.g. w h e n t h e s u r f a c e is
so w e t t h a t t h e o x y g e n d i f f u s i o n t h r o u g h t h e c o r r o s i o n p r o d u c t s is
r e p r e s s e d . T h i s a g r e e s w i t h t h e r e s u l t s o b t a i n e d in t h e
investigation. Corrosion products from the climate chamber exposure
contain considerably more magnetite (Fe304) t h a n t h o s e f r o m t h e f i e l d
exposures. This can be explained by the assumption that the oxygen
diffusion becomes insufficient, at l e a s t d u r i n g r a i n p e r i o d s , to
s u p p o r t t h e h i g h r a t e s of c o r r o s i o n w h i c h e x i s t in t h e c l i m a t e
chamber exposure, in c o m p a r i s o n w i t h t h a t for o u t d o o r e x p o s u r e . A
reduction in o x y g e n s u p p l y t h a t s t i m u l a t e s t h e f o r m a t i o n o f m a g n e t i t e
is s h o w n a l s o in t e s t s e r i e s i. T h e c o n t e n t of m a g n e t i t e d e c r e a s e s
w h e n t h e l e n g t h of t h e r a i n p e r i o d s d e c r e a s e s .
The wetness conditions during the climate ch~nber exposures
are more severe than during outdoor exposure. This has obviously
changed the conditions for the cathodic reactions possible. During
outdoor exposure damp conditions rather than wet ones seem to
p r e v a i l . D u r i n g t h e s e d a m p c o n d i t i o n s t h e d i f f u s i o n b a r r i e r in t h e
form of a water film does not exist. Instead the porous corrosion
p r o d u c t s c a n b e p e n e t r a t e d b y o x i d i z i n g air.
In n e u t r a l a n d s l i g h t l y a c i d s o l u t i o n s , t h e c o r r o s i o n o n i r o n
b e g i n s b y t h e f o r m a t i o n of y - F e O O H (9) a c c o r d i n g to:
Fe ~ F e 2§ + 2e-
F e 2+ + OH- ~ FeOH +
2 F e O H + + H20 + 89 02 - 2 FeOOH + 2H +
A h i g h r a t e of S O 2 d e p o s i t i o n a l s o i n c r e a s e s t h e t r a n s f o r m a t i o n
f r o m y - F e O O H to ~ - F e O O H . T h i s t r a n s f o r m a t i o n , w h i c h is f a v o u r e d b y a
high sulfate content, has also been observed previously at S w e d i s h
field stations (i0). D u r i n g t h e f i e l d e x p o s u r e s r e p o r t e d here, it h a s
b e e n s h o w n t h a t the t r a n s f o r m a t i o n f r o m y - F e O O H to ~ - F e O O H is m o r e
extensive during the rain-protected exposures, where no washing takes
place than during open exposures. In t e s t s e r i e s i, it h a s a l s o b e e n
shown that shorter rain periods, which causes higher oxygen diffusion
in t h e c o r r o s i o n p r o d u c t s , g i v e a h i g h e r r e l a t i v e a m o u n t o f ~ - F e O O H .
In t e s t s e r i e s 2, in w h i c h t h e i n f l u e n c e of t e m p e r a t u r e on the
corrosion was investigated, no y-FeOOH was obtained during the
20~ in c o n t r a s t t o t h e 3 0 ~ - a n d 4 0 ~
In t h e c l i m a t e c h a m b e r e x p o s u r e s , t h e r a t e of c o r r o s i o n of
z i n c w a s v e r y h i g h d u r i n g t h e f i r s t w e e k . T h e r a t e of c o r r o s i o n w a s
in m o s t c a s e s c o n s i d e r a b l y lower after two weeks exposure. The most
i m p o r t a n t e x c e p t i o n was o b s e r v e d d u r i n g e x p o s u r e at 20~ a s s h o w n in
F I G 6. A p o s s i b l e e x p l a n a t i o n for t h i s is t h a t u n d e r m o s t t e s t
conditions t h e z i n c is c o a t e d w i t h a p r o t e c t i v e l a y e r of c o r r o s i o n
p r o d u c t s a f t e r t h e i n t r o d u c t o r y p e r i o d . T h i s is w e l l - k n o w n from
outdoor exposure. During the climate chamber exposure, these layers
h a v e b e c o m e v e r y thin. A t t e m p e r a t u r e s b e l o w c a 30~ it s e e m s t h a t
t h e y a r e n o t f o r m e d at all. In t h e f i e l d e x p o s u r e s , it w a s e v i d e n t
that the protective l a y e r c o n s i s t s m o s t l y of b a s i c z i n c s a l t s . T h e s e
layers decompose in a n a c i d e n v i r o n m e n t . T h e y a r e r e f o r m e d if t h e r e
is s u f f i c i e n t sulf~Lte or c a r b o n a t e o n t h e s u r f a c e a n d if t h e p H is
n o t t o o low. D u r i n g t h e c l i m a t e c h a m b e r e x p o s u r e , s u l f a t e h a s b e e n
s u p p l i e d in t h e f o r m of s u l f a t e - c o n t a i n i n g r a i n a n d as S O 2 - g a s w h i c h
has been oxidized after deposition on the surface. With such a strong
a d d i t i o n of acid, t h e c o r r o s i o n r e a c t i o n s c a n b e SUl~,arized as
follows:
02 + B20 + 2e- ~ 2OH- (i)
Zn ~ Z n 2+ + 2e- (2)
SO2(g) ~ SO 2 (aq) (3)
SO 2 (aq) + H20 ~ 2H + + SO32- (4)
02 + S032- ~ SO42- (5)
02 + SO 2 + Zn ~ Z n 2+ + SO42-
T h i s m e a n s t h a t n o b a s i c s a l t is f o r m e d o n t h e s u r f a c e . T h e s u r f a c e
is i n s t e a d c o v e r e d b y a n a q u e o u s s o l u t i o n of z i n c s u l f a t e . T h e
condition f o r t h e f o r m a t i o n of b a s i c s u l f a t e is t h a t r e a c t i o n (I) is
faster than the adsorption of SO 2 (g) o n t h e s u r f a c e , r e a c t i o n (3).
W h e n S O 2 is a d s o r b e d o n t h e s u r f a c e , it c a u s e s h y d r o g e n i o n s t o b e
produced, reaction (4). T h i s l e a d s to a d e c r e a s e in p H o n t h e s u r f a c e
whereas reaction (1) l e a d s t o a n i n c r e a s e in t h e p H - v a l u e . B e s i d e s
basic zinc sulfate, zinc oxide can also be formed. Grauer (Ii) s a y s
t h a t Z n O is f o r m e d at t h e r e l a t i v e l y l o w p H in t h e a n o d e s o l u t i o n
during the zinc corrosion. This zinc oxide forms crystals which do
not give surface protection.
The results of the investigation show great similarities
between the climate chamber exposures and the field exposures. During
the tests, all the factors which accelerate corrosion have been
i n c r e a s e d e x c e p t t h e o x y g e n c o n t e n t o f t h e air. It s e e m s t h e r e f o r e t o
h a v e b e e n l i m i t i n g in s o m e c a s e s for t h e s t e e l a n d z i n c c o r r o s i o n as
i n d i c a t e d in t h e d i s c u s s i o n above.
T h e r e s u l t s s h o w t h a t in f u r t h e r e f f o r t s to d e v e l o p a n
accelerated t e s t m e t h o d , t h e o t h e r f a c t o r s s h o u l d b e k e p t at s u c h a
l e v e l t h a t t h e o x y g e n s u p p l y is n o t l i m i t i n g . F o r e x a m p l e t h e l e n g t h
of t h e r a i n p e r i o d s h o u l d b e s h o r t e n e d , t h e g a s c o n t e n t s h o u l d b e
reduced and the temperature should be adapted so that the conditions
a g r e e b e t t e r w i t h o u t d o o r c o n d i t i o n s . T h i s also m e a n s t h a t c o n d i t i o n s
should be sought so that a disproportionately long part of the test
period does not give very wet conditions on the test plates.
CONCLUSIONS
By s t u d y i n g t h e c o r r o s i o n , w i t h r e g a r d to b o t h m a s s l o s s and
corrosion products formed, during climate chamber exposures and field
exposures, valuable knowledge has been obtained regarding the
improvement of test methods. Some of the most important results are
s u m m a r i z e d as f o l l o w s .
Field exposure
- T h e m a s s l o s s e s f o r c a r b o n s t e e l a f t e r f i v e y e a r s e x p o s u r e in
i n d u s t r i a l a n d m a r i n e a t m o s p h e r e s w e r e g r e a t e r in r a i n - p r o t e c t e d
locations where corrosive salts are accumulated t h a n in o p e n
l o c a t i o n s w h e r e t h e c o r r o d i n g s u r f a c e s a r e w a s h e d b y rain.
T h e c o r r o s i o n p r o d u c t s o n c a r b o n s t e e l f o r m e d d u r i n g e x p o s u r e in
rural, urban and industrial atmospheres contained primarily y-FeOOH
a n d ~ - F e O O H . A f t e r e x p o s u r e in a m a r i n e a t m o s p h e r e , the corrosion
products also contained ~-FeOOH.
The mass losses for zinc after five years exposure in rural, urban
a n d i n d u s t r i a l a t m o s p h e r e s w e r e g r e a t e r in o p e n l o c a t i o n s t h a n in
rain-protected locations where the corrosive salts are transformed in
sparingly soluble basic zinc salts.
- Zinc hydroxide carbonate was f o r m e d d u r i n g o p e n e x p o s u r e in r u r a l

