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JOURNAL OF IRON AND STEEL RESEARCH, INTERNATIONAL. 2008, 15(5): 42-48

Corrosion Products and Formation Mechanism During Initial


Stage of Atmospheric Corrosion of Carbon Steel
XIAO Kui ' , DONG Chao-fang' , LI Xiao-gang' , WANG Fu-ming"
(1. Beijing Key Laboratory for Corrosion, Erosion and Surface Technology, University of Science and
Tcchnology Beijing, Beijing 100083, China; 2. School of Metallurgical and Ecological Engineering,
University of Science and Technology Beijing, Beijing 100083, China)

Abstract: The formation and development of corrosion products on carbon stcel surface during the initial stage of at-
mospheric corrosion in a laboratory simulated environment have been studied by scanning electron microscopy (SEM)
and Raman spectroscopy. The results showed that two different shapes of corrosion products, that is, ring and
chain, were formed in the initial stage of corrosion. MnS clusters were found in the nuclei of corrosion products at
the active local corrosion sites. The ring-shaped products were composed of lepidocrocite (y-FeOOH) and maghemite
(y-Fe Z 0 3 ) transformed from lepidocrocite. The chain-type products were goethite (a-FeOOH). A formation mecha-
nism of the corrosion products is proposed.
Key words: atmospheric corrosion; corrosion product; carbon steel

The atmospheric corrosion of steel is controlled ist partly as crystalline and partly as amorphous
by the type of steel and the environmental condi- structures, the relative amounts of which will vary
tions, such as wetting time, air pollutants, temper- depending on the environmental conditions. When
ature, and dust content. Corrosion products on car- steel is exposed in a marine atmosphere, the initial
bon steel formed in the atmosphere tend to be pro- corrosion product is mainly y-FeOOH, which gradu-
tective, thus the corrosion rate decreases with in- ally transforms to a-FeOOH in intermittently wet/
creasing time, reaching a steady state in a few dry conditions. Although a-FeOOH and y-FeOOH
years. The exposure test provides the most reliable can be found in the corrosion products on carbon
information on atmospheric corrosion of metals, but steels, they are porous in nature and the adhesion of
this test is rather time-consuming. The accelerated rust layers to the substrate is also poor. Conse-
laboratory tests can produce useful data in a short quently, the corrosive species could readily penetrate
time and are suitable for assessing the durability of the porous rust layers to the substrate where corro-
metals in certain specific atrnospher es'{T". sion reactions proceed continuously. It is apparent
X-ray diffraction and Raman microscopy are two that the rust layers on carbon steels provide little or
very powerful methods for the characterization of atmos- no protection to the substrate.
pheric corrosion products[S-9]. Many researchers have In the present work, SEM/EDX and Raman
studied the corrosion products formed on carbon steels spectrometry were used to characterize the corrosion
exposed to various atmospheres'J'< ':". The main corro- products formed on carbon steel during the initial
sion products on the surface of steel reported are mainly stage when exposed to a simulated atmospheric cor-
y-FeOOH (Iepidocrocite i , a-FeOOH (goethite), Fe:;C), rosion environment with constant temperature and
(magnetite), and Y:Fez ()3. These products can coex- humidity.

Foundation Item: Item Sponsored by National Natural Science Foundation of China C50499331-8); Ministry of Science and Technology of China
CZ004DKAI0080)
Biography: XIAO KuiCl969-), Male, Doctor; E-mail: xiaokui@sina.com; Revised Date: August 30, Z007
Issue 5 Corrosion Products and Formation Mechanism of Atmospheric Corrosion of Carbon Steel • 43 •

