Materials Science Forum Online: 2016-03-20

ISSN: 1662-9752, Vol. 850, pp 78-85

doi:10.4028/www.scientific.net/MSF.850.78
© 2016 Trans Tech Publications, Switzerland

Corrosion Behavior of Austenitic Stainless Steel in Hydrochloric Acid

Solution and Flow
Bingyi Liu 1,2,a*, Yajun Xue 1,2, b, Zonghui Yang 1, 2,c and Xinxian Fang 1, 2,d
1
School of Materials Science and Engineering, Nanjing Institute of Technology, 1 Hongjing Dadao
Road, Nanjing 211167 China
2
Jiangsu Key Laboratory of Advanced Structural Materials and Application Technology, Nanjing
Institute of Technology, 1 Hongjing Dadao Road, Nanjing 211167 China
a
liuby@njit.edu.cn, bxdx01@126.com, cyzh@njit.edu.cn, dfangxinxian@sohu.com

Keywords: 304 austenitic stainless steel, Hydrochloric acid, Corrosion, Erosion corrosion,
Corrosion mechanism.

Abstract. The corrosion behaviors of austenitic stainless steels, 304 and 316L as a contrast material,
are investigated in hydrochloric acid corrosion under different conditions including immersion
corrosion, single-phase flow and two-phase flow, respectively. The corrosion mass loss test and
electrochemical test were carried out to evaluate the influence of medium temperature and
concentration. The specimen surface morphologies and chemical compositions were obtained using
scanning electron microscope to analyze the corrosion mechanism. The results show that the static
corrosion rates of 304 and 316L steels and erosion corrosion rates of 304 steel increase obviously
with the medium temperature increasing, but, the effect of hydrochloric acid concentration on their
corrosion rate is less than that of the temperature. The corrosion current density values of 304
stainless steel increase and its passivation region of the polarization curve becomes narrowing and
disappeared as the medium temperature increase. Uniform corrosion is the main way found on the
surfaces of the stainless steels at room temperature in the hydrochloric acid solution. However, the
selective corrosion occurs on their surface with the medium temperature increasing, and the higher
temperature and concentration of corrosion medium, the more serious selective corrosion．

Introduction
Austenitic stainless steels are widely used in food, chemical, petroleum, mining industries to
produce many components where corrosion resistance is crucial. The materials are often exposed to
corrosive environments of relatively high temperature or contacting fluid media. These
environments lead not only to high costs maintaining the components but also to shorting their
service life [1-4]. For reducing the material failure caused by corrosion, it has important engineering
significance to research their corrosion mechanism under these corrosive conditions. In this paper
the corrosion behaviors of 304 stainless steel and 316L stainless steel as contrast material, which are
two austenitic stainless steels in common use, were investigated systematically to explain the effects
of concentration and temperature of hydrochloric acid solution, as well as the erosion of
single-phase flow and solid-liquid two-phase flow containing hydrochloric acid at different
temperatures on the corrosion process of austenitic stainless steels.

Materials and Methods

304 and 316L stainless steel specimens (10mm×11mm×2mm and 10mm×11mm×4mm) were
obtained from cold-rolled steel plate by means of electric discharge line cutting method, burnished
with sand paper, cleaned with ultrasonic in alcohol and dried by airing.

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 Materials Science Forum Vol. 850 79

The static corrosion rate was measured with immersion corrosion method. 304 and 316L
specimens were immersed for 1h respectively in 80℃ water solutions with hydrochloric acid
concentration (volume fraction, the same below) of 5%, 10%, 15% and 20%, and in 20℃, 50℃, 65
℃ and 80℃ 20% HCl water solutions for 2h, 2h, 1h and 1h respectively. FA1004 electronic
balance (precision 0.1mg) was used to measure original mass m0 and the mass after static
immersion corrosion m1 of the specimens respectively. The static corrosion rate was calculated as
the formula v=∆m/St, and wherein, ∆m=m0 － m1, S and t indicate original surface area and
immersion corrosion time of specimens respectively.
The erosion corrosion experiments were performed with a modified erosion corrosion apparatus
shown in Figure 1. The specimens were fixed at 30mm away from the center of rotating bar which
rotated at speed of 500r/min. The linear speed of specimens was 1.5m/s. 20% HCl water solution
and 20% HCl water solution + 20g/L sand (average grain size 120µm) were prepared as fluid media
to measure the mass losses of 304 specimens under single-phase flow erosion and two-phase flow
erosion at the temperature of 20℃, 50℃, 65℃ and 80℃ respectively, and erosion rate was
calculated as the formula v=∆m/St.

Fig.1 Schematic diagram of erosion corrosion tester.

