British Corrosion Journal

ISSN: 0007-0599 (Print) (Online) Journal homepage: http://www.tandfonline.com/loi/ycst19

Atmospheric corrosion of carbon steels and

weathering steels in Taiwan

Feng Iwei

To cite this article: Feng Iwei (1991) Atmospheric corrosion of carbon steels and weathering
steels in Taiwan, British Corrosion Journal, 26:3, 209-214, DOI: 10.1179/000705991798269215

To link to this article: http://dx.doi.org/10.1179/000705991798269215

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 Atmospheric corrosion of carbon steels and weathering
steels in Taiwan
FENG-IWEI The corrosion performance of carbon steels AS1M A36 and JIS SS41 and weathering
steels AS1M A588 Grade Band J IS SP AH (Acr- Ten A) were studied after exposure for
several periods up to 8 years in three atmospheric environments in Taiwan. The results are
in agreement with kinetic equations of the form C = AtB, where C is the corrosion loss, t is
time, and A and B are constants. The weathering steels have better corrosion resistance
than carbon steels, especially in an industrial coastal area, and a marked decrease in the
corrosion rate is observed when the weathering steel contains high phosphorus. However,
the rating of corrosion resistance of weathering steels relative to carbon steels does not
conform to the specification AS1M A242-87. These results, correlated with the compos-
ition and the structure of the rust as well as with environmental factors, are examined mid
discussed.
Manuscript received 2 March 1990; infinalform 14 November 1990. The author is 'in the
Research and Development Department, China Steel Corp., Kaohsiung, Taiwan.
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INTRODUCTION weathering steels with and without phosphorus

Atmospheric corrosion can be a serious problem for steel
structures, although it can be inhibited by application of
suitable protective systems. However, these are usually
complex, expensive and laborious, especially with regard
to their maintenance. Therefore weathering steels have
been widely used since they were developed by US Steel
Corp. in the 1930s.1,2 The weathering steels contain small
amounts of alloying elements, such as copper, chromium,
nickel, silicon, and phosphorus, which promote the forma-
tion of a tightly adherent protective rust layer resulting in
an atmospheric corrosion resistance which is superior to
carbon steels.
Most commercial weathering steels are specified in
ASTM A588, A242,3and JIS G3125;4 however, their various
commercial names, such as Cor-Ten, River-Ten, Acr-Ten,
Mayari R, etc. have been much used. Owing to the
detrimental effect of addition of phosphorus on' steel
toughness, cracking susceptibility and embrittlement of
steel weldments during welding5,6 the thickness of rephos-
phorised weathering steels is limited to about 16 mm,
although phosphorus can significantly strengthen steel
through the mechanism of solid solution6,7 and improve
atmospheric corrosion resistance as shown in Fig. 1.B
The atmospheric corrosion resistance of weathering steels
varies with the environment;9,10 however, in Taiwan, no
such test results have been published. The purposes of this
paper are:
(i) to present the results of outdoor exposure tests of
additions in various environments
(ii) to compare the performance of weathering steels and
carbon steels .
(iii) to investigate the rust compositions and the elemental
distribution in the rust layer by electron optical
techniques.
EXPERIMENTAL PROCEDURE
Materials examined were commercial hot rolled steel plate
and strip manufactured by China Steel Corporation.
Table 1 gives the thickness and the analysis of these steels.
As rolled specimens were cut to about 100 x 150 mm,
followed by mechanical polishing with 600 grade silicon
carbide paper.
According to ASTM G50-76 specification, the test panels
were exposed at 30° to the horizontal, with skyward surface
facing south, at three test sites: i.e. National Tsing-Hua
University (windy rural-urban site), National Sun Yat-Sen
University (coastal site), and China Steel Corporation
(coastal-industrial site). These locations are shown in
Fig. 2. After exposure, some specimens were cleaned in
HCI solution containing a pickling inhibitor to remove the

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Phosphorus content, wt-% EBNational Tsing-Hua University in Hsinchu; 0 National Sun Yat-
Sen University near Kaohsiung Harbour; 0 China Steel Corp. in Hsiao
Effect of phosphorus content on atmospheric corrosion rate of Kang Industrial District
steel after 3 years' exposure at China Steel Corp. 2 Location of exposure sites in Taiwan

Dr. Corros. J., 1991, Vol. 26, No.3 209.

