Corrosion Science 51 (2008) 242–251

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Corrosion Science
j o u r n a l h o m e p a g e : w w w . e l s e v i e r. c o m / l o c a t e / c o r s c i

Influence of carbon content and microstructure on corrosion behaviour

of low alloy steels in a Cl¡ containing environment
Jia Guo a, Shanwu Yang a,*, Chengjia Shang a, Ying Wang b, Xinlai He a
a
School of Mate­ri­als Sci­ence and Engi­neer­ing, Uni­ver­sity of Sci­ence and Tech­nol­ogy Bei­jing, Hai­dian Dis­trict, Xuey­u­an Road 30, Bei­jing 100083, China
b
School of Met­al­lur­gi­cal and Eco­log­i­cal Engi­neer­ing, Uni­ver­sity of Sci­ence and Tech­nol­ogy Bei­jing, Bei­jing 100083, China

a r t i c l e i n f o a b s t r a c t

Article history: Cor­ro­sion behav­iour of low alloy steels (A and B) with dif­fer­ent car­bon con­tent was stud­ied by a salt fog
Received 22 May 2008 test and an out­door test. A com­mer­cial weathering steel 09CuP­CrNi was used for com­par­i­son. The cor­
Accepted 30 October 2008 ro­sion resis­tance of steels A and B with homo­ge­neous micro­struc­tures was bet­ter than that of the com­
Available online 06 November 2008
mer­cial weathering steel 09CuP­CrNi in the salt fog test. Steel A with an ultra-low-car­bon con­tent had far

less weathering resis­tance than the other steels in the out­door test. Selec­tive cor­ro­sion of large pearl­ite
pro­duces stress in ini­tial cor­ro­sion prod­uct films. Uniform cor­ro­sion prod­uct films with few cracks tend
Key­words:
to form on homo­ge­neous micro­struc­tures such as fer­rite and ba­i­nite, and this is advan­ta­geous for the
A. Low alloy steel
B. EIS
for­ma­tion of a com­pact rust layer in the ini­tial stage of atmo­spheric cor­ro­sion. How­ever, uniform micro­
B. XRD struc­tures will result in over even inter­faces between rust lay­ers and bases, which will lead to fre­quent
C. Rust peel­ing of rust lay­ers from bases because stress is induced by large tem­per­a­ture fluc­tu­a­tions and wet-dry
C. Atmo­spheric cor­ro­sion alter­na­tions. Pro­tec­tion of the rust layer on a low alloy steel is depen­dent on the rust den­sity and the
bond­ing per­for­mance of the rust-base rather than the pro­por­tion of the rust phase in the ini­tial stage
of atmo­spheric cor­ro­sion. These results indi­cate that homog­e­nous micro­struc­tures, proper amounts of
car­bon con­tent and fine car­bon-rich phases that are pro­duced by appro­pri­ate pro­cesses are ben­e­fi­cial for
the cor­ro­sion resis­tance of steels.
© 2008 Published by Elsevier Ltd.