and marine atmospheres. During e x p o s u r e in a r a i n - p r o t e c t e d location
in r u r a l a n d u r b a n a t m o s p h e r e s Zn4(OH) 6 S O 4 - n H 2 0 w a s f o r m e d . T h i s
c o m p o u n d w a s a l s o f o u n d in t h e corrosion products after open exposure
in a n u r b a n a t m o s p h e r e .
Climate chamber exDosure
- F o r b o t h c a r b o n s t e e l a n d z i n c t h e r e is a l o w e r c o r r o s i o n r a t e a t
l o n g e r e x p o s u r e s c o m p a r e d t o i n i t i a l p e r i o d s . T h i s e f f e c t is d u e t o
f o r m a t i o n of p a r t i a l l y p r o t e c t i v e corrosion products which are formed
b o t h o u t d o o r s a n d for c l i m a t e c h a m b e r e x p o s u r e .
- The corrosion products formed on carbon steel during the climate

chamber exposure contained relatively l a r g e a m o u n t s of m a g n e t i t e
(Fe304) in a d d i t i o n t o y - F e O O H a n d ~ - F e O O H .
- The corrosion attack on zinc was markedly higher at lower

temperature, 20 ~ t h a n at h i g h e r t e m p e r a t u r e 30 ~ a n d 40 ~ during
climate chamber exposure with high wetting time and addition of
sulfur dioxide.
- O n zinc, n o d e t e c t a b l e l a y e r of b a s i c s a l t w a s f o r m e d o n t h e
s u r f a c e d u r i n g t h e c l i m a t e c h ~ i b e r e x p o s u r e , a l t h o u g h it w a s f o r m e d
d u r i n g t h e f i e l d e x p o s u r e s . A v e r y t h i n l a y e r may, h o w e v e r , h a v e b e e n
formed.
- The corrosion products formed on carbon steel imply that the oxygen
transport has been repressed during the climate ch~nber exposure with
respect to the outdoor exposure conditions.
In f u t u r e c l i m a t e c h ~ n b e r e x p o s u r e , t h e e n v i r o n m e n t a l parameters
s h o u l d b e k e p t at s u c h a l e v e l t h a t t h e o x y g e n s u p p l y d o e s n o t b e c o m e
the limiting factor for the corrosion reactions. This means among
o t h e r t h i n g s t h a t t h e l e n g t h of t h e r a i n p e r i o d s h o u l d b e s h o r t e n e d .
T h e a d v a n t a g e of m e a s u r i n g the consumption of t h e s u l f u r d i o x i d e
d u r i n g t h i s t y p e of c l i m a t e c h a m b e r e x p o s u r e s w a s s h o w n .
A C K N O W L E D G E M E N T S
W e w i s h to t h a n k M r L a r s - E r i k T e r g e n i u s , U p p s a l a U n i v e r s i t y for the
skilful work on taking up powder diffraction d a t a of c o r r o s i o n
p r o d u c t s . W e a l s o w i s h to t h a n k M r T o r - G u n n a r V i n k a , S w e d i s h
Corrosion Institute for creative discussions and to Ms Inger
O d n e v a l l , R o y a l I n s t i t u t e of T e c h n o l o g y , Stockholm for placing her
diffraction d a t a at o u r d i s p o s a l .
R E F E R E N C E S
I. M c I n t y r e , P & M e r c e r , A D: A c c e l e r a t e d tests Simulated

enviro~t*ents, p p 1 9 . 4 8 - 1 9 . 5 7 in: C o r r o s i o n , 3 r d ed. (L L S h r e i r &
R A J a r m a n & G T B u r s t e i n , eds), B u t t e r w o r t h - K e i n e m a n n , London,
1993.
2. Johansson, E: S h o r t - t e r m m e t h o d s f o r a t m o s p h e r i c corrosion
t e s t i n g - S u r v e y of t h e l i t e r a t u r e . KI R e p o r t 1 9 8 5 : 3 ( I S S N 0348-
7199), S w e d i s h C o r r o s i o n Institute, Stockholm, 1985, Pp 54. (In

