Mechanical and Microstructural Evaluation of Corrosion

and Hydrogen-Induced Degradation of Steel

Muhammad Wasim 1; Chun-Qing Li 2; Mojtaba Mahmoodian 3; and Dilan Robert 4
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Abstract: Mild steel is one of the most commonly used materials in the construction industry throughout the world, but it is also very
vulnerable to corrosion in aggressive environments. There is little research on how corrosion and the hydrogen released from the corrosion
process affect the mechanical properties of the corroded steel. The intention of this paper is to present results produced from a comprehensive
experimental program designed to investigate the effects of corrosion and corresponding hydrogen on the degradation of mechanical proper-
ties of mild steel in corrosive soil environments. Both microstructural analysis and mechanical tests on corroded steel are undertaken at
different exposure times and conditions of corrosion. The effects of corrosion and the released hydrogen on steel are examined phenom-
enologically and analyzed quantitatively at the microstructural level in terms of constituent elements and phase changes, and at the macro-
structural level in terms of mechanical properties of strength and ductility. From the analysis of test results, a relationship of cause and effect
of corrosion, hydrogen release, and strength reduction is established. The results and their analysis presented in the paper can contribute to the
body of knowledge related to the degradation of mild steel, which helps in determining its service life prediction under corrosive environ-
ments. DOI: 10.1061/(ASCE)MT.1943-5533.0002560. © 2018 American Society of Civil Engineers.
Author keywords: Mild steel; Corrosion; Hydrogen; Mechanical properties; Microstructural analysis.

Introduction microstructure of the steel and subsequently increasing its lattice

Corrosion causes serious degradation of metals and metal-related
structures like pipelines, water tanks, and reinforced concrete struc-
tures when exposed to various aggressive environments, such as
saline marine, high humidity and temperature, and underground
environments. Annually, about $2.5 trillion in costs are estimated
due to corrosion globally (El-Sherik 2017), and in the United States
of America alone this cost is estimated as more than $1.1 trillion in
2016. Researchers have developed and employed various corrosion
protection techniques, such as coatings and cathodic protection, to
minimize or prevent corrosion (Kim and Kim 2011; Sparks 2003;
Cristiani et al. 2008; Yan et al. 2008). Despite the availability of
these protective techniques, corrosion-induced deterioration of
steel continues, causing serious concerns to asset managers and
owners of civil infrastructure.
Corrosion is an electrochemical process in which hydrogen can
be produced as a by-product of cathodic reaction in some environ-
ments (Davis 2000). This hydrogen may penetrate into the body of
steel due to the concentration gradient between the surface and
underlayer (Stroe 2006). The absorbed hydrogen can cause severe
damage to the steel in the form of cracking due to the embrittlement
of steel. The existence of hydrogen as a result of corrosion reactions
aggravates the steel degradation process by penetrating into the
1
Ph.D. Candidate, School of Engineering, RMIT Univ., Melbourne,
VIC 3001, Australia. Email: s3442859@student.rmit.edu.au
2
Professor, School of Engineering, RMIT Univ., Melbourne, VIC 3001,
Australia (corresponding author). Email: chunqing.li@rmit.edu.au
3
Lecturer, School of Engineering, RMIT Univ., Melbourne, VIC 3001,
Australia. Email: mojtaba.mahmoodian@rmit.edu.au
4
Senior Lecturer, School of Engineering, RMIT Univ., Melbourne,
VIC 3001, Australia. Email: dilan.robert@rmit.edu.au
Note. This manuscript was submitted on February 18, 2018; approved
on July 9, 2018; published online on October 31, 2018. Discussion period
open until March 31, 2019; separate discussions must be submitted for in-
dividual papers. This paper is part of the Journal of Materials in Civil
Engineering, © ASCE, ISSN 0899-1561.
strain. Hydrogen also migrates and accumulates at the plastic zone
near the crack tip, resulting in a reduction of fracture resistance of
the crack tip and accelerating the crack propagation into the
material (Mao and Li 1998; Cheng 2007).
There are a variety of hydrogen sources, such as hydrogen
sulfide product contaminants, groundwater, gas product streams,
welding, electroplating, acid pickling, forming, casting, and oil
and gas contained in vessels. However, with the worldwide use
of cathodic protection, there is more likelihood of hydrogen accu-
mulating during the corrosion process, which causes embrittlement
of steel as manifested in cracking and loss of ductility of steel pipes
buried in soils (Hardie et al. 2006). The reduction in ductility of
steel is due to the cathodic charging, which results in the absorption
of hydrogen during that process. Hydrogen embrittlement of steel
can be caused internally by preexisting hydrogen within the
steel (internal hydrogen embrittlement) and environmentally as-
sisted hydrogen embrittlement, where hydrogen is generated from
environments, like gaseous hydrogen or a corrosion reaction. A
comparison of internal and environmental hydrogen embrittlement
was carried out by Symons (2001).
Various studies have been undertaken to investigate the deleteri-
ous effect of hydrogen on metals mostly by experiments. One ap-
proach is to charge the samples with hydrogen using different
techniques and then study its effect by comparing their mechanical
properties with those of uncharged samples (Zakroczymski et al.
2005; Zucchi et al. 2006). However, for such experiments, several
parameters can be changed or set in different ways, which may
cause variations in the findings obtained from the same material.
Djukic et al. (2015) found that hydrogen reduces the fracture re-
sistance of the crack tip, leading to the enhanced progression of
the crack into the low carbon steel. Djukic et al. (2016) investigated
the hydrogen embrittlement (HE) mechanism and high-temperature
hydrogen attack by microstructural analysis of fractured surfaces of
Charpy specimens made of steel taken from failed boiler evaporator
tubes. Li et al. (2016) studied the effect of hydrogen on the tensile
properties and fracture behavior of PH 13-8 Mo, a precipitation

© ASCE 04018349-1 J. Mater. Civ. Eng.