1. Intro­duc­tion be neglected after the sur­face of steel is cov­ered by cor­ro­sion

The cor­ro­sion resis­tance of Cor­ten A [1] is far bet­ter than car­
bon steel and this is attrib­uted to the addi­tion of small amounts
of alloy ele­ments such as Cu, Cr and Ni. To achieve fur­ther
enhance­ment of cor­ro­sion resis­tance the alloy con­tent (espe­
cially Ni) is increased for weathering steels [2–6]. Despite their
improved cor­ro­sion resis­tance the increased cost results in a
restricted appli­ca­tion range.
In addi­tion to alloy con­tent the type of micro­struc­ture will
­con­ceiv­ably also affect cor­ro­sion prop­er­ties of steels. Dif­fer­ent
micro­struc­tures can be inves­ti­gated by mak­ing use of their dif­fer­
ent ero­sion rates in metal­lo­graphic etch­ing.
It is gen­er­ally believed that the weath­er­abil­ity of weathering
steels is due to the enrich­ment of alloy ele­ments such as Cu, P,
Cr and Ni in the inner rust layer. These ele­ments pro­mote the
den­si­fi­ca­tion of rust lay­ers which obstruct the cor­ro­sion media
in the envi­ron­ment from com­ing into con­tact with the steel
sub­strate [7–13]. Most research­ers assume that micro­struc­tures
only affect the cor­ro­sion behav­iour of bare steel and thus can
* Cor­re­spond­ing author. Tel.: +86 1062334778; fax: +86 1062332428.
E-mail address: yangsw@mater.ustb.edu.cn (S. Yang).
prod­ucts.
The cor­ro­sion char­ac­ter­is­tics of bare steel may have an
influ­ence on the subsequent cor­ro­sion behav­iour of steel after
the for­ma­tion of rust lay­ers. The weath­er­abil­ity of tra­di­tional
weathering steels may thus be improved by opti­miz­ing micro­
struc­tures with­out sig­nif­i­cantly chang­ing chem­i­cal com­po­si­tions.
Cur­rently, excel­lent cor­ro­sion resis­tance and high strength are in
demand for new weathering steels. Low-car­bon ba­i­nite is grad­
u­ally tak­ing the place of fer­rite and pearl­ite as the weathering
steel of choice [14].
Chang­ing the car­bon con­tent is a sim­ple method for the pro­
duc­tion of dif­fer­ent kinds of micro­struc­tures and thus two steels
with a large dif­fer­ence in car­bon con­tent were smelted for this
work. Micro­struc­tures of pure fer­rite and low-car­bon ba­i­nite were
obtained by con­trolled roll­ing and accel­er­ated cool­ing. Their cor­
ro­sion behav­iour was stud­ied and com­pared with the com­mer­cial
weathering steel 09CuP­CrNi.
Because steel weath­er­abil­ity is relate to envi­ron­ments and
var­i­ous cor­ro­sion tests exist that reflect dif­fer­ent cir­cum­stances.
Thus two cor­ro­sion tests with dif­fer­ent con­di­tions were selected
for this work to ensure a com­pre­hen­sive assess­ment of steel
weath­er­abil­ity.

0010-938X/$ - see front matter © 2008 Published by Elsevier Ltd.

doi:10.1016/j.corsci.2008.10.025
 J. Guo et al. / Corrosion Science 51 (2008) 242–251 243

Table 1
Chem­i­cal com­po­si­tions of test mate­ri­als (mass%).

Steel C Si Mn P S Ni Ti Mo Cu Nb Cr
A 0.0036 0.30 1.77 <0.01 0.005 0.34 0.02 0.20 0.50 0.04 –
B 0.10 0.31 1.79 <0.01 0.005 0.33 0.02 0.20 0.50 0.04 –
09CuP­CrNi 0.08 0.454 0.347 0.089 0.005 0.30 – – 0.298 – 0.45

2. Exper­im
­ en­tal vac­uum induc­tion fur­nace. Chem­i­cal com­po­si­tions of both steels
and the com­mer­cial weathering steel 09CuP­CrNi are listed in
2.1. Com­po­si­tion of tested steels Table 1.

Two steels of dif­fer­ent car­bon con­tent and con­tain­ing sim­ 2.2. Roll­ing pro­cess
i­lar amounts of the other ele­ments were melted with a 200 kg
Steel ingots were reheated and forged into
42 mm £ 120 mm £ 600 mm slabs for con­trolled roll­ing. The slabs
were homog­en ­ ized at 1200 °C for 2 h and then rolled above 1000 °C
for 2 passes to a thick­ness of 20 mm fol­lowed by 3 roll­ing passes
between 930 °C and 850 °C. The final thick­ness of the plate was
about 7 mm. The plates were cooled with water after roll­ing.

2.3. The cor­ro­sion test in a salt fog cham­ber and in an out­door

envi­ron­ment

Spec­i­mens for cor­ro­sion tests were cut to 60 mm £ 40 mm £ 5 mm.

All spec­i­mens were ground with 400–1000 grit sil­i­con car­bide
paper and cleaned with ace­tone after which they were rinsed with