Swedish)
3. K e t c h a m , S J & Jankowsky, E J: E e v e l o p i n g an a c c e l e r a t e d test:

P r o b l e m s a n d p i t f a l l s . Pp 14-23 in: L a b o r a t o r y c o r r o s i o n test a n d
s t a n d a r d s . A S T M STP 866. G S H a y n e s & R Baboian, eds, ASTM,
P h i l a d e l p h i a , 1985.
4. Lyon, S B & Thompson, G E & J o h n s o n J B: M a t e r i a l s e v a l u a t i o n

u s i n g w e t - d r y m i x e d s a l t - s p r a y tests. Pp 2 0 - 3 1 in: N e w m e t h o d s
for c o r r o s i o n t e s t i n g of a l u m i n i u m alloys, A S T M STP 1134. (V S
A g a r w a l a & G M Ugiansky, eds.). ASTM, P h i l a d e l p h i a , 1992.
5. Odnevall, I & W e s t d a h l , M: Zinc c h l o r o h y d r o x o s u l f a t e s : N e w l y

d i s c o v e r e d c o r r o s i o n p r o d u c t s on zinc. S t r u c t u r e d e t e r m i n a t i o n of
N a Z n 4 C I ( O H ) 6 S O 4 . 6 H 2 0 a n d X - r a y s t u d y of Zn4CI2(OH)4SO4.5H20.
C o r r o s i o n S c i e n c e Vol. 34, 1993, pp 1231-1242.
6. C o r r o s i o n of m e t a l s a n d a l l o y s - C o r r o s i v i t y of a t m o s p h e r e s -
C l a s s i f i c a t i o n , I n t e r n a t i o n a l Standard, ISO 9223. ISO, Geneva,
S w i t z e r l a n d , 1992. 13 pp.
7. Schwarz, H: Die t h e o r e t i s c h e D e u t u n g d e r E i s e n ( I I ) - s u l f a t - N e s t e r
in a t m o s p h & r i s c h e m Rost, Teil II, W e r k s t o f f e u n d K o r r o s i o n ,
V o l . 1 6 , 1965, p p 208-212.
8. Evans, U R: T h e c o r r o s i o n a n d o x i d a t i o n of metals, 2nd Suppl.

Vol., E d w a r d Arnold, London, 1976, p 247.
9. Misawa, T & Asami, K & Hashimoto, K & Shimodaira, S: T h e

m e c h a n i s m of a t m o s p h e r i c r u s t i n g a n d the p r o t e c t i v e a m o r p h o u s
rust on low a l l o y steel, C o r r o s i o n S c i e n c e Vol. 14, 1974, p p 279-
289.
I0. Singh, A K & Ericsson, T & H&ggstr6m, L & G u l l m a n , J: M 6 s s b a u e r

a n d X - r a y d i f f r a c t i o n p h a s e a n a l y s i s of r u s t s f r o m a t m o s p h e r i c
t e s t sites w i t h d i f f e r e n t e n v i r o n m e n t s in Sweden. C o r r o s i o n
S c i e n c e Vol. 25, 1985, pp 931-945.
Ii. Grauer, R: F e s t e K o r r o s i o n s p r o d u k t e - I M a g n e s i u m , Zink, Cadmium,

B l e i u n d Kupfer; W e r k s t o f f e u n d K o r r o s i o n , Vol.31, 1980, p p 837-
850.
Manuel Morcillo I
ATMOSPHERIC CORROSION IN I B E R O - A M E R I C A : THE MICRT PROJECT
REFERENCE: Morcillo, M., "Atmospheric Corrosion in Ibero-

America: The MICAT Project," Atmospher%c Corrosion, ASTM
STP 1239, W. W. Kirk and Herbert H. Lawson, Eds., American
society for Testing and Materials, Philadelphia, 1995.
ABSTRACT: The Ibero-American Map of Atmospheric

Corrosiveness (MICAT) project was set up in 1988 sponsored
by the International Ibero-American Programme "Science and
Technology for Development (CYTED)". Fourteen countries are
currently involved in the project: Argentina, Brazil,
Chile, Colombia, Costa Rica, Cuba, Ecuador, Mexico, Panama,
Peru, Portugal, Spain, Uruguay and Venezuela. Research is
conducted both at laboratories and in a network of 72
atmospheric exposure test sites throughout the Ibero-
American region, thus considering a broad spectrum of
climatological and pollution conditions. Although with its
own peculiarities, the project basically follows the
outline of the ISOCORRAG and ICP/UNECE projects, with the
aim of a desirable link between the three projects. In the
paper the update annual corrosion results are reported. An
attempt is also made to correlate corrosion data with
meteorological and pollution parameters.
KEYWORDS: atmospheric corrosion, cooperative international

project, annual corrosion, low-carbon steel, zinc, copper,
aluminum, rural environment, urban environment, industrial
environment, marine environment, statistical processing.
INTRODUCTION
In January 1988, the 4th General Assembly of the

International Ibero-American Programme "Science and
Technology for Development (CYTED)" approved the project
"Ibero-American Map of Atmospheric Corrosiveness (MICAT)".
I Centro Nacional de Investigaciones Metal~rgicas. Avda.

Gregorio del Amo, 8. 28040-Madrid (Spain). Head of the
MICAT Project. In the Acknowledgment Section of the paper
the member list of the international working group
participating in the project is included.
257
Copyrightm1995by
Administrative and organization details of the CYTED

program were given in previous papers [1-2].
In August 1988, the working group that was to realize
the project was formed in Caracas. Initially, it was
composed by the following countries: Argentina, Chile,
Colombia, Mexico, Panama, Peru, Portugal, Spain and
Venezuela. Costa Rica and Cuba joined the project at the
second coordinators meeting held in Rio de Janeiro (June
1989). Finally, Ecuador and Uruguay joined the group at the
third annual meeting in Costa Rica (September 1990).
The research group in each participating country is
made up of specialists in atmospheric corrosion from
research institutions, universities and private companies.
One representative acts as coordinator of the research
group and attends the general meetings of the project that
are held periodically. The general meetings were held in
Caracas (1988), Rio de Janeiro (1989), Costa Rica (1990),
Buenos Aires (1991), Madrid (1992), and Santiago de Chile
(1993).
Each country supports its own research, whereas the
coordination activities are financed by Spain.
AIMS
Among the objectives to be fulfilled in the MICAT

project the following are of special interest:
(a) increasing the present knowledge on the mechanisms

of atmospheric corrosion,
(b) developing mathematical relations to predict
atmospheric corrosion from climatological and
contamination parameters,
(c) drawing up the Ibero-American Map of Atmospheric
Corrosiveness (MICAT), and
(d) elaborating practical guides for optimal selection
of metals and coatings (conventional and advanced)
in function of the atmospheric aggressiveness. This
aim is considered in a second phase of the MICAT
project, not approved yet, where a variety of
protective systems would be tested in a network of
representative atmospheric corrosion stations.
Objectives (c) and (d) are not covered in this paper.
Although with its own peculiarities, the project