J. Mater. Civ. Eng., 2019, 31(1): 04018349

 hardening martensitic stainless steel, by first aging it at very high
temperatures and then charging it with hydrogen for a few hours.
Shim et al. (2017) examined the resistance to hydrogen embrittle-
ment of steels composed of granular bainite microstructure by
tensile testing and various characterization techniques. Further-
more, Shen et al. (2017) investigated the effect of solution-treated
temperature on hydrogen embrittlement of 17-4 PH stainless steel.
The susceptibility of 17-4 stainless steel to hydrogen embrittlement
was determined by electrochemical hydrogen charging and slow
strain rate tensile tests.
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A thorough review of the published literature suggests that
existing research on hydrogen-induced embrittlement of steel is
limited to charging the steel with a high concentration of hydrogen
under extreme conditions of high temperature. The embrittlement
of steel caused by corrosion process and subsequent release of hy-
drogen has not been investigated. There is little or no research on
how corrosion process and its subsequent release of hydrogen
affect the mechanical properties of mild steel when exposed to vari-
ous corrosive environments.
This is the objective of the current research, which investigates
the effects of corrosion and hydrogen released in the corrosion pro-
cess on the degradation of mechanical properties of steel in corro-
sive soil environments. Both the microstructural analysis and
mechanical tests on corroded steel are undertaken at different ex-
posure times and conditions of corrosion. The effects of corrosion
and the released hydrogen on corroded steel are examined phenom-
enologically and analyzed quantitatively at the microstructural level
in terms of constituent elements and phase changes, and at the mac-
rostructural level in terms of mechanical properties of strength and
ductility. From the observation of tests and analysis of test results, a
cause-effect relationship of corrosion, hydrogen release, micro-
structural change, and strength reduction has been established.
Furthermore, functional relationships between corrosion and hy-
drogen concentration and strength degradation of steel are derived.
The significance of this research is that the effect of corrosion and
hydrogen-induced embrittlement of mild steel in acidic and soil
environments can be quantified, which advances the knowledge
of material science relating to corrosion and hydrogen-induced
damage of steel.
Experimental Methodology
Design of Specimen
Mild steel specimens with known composition as shown in Table 1
were used for corrosion tests and corrosion-released hydrogen
in this research. The specimens were made according to ASTM
E08 (ASTM 2001) with the dimension and shape of the specimen
commonly used for tensile testing. A schematic representation of
the 6-mm-thick test specimen is shown in Fig. 1(a).
In this study, corrosion-induced hydrogen embrittlement of mild
steel was studied by using two types of solutions. The first solution
was based on simulated soil solution, and the second solution was
obtained from the acidic HCl solution to create hydrogen-releasing
environments. The reason for not using the original soil for experi-
ments was its heterogeneous structure, which could result in erro-
neous measurements. The simulated soil solutions were prepared
by using the key chemical components of soil. Moreover, research-
ers often carry out accelerated corrosion experiments in laboratories
to achieve their desired objective in a given time frame because
corrosion is a very slow process. Therefore, in the current research,
low-pH soil solutions, i.e., 2.5 and 5 pH, and hydrochloric acid
(HCl) solutions of 1 and 3 M with very low corresponding pH
© ASCE 04018349-2
J. Mater. Civ. Eng., 2019, 31(1): 04018349
Table 1. Chemical composition of test specimen
Chemical Composition (%)
C 0.22
Si 0.55
Mn 1.70
P 0.04
S 0.03
Cr 0.25
Ni 0.5
Cu 0.4
Mo 0.35
Al 0.1
Ti 0.04
Fe 95.82
(0 and −0.48) were used to examine the effect of variation of
pH in the corrosion process and hydrogen produced. The range
of pH selected for the tests was also used by previous researchers
(Finsgar and Jackman 2014; Sheoran et al. 2010). For the simulated
soil solution, the chemical composition of natural clay soil obtained
from the field was used. The method and steps involved in the
preparation of this solution can be referred to in Wasim et al.
(2017). The pH of the resulting solution for natural soil was found
to be around 8, which is similar to the original natural soil. The
composition of the simulated soil solution is shown in Table 2.
In this solution, pH was adjusted by adding HCl to achieve the tar-
get pH of 2.5 and 5. The experimental plan followed in this research
with different solutions, numbers of specimens, and time periods of
the tests is shown in Table 3.
Test Procedure
Test specimens were immersed in soil and HCl solutions in contain-
ers for accelerated corrosion process according to ASTM G31
(ASTM 1990). For better understanding and statistical analysis
of corrosion-induced hydrogen embrittlement, nine specimens
were immersed in each of these four set of solutions to obtain re-
sults at time periods of 7, 14, and 28 days for three duplicates. In-
cluding the three initial tests on uncorroded steel, the total number
of specimens for tensile tests was 3 þ 3 × 3 × 4 ¼ 39. In addition
to the tensile test specimens, 36 small steel samples with dimen-
sions of 50 × 14 × 6 mm, equal to the gauge length of the tensile
test specimen, were added to the test container to determine the
accuracy of hydrogen measurements, as shown in Table 3.
Before immersion in the test solutions, the specimens’ initial
weights were measured. Samples were then wrapped with chemi-
cal- and acid-resistant plastic tape except the specimens’ gauge
length area as defined in ASTM E08 (ASTM 2001). The purpose
of exposing only the gauge length area of the specimens to the cor-
rosive solutions was to provide focus in the measurement of test
results, i.e., corrosion rate, hydrogen released, and mechanical
properties. The wrapped specimens and test containers of experi-
ments are shown in Figs. 1(b and c). The test containers containing
specimens and solutions were covered with lids having holes to
allow oxygen entry to the test specimens and to minimize the
chemical interaction with the surroundings and evaporation of so-
lutions with time.
The pH of the four test containers was continuously monitored
and adjusted by adding small amounts of HCl to keep it uniform for
the duration of the test. The specimens were taken out from each of
the test containers on the 7th, 14th, and 28th day for hydrogen mea-
surements, mass loss, tensile testing, and microstructural analysis.
J. Mater. Civ. Eng.
 57