Fig. 2. Rela­tion­ship between the weight loss (mg/cm2) of steel sam­ples and the time
of accel­er­ated cor­ro­sion in dif­fer­ent envi­ron­ments: (a) the salt fog test and (b) the
Fig. 1. SEM micro­graphs of spec­i­mens: (a) steel A, (b) steel B and (c) 09CuP­CrNi. out­door test.
244 J. Guo et al. / Corrosion Science 51 (2008) 242–251
Fig. 3. EIS for pre-cor­roded sam­ples in a 0.1 M aque­ous NaCl solu­tion.
dis­tilled water. After dry­ing the sam­ples were weighed. The weight
was recorded as W0.
An ATLAS fog cham­ber was used for the cyclic wet/dry test
[15]. The fog was com­posed of a 3.5 mass% aque­ous NaCl ­solu­tion.
Fig. 4. EIS of steels A and B that were sub­jected to a salt fog test for 18 days and 63 days, respec­tively.
Each wet/dry cycle (24 h) con­sisted of a wet­ting period (8 h at
35 °C, 97 ± 1% RH) and a dry­ing period (16 h at 60 °C, 20% RH). The
tests cov­ered 63 cycles. Four sam­ples were col­lected for each steel
tested (three for a weight loss mea­sure­ment and one for the rust
layer anal­y­sis) after 9 days. For the weight loss mea­sure­ment the
cor­ro­sion prod­ucts on spec­i­men sur­faces were removed chem­i­
cally by immers­ing in Clark’s solu­tion (100 ml (1.19 g/ml) HCl + 20 g
Sb2O3 + 50 g SnCl2) and stirred for about 10 min at 25 °C [16]. After
cor­ro­sion prod­uct removal the sam­ples were rinsed with dis­tilled
water, dried in air and weighed. Weight loss of a unit area was cal­
cu­lated by (W0 ¡ W1)/S in which W1 is the sam­ple weight after cor­
ro­sion and S is the cor­ro­sion area on the sam­ple.
In the out­door test the sam­ples were inclined at an angle of
45° to the hori­zon and faced south. The cor­ro­sion pro­cess dur­ing
out­door expo­sure was accel­er­ated by inter­mit­tently spray­ing an
aque­ous NaCl solu­tion (3 mass%) onto sam­ple sur­faces 3 or 4 times
weekly accord­ing to ISO11474 [17]. Addi­tion­ally sam­ples were
washed with deion­ized water before spray­ing to avoid the accu­
mu­la­tion of salt. The spec­i­mens were col­lected in batches after 15,
30, 45, 75, 120, 180 and 230 days for weight loss mea­sure­ment.
2.4. Elec­tro­chem­i­cal imped­ance mea­sure­ments
The elec­tro­chem­i­cal imped­ance [18] mea­sure­ments were car­
ried out using a So­lar­tron 1255B fre­quency response ana­lyser in
 J. Guo et al. / Corrosion Science 51 (2008) 242–251 245
Fig. 5. Equiv­a­lent cir­cuit for spec­i­mens immersed in a 0.1 M NaCl solu­tion.
com­bi­na­tion with a PAR 1287A po­ten­tio­stat at room tem­per­a­
ture. A 0.1 M aque­ous NaCl solu­tion was used and the sinu­soi­dal
potential for mea­sure­ments was close to open cir­cuit potential
with an ampli­tude of 10mv and a fre­quency rang­ing from 106 to
10¡2 Hz.
2.5. Quan­ti­ta­tive phase anal­y­sis of rust lay­ers
Adhe­sive plas­ters were attached to sam­ple sur­faces after cor­
ro­sion and then stripped mechan­i­cally. The outer rust lay­ers were
sep­a­rated from the inner rust lay­ers and both lay­ers were care­
fully col­lected. Rust powder sam­ples were prepared for quan­ti­ta­
tive phase anal­y­sis and this was car­ried out by an inter­nal stan­
dard X-ray dif­frac­tion (XRD) method using a Cu tar­get. The scan
speed was 2.0°/min and the 2h angle ranged from 10° to 50°. ZnO
[19] was used as an inter­nal stan­dard. Crys­tal­line rust phases were
Fig. 6. EIS of steels sub­jected to an out­door test for 45 days and 230 days, respec­tively.
Goe­thite (a-Fe­O­OH), Ak­ag­ane­ite (b-Fe­O­OH), Lep­i­do­cro­cite (c-Fe­
O­OH) and Mag­ne­tite (Fe3O4). The dif­frac­tion inten­si­ties of the
(0 1 1) reflec­tion of a-Fe­O­OH, the (1 1 0) reflec­tion of b-Fe­O­OH, the
(0 2 0) reflec­tion of c-Fe­O­OH and the (2 2 0) reflec­tion of Fe3O4 were
mea­sured and com­pared with the (1 0 0) reflec­tion of ZnO powder.
The ratio of ZnO to cor­ro­sion prod­ucts was 3:7.
2.6. Obser­va­tion of ini­tial cor­ro­sion
Sam­ple sizes of 15 mm £ 15 mm £ 5 mm were used to inspect
the ini­tial cor­ro­sion. Pol­ished sur­faces were etched with an aque­
ous 0.5 mass% NaCl solu­tion for 4 h, 24 h and 60 h before inspec­
tion with an opti­cal micro­scope. When the sur­faces were cov­ered
by cor­ro­sion prod­ucts cor­ro­sion mor­phol­o­gies were sur­veyed by
SEM.
2.7. N2 adsorp­tion test
The adsorp­tion iso­therms of N2 on the rusted sam­ples were
mea­sured at the boil­ing point of liquid N2 using an AUTO­SORB-6B.
Sam­ples were degassed at 100 °C under 10¡3 Torr for 2 h before
the tests. The spe­cific sur­face area (SSA) of cor­ro­sion prod­ucts
was deter­mined by fit­ting the BET equa­tion to the adsorp­tion
iso­therms using the cross sec­tional area (0.162 nm2) of the N2
mol­ec­ ule.
246 J. Guo et al. / Corrosion Science 51 (2008) 242–251