1. 3 Analysis methods
1 Experimental
The growth of rust layers after vanous expo-
1. 1 Material and sample preparation sure periods was observed by optical microscopy,
The material was carbon steel, and its chemical and the surface morphology of the corrosion prod-
composition (mass percent, %) is given in Table 1. ucts was observed by SEM. The compositions of the
The size of each specimen was about 40 mmX 20 mm X corrosion products were identified by EDX and mi-
4 mm. Before exposure, the samples were polished cro-Raman spectrometry. Raman spectroscopy was
to 2000 SiC grit, ultrasonically cleaned in ethanol, undertaken using a JY-HR800 Confocal Microprobe
dried in air, and stored in a desiccator for 24 h be- Raman spectrometer with an exciting wavelength of
fore testing. 532 nm from the light source of an argon ion laser.
Micro-Raman microscopy was employed to give the
1. 2 Simulated test method dependence of the spectra of related oxides and oxy-
Alternating wetl dry equipment was used in the hydroxides on laser power. Low laser power was
laboratory test environments. The temperature and used for the reference spectra to minimize the risks
the relative humidity in the corrosion chamber were of spectral changes because of sample degrada-
controlled at 25 'C, 90 % RH, and 40 'C, 100 % RH tion[14]. Excitation laser power on the samples was
by the temperature controller and the humidifier at- filtered to O. 6 mW to avoid thermal effects for the
tached to the chamber. sensitive iron oxides and oxyhydroxides,

2 Results and Discussion


Table 1 Chemical composition of the carbon steel %
Composition 2.1 Morphologies of corrosion products in initial stage
Test material
C S Al Cu Mn P Si Cr Fig. 1 shows the optical micrographs of the
sample surface after different exposure periods. The
Carbon steel o. 16 O. 2 O. 65 0.018 0.2
carbon steel showed almost the same annular shaped

(a) 25 ·C. 90% RH. 120 h; (b) 40 'C, 100% RHo 120 h; (e) 25 'C o 90% RHo 360 h , (d) 40 'C, 100% RH, 360 h
Fig. 1 Optical morphologies of the corrosion products
• 44 • Journal of Iron and Steel Research. International Vol. 15
---_._---.

corrosion products In both laboratory test environ- observed after 48 h , is shown in Fig. 2 (a). Each in-
ments after exposing for 120 h , although the corro- clusion was surrounded by the annular corrosion
sion at 40 "C and 100 % RH was more severe than product. More corrosion sites could be observed af-
that at 25 "C and 90 % RH. With increasing the ex- ter 120 h and the size of the "circles" increased with
posure time, the corrosion product shape changed time. The other type of morphology of the corrosion
under both test conditions. After 360 h , the corro- products is shown in Fig. 2 (b). The cystiform cor-
sion product morphology formed at 25 'C and 90 % rosion products were made up of the catenarian cor-
RH was basically chain-type product. rosion products.
The typical corrosion products formed on the
carbon steel after different exposure periods are 2. 2 Characterization of corrosion products
presented in Fig. 2. There were two types of mor- SEM/EDX were used to determine the composition
phologies in the initial stage of atmospheric corro- of the corrosion products in different areas. Fig. 3
sion. The first, called annular corrosion, which was shows SEM photos of the corrosion products formed

(a) Annular corrosion product; (b) Chain-type corrosion products


Fig.2 SEM morphologies of the corrosion products (40 "c • 100% RH. 360 h)

(a) Crater of the center of corrosion site; (b) Cotton-like corrosion products; (c) Branch structure; (d) Chain structure
Fig. 3 SEM/EDX analysis of the corrosion products
Issue 5 Corrosion Products and Formation Mechanism of Atmospheric Corrosion of Carbon Steel • 45 •