The polarization curve of 304 stainless steel was tested with PASTAT2273 advanced
electrochemical system. The corrosion media were 5% and 15% hydrochloric acid solutions. The
test temperatures were 25℃, 65℃ and 80℃ which were controlled by means of a
constant-temperature water bath. Standard three-electrode system consists of a saturated calomel
electrode (SCE) as the reference electrode, a platinum electrode as the auxiliary electrode and the
sample as the working electrode (working surface size 10 mm ×10 mm).
JSM6360LVX scanning electron microscope (SEM) was used to observe the surface
morphology of specimens after static corrosion and erosion corrosion, and the surface compositions
of specimens were analyzed with GENESIS 2000XMS60 Energy Dispersive Spectrometer (EDS).

Results and Discussion

Corrosion rate. Figure 2 shows the static corrosion test results of 304 and 316L stainless steel in
20% hydrochloric acid solution at different temperatures. According to Figure 2, raising the
temperature of corrosion media could increase the corrosion rate of both materials, but there exists
obvious difference in the degree of media temperature’s influence on the corrosion rate of 304 steel
80 Methods of Design and Characterization of Materials, Research and
Development of Technological Processes

and 316L steel. 304 and 316L stainless steels have 122 times and 84 times higher corrosion rate at
80℃ than at 25 ℃ respectively, and the corrosion rate of 304 stainless steel is around double that of
316L stainless steel at 80 ℃. The above mentioned results show that, both materials have similar
corrosion rate and good corrosion resistance at room temperature, but in high-temperature HCl
solution, the corrosion resistance of 316L steel is better than that of 304 steel.

Fig.2 Variation of static corrosion rates of 304 Fig.3 Effect of HCl concentration on
and 316L steels with different medium corrosion rate of 304 and 316L stainless steels
temperature. at 80℃
Figure 3 shows the influence of HCl concentration on the static corrosion rate of 304 and 316L
stainless steels at the temperature of 80℃. According to Figure 3, HCl concentration has greater
influence on 304 steel than on 316L steel at high-temperature. When HCl concentration is raised
from 5% to 20%, the corrosion rate of 304 steel is increased by around 9 times, while that of 316L
steel is increased by around 5 times. It shows the influence of HCl concentration on their corrosion
rate is less than that of the temperature. It also be seen that 304 steel has relatively big absolute
value of corrosion rate and relatively poor corrosion resistance, while 316L steel has comparatively
good anti-corrosion performance in HCl solution of different concentration.
Figure 4 shows the influence of media temperature on the erosion rates of 304 stainless steel in
20% HCl solution, and the static corrosion rate–temperature curve of this steel is also introduced for
comparison in Fig. 4. According to the Figure, the erosion rate of 304 steel in single-phase flow and
two-phase flow increases along with increasing medium temperature. The sequence of corrosion
rate from high to low is two-phase flow erosion, single-phase flow erosion and static immersion
corrosion at temperatures less than 50℃, while at temperatures above 60℃ the sequence becomes
static immersion corrosion, two-phase flow erosion and single-phase flow erosion respectively. The
influence factor of erosion corrosion is more complicated than that of static corrosion due to the
synergistic effect between erosion and corrosion [5-9]. On the one hand, fluid erosion accelerates
the process of mass transfer on corrosion surface and the peeling of corrosion products from metal
surface. It can make corrosion media contact metal surface sufficiently and promote corrosion
process. On the other hand, for blunt metals such as austenitic stainless steel, in condition that flow
rate is not high, the flowing of media not only promotes the conveying of dissolved oxygen to metal
surface, but also changes the adsorption of some active anions (such as Cl¯) on metal surface. It can
raise the ability of passive film formation and repair, thus slows down corrosion process. When the
latter effect is relatively strong (such as at higher temperature), static corrosion rate is higher than
erosion corrosion rate. In addition, micro-cutting on metal surface produced by suspended
solid-phase particles in two-phase flow generally increases the loss of materials.
Polarization curve. In order to analyze the electrochemical behavior of hydrochloric acid on 304
stainless steel cathode and anode corrosion, its polarization curve was measured in hydrochloric
 Materials Science Forum Vol. 850 81

acid solutions of different concentrations and different immersion temperatures. Figure 5 shows the
polarization curve of 304 steel in 5% hydrochloric acid solution from 25℃ to 80℃. According to
Figure 5, self-corrosion potential (Ecorr) at 25℃ is －0.31 V, and along with potential increase,
corrosion current density will increase; at 0.08V, electrode converts from transition state to passive
state, its stable passive region maintains until potential is 0.16V, and then, along with the increase of
corrosion potential, corrosion current density also increases quickly, indicating that the stable
passive film with good corrosion resistance is destroyed and local exposed metal is corroded [10,11].
At 65℃ and 80℃, self-corrosion potential drops slightly, but current density increases sharply
along with potential increase, and stable passive region does not appear in the curve any longer. The
polarization curve of 304 stainless steel in 15% HCl solution presents similar situation.
Self-corrosion current density reflects corrosion rate, and within the temperature scope of 25～80℃,
the self-corrosion current density of 304 steel increases along with the temperature rise of
hydrochloric acid solution, indicating that its corrosion rate increases along with temperature rise of
corrosion media, and this is accordant with the experimental result of immersion corrosion.