R 18

50

14
53.5 93 53.5
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(a)

(b) (c)

Fig. 1. Experimental setup: (a) dimensions of test specimen (filled area indicates protected area from corrosion); (b) wrapped test specimens; and
(c) specimens in test containers.

Table 2. Chemical composition of simulated soil solution PC connected

Sample in
Chemical Composition (g=L) to Data logger
contact with
NaHCO3 0.695
NaOH and to
MgSO4 · 7H2 0 0.109
CaCl2 · 2H2 0 1.476 Resistance
KCl 0.389
NaNO3 0.505
Data Logger

Table 3. Test plan

Number of specimens
Hydrogen Fig. 2. Setup for hydrogen measurement.
Tensile testing measurements
Solution pH (7, 14, and 28 days) (7, 14, and 28 days)
3 M HCl −0.48 3×3¼9 3×3¼9 current was calculated and divided by the exposed area to obtain the
1 M HCl 0 3×3¼9 3×3¼9 current density or ip. The current was measured at three points of
Simulated soil 2.5 3×3¼9 3×3¼9
time, i.e., 7, 14, and 28 days, respectively for all specimens to ex-
Simulated soil 5 3×3¼9 3×3¼9
amine the change of corrosion with time. The relationship between
current (ip ) and concentration of hydrogen in test specimens was
established by Danford (1983) as follows:
Hydrogen Concentration Measurement  1=2
D
ip ¼ ZFC0 ð1Þ
For accuracy and repeatability of the test data, three hydrogen con- πt
centration measurements on each specimen at on the 7th, 14th and
28th day were carried out. Hydrogen concentration on the surface where ip is the current density in μA=cm2 , Z is the number of
of the specimens resulted from corrosion was measured using a electrons involved in the reaction, F is Faraday’s constant
Barnacle cell according to ASTM F1113-87 (ASTM 2011). (96,485.3 C=mol), C0 is the concentration of hydrogen in ppm,
The hydrogen measurements consisted of a Barnacle cell, resis- D is the diffusion coefficient for mild steel [2.5 × 10ð−7Þ cm=s2 ],
tance of 10 kΩ, and a datalogger connected to a computer for re- and t is the recording time (30 min by standard). From Eq. (1),
cording volts at 30 min is shown in Fig. 2. Using Ohm’s law, the the hydrogen concentration (C0 ) can be determined.

© ASCE 04018349-3 J. Mater. Civ. Eng.

J. Mater. Civ. Eng., 2019, 31(1): 04018349

 Corrosion Effect and Analysis 12
5 pH
2.5 pH
10

Corrosion rates (mm/yr)

0 pH (1M)
Hydrogen Concentration -0.48 pH (3M)
8
The hydrogen concentration was measured after removing speci-
mens from the solutions. Hydrogen measurements of the test spec-
6
imens immersed in 3 M (−0.48 pH), 1 M (0 pH), 2.5 pH, and 5 pH
solutions were carried out at periods of 7, 14, and 28 days using a 4
Barnacle cell. For consistency and to compare the various solutions,
the results of 3 and 1 M (HCl) solutions are also represented in pH 2
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in this paper, as shown in Fig. 3. The results indicate that from

specimens immersed in −0.48 and 0 pH acidic solutions, high hy- 0
drogen concentrations are obtained. The absorbed hydrogen con- 0 5 10 15 20 25 30
centration was found to be 0.94 ppm in 0 pH after 7 days, while it (a) Time (days)
was measured as 1.315 ppm in −0.48 pH solution. This is higher
than that in 0 pH solutions because of the high acid concentration of 0.2
5 pH
HCl and subsequent corrosion reaction. Similarly, after 14 and
2.5 pH
28 days, 4.47 ppm and 5.03 ppm were measured from specimens

Corrosion rates (mm/yr)