at 40 "C and 100 % RH after 120 h. A crater-like site A contained several intense peaks at 123, 225, 553,
morphology was observed in the center of the" cir- and 689 em -1. In a previous work! 16 J , several nar-
cle" [Fig. 3 (a)], which clearly indicated that nucle- row peaks (bands) in the corresponding Raman
ation of the corrosion products started preferentially spectrum in the range of 130 - 220 cm -1 appeared,
from the active local corrosion sites. Cotton-like and they were concluded to be associated with the
corrosion products, the typical structure of semic- formation of sulphur-containing compound, such as
rystalline goethite, were found on the rim of the cra- MnS clusters. In the present work, EDX analysis of
ter [Fig. 3 (b)]. Also, branch structures were the bottom of the crater revealed the existence of S
found at the edge area of the annular corrosion prod- and Mn. Thus, it could be deduced that MnS clusters
ucts [Fig. 3 (c)]. Fig. 3 (d) shows the details of the should be the nuclei of corrosion products. The stron-
cyathiform corrosion products, which formed the gest peaks at 553 and 689 cm- 1 indicated the forma-
chain structure by interconnecting with each other. tion of magnetite (Fe, 0 4 ) , as shown in Table 3[15 J.
The composition (atomic percent, %) of the Fig. 5 (b) is the Raman spectrum of the site
corrosion products of different morphologies was an- marked as B in Fig. 4 (a). There were peaks at 248,
alyzed by EDX, and the corresponding results are 377, and 526 cm- I , which are typical of the Raman
listed in Table 2. The Fe content decreased from the spectrum of lepidocrocite (y-FeOOH), showing that
bottom to the rim of the crater, and Mn and S could the brown product was composed of y-FeOOH. Cor-
also be detected at the bottom. respondingly, the intensive bands in the range of
Table 2 lists the important bands of some com- 600- 800 cm- I proved the formation of maghemite
mon corrosion products of iron[15J. Minor differences (y-Fe z 0 3) ' The Raman spectrum of point C shown in
have been noted in the literature because of differ- Fig. 5 (c) is quite similar to that of B [Fig. 5 Cb)], so
ences in specimen composition, morphology, sam- the corrosion product composition at the two sites
pling , and source power. should be similar too. The Raman spectrum for point
From the corrosion morphologies shown in D [Fig. 5 Cd)] was different from the others, giving
Fig. 4, it can be clearly concluded that the nucleation four strong peaks at 248,300,387, and 694 cm- I •
of corrosion preferentially started at the local active The strongest peak at 387 ern - I indicated the exist-
corrosion sites. The Raman spectrum obtained at the ence of goethite (a-FeOOH); whereas, the peak at
694 cm- I corresponded to FeCOH)3.
Table 2 EDX analysis results of the corrosion products
Element/% 2. 3 Formation mechanism of corrosion products in
Corrosion product shape
a Fe Mn S initial stage
(a) 43.28 56.36 1. 26 0.83 Bottom of the crater On the basis of the above observations and anal-
(b) 63.57 36.43 Cotton-like product ysis results, the initiation of atmospheric corrosion
(c) 61. 26 38.74 Branch structure of carbon steel is divided into four steps, which are
(d) 71. 87 28. 13 Chain structure illustrated schematically in Fig. 6.

Fig. 4 Optical morphologies of the corrosion products


• 46 • ] ournal of Iron and Steel Research, International Vol. 15

Table 3 Main Raman bands of reference iron oxide compounds


Species Peak/ cm-[
a-FeOOH 245 300 390 420 480 550 685
a-FcOOH 299 397 479 550 685 1 003
a-FeOOH 250 300 385 470 560
a-FeOOH 298 397 414 474 550
y-FeOOH 255 380 528 654 1 054 1 307
y-FeOOH 252 380
y-FeOOH 252 380 526 650 1 307
y-FeOOH 252 380 660
y-FeOOH 252 380
a-Fe,03 225 245 lli 415 500 615 1 320
a-Fe 203 226 245 293 413 500 612
a-Fe 203 227 245 293 f98 414 501 612
y-Fe 203 265 300 345 395 515 645 670 715 1 440
y-Fe 203 263 350 380 505 650 740
y-Fe 203 350 505 660 710
Fe 3 0 , 300 320 420 560 560 680
F e 3 0, 540 665
Fe 3 0 , 550 670
Fe 30, 613 663
Note: The strongest peak in each compound has been underlined.

