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J. Mater. Sci. Technol., Vol.20 No.2, 2004

Fig.7 Anodic polarization curves for the unalloyed and 4%

Cu alloyed 316L stainless steel cladding samples in
0.1 mol/L FeCl3
that of the sample with unalloyed 316L stainless steel cladding
layer. The alloyed cladding sample showed better behaviour
than unalloyed cladding ones.
These results complemented the immersion tests. The
electrochemical test was more and more utilized to study
the corrosion behaviour of sintered materials because of the
obtained useful information[1214] . However, electrochemical
tests (including electrochemical reactivation ) applied to sintered materials are highly affected by interconnected porosity.
4. Conclusions
(1) The sintering density of alloyed 316L stainless steels
was improved as Cu and bronze content increased when sintered at 1423 K. Copper and bronze promoted liquid sintering
that activated this process.
(2) Both alloyed and unalloyed 316L surface layers produced by PM cladding on a plain carbon steel had an effect
to improve corrosion resistance in H2 SO4 solution and FeCl3
solution.
(3) The corrosion resistance of alloyed 316L surface layer
with 4% Cu or bronze was better than that of unalloyed 316L

surface layer in H2 SO4 solution and FeCl3 solution. The addition of 4% Cu or bronze enhanced 316L stainless steel passivation tendency in 10% H2 SO4 and reduced corrosion rate
of 316L stainless steel in 0.41 mol/L FeCl3 .
(4) 4% Cu alloyed 316L surface layer by PM cladding had
similar anodic polarization behaviour to the unalloyed 316L
surface layer. In 1 mol/L H2 SO4 solution, the critical current density was slightly smaller in the 4% Cu alloyed 316L
stainless steel cladding sample compared with the unalloyed
one. In 0.1 mol/L FeCl3 solution, the anodic current density
increased continuously as the potential increased. The anodic current density of the sample with 4% Cu alloyed 316L
cladding layer was a little smaller than that of unalloyed 316L
cladding sample.
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Han-Cheol Choe: Surf. Coatings Technol., 1999, 112, 299.

Corrosion and Runoff Behavior of Carbon

Steel in Simulated Acid Rain
Baigang AN1,2) , Xueyuan ZHANG1) , Enhou HAN1) and Honxi LI1)
1) State Key Lab. for Corrosion and Protection of Metal, Institute of Metal Research, Chinese Academy of Sciences,
Shenyang 110016, China.
2) School of Chemical Engineering, Anshar University of Science and Technology, Anshar 114002, China.
[ Manuscript received September 4, 2002, in revised form December 24, 2002]

Under the condition of simulated rain precipitation in the laboratory, with EIS and SEM observation, the effects of pH value
of simulated rain on corrosion and runoff behavior of carbon steel A3 were studied. The corrosion rate of A3 steel increased
and runoff action of rain precipitation on A3 steel surface was intensified with decreasing pH value, of simulated rainwater.
The runoff and corrosion traces were formed along the flowing direction of rainwater, which appeared more apparently with
decreasing pH value.
KEY WORDS: Simulated acid rain, Carbon steel, Corrosion
1. Introduction
Atmosphere is the most common environment in which
materials suffered corrosion. Due to complex atmosphere environment, atmospheric corrosion of material was influenced
by many factors such as relative humidity, pollutant, rain,
etc. Because it was well known that the corrosion of metal
exposed to an atmosphere is electrochemical reaction under
thin liquid film in nature, the most of investigations[14] were
Assi. Prof., Ph.D., to whom correspondence should be addressed,
E-mail: xyzhang@imr.ac.cn.

focused on metal corrosion under thin liquid film including

study for effects of pollutant, liquid film thickness and composition of electrolyte. During precipitation of rain, not only
complete liquid film could be formed on the surface of metal
but also rain could supply abundantly active electrolyte in
that rainwater dissolved many corrode components such as
chloride, sulfate, nitrate, hydrogen ion etc, which could influence atmospheric corrosion behavior of metal. Sometimes
according to the nature of metal or corrosion products rain
could runoff or strike metal and thus accelerate corrosion of
metal. In present paper, effects of pH value of simulated acid
rain on corrosion of carbon steel with a lab. system to sim-