 210 Feng-i Wei Atmospheric corrosion of steels in Taiwan

Table 1 Thickness and chemical composition of steels, wt-%

C Si Mn P S Cu Cr Ni v Al

A36* 0·13 0·25 0·85 0·018 0·015

A588* 0·15 0·25 1·50 0·022 0·015 0·28 0·44 0·18 0·035
SS41t 0·13 0·19 0·81 0·015 0·008 0·063 0·021 0'049 0·024
Acr-Ten At 0·10 0·44 0·47 0·10 0·008 0·31 0·55 0·30 0·02

* A366 and A588: thickness 12 mm.

t SS41 and Acr-Ten A: thickness 4 mm.

corrosion products and their metal loss was determined
by comparing the weights before and after the exposure.
Other specimens were examined in situ, i.e. without
stripping the rust, in surface and cross-section by various
electron optical techniques, particularly analytical scanning
electron microscopy (SEM), X-ray diffraction (XRD),
electron probe microanalysis (EPMA) and infrared
spectroscopy (IR).
Owing to the influence of climatic parameters on
atmospheric corrosion, the climatic charac~eristics and the
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different materials, but in the rural-urban area the initial
corrosion rate was quite high. This ~eems to be due to its
windy and rainy climate. Additionally, in an industrial
environment, the phosphorus containing weathering steel
Acr-Ten A shows a high atmospheric corrosion resistance
in the initial stage. In contrast, the exponent B reflects the
change of corrosion loss with time. In these tests, the
values of B for weathering steels are close to 0·5 which
means that an adherent rust layer was formed at the
surface and acted as a diffusion barrier.

main environmental parameters measured are listed in
Table 2. The Cl- and S02 were collected by the wet candle
methodll,12 and lead peroxide candle method (ASTM
D2010) respectively. The former were analysed by the
atomic absorption spectrometer and potential titration.
RESULTS
Corrosion loss
Several workersl3-15 have reviewed three general methods
of calculating the corrosion rate of weathering steels. The
method of estimated exposure time for a given corrosion
loss to occur has been widely used since it was proposed
by Townsend and Zoccola 15using linear regression analysis
to fit a straight line on a log-log plot of corrosion loss v.
time.
Results of the present corrosion tests show that the
corrosion resistance of steels can be ranked as follows:
Acr-Ten A> A588 > A36 ~ SS41. The corrosion of each
steel is described by the equation,
log C=log A+B log t (1)
or
C=AtB
where C is the corrosion loss (~m), t is the time (months),
and A and B are constants. These constants obtained by
linear regression analysis along with the square of the
associated correlation coefficient (R2) are summarised in
Table 3 which indicates that over 93°A>(R2) of the changes
with time are accounted for by the kinetic equations in
each environment. From equation (2), it is clear that A is
numerically equivalent to the corrosion loss when time is
unity. Therefore, A is generally considered as a measure of
the initial reactivity of the material with the environment.
Table 3 reveals no general trend for values of A among
From equation (2), Townsend and Zoccola 15 have
developed and applied relationships to compare quantita-
tively the corrosion resistance of steels on the basis of the
ratio of times required to achieve a particular loss of
thickness. A loss of 250 Jlm was selected to calculate the
time
t* =(C* IA)I/B
where t* is the time in months to achieve 250 !..lmcorrosion
loss. C * is the corrosion loss selected (250 ~m) and A and
B are constants of the rate equation, as given in Table 3.
The times required to achieve 250 J.lmcorrosion loss and
the ratio of these times for the experimental steels are
given in Table 4 which shows that the weathering steels,
especially the high phosphorus containing steel (Acr-Ten
A), have better corrosion resistance than carbon steels.
However, these results cannot meet the ASTM A242-87
specification, which indicates that A242 type (rephosphor-
ised weathering) steels have enhanced atmospheric cor-
rosion resistance of approximately four times that of carbon
structural steels without copper, although the specification
does not provide a means of comparing the corrosion
resistance, as has been discussed by Komp.14 However,
(2)
Shastry et al.16 have shown that the weathering steels have
much better corrosion resistance than carbon steels. This
suggests that the environments of the present tests in
Taiwan are severer than those of Shastry et al. in the USA
although no detailed environmental conditions at their
chosen test sites are given. In addition, Table 4 apparently
shows that the corrosion resistance of A588 is only slightly
better than that of A36 in the coastal site. It reveals that
the phosphorus free weathering steel is inadequate for use
in the coastal environment and also that weathering steels
have greater relative durability than carbon steels in the
industrial environment.