9000 (a) 1600 (b)

r
689 248

!~
~
8000 123 553 1200

,~!/~~I<\'~
1\ 377 645-725

800
i\~!\~;t\
I
526
\
7000
vwJ \
400
.0 6 000 L-_~ ~ ~ --'
'fiJ
<=
.s~ 3500 (c) 249 4000 (d)

3500
387 694
2500

1\
I

378 655
3000

2 500
248
J 300 1/
t~/~"'"'
I~
1500 ,1\\ 1\f
\¥'"'~ ~
527
2 000
~IJ"
500 L-_~ ~ """,- - ' 1 500 L-.._~ ~ ~ -'

200 400 600 800 200 400 600 800


Raman shin/em"

Fig. 5 Raman spectra of the corrosion products labeled with A, B, C, and D in Fig. 4

(a) The initiation of corrosion after the forma- more rapid. Corrosion occurs at the edge of the wa-
tion of water droplets [Fig. 6 (a) ] ter droplet on the surface of the carbon steel because
Water droplets condense from the air onto the of high oxygen concentration. The oxygen concen-
surface of the carbon steel. As the edge of a water tration cell forms when the cathodic reaction is oxy-
droplet is thinner than the inside, diffusion of oxy- gen reduction. Electrons flow from the low oxygen
gen from the atmosphere to the surface of the steel is region, which serves as the anode, to the high oxygen
Issue 5 Corrosion Products and Formation Mechanism of Atmospheric Corrosion of Carbon Steel 47 •

Fig. 6 Formation mechanism of the corrosion products in initial stage of atmospheric corrosion of carbon steel

region, which serves as the cathode. sion- barri er layer formed on the surface. The 0 H-
Anodic reaction: ions react with Fe2+ ions to form ferrous hydroxide:
Fe-2e---FeZ I (1) 1
Fe2+ +20z (g) + HzO--Fe(OH)z (3)
Ca thodic reaction:
(c) The formation of FeOOH [Fig. 6 (c) ]
+02 (g) + H zO+2e- --20H- (aq) (2)
The solubility of Fe(OH)z corrosion products
(b) The formation of corrosion products Fe(OH)z in the electrolyte and the formation of passive films
in thin film electrolyte [Fig. 6 (b) ] affect the overall rate of the anodic metal dissolution
Thin film electrolytes tend to form on metallic process, and cause deviations from simple rate equa-
surfaces under atmospheric exposure conditions after tions. The reaction continues as the Fe(OH)z reacts
reaching a certain critical humidity level. Molecular with more oxygen and water:
water absorbs on the surface and hydrolyzes. The 1
2Fe(OH)z +2-0z + HzC)--2Fe(OH)3 (4)
convection currents within these thin film electro-
lytes may playa part in further decreasing concen- Access to dissolved oxygen converts ferrous ox-
tration polarization of this cathodic process. Oxygen ide to ferric hydroxide according to the following re-
may also oxidize soluble corrosion films to less solu- action:
ble corrosion products. As corrosion films have 1
2Fe(OH)2 +20z--2FeOOH + HzO (5)
cracks and partially dissolve, oxygen easily reaches
the metal interface from the electrolyte solution in- (d) The formation of y- Fezo, and FelO, [Fig. 6 (d) ]
terface. Some granular corrosion products form on FeOOH is unstable and will transform to FezOJ •
the corrosion films. The corrosion products increase Hz 0, of which there are a number of varieties, and
with the continuation of corrosion. A great deal of the most common varieties being a form goethite (a-
granular corrosion products overlay corrosion films. FeOOH) and y form lepidocrocite (y-Fe()OH) when
In the presence of thin film electrolytes, atmos- it reacts with oxygen. In this paper, the final prod-
pheric corrosion proceeds by balancing anodic and uct is the familiar reddish brown rust maghemite (y-
cathodic reactions. The anodic oxidation reaction in- FeZ03) from lepidocrocite (y-FeOOH).
volves the dissolution of the metal, whereas, the ca- 2FeOOH--Fez03 + H 20 (6)
thodic reaction is often assumed to be the oxygen re-
3 Summary
duction reaction.
Ferrous hydroxide [Fe( OH) z] is the first diffu- During the initial period of atmospheric corro-
• 48 • J~urnal of Iron and Steel Research, International Vol. 15
"------"---"----

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