Fig. 7. Quan­ti­ta­tive XRD phase anal­y­sis of rust lay­ers from steels A and B after expo­
sure in a salt fog cham­ber for 18 days and 63 days, respec­tively.

3. Results

3.1. Micro­struc­tures of tested steels

Micro­struc­tures of steels A, B and 09CuP­CrNi are shown in

Fig. 1. The micro­struc­ture of steel A con­sists mainly of polyg­
o­nal fer­rite (Fig. 1a). The micro­struc­ture of steel B con­sists
of fine bain­it­ic fer­rite and some acic­u­lar fer­rite as dom­i­nant
phases with a small amount of car­bon-rich phases (retained
aus­ten­ite or its trans­formed prod­ucts) that are dis­trib­uted ran­
domly (Fig. 1b). Micro­struc­tures of the com­mer­cial weathering
steel 09CuP­CrNi con­sist of polyg­o­nal fer­rite and pearl­ite (Fig.
1c). It is also much larger com­pared to the car­bon-rich phase
in steel B.

Fig. 8. Quan­ti­ta­tive XRD phase anal­y­sis of rust lay­ers from steels cor­roded in an out­
3.2. Cor­ro­sion rates in dif­fer­ent envi­ron­ments
door test for dif­fer­ent times: (a) steel A, (b) steel B and (c) 09CuP­CrNi.

Rela­tion­ships between weight loss and cor­ro­sion time are listed
in Fig. 2. Weight loss data in this study are expressed as the weight
loss per unit sur­face area.
Fig. 2a shows the weight loss curve of the spec­i­mens in the
salt fog test. The weight loss curves of steels A and B are close to
but obvi­ously lower than that of steel 09CuP­CrNi. The devi­a­tion
between the curves of steels A, B and 09CuP­CrNi increases with
cor­ro­sion time. A decline in cor­ro­sion rates of the three steels was
appar­ent from about 36 day which indi­cates that rust lay­ers started
to pro­tect the steels from this time.
Weight loss curves of the out­door test are shown in Fig. 2b.
The cor­ro­sion behav­iour of steel A in this test was com­pletely dif­
fer­ent to that seen in the salt fog test. The cor­ro­sion rate of the
steel increased con­stantly and this steel has the larg­est amount
of weight loss of the three steels. Both other steels exhib­ited high
weathering resis­tance. Their cor­ro­sion rates decreased after 15
 J. Guo et al. / Corrosion Science 51 (2008) 242–251 247