basically follows the outline of the ISOCORRAG [!] and
ICP/UNECE [4] projects, with the aim of a desirable link
between the three projects. Standardized procedures (ISO
8565 [~], ASTM G50 [~]) have been followed.
MORCILLO ON THE MICAT PROJECT 259
Test sites
Figure 1 shows the location of the I b e r o - A m e r i c a n

n e t w o r k of a t m o s p h e r i c corrosion test stations. The names
and some e n v i r o n m e n t a l features of the test sites are
listed in Table i. As can be seen, the n e t w o r k p r o v i d e s a
v a r i e t y of c l i m a t o l o g i c a l and p o l l u t i o n conditions.
The a t m o s p h e r e at each test site is c h a r a c t e r i z e d from
meteorological and a t m o s p h e r i c p o l l u t i o n d a t a (ISO 9223
[!], A S T M G92 [8]). The former include basically the
temperature, relative humidity (RH) of the air and
rainfall. These p a r a m e t e r s are r e c o r d e d at the station
57 987
~ ""- "'~3"13 ~" hl,3
~ 6 I 64
5 ~
FIG. i-- N e t w o r k of a t m o s p h e r i c corrosion stations.
TABLE 1--List of test sites. Environmental characteristics
No. Country Test site Atmosphere

(Fig.l)
1 Argentina Camet Marina

2 V. M a r t e l l i Urban
3 Iguazu Rural
4 San Juan Rural
5 Jubani Marine
6 La Plata Rural
7 Brazil Caratinga Rural
8 Ipatinga Industrial
9 A r r a i l do Cabo Marine
10 Cubatao Industrial
ii Ubatuba Marine
12 Sao Paulo Urban
13 Rio de J a n e i r o Marine
14 Belem Rural
15 Fortaleza Marine
16 Brasilia Rural
17 Colombia Isla Naval Marine
18 San Pedro Rural
19 Cotove Rural
20 Costa Rica Puntarenas Marine
21 Limon Marine
22 Arenal Marine
23 San Jose Rural
24 Cuba Ciq Urban
25 Cojimar Marine
26 Bauta Rural
27 Chile Cerrillos Urban
28 Valparaiso Marine
29 Idiem Urban
30 Petrox Industrial
31 Marsh Marine
32 Isla de P a s c u a Marine
33 Ecuador Guayaquil Rural
34 Riobamba Rural
35 Salinas Marine
36 Esmeraldas Industrial
37 Galapagos Marine
TABLE l--(Cont.)
No. Country Test site Atmosphere
(Fig.l)
38 Spain Leon Rural

39 E1 Pardo Rural
40 Barcelona Urban
41 Tortosa Rural
42 Granada Rural
43 Lagoas Marine
44 Labastida Rural
45 Arties Rural
46 Mexico Mexico Urban
47 Cuernavaca Rural
48 Potosi Urban
49 Acapulco Marine
50 Panama Panama Urban
51 Colon Marine
52 Veraguas Urban
53 David Rural
54 Peru Piura Rural
55 V i l l a Salvador Marine
56 San Borja Marine
57 Arequipa Rural
58 Cusco Rural
59 Pucallpa Rural
60 Portugal Leixoes Marine
61 Sines Marine
62 Pego Rural
63 Uruguay Trinidad Rural
64 Prado Urban
65 Melo Rural
66 Antartida Marine
67 Venezuela E1 Tablazo Marine
68 Punto Fijo Marine
69 Coro Marine
70 Matanzas Marine
71 Barcelona Marine
72 Puerto Cabello Marine
itself - most lie in m e t e o r o l o g i c a l stations of the

M e t e o r o l o g i c a l Service of the country in q u e s t i o n - or at
a neighbouring meteorological station. The recorded
thermohydrograms are used to show the time of wetness
(TOW), the fraction of the year in w h i c h RH Z 80% and T >
0gC. The d e p o s i t i o n rates of S02 and chloride are measured
f o l l o w i n g ISO 9225 [9] (ASTM G91 [10]).
Materials
The m a t e r i a l s i n v e s t i g a t e d are structural metals, in

the form of flat plate specimens, w i t h the f o l l o w i n g
features: steel (unalloyed, low carbon); zinc (98.5% min);
copper (99.5% min), and aluminum (99.5% min). Some
c o u n t r i e s are also t e s t i n g hot dip g a l v a n i z e d steel. The
test specimens are u s u a l l y i0 x 15 cm 2 and cut out from 1 m m
thick sheets.
Exposure Seauences
The e x p o s u r e sequences include: 3 o n e - y e a r exposures,

one t w o - y e a r exposure, one three-year exposure, and one
f o u r - y e a r e x p o s u r e (Fig. 2).
F o u r specimens of each m a t e r i a l are e x p o s e d in each
sequence, three of w h i c h are used to d e t e r m i n e weight
losses a c c o r d i n g ISO 9226 [ii] (ASTM G1 [12]).
4 years
I/1
3 years
U
e'-
~J
2 years
3
{3-
(/1
1 year
{/1 1year
0
r-~
X 1 year
UJ
I I I I
1 2 3 4
Time, years
FIG. 2-- D i a g r a m of exposure sequences.
The removal of corrosion products by chemicals to

determine the weight loss involves a loss of valuable
information of the atmospheric corrosion process.
Therefore, a fourth specimen (Fig. 3) of each sequence was
used for laboratory studies: (a) analysis of the corrosion
products by means of diverse experimental techniques: XRD,
IR, M~ssbauer spectroscopy, water-soluble contaminants,
etc.; (b) microscopical examination (surface and cross-
section) of the morphology of the corrosion products
layers; and (c) electrochemical studies: polarization
resistance, impedance spectroscopy, electrochemical noise,
etc.
MICROSCOPICAL CORROSION
EXAMINATION PRODUCTS
ANALYSIS
._1.
I
:LECTROCHEMICAL I MASTER
TESTING SAMPLE
FIG. 3-- The "fourth sample". The discontinuous lines show

the sections in which the sample was divided for different
laboratory studies.
RESULTS
In the paper only the update annual corrosion data

reported by the different test sites are analyzed. Figs. 4
and 5 show the average values of the meteorological and
pollution factors at the different test sites and
corresponding to the three 1-year exposure sequences. Figs.
6 and 7 show the average annual corrosion data obtained.
~3~1
4 8 12 16 20 24 28 32 36 40 44 48 52 56 60 64 68 72
Test sites
100
IIIIII!1
!1!! 0 I I II
flllllll{!lllll!l
:f
n.- 20
4 8 12 16 20 24 28 32 36
Test sites
40 44 48 52 56 60 64 6B 72
~
u~ 4
03
~ 0 ?I ,
~]~,!',
1 4 8 12 16 20 24 28 32 36 40 44 4B 52 56 60 64 68 72
Test sites
P, d a t a in p r o g r e s s
FIG. 4-- T e m p e r a t u r e , RH, a n d r a i n average values during the