0.16
in 0 pH, while in the −0.48 pH solution the readings obtained were
5.19 ppm and 5.972 ppm, respectively. These results indicate that 0.12
hydrogen concentration increases with the increase of time both in
the −0.48 and 0 pH solutions due to the diffusion of hydrogen into
the steel with time. 0.08
Hydrogen concentrations of 2.51, 4.01, and 4.29 ppm were ob-
tained on the 7th, 14th, and 28th days, respectively, for specimens in 0.04
2.5 pH solution (Fig. 3). Interestingly, however, from specimens im-
mersed in the 2.5 pH soil solution, high hydrogen concentration was 0
obtained initially at the 7th day as compared to −0.48 and 0 pH 0 5 10 15 20 25 30
solutions due to the presence of other hydrogen-containing com- (b) Time (days)
pounds like NaHCO3 and hydrated compounds of MgS04 and
CaCl2 in the solution. The specimens immersed in 5 pH soil solution Fig. 4. Corrosion rate of specimens in various solutions: (a) corrosion
were the lowest in hydrogen concentration after 28 days as compared rate of specimens immersed in various solutions; and (b) enlarged view
to the other specimens immersed in different solutions. However, on of (a) for specimens in 2.5 and 5 pH.
the 7th day, the hydrogen concentration was found to be higher than
the −0.48 and 0 pH solutions, respectively, due to the same reasons
as explained above for the specimens in 2.5 pH solution. Corrosion Progress
From the aforementioned results for specimens immersed in
various solutions, it can be seen that hydrogen concentration in At the end of each period of immersion time, specimens were taken
specimens immersed in all solutions increases with time as corro- out of the solution, and then chemically cleaned using Clark’s sol-
sion progresses, indicating the direct relation between corrosion ution [ASTM G1 (ASTM 2003)]. Soon after the removal of
and hydrogen concentration. To further investigate the relationship corrosion products, specimens were dried and then weighed.
between corrosion and hydrogen released, the percentage mass loss The mass loss was measured after completion of hydrogen meas-
and corresponding corrosion rates were calculated. urement at each of the three time periods for the four solutions.
The corresponding corrosion rates of the specimens were calculated
from the mass loss by following ASTM G1 (ASTM 2003). The
corrosion rates of specimens immersed in −0.48 pH were found
7 to be the highest as compared to the other specimens after 28 days
5 pH
2.5 pH
of corrosion. The highest corrosion rates of 11.15, 6.93, 0.149, and
0.0695 mm=year were found from the specimens in −0.48, 0, 2.5,
Hydrogen Concentration (ppm)

6 0 pH (1M)
-0.48 pH (3M) and 5 pH solutions, respectively, after 28 days as shown in Fig. 4.
5 Meanwhile on their 7th day, the corrosion rates were 5.32, 3.02,
and 0.145, and 0.056 mm=year, respectively, as shown in Fig. 4.
4
From these results, it can be inferred that the corrosion rates are
3
nearly doubled on the 28th day to those on the 7th day of the speci-
men in −0.48 pH and 0 pH solution, which indicates the severity of
2 the corrosive environment. The high corrosion rates can be attrib-
uted to the coupled effect of chloride and hydrogen ions, which can
1 decrease pH and the passivity of steel with time. Therefore, it is
possible to have a lower pH in the corroded areas of specimens
0 as compared to the surrounding pH environment.
0 5 10 15 20 25 30
Based on the results of corrosion rates and hydrogen concentra-
Time (days) tion, an empirical relation can be derived using the statistics soft-
ware SPSS with R2 ¼ 0.72 and a very high statistical significance
Fig. 3. Hydrogen concentration of specimens in various solutions.
i.e., p ≪ 0.05, as follows:

© ASCE 04018349-4 J. Mater. Civ. Eng.

J. Mater. Civ. Eng., 2019, 31(1): 04018349

 H ¼ 0.083 × CR þ 0.149 × T þ 0.233 ð2Þ
where H is the hydrogen concentration in ppm, CR is the corrosion
rate in mm=year, and T is the time (in days). Eq. (2) can be used to
predict the hydrogen concentration in corrosive environments once
the corrosion rates of the mild steel are known, i.e., measured.
Mechanical Properties
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Mechanical tests were conducted at the designated times for the
specimens in four sets of solutions to obtain the yield strength, ul-
timate strength, and failure strain. They were then compared with
those of uncorroded specimens. The most affected specimens due
to the corrosion and subsequent hydrogen released were found to
be the ones immersed in −0.48 and 0 pH (HCl) solutions. It was
found that the specimens in −0.48 and 0 pH solutions lost ductility
as their failure strains, i.e., strains at rupture of the specimens, re-
duced successively over the time of 28 days as shown in Fig. 5(a).
The failure strains of specimens at the 7th day were found to be
0.38, 0.36, 0.3, and 0.21 for 5, 2.5, 0 and −0.48 pH solutions re-
spectively. These failure strains were lower than the uncorroded
specimens’ failure strain of 0.45, indicating the reduction in duc-
tility with the increase of corrosion. When the specimens were
tested on the 28th day, the failure strains were further reduced to
0.2, 0.12, and 0.0045 and 0.0031 in the 5, 2.5, 0, and −0.48 pH
Fig. 5. Change in mechanical property of specimens in various solutions: (a) failure strains; (b) yield strength; and (c) ultimate strength.
© ASCE 04018349-5
J. Mater. Civ. Eng., 2019, 31(1): 04018349
solutions, respectively. These measurements clearly indicate that
there was a decline in ductility of the specimens as the corrosion
progresses in all four solutions. Also, Fig. 5(a) indicates that the
failure strains of the specimens in the −0.48 pH solution were the
most reduced as compared to those of specimens in other solutions
due to the highest concentration of Hþ ions in this solution, which
causes embrittlement of steel due to Hþ ion diffusion into the steel
body. These results were in agreement with the recently published
research (Li et al. 2016) related to hydrogen effect on tensile prop-
erties. Importantly, in the current research, the hydrogen embrittle-
ment was observed by immersing the specimens in the solutions
rather than charging it with different techniques such as galvanostat
or high-temperature hydrogen charging, etc. Hence, the methodol-
ogy adopted in the current research distinguishes it from the pre-
vious research.
The yield strengths of the specimens at the 7th, 14th, and 28th
day of immersion in different solutions are shown in Fig. 5(b). It
can be seen that the specimens immersed in −0.48 pH solution de-
grade the most, i.e., the yield strength is the smallest (306.45 MPa)
as compared to that of other specimens at the 7th day. The yield
strength of the uncorroded specimen was 347.49 MPa. Similar to
failure strain results, the yield strength of specimens was further
degraded to 214.48 MPa in −0.48 pH solution after 28 days
of corrosion. The yield strength of specimens immersed in 0 pH
solution was found to be 288.30 MPa after 28 days of corrosion.
J. Mater. Civ. Eng.
 Table 4. Change in mechanical property of test specimens
pH Time (days) Average failure strain Average yield (MPa) Average ultimate (MPa)
−0.48 0 0.45 347.49 426.84
7 0.21 306.45 413.54
14 0.139 289.858 401.85
28 0.0031 214.48 214.8
0 0 0.45 347.49 426.84
7 0.30 327.48 423.83
14 0.145 323.946 418.55
28 0.0045 288.30 351.48
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2.5 0 0.45 347.49 426.84