days. The curve of steel B is very close to but slightly lower than was higher than that in the outer rust lay­ers while the quan­ti­ties
that of steel 09CuP­CrNi. of the other phases are sim­i­lar.
Fig. 8 shows weight frac­tions of dif­fer­ent rust phases of steels
3.3. Elec­tro­chem­ic­ al imped­ance spec­tra A, B and 09CuP­CrNi that were exposed to an out­door envi­ron­ment
for 45, 120, 180 and 230 days. The results also show that the pro­
Elec­tro­chem­i­cal imped­ance spec­tra (EIS) of bare steels A and por­tion of X-ray amor­phous com­pounds in every spec­i­men was
B are shown in Fig. 3. Each spec­trum includes a semi­cir­cle. The higher than that of the var­i­ous crys­tal phases.
semi­cir­cle diam­e­ter of steel A is larger than that of steel B which For steel A (Fig. 8a) the amount of b-Fe­O­OH increased as the
means that the cor­ro­sion resis­tance of bare steel A is higher than test pro­gressed, but the change in the other crys­tal phases and the
that of bare steel B. Steel 09CuP­CrNi has the small­est semi­cir­cle of X-ray amor­phous sub­stance was very small.
these steels. This result indi­cates that decreas­ing car­bon con­tent For steel B (Fig. 8b) the quan­ti­ties of all crys­tal con­stit­u­ents
and improv­ing micro­struc­ture homo­ge­ne­ity are advan­ta­geous for increased from 45 to 120 days. After 120 days the amounts of
cor­ro­sion resis­tance of bare steel. Fig. 4 shows the EIS of steels A b-Fe­O­OH and c-Fe­O­OH were reduced while a-Fe­O­OH increased
and B that were sub­jected to a salt fog test for 18 days and 63 days, although the incre­ments were small. Mag­ne­tite con­tent is nearly
respec­tively. The spec­tra of the two steels that were cor­roded for con­stant.
18 days con­sisted of a depressed semi­cir­cle at the high fre­quency For steel 09CuP­CrNi (Fig. 8c) the amount of crys­tal phases
region and a long tail at the low fre­quency region. After 63 days increased from 45 to 180 days. As the test pro­gressed from 180 to
the spec­tra of the spec­i­mens were com­posed of two com­pressed 230 days the amount of a-Fe­O­OH kept increas­ing while b-Fe­O­OH
semi­cir­cles at the high and inter­me­di­ate fre­quen­cies region and a and c-Fe­O­OH decreased. Mag­ne­tite con­tent was almost con­stant.
dif­fu­sion tail at the low fre­quency region. An equiv­a­lent elec­tri­cal
cir­cuit (as shown in Fig. 5) is pro­posed for the sim­u­la­tion of the 3.5. Results from the N2 adsorp­tion test
elec­tro­chem­i­cal pro­cess of the steel that was cor­roded in the test.
Rs is the resis­tance of the solu­tion, Rr the resis­tance of the rust layer XRD results indi­cate that the pro­por­tion of X-ray amor­phous
while Crust and Cd1 are the capac­it­ ances of the rust layer and the com­pounds in every spec­i­men was much higher than that of the
dou­ble lay­ers, respec­tively. Because the cor­ro­sion pro­cess of steel var­i­ous crys­tal phases. X-ray amor­phous com­pounds are mainly
is con­trolled by the dif­fu­sion of ele­ments the Far­a­day imped­ance com­posed of micro­crys­tal­line oxides or hydrox­ides. Their size is
is divided into two parts: the charge trans­fer resis­tance Rt and the
War­burg imped­ance W. The lat­ter rep­re­sents the influ­ence of con­
cen­tra­tion polar­i­za­tion and ele­men­tal dif­fu­sion on the elec­trode
reac­tion which only exists at low fre­quen­cies. The rust layer resis­
tance that rep­re­sents the bar­rier against migra­tion of ions asso­
ci­ated with the cor­ro­sion reac­tion can be eas­ily deduced from an
extrap­o­la­tion of the EIS to the real axis of the semi­cir­cle and is
most use­ful for esti­mat­ing pro­tec­tive prop­er­ties of the rust layer.
Fig. 5 shows the var­i­a­tion of Rr with test time for the two sam­ples.
Rr val­ues for steel A increase from about 40 X cm2 to 80 X cm2 while
that of steel B increases from about 40 X cm2 to 50 X cm2 from 18 to
63 days. Incre­ments of rust resis­tances of both steels are small.
Fig. 6 shows the EIS of steels A and B that had been cor­roded
outdoors by inter­mit­tent spray­ing for 45 and 230 days. Rust layer
resis­tances of both steels are sim­i­lar at about 150 X cm2 after
cor­ro­sion for 45 days. After 230 days of cor­ro­sion the dif­fer­ence
between resis­tances increased. The resis­tance of steel A was about
500 X cm2 and that of steel B was about 5000 X cm2.