Table 2 . Environmental conditions of exposure sites

Average
Average Average wind
Test Average rainfall, relative velocity, CI-, SO~-,
site Environment temp.,oC mm/year humidity, % ms-1 mgm-2/day mg m-2/day

National Tsing Windy

Hua University rural-urban 22·2 1999 81 4·0 11 90
National Sun
Yat-Sen University Coastal 24'5 1806 77 2·6 22 70
China Steel Coastal-
Corp. industrial 24'5 1806 78 2·4 18 ·130

Br. Corros. J., 1991, Vol. 26, No.3


Table 3 Regression coefficients of atmospheric corrosion data
A36 A588
2 2
Test site A B R A
China Steel Corp. 8·05 0·745 0·943 15,66
Sun Vat-Sen University 10·25 0·575 0·979 8·57
Tsing-Hua University
Rust composition and structure
The surface appearance of weathering steels gradually
changed to dark red; thereafter, the corrosion rate decreased
remarkably. It is thought that, in this state, a protective
and stable rust layer has developed on the steel surface.
This change depends on the environmental condition. In
the present study, a stable rust ,layer developed more
rapidly in the windy rural-urban site (after about 0·5 years)
than in industrial-coastal (2'5-3 years) and coastal (2·5-3
years) sites. However, the surface of carbon steels is always
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red or brown red. In addition, the rust layer on the back
face is thicker, rougher, and redder than that on the front
face in all steels.
After exposure, examination of the surface rust showed
that it consisted of very porous discrete globules and flats
of rust in all carbon steels, as shown in Fig. 3a. Figure 3b
shows that at high magnification, some of them may be
seen to have developed into a platelike structure, which
sometimes contains some sulphur. Similar observations
were also made by Fyfe et al.17 in Fe-0'03S and Fe-
0'07Cu after exposure for 48 weeks. In A588 with low
phosphorus content, this porous rust structure can be
investigated in some small areas, as shown in Fig. 4.
However, in windy rural-urban and industrial-coastal
sites, usually no similar rust structure was observed in
high phosphorus containing Acr-Ten A exposed for 5 years.
In the industrial-coastal site, the rust was finer on Acr-
Ten A (Fig. 5) than that on carbon steels (Fig.3a). The
rust on the latter was also denser, but due to large rust
particles and easy spallation of large flaky rust, the surface
of carbon steels became much rougher than that of
weathering steels, especially after longer exposure. In the
coastal site, similar results were also observed, but more
globules of rust developed on the surface. EDAX semi-
quantitative analysis revealed that these contained mainly
iron, some silicon, sulphur, aluminium and a little potas-
sium. In the windy rural-urban site, the extremely high
density with which cracks formed in the rust on Acr-Ten
A can be seen in Fig. 6a, out small rust globules containing
some sulphur also developed on the surface. Spallation of
the rust and development of porous rust are easily
observable on the surface of carbon steels (Fig. 6b). In
weathering steels, most surfaces were covered with an
optically isotropic rust layer which in turn was covered by
an optically active layer after exposure for several years,
as reported by Okada et ai.IS A typical electron beam
scanning image is shown in Fig. 7a. The inner rust layer is
dense and almost crack free, but the outer layer is
sometimes discontinuous and loose, especially on the front
Table 4 Time required to reach a thickness loss of 250 pm, months
Test site A36 A588
China Steel Corp. 101 310 .
San Vat-Sen University 259 353
Tsing-Hua University
Feng-i Wei Atmospheric corrosion of steels in Taiwan 211
SS41 Acr-Ten A
2
B R A B R A B R2
0·483 0·930 7·57 0·724 0·982 4·79 0·64 0·990
0·575 0·993 7·73 0·689 0·997 8·18 0,564 0·991
14·28 0·587 0·975 14·51 0-482 0·932
side (with face to the sunlight) of the test panels. However,
in carbon steels, most of the rust layers contain voids and
microcracks which penetrate from the outside of the rust
into the steel substrate (Fig. 7b), and no continuous
optically isotropic layer could be observed.
The compositions of rust were analysed by X-ray
diffraction using the Debye-Scherrer method and IR. The
inner rust layer on weathering steels was composed of
amorphous ferric oxyhydroxide and some y-FeOOH,
tX-FeOOH, and c5-FeOOH, while the outer layer was
composed of y-FeOOH, tX-FeOOH, and some Fe304 and
a-Fe203' Early in the testing period, the y-FeOOH is
present in larger amounts than the tX-FeOOH, but sub-
sequently the amount of tX-FeOOH gradually increases.
However, rust composition also depends on the atmos-
phere. After exposure for 4-5 years in the industrial-
coastal site, the amount of crystalline atmospheric
corrosion products may be ranked in the order tX-FeOOH,
y-FeOOH, and others, but in the coastal site, the amount
of tX-FeOOH is approximately equal to that of y-FeOOH.
In the windy rural-urban site, the amount of y-FeOOH
exceeds that of a-FeOOH. In carbon steels, the principal
crystalline components of the corrosion products are
y-FeOOH, a-FeOOH, Fe304 and some a-Fe203'
According to an examination of the cross-section· of the
rust layer by EPMA,' chromium, copper and sulphur
became slightly enriched in the inner rust layer of A588,
which contained lower phosphorus, after exposure for 3
years in the industrial-coastal site. After 8 years, this
enrichment of chromium became quite apparent. However,
in the coastal site, these phenomena were not apparent,
while some chloride, calcium and sulphur existed in the
inner rust layer formed on the back face. In Acr- Ten A .
with high phosphorus content, chromium, sulphur and
some silicon were usually observed within the inner rust
layer after exposure for 3 years in the three environments.
After 5 years in the industrial-coastal site, chromium and
phosphorus were apparently rich in the inner rust layer
(Fig. 8). In the coastal site, chromium, chloride, phos-
phorus, and copper were rich In the inner rust layer,
especially the first two. In the windy rural-urban site, the
inner rust layer was enriched in chromium and contained
some phosphorus, sulphur and silicpn.
DISCUSSION
In the present investigations, in the initial stage, y-FeOOH
was the main corrosion product, but after 3 years,
tX-FeOOH became the predominant one in a relatively dry
8S41 Acr-Ten A A588/A36 Acr- Ten A/SS41
125 460 3·07 3·68
155 430 1·26 2·77
131 367 2·87
Hr. Corros. J., 1991, Vol. 26, No.3
 212 Feng-i Wei Atmospheric corrosion of steels in Taiwan
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4 Rusted front surface of A588 steel exposed for 8 years at China