7 0.36 331.40 425.12
14 0.33 328.16 420.45
28 0.12 324.56 418.5
5 0 0.45 347.489 426.84
7 0.38 346.14 425.08
14 0.378 344.19 423.26
28 0.2 342.76 422.36

The percentage reduction after 28 days was 38% and 18% in the ft ¼ −10.366 × CR − 1.139 × T þ 443.456 ð4Þ
−0.48 and 0 pH solutions, respectively. However, the decline in
yield strength in the other two soil solutions was not that significant where f t is yield strength in MPa. Eqs. (3) and (4) can be used to
due to their relatively high pH (2.5 and 5) as compared to the −0.48 predict the residual strength of mild steel in highly aggressive envi-
and 0 pH (HCl) solutions. It was found that the coupled effect of Cl ronments, which can be very useful for predicting the failures of
and Hþ resulted in more decline of the yield strength of specimens steel structures.
in HCl solutions.
The results of reduction of ultimate strength of specimens in
different solutions are presented in Fig. 5(c). As can be seen, Microstructural Analysis
the ultimate strength of the specimens at the 7th day of corro-
X-ray fluorescence (XRF) was used to determine the constitutent
sion shows a similar trend as that from the yield strength results,
element variation of steel specimens due to the corrosion process.
i.e., not a significant change in the ultimate strength. However, after
The results were compared with the uncorroded specimen to deter-
28 days of corrosion, the ultimate strength of the specimens in
mine the reduction or inclusion of elements during the corrosion
−0.48 pH solutions was significantly reduced from 426.84 MPa
process. A scanning electron microscope (SEM) and electronic
to 214.8 MPa, indicating the severity of the corrosive environment.
back-scattered diffraction (EBSD) mapping of the corroded spec-
The change in mechanical properties of the specimens in the 2.5
imens for various corrosive environment solutions were taken at 7,
and 5 PH solutions was small because of the low acidity of these
14, and 28 days. The EBSD measurements were performed with an
solutions as compared to the −0.48 and 0 pH solutions. Corrosion
FEI Nova NanoSEM with the Aztec software suite. The purpose of
is a slow process that takes time to occur. In the current research,
using EBSD in this research was to quantify any microstructural
the duration of testing is 28 days, which probably is not enough to
degradation and phase transformation due to the corrosion process
cause mechanical change for a pH of 2.5 and 5 in this short period
with time. The results of the corroded specimens from different
of time. The average change in mechanical properties of failure
environments were compared with each other and also with the un-
strain, yield strength, and ultimate strength of the specimens in vari-
corroded steel specimens to determine any microstructural changes
ous solutions is shown in Table 4.
due to corrosion over time.

Corrosion and Strength Degradation Change in Elemental Composition

There is a difference of opinions among researchers about the
change, mostly degradation, in mechanical properties, especially
yield strength due to corrosion, as discussed in the Introduction.
The effect of corrosion on strength degradation has been examined
thoroughly as a phenomenon as shown in Fig. 5. Based on the
observation and test results, an empirical relation between yield
strength and corrosion rate with time can be derived using the sta-
tistics software SPSS with R2 ¼ 0.721 and statistical significance
of 0.001, which is expressed as follows:
f y ¼ −9.476 × CR − 0.353 × T þ 343.359 ð3Þ
where fy is yield strength in MPa, CR is corrosion rate in mm=year,
and T is time in days. Likewise, an empirical relation between
ultimate strength and corrosion rate with time can be derived with
R2 ¼ 0.675 and statistical significance of 0.001, which is expressed
as follows:
The elemental composition of the specimens immersed in different
solutions was determined upon completion of each time period to
observe any elemental change with time due to corrosion. For this
purpose, the results obtained were compared with the elemental
composition of uncorroded steel specimens. The results obtained
from specimens immersed in 0 pH (1 M) and −0.48 pH (3 M),
and 2.5 and 5 pH soil solutions are shown in Table 5 as well as
Figs. 6(a–f). From these results, it can be clearly seen that the
Fe percentage was reduced successively with time in all solutions.
It was almost 100% when there was no corrosion, but after 7, 14,
and 28 days of corrosion, this percentage declined respectively to
75.18%, 68.14%, and 51.61% in −0.48 pH specimens in these time
period as shown in Fig. 6(a). The Fe reduction of specimens in 0 pH
solution was also obvious with time, being 82.23%, 62.83%, and
58.6% at 7, 14, and 28 days, respectively, as shown in Fig. 6(a).
The reason for the reduction in Fe is due to the fact that during
the corrosion process Fe ions are released from the steel. As the

© ASCE 04018349-6 J. Mater. Civ. Eng.