Fig.4 Variation of static and erosion corrosion Fig.5 Polarization curves of 304 stainless
rates of 304 steel with different medium steel in 5% HCl solution at different
temperature. temperature.
Surface morphology and corrosion mechanism. Figure 6 shows the surface morphology of 304
stainless steel in 20% HCl solution of different temperatures. According to the figure, along with
the temperature rise, the corrosion on surface of specimens becomes severe and develops from even
corrosion to uneven corrosion. The phenomenon is much related to the change of passive film
structure on metal surface as a result of the temperature rise. EDS analysis shows that, along with
temperature rise of media, the mass fracture of Fe and Cr on surface of stainless steel drops, while
that of Ni rises. Compared with the matrix compositions of 304 stainless steel, the mass fraction of
Fe, Cr and Ni on surface of 25℃ corrosion specimens is the same as that of matrix; while on the
surface of 50～80℃ corrosion specimens, the mass fraction of Fe and Cr is lower than that of
matrix. Especially, the mass fraction of Fe drops obviously, while the mass fraction of Ni is higher
than that of matrix; and the higher the temperature is, the greater the difference will be. On the one
hand, it shows that elevated temperature promote selective corrosion; on the other hand, it shows
that the passive film formed from corrosion of 304 stainless steel at high temperature is different
from that at room temperature, and it is a passive film with high Ni content. In high-temperature
hydrochloric acid solution, Cl¯ adsorption induces the dissolution of Cr-rich passive film consisting
of Cr2O3, NiO and FeO on surface of 304 stainless steel and loss of Fe and Cr, so Ni-rich passive
film is formed on the surface.
82 Methods of Design and Characterization of Materials, Research and
Development of Technological Processes

(a) (b)

(c) (d)

Fig.6 SEM images of the surface morphologies of 304 steel specimens after static erosion in 20%
HCl solution at 25℃(a), 50℃(b), 65℃(c) and 80℃(d).
Figure 7 shows the surface morphologies of 304 stainless steel after corrosion in 80℃
hydrochloric acid solution of different concentrations. According to the figure, if the temperature of
HCl solution is the same, then along with the rise of hydrochloric acid concentration, the degree of
corrosion on surface of specimens will increase. EDS analysis shows that, along with the rise of
hydrochloric acid concentration, the mass fraction of Fe and Cr will drop, while that of Ni will rise
(Figure 8), and such change of chemical composition will increase along with the rise of
hydrochloric acid concentration. This shows that, the greater the hydrochloric acid concentration is,
the more severe the selective corrosion will be, and the Stronger the tendency of forming Ni-rich
passive film on metal surface will be. In the environment of high-temperature hydrochloric acid
corrosion, it is impossible to form stable passive film which could provide continuous and dense
protection for surface of stainless steel, but instead, passive film is formed, destroyed and repaired.
Local passive film on the surface is broken and peeled, and fresh metal matrix is exposed, which
has high chemical activity and is eroded quickly, inducing the formation of pits on the surface;
meanwhile, selective corrosion induces the accumulation of Ni and formation of new rich Ni
passive film, namely the passive film is repaired. The passive film is constantly broken and
repaired, playing the role of inhibiting corrosion, and this is a major reason why stainless steel has
better anti-corrosion performance than non-passive metals [12]. The EDS analysis of corrosive
surface of 316L stainless steel shows that, Mo-rich and Ni-rich passive film is formed in
high-temperature hydrochloric acid. The oxidized film of Mo has higher stability for Cl¯, and also,
it has stronger self-repair ability, so 316L stainless steel has better corrosion resistance than 304
stainless steel in high-temperature hydrochloric acid [13-15].
 Materials Science Forum Vol. 850 83

(a) (b)

(c) (d)

Fig.7 SEM images of the surface morphologies of 304 steel specimens after static erosion in 80℃
HCl solution: (a)5% HCl, (b)10% HCl, (c) 15% HCl and (d) 20% HCl.

Fig.8 Surface chemical composition of 304 stainless steel corroded in different

HCl solution at 80 ℃.
Figure 9 shows the surface morphology of 304 stainless steel after erosion corrosion in 20% HCl
solution at different temperatures, and similarly, it shows the phenomenon of transformation from
uniform corrosion to local corrosion along with temperature rise of media. Figure 9(b) shows the
morphology of dense corrosion pits formed from severe intercrystalline corrosion. Figure 9(d)
shows the morphology of two-phase flow erosion in high-temperature hydrochloric acid, there
appear some narrow and long corrosive pits on the surface of specimens and they are possibly
induced by aggravation of corrosion at the position where passive film on metal surface is scratched
by solid-phase particles in fluid [16]. EDS analysis shows that the change of chemical compositions
84 Methods of Design and Characterization of Materials, Research and
Development of Technological Processes

on the surface of 304 stainless steel in condition of erosion is basically the same as that in condition
of static corrosion.