three 1-year exposure sequences at the different test sites.
~_ 0,8
~. 1 0 0 -
12 16 20 24
ll!ll{llll!lll{
28
I32 36 40
Test s i t e s
44 48 52 56 60 64 68 72
~ s~I
6O
,111
-~ 40
==
- 20 I
o,~t, ,, - L t , h ,
1 4 8 12 16 20 24 28 32 36 40 44 48 52 56 60 64 68 72
Test s i t e s
250
200
150
1001
O
1 4 12 16 20 24 28 32 36 40 44 48 52 56 60 64 68 72
Test s i t e s
P, data in p r o g r e s s
FIG. 5-- Time of w e t n e s s (TOW), S02, and Cl" a v e r a g e values

d u r i n g the three 1-year e x p o s u r e sequences at the d i f f e r e n t
test sites.
400
o 300
~3
o
i-
o
0
"~ 200
~" 100
0
4 8 12 16 20 24 28 32 36 40 44 48 52 56 60 64 68 72
Test sites
14
12
E
,- 10
o
2 8
o
--~ 6
r-
t--
~ 4
d
_z 2
a
,,dl,,,l,,, i J i,,]ii11~i ,ll,, I

, b , I , , ,
4 8 12 16 20 24 28 32 36 40 44 48 52 56 60 64 68 72
Test sites
P, d a t a in p r o g r e s s
FIG. 6-- A v e r a g e a n n u a l c o r r o s i o n d a t a of l o w - c a r b o n steel and

zinc for the t h r e e 1-year e x p o s u r e s e q u e n c e s at the d i f f e r e n t
t e s t sites.
10
s
~8
o"
12 16 20 24 28 32 36
,,ill
40 44 48
!! !!,i ,ll
52 56 60 64 68 72
Test s i t e s
"E 6
0'1
'-
0
5
4
0
"-'
r 3
t""
.lill,.
~ 2
z
_,1
<
~, . . . . . ,' '~'' ;,',,. ',''' "'' , mP P ' P' i ' I ' ' "l ' " ' ' ! ~'
0
4 8 12 16 20 24 28 32 36 40 44 48 52 56 60 64 68 72
Test sites
P, data in p r o g r e s s
FIG. 7-- A v e r a g e annual c o r r o s i o n d a t a of c o p p e r and

aluminum for the three 1-year e x p o s u r e sequences at the
d i f f e r e n t test sites.
DISCUSSION
Models for p r e d i c t i n g the corrosion d a m a g e of m e t a l s

in the a t m o s p h e r e are useful for a n s w e r i n g questions
regarding the durability of metallic structures,
d e t e r m i n i n g the economic costs of damages a s s o c i a t e d w i t h
the d e g r a d a t i o n of materials, and acquiring k n o w l e d g e about
the effect of environmental variables on corrosion
kinetics. The s p e c i a l i z e d literature offers a large number
of damage functions that relate the a t m o s p h e r i c c o r r o s i o n
rate to e n v i r o n m e n t a l data [13 - 16].
In this paper an attempt is also m a d e to correlate

corrosion data with meteorological and pollution
parameters.
Statistical Analvsis
W i t h the aim o b t a i n e d damage functions a s t a t i s t i c a l

analysis was performed with the aid of commercially
a v a i l a b l e computer software [17], following the p r o c e d u r e
in a previous p a p e r [16]; individual data c o r r e s p o n d i n g to
each e x p o s u r e sequence were considered in the analysis.
Table 2 shows the high v a r i a b i l i t y of the c o r r o s i o n and
e n v i r o n m e n t a l data used in the statistical treatment.
Data were fitted to a linear equation
C = a, + a2T + a3RH + aaP + a 5 TOW + ~ S + aTCl (I)
w h e r e the a i coefficients (i = 1 to 7) are constants, C(~m

for steel, zinc and copper, and g/m 2 for aluminium) is the
annual corrosion, T is the temperature annual a v e r a g e (~
RH is the relative h u m i d i t y annual average (%), P is the
total annual volume of p r e c i p i t a t i o n (mm), TOW is the time
of w e t n e s s (annual fraction), S is the annual a v e r a g e of S02
p o l l u t i o n (mgS02/m2.d), and Cl is the annual a v e r a g e of
c h l o r i d e p o l l u t i o n (mg C l / ~ . d ) .
Equation 1 is quite simple. Probably, other
c o m b i n a t i o n s b e t w e e n the different v a r i a b l e s m a y y i e l d
b e t t e r fits; yet in this w o r k using as simple r e l a t i o n as
p o s s i b l e was the goal. One possible w a y of i m p r o v i n g the
above linear e q u a t i o n is by introducing terms m a d e up of
p r o d u c t s of two variables (e.g. RH x CI, S x TOW, etc.).
In a d d i t i o n to the simultaneous use of all the c o r r o s i o n
data, the present study included a separate t r e a t m e n t of
data from rural atmospheres, including in the c a t e g o r y of
a t m o s p h e r e s those with annual pollution a v e r a g e s less than
i0 mg S02/m2.d and 3 mg Cl/m2.d, the lowest p o l l u t i o n
c a t e g o r i e s a c c o r d i n g to ISO 9223 [!].
The goodness of fit of experimental data to a p r o p o s e d
m o d e l is often m e a s u r e d by the statistical R z, i.e., the
square of the c o r r e l a t i o n coefficient (R) b e t w e e n the
observed values of the dependent variable and those
p r e d i c t e d from the fitted line.
TABLE 2-- C h a r a c t e r i s t i c s of the c o r r o s i o n

and e n v i r o n m e n t a l data used in
statistical treatment.
Material Variable Mean Smallest Largest

and value value
number
of data
C (um) 50.0 1.0 411.2

T (~ 19.4 -3.1 28.1
RH (%) 72.6 33.3 91.1
Steel p (mm) 1077.7 13.0 4656.0
(N= 137)
TOW (annual 0.47 0.00 0.95
fraction)
S (mgSO2/m:.d) 14.58 0.00 83.10
Cl (mgCl/m2.d) 26.00 0.00 359.80
C (~m) 1.69 0.09 8.06

T (~ 18.5 -3.1 28.1
RH (%) 72.6 33.3 91.1
p (nun) 916.2 13.0 2624.0

Zinc
(N=I20)
TOW (annual 0.46 0.00 0.95
fraction)
S (mgSOJm2.d) 14.15 0.00 83.10

Cl (mgCl'/m2.d) 24.66 0.00 359.80
C (~m) 1.64 0.09 8.22

T (~ 18.2 -3.1 28.0
RH (%) 73.0 33.3 91.1
Copper P (mm) 997.6 13.0 3677.0
(N = 115)
TOW (annual 0.46 0.00 0.95
fraction)
S (mgso2/m2.d) 13.67 0.00 83.10
Cl (mgC1-/ma.d) 24.15 0.00 359.80
C (g/m:) 0.92 0.00 5.43