J. Mater. Civ. Eng., 2019, 31(1): 04018349

 Table 5. Change in percentage of elemental composition of test specimens
Percentage of element contents with time
Element pH Uncorroded 7 days 14 days 28 days Total percentage change after 28 days
Fe −0.48 (3 M) 98.73 75.18 62.830 51.61 47.73
0 (1 M) 98.73 82.236 68.14 58.6 40.65
2.5 98.96 0 0 90.56 8.49
5 98.96 0 0 98.73 0.23
Cl −0.48 (3 M) 0 1.07 1.650 1.866 1.87
0 (1 M) 0 0.478 1.1 1.36 1.36
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2.5 0 0 0.049 0.186 0.19

5 0 0 0 0 0.00
Mn −0.48 (3 M) 0.491 0.389 0.331 0.386 21.38
0 (1 M) 0.491 0.431 0.401 0.29 40.94
2.5 0.491 0.491 0.491 0.474 3.46
5 0.491 0.491 0.491 0.491 0.00
O −0.48 (3 M) 0 21.3 34.100 46.08 46.08
0 (1 M) 0 13.258 28.6 38.27 38.27
2.5 0 0 0 0 0.00
5 0 0 0 0 0.00
Si −0.48 (3 M) 0.61 0.267 0.218 0.14 77.05
0 (1 M) 0.61 0.437 0.229 0.155 74.59
2.5 0.61 0.573 0.53 0.474 22.30
5 0.61 0.6 0.61 0.58 4.92
Cr −0.48 (3 M) 0.08 0.0562 0.050 0.0351 56.13
0 (1 M) 0.08 0.060 0.053 0.033 58.75
2.5 0.08 0.0633 0.053 0.051 36.80
5 0.08 0.0656 0.0593 0.053 33.75

corrosion process continues, the liberation of Fe ions from the steel
surface continues, and consequently reduces the percentage of Fe
in the steel with time. The reduction in Fe was highest in the
−0.48 pH solution, being subjected to the severest corrosive envi-
ronment, then it was followed by 0, 2.5 and 5 pH solution.
Pickering (1971) has developed empirical equations for yield
(fy ) and tensile (f t ) strength of ferrite-pearlite steel under
0.25% C content that relate to contents of constituent elements
and grains diameter as follows:
fy ¼ 53.9 þ 32.34ðMnÞ þ 83.2ðSiÞ þ 354.2ðNfÞ þ 17.4ðd1=2 Þ
ð5Þ
f t ¼ 294.1 þ 27.7ðMnÞ þ 83.2ðSiÞ þ 3.9ðPÞ þ 7.7ðd−l=2 Þ ð6Þ
where Mn is manganese, Si is silicon, Nf is nitrogen, and d is the
grain size of Fe and P is pearlite. All elements are given in percent-
age while the diameter is in micrometers.
As shown in Table 5 and Fig. 6, those elements that are prone to
corrosion have increased and those that contribute to the strength
have been reduced. In Table 5, the percentage of large grains of Fe
in specimens was successively reduced with corrosion progress.
From Figs. 6(a and c–e), it can be seen that the contents of elements
iron (Fe), manganese (Mn), silicon (Si), and chromium (Cr) all de-
crease over time with the progress of corrosion, in particular in the
more acidic solutions, i.e., 1 M (0 pH) and 3 M (−0.48 pH) solu-
tions. From Figs. 6(b and f), it can be seen that contents of oxygen
(O) and chloride (Cl) both increase successively with time, again
more obvious in the 1 M (0 pH) and 3 M (−0.48 pH) solutions.
These are the causal factors for strength reduction of corroded
steel.
Microcracks and Blisters
From SEM analysis of specimens immersed in the 0 and −0.48 pH
HCl solutions, microcracks can be observed as shown in Fig. 7.
These microcracks appear to be hydrogen embrittlement cracks
due to the existence of hydrogen blisters, which are signs of
hydrogen accumulations (Jin et al. 2010). High hydrogen concen-
tration favors rapid initiation of cracks, as there were more cracks
discovered in the −0.48 pH solution (hydrogen concentration of
5.97 ppm) compared with 0 pH HCl (hydrogen concentration of
5.03 ppm). The pits and cracks were clearly visible in specimens
immersed in the −0.48 and 0 pH solutions that could have caused
strength reduction (Jakubowski 2011). Pits and cracks were not
visible in specimens of the 2.5 and 5 pH solutions even after 28 days
of corrosion.
Phase Analysis
To further authenticate the grain sizes and phases of the corroded
areas and the surrounding regions, the EBSD technique was used
for analysis. Operating at 20 kV and using 6 spot sizes, EBSD maps
of the corroded areas of various samples were taken. The purpose
was to find which phase of steel had the maximum corrosion and
then its subsequent hydrogen effect. After EBSD analysis of several
samples, the software Channel 5 (Oxford Instrument), an EBSD
postprocessing software, was used to calculate the phases and grain
sizes of EBSD maps. Using this software, the average of selected
larger grains was found to be 12.65 μm while the average of
selected smaller grains was 5.73 μm.
Moreover, from the EBSD map data of uncorroded samples, it
became evident that 98.15% was the ferrite phase, and the remain-
ing percentage was cementite. Further, from the analysis of EBSD
maps of severely corroded areas of various test specimens, it was
established that most of this central area was dominated by the fer-
rite phase (Fe) and the other phases were cementite (Fe3 C) and iron
oxide (Fe2 O3 ). Ferrite is more prone to corrosion as it quickly
oxidizes, while cementite provides the resistance to corrosion
(Syugaev et al. 2008). Fig. 8 represents the morphology and phase
maps analysis of corroded specimens immersed in −0.48, 0, and
2.5 pH solution near the pit areas after 28 days of corrosion.

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J. Mater. Civ. Eng., 2019, 31(1): 04018349

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Fig. 6. Change of elemental composition of specimens in various solutions: (a) iron; (b) oxygen; (c) manganese; (d) silicon; (e) chromium; and
(f) chloride.