Steel Corp.

than that in other sites perhaps because of the production

of a greater proportion of y- FeOOH as the predominant
corrosion product as well as the reduction of the drying
out period which is the only stage in which the beneficial
effects of copper occur.
In the coastal site, the atmospheric chloride content is
slightly higher than that in other sites, but its relatively
low SOl concentration and humidity lead to reduction of
its corrosivity. However, increase of phosphorus content
and decrease of carbon and manganese strongly affect the
corrosion resistance of weathering steels in the coastal site,
as shown in Table 4. Misawa et al.23 proposed that
dissolved phosphorus, copper, and chromium ions can

a general view; b detailed platelike rust structure

3 Rusted front surface of SS41 steel exposed for 5 years at China
Steel Corp.

atmosphere slightly rich in S02' Similar results were also

observed by Sugawara et al.19 According to Misawa et
al.,20 the initial corrosion product is FeOH +, which is
subsequently oxidised and precipitated as y-FeOOH. Sul-
phur dioxide in the atmosphere lowers the pH of water
wetting the rust film and dissolves y-FeOOH from which
amorphous ferric oxyhydroxide is precipitated. This further
transforms to cx-FeOOH by drying. However, when the
climate is usually humid or rainy, this effect is reduced.
Kaneko and Inouye21 indicated that, compared with that
of cx-FeOOH, the electrical conductivity of y-FeOOH
increases remarkably with S02 chemisorption. In addition,
Stratmann et al.22 demonstrated that the addition of
copper to the steel can remarkably reduce the corrosion
rate only during the drying out period which is the stage
in which metal loss is the greatest. Weathering steels have 5 Rusted front surface of Acr- Ten A steel exposed for 5 years at
a worse corrosion performance in windy rural-urban sites China Steel Corp.