3.4. XRD of rust lay­ers

Cor­ro­sion prod­ucts of steels A and B that had been cor­roded

in the ATLAS fog cham­ber for var­i­ous times were ana­lysed by
XRD. The results indi­cate that the phase con­sti­tu­tion of inner
rust lay­ers on both steels was sim­i­lar and so was that of the outer
rust lay­ers. The phase con­sti­tu­tion of the inner rust lay­ers and
that of the outer rust lay­ers that were formed on the same type
of sam­ple were quite dif­fer­ent. Fig. 7 shows the rust con­stit­u­
ents of steels A and B from a quan­ti­ta­tive deter­mi­na­tion. The rust
lay­ers were found to be com­posed of a-Fe­O­OH, b-Fe­OO ­ H, c-Fe­
O­OH, Fe3O4 and large amounts of X-ray amor­phous com­pounds.
These com­pounds are mainly micro­crys­tal­line oxides or hydrox­
ides and could not be iden­ti­fied by XRD. By com­par­ing the inner
rust phases formed after 18 days of cor­ro­sion with that formed
after 63 days of cor­ro­sion on both steels it can be seen that the
quan­tity of a-Fe­O­OH increased slightly, the b-Fe­O­OH and the
c-Fe­O­OH also increased while the Fe3O4 reduced slightly. X-ray
amor­phous com­pounds also reduced in quan­tity. A com­par­i­son
of the rust lay­ers formed after 18 days of cor­ro­sion and 63 days Fig. 9. SSA of cor­ro­sion prod­ucts formed dur­ing the indoor and out­door accel­er­ated
of cor­ro­sion reveals that b-Fe­O­OH con­tent in the inner rust layer cor­ro­sion of steels.
248 J. Guo et al. / Corrosion Science 51 (2008) 242–251

one of the key param­e­ters for deter­min­ing the pro­tec­tion abil­ity
of rust lay­ers. Is­hik­a­wa et al. [20] pointed out that finer cor­ro­sion
prod­ucts are advan­ta­geous for the pro­tec­tion per­for­mance of rust
lay­ers. Smaller micro­crys­tal­line oxides/hydrox­ides result in more
com­pact rust lay­ers. Finer cor­ro­sion prod­ucts mean larger SSA. The
SSA of cor­ro­sion prod­ucts can be deter­mined by mea­sur­ing their
N2 adsorp­tion iso­therms. Fig. 9 shows that the SSA of rust prod­ucts
formed in the salt fog test are smaller than that formed in the out­
door test. The increase of SSA with cor­ro­sion time in the salt fog
test is small. These results indi­cate that there is no com­pact rust
layer formed dur­ing the salt fog test.
As shown in Fig. 9 the SSA of steel B and 09CuP­CrNi increased
mark­edly with out­door expo­sure time and this led to finer cor­
ro­sion prod­ucts with time. Steel A showed oppo­site behav­iour
because the SSA of the cor­ro­sion prod­ucts formed at 230 days was
smaller than that of the spec­i­men that was cor­roded for 45 days
which implies that cor­ro­sion prod­ucts in steel A coarsen with cor­
ro­sion time.
3.6. Ini­tial cor­ro­sion behav­iour of steels and mor­phol­o­gies of rust
lay­ers
The direct influ­ence of steel micro­struc­ture on cor­ro­sion behav­
iour is reflected in the ini­tial stage of cor­ro­sion. Bare 09CuP­CrNi
cor­roded faster than bare steels A and B in aque­ous NaCl solu­tion.
Micro­struc­tures in 09CuP­CrNi, espe­cially pearl­ite, appeared on the
sur­face after immer­sion in the NaCl solu­tion for 4 h (as shown in
Fig. 10a). After immer­sion for 24 h more pearl­ite and polyg­on ­ al
fer­rite appeared (as shown in Fig. 10b). With an immer­sion time
longer than 60 h the spec­i­men’s sur­face became cov­ered with films
of cor­ro­sion prod­ucts. There were cracks on the film next to the
grain bound­aries of the steel sub­strate that con­trib­uted to film
detach­ment from some polyg­o­nal fer­rite. Bright white bases were
observed at the posi­tions where films dropped off (as shown in Fig.
10c with arrows). Cracks along crys­tal bound­aries and shell­ing off
of local films can be seen more clearly using SEM (Fig. 10d).
For steel B, which was immersed for 4 h, only local cor­ro­sions
were observed. The cor­roded zones are MnS inclu­sions (as pointed
in Fig. 10e with arrows). With immer­sion times exceed­ing 24 h
steel micro­struc­tures began appear­ing (as shown in Fig. 10f). At
60 h, films of rust prod­ucts spread over spec­i­men sur­faces (as
shown in Fig. 10g). SEM indi­cated that the film was uniform and
even with only a few cracks around MnS inclu­sions (as shown in
Fig. 10h with arrows).
Steel A exhib­its sim­i­lar ini­tial cor­ro­sion char­ac­ter­is­tics to that of
steel B under the same con­di­tions. Films of rust prod­ucts on steel
A are more even than those of steel B. Film shell­ing is observed in
some zones (as shown in Fig. 10i).
Cross sec­tions of steels A, B and 09CuP­CrNi that were exposed
to an ATLAS fog cham­ber for 18 and 63 days were inves­ti­gated by