(a) (b)

(c) (d)

Fig.9 SEM images of the surface morphologies of 304 steel specimens after erosion: single-phase
flow at 25℃ (a) and 65℃ (b) and two-phase flow at 25℃ (c) and 65℃ (d).
The presence of Cl¯ ions has remarkable effect on the corrosion process of stainless steel.
Having strong adsorbing and penetrating power due to their small ion radius, Cl¯ ions can damage
the passive film to cause the local corrosion. As the temperature increases, the activity of Cl¯ ions
increases and the corrosion will be promoted. Compared with static immersion corrosion, fluid
erosion can relieve the adsorption of Cl¯ on metal surface (desorption function). When the
concentration of Cl¯ in media is the same, the concentration of Cl¯ adsorbed on metal surface in
single-phase flow and two-phase flow is lower than that of static immersed specimens, which leads
to more severe selective corrosion in static immersion at high temperature.

Conclusions
(1) The corrosion resistance of 316L stainless steel is more excellent than that of the 304
stainless steel. Hydrochloric acid concentration has greater influences on 304 stainless steel than
316L stainless steel, and the corrosion rates of 304 stainless steel and 316L stainless steel increase 9
times and 5 times respectively while increasing hydrochloric acid concentration from 5% to 20%.
(2) Temperature significantly affects the corrosion rate and synergistic effect between erosion
and corrosion of austenitic stainless steels in static corrosion, single-phase flow and two-phase flow
erosion, and compared with temperature, the hydrochloric acid concentration has lower influence on
corrosion rate. With the increase of the medium temperature, the corrosion current density values of
304 stainless steel increase and its passivation region of the polarization curve becomes narrowing
and disappeared, showing the passive film breakdown.
 Materials Science Forum Vol. 850 85

[3] The main corrosion characteristics of 304 stainless steel are uniform corrosion in static
corrosion and single-phase flow, and uniform corrosion + plough cutting in two-phase flow at room
temperature. And from 50℃ to 80℃ there are selective corrosion in static corrosion and
single-phase flow, and selective corrosion + plough cutting in two-phase flow. With the increase of
the medium temperature, the selective corrosion becomes more severe.

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Methods of Design and Characterization of Materials, Research and Development of Technological
Processes
10.4028/www.scientific.net/MSF.850

Corrosion Behavior of Austenitic Stainless Steel in Hydrochloric Acid Solution and Flow
10.4028/www.scientific.net/MSF.850.78

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[2] A.V. Levy, Erosion and erosion-corrosion of metals, Corros. 51 (1995) 872-876.
10.5006/1.3293564
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Wear. 267 (2009) 2018-(2026).
10.1016/j.wear.2009.06.041
[4] A.J. Wharton, R.J.K. Wood, Influence of flow conditions on the corrosion of AISI 304L stainless steel,
Wear. 256 (2004) 525-536.
10.1016/s0043-1648(03)00562-3
[6] A. Toro, A. Sinatora, D.K. Tanaka, A.P. Tshiptschin, Corrosion-erosion of nitrogen bearing martensitic
stainless steels in seawater-quartz slurry, Wear. 250-251 (2001) 1257-1264.
10.1016/s0043-1648(01)00765-7
[7] A. Iwabuchi, J.W. Lee, M. Uchidate, Synergistic effect of fretting wear and sliding wear of Co-alloy and
Ti-alloy in Hanks' solution, Wear. 263 (2007) 492-500.
10.1016/j.wear.2007.01.102
[8] X.X. Fang, Y.Q. Bai, Z.Z. Wang, Erosion corrosion behavior of J4 stainless steels and electroless plating
coatings of Ni-P Ni-Cu-P in liquid-solid two-phase flow, Acta Metall. Sin. 46 (2010) 239-244.
10.3724/sp.j.1037.2009.00499
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45 (2000) 2499-2513.
10.1016/s0013-4686(00)00347-9
[13] R.F.A. Jargelius-Petterson, B.G. Pound, Examination of the role of molybdenum in passivation of
stainless steels using AC impedance spectroscopy, J. Electrochem. Soc. 145 (1998) 1462-1467.
10.1149/1.1838505
[15] M.F. Montemor, M.G. S Ferreira, N.E. Hakiki, Chemical composition and electronic structure of oxide
films formed on 316L stainless steel and nickel based alloys in high temperature aqueous environments,
Corros. Sci. 42 (2000) 1635-1650.
10.1016/s0010-938x(00)00012-3
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