T (~ 18.1 -3.1 28.0
RH (%) 72.5 33.3 91.1
P (mm) 943.6 13.0 2624.0

Aluminium
(N = 115) TOW (annual 0.46 0.00 0.95
fraction)
S (mgSO:/m:. d) 14.73 0.00 83.10
C1 (mgCl/m2. d) 24.34 0.00 359.80
One way of assessing the relative importance of

i n d e p e n d e n t v a r i a b l e s is to c o n s i d e r an i n c r e a s e in R 2 w h e n
a variable is entered into an equation that already
c o n t a i n s the o t h e r i n d e p e n d e n t v a r i a b l e s . A l a r g e c h a n g e in
R2 indicates that the new variable provides unique
information about the dependent variable that is not
available from the other independent variables in t h e
equation. The procedure for selecting variables was the
well-known stepwise technique, which involves the
s e q u e n t i a l i n t r o d u c t i o n of all t h e i n d e p e n d e n t v a r i a b l e s
starting from the one with the largest positive or negative
correlation with the dependent variable. The value
of t h e F s t a t i s t i c w a s u s e d to d e t e r m i n e w h e t h e r t h i s
f i r s t v a r i a b l e a n d e a c h of t h o s e s u c c e s s i v e l y i n t r o d u c e d
s h o u l d r e m a i n in t h e r e g r e s s i o n e q u a t i o n or be e x c l u d e d
f r o m it. In t h i s way, o n l y a f e w of t h e independent
variables appeared to be i m p o r t a n t (Equations 2-13 in
T a b l e s 3-7).
F i n a l l y , it s h o u l d b e k e p t in m i n d t h a t g r e a t c a u t i o n
m u s t be u s e d in m a k i n g c o r r o s i o n p r e d i c t i o n s f o r v a l u e s of
t h e i n d e p e n d e n t v a r i a b l e s t h a t are m u c h l a r g e r or s m a l l e r
t h a n t h o s e u s e d to d e r i v e t h e s e e q u a t i o n s ( T a b l e 2).
T A B L E 3 - - R e l a t i o n s h i D s b e t w e e n the a n n u a l corrosion
of l o w - c a r b o n s t e e l a n d t h e e n v i r o n m e n t a l parameters
Equations Remarks
c~ = carbon steel annual

C~ = 0.012 P + 0.94 S + 1.06 Cl - corrosion (~m)
3.9 RH = relative humidity
annual average (%)
(R = 0.78) (Eq. 2) P = annual precipitation (mm)
TOW = time of wetness
(annual fraction)
S = SO 2 pollution annual
C~ = Cl (2.9+0.0006 P-0.03 RH) + average (mg SO2/m2.d)
1.9 S x TOW + 8.07 Cl = chloride pollution
annual average (mgCl/m2.d)
(R = 0.84) (Eq. 3) R = multiple correlation
coefficient
Analvtical Results
T h e s t a t i s t i c a l t r e a t m e n t of t h e w h o l e d a t a set b y t h e
linear model accounts for 61, 42, 48 a n d 45% of t h e
variance in c o r r o s i o n of m i l d steel, zinc, copper and
a l u m i n i u m , r e s p e c t i v e l y (Eqs. 2,4,6, a n d 8 in T a b l e s 3-6).
By using binary interaction terms together with the

main effect terms of the environmental variables (Eqs.
3,5,7 and 9 in Tables 3-6), the fits do not improve
substantially. Only a low improvement of 10% have been
found in the best cases (mild steel and zinc).
TABLE 4--Relationships between the annual corrosion

of zinc and the environmental parameters
Equations Remarks
c ~ = zinc annual
corrosion (~m)
C ~ = 2.73 TOW + 0.017 C1 + 0.03 T = temperature annual
average (eC)
(R = 0.65) (Eq. 4) RH = relative h u m i d i t y
annual average (%)
TOW = time of w e t n e s s
(annual fraction)
C ~ = TOW (0.Ii S + 0.02 Cl) + S = SO 2 p o l l u t i o n annual
0.03 RH - 0.003 S x T - 2.09 average (mg SO2/m2.d)
C1 = chloride p o l l u t i o n
(R = 0.72) (Eq. 5) annual average (mgCl/m2.d)
R = multiple c o r r e l a t i o n
coefficient

of copper and the environmental parameters
Equations Remarks
C a = copper annual
corrosion (~m)
Cc. = 0.049 RH + 0.03 S + 0.01 Cl- RH = relative h u m i d i t y
2.57 annual average (%)
TOW = time of w e t n e s s
(R = 0.69) (Eq. 6) (annual fraction)
S = SO 2 p o l l u t i o n annual
average (mg SO~/m2.d)
Cl = chloride p o l l u t i o n annual
Ccu = RH (0.04 + 0.0002 el) + average (mgCl/m2.d)
0.05 S x TOW - 1.64 R = multiple c o r r e l a t i o n
coefficient
(R = 0.71) (Eq. 7)

of aluminium and the environmental parameters
Equat ions Remarks
c~ = aluminium annual
C m = 1.32 TOW - 0.07 T + 0.03 S + corrosion (g/m 2)
0.008 Cl + 0.94 T = temperature annual
average (~
(R = 0.67) (Eq. 8) RH = relative humidity
annual average (%)
TOW = time of wetness
Cm = 0.06 (S x TOW - T) + (annual fraction)
0.009 Cl + 1.40 S = SO 2 pollution annual
average (mg SO~/m2.d)
(R = 0.66) (Eq. 9)
Cl = c h l o r i d e pollution
annual average mgCl/m2.d)
R = multiple correlation
coefficient
TABLE 7--Relationships between the annual corrosion of low-

carbon, zinc, copper and aluminium in r u r a l a t m o s p h e r e s and
the environmetal parameters
Materials
and
number
of data Equations Remarks
Steel CFe = 0.90 T -3.41