Fig. 7. SEM image of micro cracks at the 28th day of corrosion: (a) 0 pH (1 M); and (b) −0.48 pH (3 M).

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J. Mater. Civ. Eng., 2019, 31(1): 04018349

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Fig. 8. Phases of surrounding corroded area of various specimens at the 28th day (SEM images and EBSD phase maps): (a) 0 pH, 28 days
(SEM image on the left and EBSD phase map on the right); and (b) −0.48 pH, 28 days (SEM image on the left and EBSD phase map on the right);
and (c) 2.5 pH, 28 days (SEM image on the left and EBSD phase map on the right).

The selected areas for the EBSD are shown on the left-side images
of Fig. 8, while the right-side images of this figure represent the
EBSD phase analysis of these areas. From visual inspection of
these maps, a fair estimation of the phase percentage can be made
without doing calculations. For instance, from Fig. 8(a) (right side),
it can be seen that the red color, as labeled iron bcc (body-centered
cube, i.e, ferrite), dominates the whole image with few visible
yellow-colored Fe2 03 , i.e., iron oxide and tiny blue-colored dots
of FeC3 (cementite). Similarly in Figs. 8(b and c), the ferrite phase
is prevalent in specimens of 0 and 2.5 pH [red color in (b) and green
in (c), respectively].
Moreover, by using EBSD, accurate percentages of phases of
specimens can be determined as shown in Fig. 9. As it can be seen
from the EBSD analysis, ferrite, cementite, and iron oxide contents
of 71.76%, 0.92%, and 27.32% were obtained, respectively, after
28 days of corrosion from specimen immersed in the −0.48 pH
solution. These phases were determined to be 76.44%, 1.56%,
and 22% in specimens of 0 pH solution, while 81.8%, 2.98%,
and 15.22% of ferrite, cementite, and iron oxide were obtained, re-
spectively, from the 2.5 pH solution (Fig. 9). These results are
found in agreement to the XRF results, which also showed a similar
trend of Fe (ferrite) reduction due to the corrosion process when

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J. Mater. Civ. Eng., 2019, 31(1): 04018349