J. Mater. Sci. Technol., Vol.20 No.2, 2004

221

ulate rain precipitation which can control rain intensity[5] ,

combined with EIS and SEM methods were studied.
2. Experimental
2.1 Specimen and simulated rainwater
The used specimens were made of carbon steel A3. The
specimens with the size of 100 mm50 mm2 mm were
used to test that the effect of simulated acid rain precipitation on corrosion of A3 steel, and those with the size of
10 mm10 mm, which were mounted with epoxy resin and
1 cm2 area exposed, were used as electrochemical working
electrodes. All the specimens were successively ground with
150, 600, 1000 grit SiC paper, then cleaned with deionized
water and acetone prior to each experiment. The simulated
rainwater was prepared from bidistilled water and analytical
grade reagents according to the research results on Chongqing
rainwater[6] . Its composition is given in Table 1. Its normal
pH value was 5.72 at room temperature (20 C and varied with
the addition of H2 SO4 .
2.2 Lab. tests for simulated raining
The
specimens
of
A3
steel
with
size
of
100 mm50 mm2 mm were placed in simulated raining system which made an angle of 45 C with horizontal
direction. The specimens were tested in the raining for
12 h. The rain intensity was controlled as 5 mm/h during raining process. The 4 pieces of A3 steel specimens
were used in each experiment. After raining experiment,
the corrosion products of specimens were cleared with rust
cleaning solution, the 3 specimens of them were used to
Table 1 Composition of simulated
Chongqing
rainwater[6]
Ions
SO2
4
Cl
NO
3
NH+
4
Na+
K+
Mg2+
Ca2+

Concentration
/mgdm3
341.0
26.8
40.1
15.7
15.5
10.8
20.8
97.2

determinate mass loss and 1 specimen was used to observe

surface morphology with SEM.
2.3 Electrochemistry tests
A three-electrode cell was used for the electrochemical
impedance measurement. SCE and platinum electrode were
for reference electrode and counter electrode respectively.
Electrochemical impedance was measured by Gamry PC4/750
general electrochemical system. Impedance measurements
were conducted at the (open circuit potential) OCP in the
frequency range of 10000 Hz0.06 Hz. The amplitude of potential modulation was 5 mV.
3. Results and Discussion
The electrochemical impedance spectrum of A3 steel in
simulated rainwater solution is shown in Fig.1. All impedance
spectrum included straight line in higher frequency and compressed semicircle in lower frequency. Amplitude of loop in
lower frequency decreased with decreasing pH value. The
semicircle in low frequency is attributed to parallel double capacitors and Faraday resistance which represented corrosion
rate of A3 steel. Therefore, it can be suggested that corrosion rate of A3 steel increased with decreasing pH value of