(N = 13) C = annnual corrosion
(R = 0.48) (Eq.10) (in ~ m f o r s t e e l , z i n c
and copper, and g/m 2 for
zinc Czn = 3.04 TOW - 0.06 aluminium)
(N = 35) T = temperature annual
(R = 0.63) (Eq.ll) average (~
RH = relative humidity
Copper Ca = 0.02 RH - 0.80 annual average (%)
(N = 37) TOW = time of wetness
(R = 0.52) (Eq.12) (annual fraction)
R = multiple
Aluminium C^~ = 0.33 TOW + 0.06 correlation coefficient
(N = 36)
(R = 0.33) (Eq.13)
It should be noted that the variance accounted for in

the regression equations decreases sharply if the
statistical treatment is applied to rural atmospheres only
(Table 7), which is in agreement with results obtained in
a previous paper [16]. In the best case (zinc) the
statistical treatment accounts for ca 40% of the variance.
A significant effect of S02 and C l pollutants have been
observed in the corrosion values of different materials
(Eqs. 2-9 in Tables 3-6). The effect of chlorides seem to
be associated with the relative humidity for copper and
with the time of wetness for zinc. The effect of sulfur
dioxide seems to be associated with the time of wetness in
the four materials, which was found in a previous paper
[16].
CONCLUSIONS
In the paper an update of annual atmospheric corrosion

data for low-carbon steel, zinc, copper, and aluminum
obtained in a corrosion stations network on the Ibero-
America region are reported. The network included a wide
spectrum of climatological and pollution conditions.
General damage functions for low-carbon steel, zinc,
copper, and aluminum in terms of simple environmental
parameters were obtained. The goodness of fit does not
increase substantially as a result of including the effect
of some binary interactions between the independent
variables in the statistical treatment. In the best cases,
the regression equations account for up to 71% of the
variance of mild steel, 52% of zinc, 50% of copper, and 45%
of aluminum.
If the statistical analysis is rectricted to the rural
atmospheres then the unexplained variance is even lower.
ACKNOWLEDGMENTS
The authors wish to express their gratitude to the

Programa Iberoamericano de Ciencia y Tecnologia para el
Desarrollo (CYTED) for financial support granted for the
realization of this work. They are also indebted to Liboria
Mariaca (Mexico) for her cooperation in the statistical
data processing.
Members of the working group participating in the

project: B. Rosales (Argentina), L. Uller and M. Marrocos
(Brazil), G. Joseph (Chile), A. Valencia (Colombia), J.
Fernando Alvarez (Costa Rica), A. Cabezas (Cuba), J. Pe~a
(Ecuador), J. Urruchurtu and J. Genesca (Mexico), A. de
Bosquez and A. Hassel~ (Panama), G. Salas (Peru), E.
Almeida and M. Ferreira (Portugal), M. Morcillo (Spain), S.
Rivero (Uruguay) and M.R. Prato (Venezuela).
REFERENCES
[!] Uller, L. and Morcillo, M., Proceedinos 3rd

Iberoamerican Congress on Corrosion and Proteccion,
Vol. i, ABRACO, Rio de Janeiro, 1989, p 462.
[2] Uller, L. and Morcillo, M., Proceedings llth

International Corrosion Conaress. Vol. 2. AIM, Milano,
1990, p 2.35.
[3] Knotkova, D. and Vrobel, L. Proceedings llth

International Corrosion Congress, Vol. 5, AIM, Milano,
1990, p 5.581.
[4] Kucera, V., Coote, A.T., Kenriksen, J., Knotkova, D.,

Leygraf, C, and Reinhardt U., Proceedings llth
International Corrosion Congress, Vol. 2, AIM, Milano,
1990, p 2.433.
[5] ISO 8565, "Metals and alloys. Atmospheric corrosion

testing. General requirements for field tests"
International Standards Organization, Geneve.
[6] ASTM G50, "Conducting atmospheric corrosion tests on

metals". American Society for Testing of Materials,
Philadelphia, 1991.
[!] ISO 9223, "Corrosion of metals and alloys.

Clasiffication of corrosivity of atmospheres",
International Stantards Organization, Geneve, 1991.
[8] ASTM G92, "Characterization of atmospheric test sites"

American Society for Testing of Materials,
Philadelphia, 1991.
[9] ISO 9225, "Corrosion of metals and alloys. Corrosivity

of atmospheres. Methods of measurement of pollution",
International Standards Organization, Geneve, 1991.
[10] ASTM G91, "Monitoring atmospheric $02 using the

sulfatation plate technique". American Society for
Testing of Materials, Philadelphia, 1991.
[II] ISO 9226, "Corrosion of metals and alloys. Corrosivity

of atmospheres. Method for determination of corrosion
rate of standard specimens for the evaluation of
corrosivity", International Standards Organization,
Geneve, 1991.
[12] ASTM GI, "Preparing, cleaning, and evaluating

corrosion tests specimens". American Society for
Testing of Materials, Philadelphia, 1991.
[13] S. Haagenrud, J.f. Henriksen and F. Gram, "Dose-

response functions and corrosion mapping for a small
geographical area", Report, Norwegian Institute for
Air Research, Lillestrom, Norway, 1986.
[I__44] V. Kucera, S. Haagenrud, L. Atteraas and J. Gullman,

"Corrosion of steel and zinc in Scandinavia with
respect to the classification of the corrosivity of
atmospheres", in Degradation of Metals in the
Atmosphere. ASTM STP 965, S.W. Dean and T.S. Lee,
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[15] M. Benarie and F.L. Lipfert. "A general corrosion

function in terms of atmospheric pollutant
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[16] Feliu, S., Morcillo, M., and Feliu Jr., S., "The
prediction of atmospheric corrosion from
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corrosion", Corrosion Science, Vol. 34, No. 3, 1993,
pp 403-414.
[17] BMDP Statistical Software.
STP1239-EB/Mar. 1995
Author Index
A M
Ajiboye, P., 26 Morcillo, M., 137, 195, 257
B O
Boschek, P., 38 O'Brien, D. J., 167
Odnevall, I., 215
C
R
Coburn, S. K., 101
Cooper, T. L., 152 Reiser, D. B., 3
D
S
Dean, S. W., 3, 56
Drigel, G. S., 152
Sabata, A., 152
F Scrivener, K. L., 137
Simancas, J., 137, 195
Feliu, S., 195
G T
Gullman, J., 240 Tidblad, J., 11
Townsend, H. E., 85
J
V
Johansson, E., 240
K Valeriote, E. M., 230
Vlckova, J., 114
King, G. A., 167
Knotkova, D., 38, 114
Komp, M. E., 101 W
Kreislova, K., 38
Kucera, V., 11
Wong, C. W., 26
L
Z
Leygraf, C., 11, 215
Lore, S. C., 101
Lyon, S. B., 26 Zhang, X. G., 230
277
Copyright* 1995byby ASTM lntcrnational
Downloaded/printed www.astm.org
STP1239-EB/Mar. 1995
Subject Index
A Electrochemical impedance
spectroscopy, 152
Electrolytes, thin layer, 230
Accelerated tests, 152, 240 Electron imaging, backscattered,
Acid deposition, 11, 101 137
Aluminum, 38, 56, 195, 257 Energy dispersive X-ray analysis,
and zinc alloy, 167 137
ASTM standards
A 242:101 F
A 588: 85, 101
G 101:85 Flat specimens, 38
Automotive trim material, 152
G
B
Galvanic action, 230
Backscattered electron imaging,
137 H
C Helix specimens, 38
Humidity, 3
Carbon steel, 101, 114
Chloride, 215
Chloride candle, 56
Chromium, 152 Ibero-American Map of
Classification system, 38, 56 Atmospheric Corrosiveness,
Climate chamber, 240 257
Condensation, 3, 26, 56, 240 International Organization for
Copper, 11, 38, 195, 257 Standardization
copper-bearing steel, 101 CORRAG, 38, 56, 257
CORRAG program, 38, 56, 257
COR-TEN A, 101
COR-TEN B, 101 J
Cracking, micro, 167
Crevice corrosion, 114 Joints, bolted lap, 114
Crystal structure, 215
CYTED, 257 M
D MICAT project, 257