Fig. 10. Micro­graphs of steels after immer­sion in 0.5 mass% aque­ous NaCl solu­tion for 4 h, 24 h and 60 h, respec­tively. Opti­cal micro­pho­to­graphs of steel 09CuP­CrNi for (a) 4 h,
(b) 24 h and (c) 60 h; SEM pho­to­graph of steel 09CuP­CrNi for (d) 60 h; Opti­cal micro­pho­to­graphs of steel B eroded for (e) 4 h, (f) 24 h and (g)60 h; SEM pho­to­graph of steel B
for (h) 60 h; SEM pho­to­graph of steel A for (i) 60 h.
 J. Guo et al. / Corrosion Science 51 (2008) 242–251 249
SEM (as shown in Fig. 11). This fig­ure reveals that rust lay­ers on
the three steels after 63 days of cor­ro­sion were more com­pact and
thicker than those after 18 days of cor­ro­sion. There were more
and larger pores as well as longer cracks in the rust lay­ers of steel
09CuP­CrNi than in steels A and B. The char­ac­ter­is­tics of rust lay­ers
formed on steels A and B are sim­i­lar.
Fig. 12 shows SEM pho­to­graphs of steels A, B and 09CuP­CrNi
exposed to the out­door envi­ron­ment for 45 and 230 days. From
this fig­ure it can be seen that rust lay­ers formed on steel A are
the most com­pact and the inter­face between rust lay­ers and the
base are more even than for the other steels. The cor­ro­sion rate
of steel A was the fast­est among the three spec­i­mens. This might
be because of the rust on the steel eas­ily under­go­ing a spall­
ing pro­cess (as shown in Fig. 12d with arrows). New loose rust
between the large cracks and bases was formed after the gen­
er­a­tion of a large cleav­age. The other sam­ples had more flaws
such as cracks and pores but the rust lay­ers were bonded well
to the sub­strates. By care­ful obser­va­tion, the inter­faces between
rust lay­ers and bases of the two other spec­i­mens were seen to
be conc­avo-con­vex. The irrup­tive cor­ro­sion fronts anchored the
rust onto the sub­strate to a cer­tain extent. Decreas­ing the car­
bon con­tent to an ultra-low degree and improv­ing the micro­
struc­ture uni­for­mity are pos­si­bly the major rea­sons for steel
A exhib­it­ing dif­fer­ent cor­ro­sion behav­iour under dif­fer­ent cir­
cum­stances. Spe­cif­i­cally, the rust was com­pact and the cor­ro­
sion resis­tance was high for steel A in the salt fog test. On the
other hand, rust tended to fall off dur­ing the accel­er­ated out­
door test and this is attrib­uted to the large wet-dry stress and
the ther­mal stress of the out­door envi­ron­ment. Con­se­quently,
we con­clude that it is dis­ad­van­ta­geous for the long-term cor­ro­
sion prop­erty of steel that cor­ro­sion is micro­scop­i­cally uniform,
as the rust layer shells off from the over even inter­face which is
led by over uniform cor­ro­sion.
Fig. 11. SEM micro­graphs of cross-sec­tions of steels A, B and 09CuP­CrNi after being sub­jected to a salt fog test for 18 days and 63 days, respec­tively: (a) steel A, (b) steel B and
(c) 09CuP­CrNi for 18 days; (d) steel A, (e) steel B and (f) 09CuP­CrNi for 63 days.
4. Dis­cus­sion
The phe­nom­e­non most deserv­ing of atten­tion in the pres­ent
inves­ti­ga­tion is that the cor­ro­sion behav­iour of steel A in the salt
fog test and the out­door test were quite dif­fer­ent.
The cor­ro­sive envi­ron­ment in the salt fog cham­ber is sim­i­lar
to that of the coastal atmo­sphere in south­ern China, and is more
severe than that in the out­door test. In the salt fog cham­ber, it is
dif ­fi­cult for the rust layer to dry entirely and the con­cen­tra­tion
of the cor­ro­sive liquid is con­sid­er­ably higher. The homo­ge­neous
micro­struc­ture of naked steel A results in excel­lent cor­ro­sion resis­
tance and the rust layer formed on it is the most com­pact. The cor­
ro­sion rate of steel 09CuP­CrNi tested in the salt fog cham­ber is the
fast­est. The prob­a­ble reason for this is that local cor­ro­sions appear