 100 Ferrite
Cementite
Iron oxide
80
Percentage
60
40
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20
0
Uncorroded 2.5 pH 0 pH (1M) -0.48 pH (3M)
Fig. 9. Decrease in ferrite phase and increase in iron oxide at the 28th
day in various solutions.
compared with uncorroded specimens as discussed previously, and
hence corroborating the originality of the current research.
Conclusion
In this paper, the effects of corrosion and the hydrogen released
from the corrosion process on mild steel have been examined phe-
nomenologically and analyzed quantitatively at the microstructural
level in terms of constituent elements and phase changes, and at the
macrostructural level in terms of mechanical properties of strength
and ductility. It has been found that corrosion rates and hydrogen
concentration are directly related, and this relationship has been
derived in the paper. It has also been found that reduction in the
mechanical properties is due to the change in elemental composi-
tion and microstructure of mild steel in corrosive environments. A
relationship between corrosion rates and reduction in strength has
also been developed. It can be concluded that the corrosion and
corresponding hydrogen can adversely affect the mechanical prop-
erties of steel used in corrosive environments. It is suggested that
the effect of corrosion and characteristics of pitting corrosion on
steel properties needs to be investigated with longer times and
the larger number of specimens in the future research. The results
and their analysis presented in the paper can contribute to the body
of knowledge of degradation of steel in corrosive environments.
Acknowledgments
Financial support from Australian Research Council under
DP140101547, LP150100413, and DP17010224 is gratefully ac-
knowledged. The authors would like to thank the staff of RMIT’s
RMMF microscopy facility.
References
ASTM. 1990. Standard practice for laboratory immersion corrosion test-
ing of metals. ASTM G31. West Conshohocken, PA: ASTM.
ASTM. 2001. Standard test methods for tension testing of metallic materi-
als. ASTM E08. West Conshohocken, PA: ASTM.
ASTM. 2003. Standard practice for preparing, cleaning, and evaluating
corrosion test specimens. ASTM G1. West Conshohocken, PA: ASTM.
ASTM. 2011. Standard test method for electrochemical measurement of
diffusible hydrogen in steels. ASTM F1113-87. West Conshohocken,
PA: ASTM.
Cheng, Y. F. 2007. “Fundamentals of hydrogen evolution reaction and
its implications on near-neutral pH stress corrosion cracking of
© ASCE 04018349-10
J. Mater. Civ. Eng., 2019, 31(1): 04018349
pipelines.” Electrochim. Acta 52 (7): 2661–2667. https://doi.org/10
.1016/j.electacta.2006.09.024.
Cristiani, P., A. Franzetti, and G. Bestetti. 2008. “Monitoring of electro-
active biofilm in soil.” Electrochim. Acta 54 (1): 41–46. https://doi
.org/10.1016/j.electacta.2008.01.107.
Danford, M. D. 1983. An electrochemical method for determining hydro-
gen concentrations in metals and some applications. NASA-TP-2113.
Washington, DC: NASA.
Davis, J. R. 2000. Corrosion: Understanding the basics. Materials Park,
OH: ASM International.
Djukic, M. B., G. M. Bakic, V. S. Zeravcic, A. Sedmak, and B. Rajicic.
2016. “Hydrogen embrittlement of industrial components: Prediction,
prevention, and models.” Corrosion 72 (7): 943–961. https://doi.org/10
.5006/1958.
Djukic, M. B., V. S. Zeravcic, G. M. Bakic, A. Sedmak, and B. Rajicic.
2015. “Hydrogen damage of steels: A case study and hydrogen embrit-
tlement model.” Eng. Fail. Anal. 58: 485–498. https://doi.org/10.1016/j
.engfailanal.2015.05.017.
El-Sherik, A. M., ed. 2017. Trends in oil and gas corrosion research and
technologies: Production and transmission. Cambridge, UK: Wood-
head Publishing.
Finšgar, M., and J. Jackson. 2014. “Application of corrosion inhibitors for
steels in acidic media for the oil and gas industry: A review.” Corros.
Sci. 86: 17–41. https://doi.org/10.1016/j.corsci.2014.04.044.
Hardie, D., E. A. Charles, and A. H. Lopez. 2006. “Hydrogen embrittle-
ment of high strength pipeline steels.” Corr. Sci. 48 (12): 4378–4385.
https://doi.org/10.1016/j.corsci.2006.02.011.
Jakubowski, M. 2011. “Influence of pitting corrosion on strength of steel
ships and offshore structures.” Polish Marit. Res. 18 (4): 54–58. https://
doi.org/10.2478/v10012-011-0027-6.
Jin, T. Y., Z. Y. Liu, and Y. F. Cheng. 2010. “Effect of non-metallic
inclusions on hydrogen-induced cracking of API5L X100 steel.”
Int. J. Hydrogen Energy 35 (15): 8014–8021. https://doi.org/10.1016/j
.ijhydene.2010.05.089.
Kim, J. G., and Y. W. Kim. 2011. “Cathodic protection criteria of thermally
insulated pipeline buried in soil.” Corr. Sci. 43 (11): 2011–2021. https://
doi.org/10.1016/S0010-938X(01)00015-4.
Li, X., J. Zhang, J. Chen, S. Shen, G. Yang, T. Wang, and X. Song. 2016.
“Effect of aging treatment on hydrogen embrittlement of PH 13-8 Mo
martensite stainless steel.” Mater. Sci. Eng. A 651: 474–485. https://doi
.org/10.1016/j.msea.2015.09.116.
Mao, S. X., and M. Li. 1998. “Mechanics and thermodynamics on the stress
and hydrogen interaction in crack tip stress corrosion: Experiment and
theory.” J. Mech. Phys. Sol. 46 (6): 1125–1137. https://doi.org/10.1016
/S0022-5096(97)00054-9.
Pickering, F. B. 1971. Towards improved toughness and ductility, 9.
Greenwich, UK: Climate Molybdenum.
Shen, S., X. Li, P. Zhang, Y. Nan, G. Yang, and X. Song. 2017. “Effect
of solution-treated temperature on hydrogen embrittlement of 17-4 PH
stainless steel.” Mat. Sci. Eng. A 703: 413–421. https://doi.org/10.1016
/j.msea.2017.06.078.
Sheoran, A. S., V. Sheoran, and R. P. Choudhary. 2010. “Bioremediation
of acid-rock drainage by sulphate-reducing prokaryotes: A review.”
Minerals Eng. 23 (14): 1073–1100. https://doi.org/10.1016/j.mineng
.2010.07.001.
Shim, D. H., T. Lee, J. Lee, H. J. Lee, J. Y. Yoo, and C. S. Lee. 2017.
“Increased resistance to hydrogen embrittlement in high-strength steels
composed of granular bainite.” Mater. Sci. Eng. A 700: 473–480.
https://doi.org/10.1016/j.msea.2017.06.043.
Sparks, D. L. 2003. Environmental soil chemistry. Boca Raton, FL:
CRC Press.
Stroe, M. E. 2006. “Hydrogen embrittlement of ferrous metals.” Ph.D.
thesis, Dept. of Matter and Materials, Universite Libre De Bruxelles.
Symons, D. M. 2001. “A comparison of internal hydrogen embrittlement
and hydrogen environment embrittlement of X-750.” Eng. Frac. Mech.
68 (6): 751–771. https://doi.org/10.1016/S0013-7944(00)00123-5.
Syugaev, A. V., S. F. Lomaeva, S. M. Reshetnikov, A. S. Shuravin,
E. F. Sharafeeva, and D. V. Surnin. 2008. “The effect of the structure-
phase state of iron-cementite nanocomposites on local activation
J. Mater. Civ. Eng.
 processes.” Prot. Met. 44 (4): 367–371. https://doi.org/10.1134
/S0033173208040097.
Wasim, M., D. Robert, C. Q. Li, and M. Mahmoodian. 2017. “Corrosion
behaviour of pipes in soil and in simulated soil solution.” In Corrosion
and prevention, 1–12. ICC Sydney: Australasian Corrosion Association.
Yan, M., J. Wang, E. Han, and W. Ke. 2008. “Local environment under
simulated disbonded coating on steel pipelines in soil solution.” Corros.
Sci. 50 (5): 1331–1339. https://doi.org/10.1016/j.corsci.2008.01.004.
Downloaded from ascelibrary.org by Addis Ababa Science and Technology University on 11/02/18. Copyright ASCE. For personal use only; all rights reserved.
Zakroczymski, T., A. Glowacka, and W. Swiatnicki. 2005. “Effect of
hydrogen concentration on the embrittlement of a duplex stainless
steel.” Corr. Sci. 47 (6): 1403–1414. https://doi.org/10.1016/j.corsci
.2004.07.036.
Zucchi, F., V. Grassi, C. Monticelli, and G. Trabanelli. 2006. “Hydrogen
embrittlement of duplex stainless steel under cathodic protection in
acidic artificial sea water in the presence of sulphide ions.” Corros. Sci.
48 (2): 522–530. https://doi.org/10.1016/j.corsci.2005.01.004.

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