Models and modeling
Dew formation, 3 atmospheric corrosion, 26
Droplet evaporation, 26 atmospheric heat transfer, 3
Dry deposition, 215 Multiple linear regression
analysis, 56
E
N
Electrical contact materials, acid
deposition effects, 11 Nickel, 11, 85
279
P T
Polyvinylchloride, 167
Polyvinylfluoride, 167 Time of flight mass
Porosity, 137 spectrometer, 152
Protection area, 230 Time of wetness, 3, 56
Protection distances, 230 Tin, 11
TOFSIMS, 152
R Transmission tower, 114
Radiational cooling, 3 U
Rainwater washing, corrosion
effects, 26
Reaction sequences, 215 Ultrasound measurement, 114
Regression analysis, 195 Ultraviolet degradation, 167
Residual thickness, 114 United Nations
Resistive control, 26 Economic Commission for
Rust morphology, 137 Europe, 11
W
Weathering steel, 85, 101, 114

Wetting, 26, 240
Scanning electron microscope, time of wetness, 3, 56
152, 215 Wind velocity, 3
Science and Technology for
Development (CYTED),
257 X
Silicon, 85
Silver, 11 X-ray analysis, 137
Statistical verification, 38 X-ray diffraction, 240
Steel, 38, 114, 137 X-ray photoelectron spectroscopy,
A 588, 85, 101 215
carbon, 240
low carbon, 185, 257 Z
stainless, 152, 167
zinc coated, 230 Zinc, 38, 195, 240, 257
Sulfation plate, 56 alloy, 167
Sulfur dioxide, 215 coated steel, 230
Sulfur pollutants, 11 panels, 215
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Copyright by ASTM Int'l (all rights reserved); Thu Dec 29 01:31:47 EST 2011

W. W. Kirk and Herbert H. Lawson, Editors

ASTM Publication Code Number (PCN):

qSTl 1916 Race Street

Atmospheric corrosion / W.W. Kirk and Herbert H. Lawson, editors.

Peer Review Policy

Time of Wetness and Dew Formation: A Model of A t m o s p h e r i c Heat T r a n s f e r -

Acid Deposition Effects of Materials: Evaluation of Electric Contact Materials after

An A p p r o a c h to the Modeling of A t m o s p h e r i c Corrosion---s. B. LYON, C. W. WONG,

Results of ISO C O R R A G P r o g r a m : Processing of One-Year Data in Respect to

Analyses of F o u r Years of Exposure Data from the USA Contribution of ISO

WEATHERING STEELS AND COATED STEELS

Effects of Silicon and Nickel Contents on the Atmospheric Corrosion Resistance of

Atmospheric Corrosion Rates of W e a t h e r i n g Steels at Test Sites in the Eastern

Atmospheric Corrosion of Bolted Lap Joints M a d e of W e a t h e r i n g S t e e l - -

A Study of Rust Morphology, Contamination of Porosity by Backscattered

Corrosion Evaluation of Automotive Trim Material--A. SABATA, G. S. DRIGEL,

The Influence of M a r i n e E n v i r o n m e n t s on Metals and Fabricated Coated Metal

Long-Term Atmospheric Corrosion in Spain: Results After 13 to 16 Years of

Reaction Sequences in Atmospheric Corrosion of Zinc--1. ODNEVALL

Galvanic Protection of Steel by Zinc under T h i n Layer Electrolytes---x. G. ZHANG

Corrosion Study of Carbon Steel and Zinc-Comparison Between Field Exposure

Atmospheric Corrosion in Ibero-America: The M I C A T Project--M. MORCILLO 257

Author Index 277

Subject Index 279

TI~ 07 ~TR88 ~ DEW FOI~WATION: l NODIL OF A~Og)HHRIC

REFERENCE: Dean, S. W. and Reiser, D. B., "Time of Wetness and Dew

Abstractx Time of wetness is a critical factor in atmospheric

Ke~rdsz atmospheric corrosion, time of wetness, radiational

Atmospheric corrosion is an important degradation process affecting

Vernon [i] proposed that surface wetness occurs when a critical

iAir Products Fellow and lead materials engineer, respectively, Air

the salts on the metal surface. C o r r o s i o n of m e t a l s and alloys:

G r o s s m a n [~] p r o p o s e d a model w h e r e dew f o r m a t i o n r e s u l t e d from

UEAT TI~NSFZR MODZL

C o n s i d e r a object e x p o s e d to the night sky. The u p p e r s u r f a c e of the

~= Stefan-Boltzmann constant = 5.6686 x 10 -8 W m -2 K -4

F = v i e w factor for r a d i a t i v e exchange = 1 for this g e o m e t r y

s = emissivity of r a d i a t i n g (panel) surface, dimensionless

Tai r = a b s o l u t e air temperature, K

Tsky = absolute sky temperature, K

Tpane I = a b s o l u t e panel temperature, K

For the p u r p o s e of r e a r r a n g i n g equation (1), define two temperature

ATp = Tair- Tpanel (2)

ATs = Tair - Tsk7 (3 )

Using equation (2):

And considering that AT << T:

T~ane1 ~-~ Tair 1 -~T ~ - 4T~ATp (51

T2ky T,i4~--4 T ~3A T s (6 )

At s t e a d y state the net heat flux, Q, is zero. S u b s t i t u t i n g equations

Equation (7) will answer the question of h o w m u c h colder than

e ky= 0.711 + 0.561100,/ + 0.73

s = 24 hour average total clear sky emissivity, dimensionless

Tdp = d e w point temperature, ~

The convective heat transfer coefficient, h c, w i l l be f u n c t i o n of air

h~=0.61, , , units = W (lO)

L = the c h a r a c t e r i s t i c l e n g t h of the panel, m

N u x = 0 . 3 3 2 Pr 1/3 R e 1/2 (12)

In addition, the average convective heat transfer coefficient is twice

or, for the 0.3 m panel considered in this model:

h e = 8.35 v 1/2, W m "2 K -1 (14)

Examination of equations (ii) and (14) shows that at a wind velocity of

Equation (15) allows one to calculate the temperature depression