around pearl­ite. The vol­ume expan­sion of cor­ro­sion prod­ucts in
these areas result in local cor­ro­sion stress which pro­motes defects
and speeds up the cor­ro­sion pro­cess.
The out­door test envi­ron­ment is sim­il­ ar to that of inshore
areas in the north of China that have mild cor­ro­sion con­di­tions.
Large tem­per­a­ture fluc­tu­a­tions and wet-dry alter­na­tions induce
stress in rust lay­ers. As a result of the even inter­faces between
rust and base and fewer cor­ro­sion fronts extrud­ing into the base,
the bond­ing force between the rust and the base is weak. Rust
lay­ers tend to peel from the base, and the exposed base accel­er­
ates the cor­ro­sion pro­cess. Com­par­at­ ively mild con­di­tions lim­
ited local cor­ro­sion.
The cor­ro­sion resis­tance of steel B is excel­lent in both envi­
ron­ments. The car­bon con­tent in steel B is sim­i­lar to that in steel
09CuP­CrNi. The fine size and random dis­tri­bu­tion of car­bon-rich
phases play a key role in anchor­ing bases and rust lay­ers. The local
cor­ro­sions caused by them would thus not result in high stress.
The ini­tial cor­ro­sion behav­iour can be influ­enced by the type
of micro­struc­tures. Addi­tion­ally, this effect was mainly reflected
250 J. Guo et al. / Corrosion Science 51 (2008) 242–251
Fig. 12. SEM micro­graphs of cross-sec­tions for steels A, B and 09CuP­CrNi after being sub­jected to an out­door test: (a) steel A, (b) steel B and (c) 09CuP­CrNi for 45 days; (d)
steel A, (e) steel B and (f) 09CuP­CrNi for 230 days.
in the rust den­sity and the bond­ing per­for­mance of the rust-base
rather than the pro­por­tion of rust phases in the ini­tial stage of
atmo­spheric cor­ro­sion. Low-car­bon con­tent is dis­ad­van­ta­geous for
cor­ro­sion prop­er­ties whereas appro­pri­ate car­bon con­tent in steel
can pro­duce car­bon-rich phases with a fine size and a uniform
dis­tri­bu­tion by proper pro­cesses; and these are ben­e­fi­cial for
weathering resis­tance.
5. Con­clu­sions
(1) Cor­ro­sion resis­tance of steels A and B with homo­ge­neous
micro­struc­tures is bet­ter than that of a com­mer­cial weathering
steel in the salt fog test. How­ever, steel A with ultra-low-car­
bon con­tent had far less weathering resis­tance than that of
the other steels in an out­door test. Cor­ro­sion behav­iour of the
same steel may be abso­lutely dif­fer­ent under diverse envi­ron­
ments.
(2) Selec­tive cor­ro­sion of large pearl­ite pro­duces stress in films
of ini­tial cor­ro­sion prod­ucts. Films of uniform cor­ro­sion
prod­ucts that con­tain few cracks tend to form on homo­ge­
neous micro­struc­tures such as fer­rite and ba­i­nite and this
is advan­ta­geous for the for­ma­tion of com­pact rust lay­ers
dur­ing ini­tial cor­ro­sion. Inter­faces between rust lay­ers and
bases fre­quently result in peel­ing of rust lay­ers from bases
under stress induced by large tem­per­a­ture fluc­tu­a­tions and
wet-dry alter­na­tions.
(3) Pro­tec­tion of rust lay­ers on low alloy steels derives mainly
from the rust den­sity and the bond­ing per­for­mance of the
rust-base rather than the pro­por­tion of the rust phase at the
ini­tial stage of atmo­spheric cor­ro­sion.
(4) Homog­en ­ ous micro­struc­tures, proper amounts of car­bon con­
tent and fine car­bon-rich phases pro­duced by appro­pri­ate pro­
cesses are ben­efi­ ­cial to the cor­ro­sion resis­tance of steels.
Acknowl­edge­ments
This research was finan­cially sup­ported by the National Key
Basic Research and Devel­op­ment Programme of China (No.
2004CB619102), the National Nature Sci­ence Foun­da­tion of
China (No. 50571016 and 50571089) and the National High Tech­
nol­ogy Research and Devel­op­ment Programme of China (No.
2006AA03Z507).
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