Br. Corros. J., 1991, Vol. 26, No.3


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a
b
a Acr- Ten A; b SS41
6 Rusted front surfaces of experimental steels exposed for 4 years
at Tsing- Hua University
enhance the formation of uniform amorphous ferric
oxyhydroxide to protect the steel substrate. Sakashita and
Sat024,25 also found that CrOi -, POl-, and SOi - can
change the ion selectivity of ferric oxides from anion
selective to cation selective in neutral chloride solution to
retard the anodic current in atmospheric corrosion. How-
ever, no compound containing phosphorus was identified
in the atmospheric corrosion products of weathering steels,
although enrichment of phosphorus in the inner rust layer
was usually observed. In the present study the reduced
rate of metal dissolution at the steel/rust interface appears
to be due to the enrichment of chromium, copper, or
phosphorus in the dense rust layer. Such an effect of
copper was also proposed by Stratmann et al.22
The porous rust structure (Fig. 3a) developed in all
carbon steels, while in weathering steels usually only a
platelike porous corrosion product (Fig. 4) formed in some
areas, but for Acr-Ten A steel, such a platelike structure
was only observed after exposure in the coastal site.
Feng-i Wei Atmospheric corrosion of steels in Taiwan 213
a
b
a Acr-Ten A; b SS41
7 Rust layers on front of experimental steels exposed for 4 years
at Tsing-Hua University
However, de Maybaum and Ayllon26 found a similar rust
structure to that in Fig. 3a on a high phosphorus A242
type steel after exposure for 2 months in a semi-industrial
climate. Kassim et al.27 indicated that the initial oxyhydrox-
ide product in the presence of the CI- ion was y-FeOOH
which was lath shaped after its formation by rapid
oxidation of Fe(OH) + and aging. According to Dias et
al.,28 y-FeOOH which formed on steel after exposure in a
humid tropical climate was platelike. In addition, Smith
and McEnaney29 observed that acicular y-FeOOH devel-
oped on the outside surface of grey cast iron. From these
observations, the platelike porous corrosion product seems
to be the y-FeOOH which develops on rust surfaces to
bring about an increase in the corrosion loss, but this
platelike product develops only with difficulty on weather-
ing steels, especially in high atmospheric corrosion resistant
weathering steel (Acr-Ten A), although the presence of the
chloride ion can enhance its development. It is thought
that Fe2 + or FeOH + ions can diffuse only with difficulty
through the adherent protective rust layer on weathering
steels to form an outer layer of y-FeOOH on the rust
surface.
CONCLUSIONS
Based on the above analysis of atmospheric corrosion test
data, microstructures and compositions of the rust for
A588, A36, Acr-Ten A and SS41 steels, five conclusions
may be summarised as follows:
1. The corrosion behaviour of the carbon and weathering
steels exposed in three different environments is well
represented by exponential kinetic equations derived by
regression analysis of the data in logarithmic form.
2. The atmospheric corrosion resistance of the steels can
be ranked in order Acr-Ten A> A588 > A36 ~ SS41,
although their relative corrosion resistance may depend
on their environment.
3. The rating of corrosion resistance of weathering steels
relative to that of carbon steels depends on the environment,
test period and calculation method. The present results
cannot in general meet the specification of ASTM A242-87
in Taiwan's environments.
Hr. Corros. J., 1991, Vol. 26, No.3
 214 Feng-i Wei Atmospheric corrosion of steels in Taiwan

3.5 100 ACKNOWLEDGMENTS

3.0
The author is grateful to S. H. Shieh, J. M. Hsu and C.
80
J to v,.-,vJ\;\A
v:
}.•A
lJ '! V' ,
F. Wu for their assistance in processing data and
0\0
2.5 0\° performing experiments.
I
I
.j.J
60 .j.J
2.0 3
3
,
1.5
0
~ 40 r.r..OJ
f,i
1.0
w~J~'.JV 20
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Br. Corros. J., 1991, Vol. 26, No.3