Fig.1 Electrochemical impedance spectrum of A3 steel in

simulated rainwater

Fig.2 Weight loss curve of A3 steel in simulated rainwater

simulated rainwater according to the variation of impedance
spectrum with pH value of rainwater, and the result of weight
loss (shown in Fig.2).
Rain can influence atmospheric corrosion process of metal
in different ways: (1) wetting metallic surface and increasing
time of wetness, (2) transporting active corrosion pollutants.
(3) cleaning metallic surface and removing pollutants. In addition, the rain can also strike and runoff metallic surface and
erode metal. In present experiment, the traces of runoff and
corrosion for A3 steel by rain could be seen evidently from
Fig.3. The runoff solutions containing rust particles from
surface of A3 steel also suggested that the part of corrosion
products had been struck and runoff. Under the condition of
different pH value of rainwater the corrosion and runoff morphology appeared differently. When pH value of rainwater
is 3.4 the surface of A3 steel formed almost successive and
narrow corrosion and runoff traces. The traces are even and
intense distribution relatively on whole surface of A3 steel.
When pH value of rainwater is 4.5 the traces were still apparent but not as continuous, even and intense distribution
on the surface as that of pH 3.4 rainwater, and some bigger
corrosion pits appeared on the surface. When pH value of
rainwater is 5.7 it seemed that the trace of rain runoff is not
very apparent and single corrosion pits with large area were
loosely distributed on surface of A3 steel.
It is well known that rust layers on iron and carbon steel
are porous[7,8] and poorly adherent[9] , therefore the falling
rain droplets could strike corrosion products poorly adherent
to the surface and make that runoff from surface. Cracks
in the rust layers are common and are concentrated in the
outmost portions of the rust[8] . Rust pores have typical diameters of a few nanometers, pore sizes as large as 15 nm in
diameter have been found, with typical pore volume consisting 5%10% of the rust volume[10] . Such a structure provides
a little barrier to the ingress of adsorbed water or precipitation and made rainwater penetrate into rust pores or cracks
and corrode matrix.
Why were corrosion and runoff morphology different when
the pH was different? In natural rust layers on iron and steel,
FeOOH, in several crystal forms, is the predominant stable
species. The rust layers generally include a dense inner re-

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J. Mater. Sci. Technol., Vol.20 No.2, 2004

Fig.3 Surface morphology of A3 steel after raining test with different pH value rainwater (a) 3.4, (b) 4.5, (c) 5.7

Fig.4 A schematic diagram for the sulfate nest and corrosion cell
gion of, amorphous FeOOH and some crystalline Fe3 O4 and a
loose outer, crystalline assemblage ofFeOOH, FeOOH
and Fe2 O3 [10] . During rain precipitation, part of outer
loose corrosion products may be lost due to the mechanical
action of rain droplets on the surface which were common for
rain with different pH values. However, protective corrosion
products and concentration of sulfate ions would change with
the variation of pH. If the pH value is less than 4, the oxyhydroxide may be reduced to soluble Fe (II) according to the
potential-pH diagram[11] , which can also occur when the concentration of ion species increases in aqueous layer[12] . Sulfate
can make carbon steel form the sulfate nest (Fig.4)[11] since
corrosion is usually localized, the influence of sulfur species
is probably spatially heterogeneous. The nests contain high
concentrations of corrosion products and electrolyte. These
products are thought to be temporarily retained by a semipermeable membrane of precipitated and colloidal oxyhydroxides. The high ionic strength of solution induces the diffusion
of water into the nest and swells the membrane. Eventually
the membrane bursts, spreading its contents to adjacent areas
to stimulate corrosion there. When the pH value is 3.4 the
high concentration of sulfate and ionic strength make more
sulfate nests form, the high concentration of hydrogen ion
makes the corrosion products to form soluble Fe (II) and membrane burst more rapidly, more nests connect with each other
along the flowing direction of the rainwater on the surface of
the A3 steel and form runoff channel, therefore corrosion and
runoff action increase. However, with increasing the pH value
of rainwater the nests formed on A3 steel would reduce and
more protective corrosion products would cover the nests and
the dissolution rate of membrane may decrease. Rainwater
would prefer to penetrate into nets with low resistance, in
which nests enlarge and may immerge each other and form
pits with large area (pH 5.7).
The effects of rain precipitation on corrosion and runoff
of A3 steel increased with decreasing pH value of rainwater
under the same rain intensity. According to An et al. previous research[13] , the corrosion rate and runoff rate of A3 steel
increase with increasing rain intensity due to the mechanical
action of rain droplet falling, corrosion rate decreases grad-

ually with raining time due to corrosion products formed on

the surface of A3 steel, showing that rain could influence atmosphere corrosion of metal in different ways.
4. Conclusion
The corrosion rate of A3 steel increased with decreasing
the pH value of simulated rainwater. Rain precipitation could
strike and runoff the corrosion products on surface of A3 steel
and make part of that to be lost into runoff solution. The
corrosion and runoff action of rain were intensified with decreasing the pH value of simulated rainwater.

Acknowledgement
The work was supported by the National Natural Science Foundation of China (No. 50101011) and the Special Foundation of
National Key Basic Research of China ( No. 1999065004).
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