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Stress corrosion cracking of new 2001 lean–duplex stainless steel


reinforcements in chloride contained concrete pore solution: An
electrochemical study

Article  in  Construction and Building Materials · December 2018


DOI: 10.1016/j.conbuildmat.2018.10.108

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Construction and Building Materials 192 (2018) 1–8

Contents lists available at ScienceDirect

Construction and Building Materials


journal homepage: www.elsevier.com/locate/conbuildmat

Stress corrosion cracking of new 2001 lean–duplex stainless


steel reinforcements in chloride contained concrete pore solution:
An electrochemical study
E. Briz a, M.V. Biezma b, D.M. Bastidas c,⇑
a
Dept. of Mechanical Engineering, Faculty of Engineering, University of the Basque Country (UPV/EHU), Plaza Ingeniero Torres Quevedo 1, 48013 Bilbao, Spain
b
Dept. of Earth and Materials Science and Engineering, University of Cantabria, UC. C/ Dique de Gamazo 1, 39004 Santander, Spain
c
National Center for Education and Research on Corrosion and Materials Performance, NCERCAMP–UA. Dept. Chemical, Biomolecular, and Corrosion Engineering, The University of
Akron, 302 E Buchtel Ave, Akron, OH 44325-3906, United States

h i g h l i g h t s

 2205 DSS and 2001 LDSS rebars SCC performance in simulated concrete pore solution.

 2205 DSS did not develop pitting corrosion under SCC conditions in 8% Cl electrolyte.
 2001 LDSS developed pitting corrosion under same conditions.
 2001 LDSS fracture surface evidence brittle fracture.

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

Article history: An experimental SCC tests has been performed on 2001 lean–duplex stainless steel (LDSS) and 2205
Received 20 March 2018 duplex stainless steel (DSS) reinforcements. Specimens were tested by loads up to 85% of their yield
Received in revised form 25 September strength and simultaneously exposed to 8% chloride in simulated concrete pore solution. Although the
2018
maximum corrosion current density value obtained for 2001 LDSS was three times higher than 2205
Accepted 15 October 2018
Available online 19 October 2018
DSS, specimens demonstrated passivity. Cycling polarization curve was performed which shows that
2205 DSS does not develop any pit but 2001 LDSS does. Finally, specimens were loaded until failure; frac-
ture surface analysis detected a combination of ductile and brittle fracture mode in 2001 LDSS. Even if
Keywords:
Lean-duplex stainless steel
2001 LDSS shows worse SCC performance, it is enough to ensure the nominal service life of reinforced
Stress corrosion cracking concrete structures with lower cost.
Constant tensile load Ó 2018 Elsevier Ltd. All rights reserved.
Concrete pore solution
Chlorides

1. Introduction neously affected by the aggressive environment and mechanical


loads, and carbon steel reinforcement can lose its ductility leading
The corrosion of reinforcing carbon steel embedded in concrete to a sudden brittle failure by stress corrosion cracking (SCC). SCC
is most frequently the result of the chloride-induced breakdown of phenomenon depends on many factors, such as chemical composi-
the passive film formed in the high alkaline condition of the con- tion of material, environmental conditions, wherein it has a key
crete. Structures are designed as to uptake design load. Steel rein- role chloride concentration, tensile stress level and it is not clear
forcements are designed to carry on tensile loads that concrete to what extent the service failure depends on each of the factors
cannot bear, so the failure of reinforcing steel will dramatically [1]. In this way, values reported by different researchers show a
lead to the collapse of the structure. This premature failure can significant scatter.
be caused due to manufacture defects, to overload or because Different solutions to face the SCC failure in service have been
material is by a corrosive environment effect. During service life- proposed. One of them, acting on the concrete chemical composi-
time, structures exposed to a corrosive environment are simulta- tion by adding corrosion inhibitor, other applying coating to struc-
tural elements surface to prevent the ingress of corrosive ions such
as chlorides, where they can reach to 3.5% wt in marine environ-
⇑ Corresponding author. ment conditions. In addition, different proposals are been applied
E-mail address: dbastidas@uakron.edu (D.M. Bastidas).

https://doi.org/10.1016/j.conbuildmat.2018.10.108
0950-0618/Ó 2018 Elsevier Ltd. All rights reserved.
2 E. Briz et al. / Construction and Building Materials 192 (2018) 1–8

directly to the steel reinforcement such as coatings, i.e., epoxy or reinforcements [20–24]. Although the use of stainless steel as rein-
hot-dip galvanizing systems However, none of the aforementioned forced bars is considering in some directives, it is supported by the
have completely palliated the problem [2–5]. regulation of carbon steel reinforcement without considering
The use of stainless steel as reinforcement is a realistic solution stainless steel benefits. There is also a lack of knowledge as regard
that during the last years is gathering wide interest and strength. to the SCC behavior of lean-duplex stainless steels in simulated
Many researches back up the great performance of these alloys concrete pore solution.
in a marine environment, but only few of them do take into This paper analyses the corrosion susceptibility of two duplex
account the effect of loads that the structure have to support [6– stainless steel reinforcements, 2205 duplex stainless steel (DSS)
9]. It is worth pointing out, that those research studies that con- and 2001 lean–duplex stainless steel (LDSS), under SCC conditions
sider both effects, environment and structural load actions, provide in chloride contaminated concrete pore solution. The specimens
data results that needs to be carefully interpreted as they differ have been simultaneously exposed to a corrosive environment
from service life conditions, for instance, at high temperature con- and subjected to a constant tensile load effect: 8% Cl– contained
ditions. Some authors checked the specimens in sequential steps: concrete pore solution [25], and 85% of their yield strength value.
firstly exposed to a corrosive environment and then by a tensile After one year testing, specimens were loaded until collapse in
stress or slow strain rate test. Other authors, reported data of a order to evaluate those reinforcements performance under SCC.
non-corrugated rebar studies, neglecting and underestimating
residual stress levels that manufacture of ribbed rebars causes
[10–13]. 2. Experimental
Nowadays, numerous investigations that were carried out pay-
ing attention to mechanical and structural behavior of stainless 2.1. Materials
steels reinforcements, proved that materials performance strongly
Chemical composition of the studied stainless steel rebars, 2205 DSS and 2001
depends on the manufacturing process. In this way, hot rolled LDSS, is shown in Table 1. Ribbed reinforcements specimens of 6 mm nominal
stainless steel reinforcements show higher ductility than cold diameter were provided. With the aim of accelerate the crack initiation during
rolled stainless steel and carbon steel reinforcements. Neverthe- stress corrosion cracking test [26,27], a 2 mm depth sharp V-notch, 1.5 mm wide
less, the elastic modulus value obtained for stainless steel rein- and 60° tip angle was machined in each of the rebar [28].
forcements is slightly lower than the defined for conventional
carbon steel rebars [14,15].
The economic cost of stainless steel reinforcements (3300 €/ton 2.2. Stress corrosion cracking (SCC) test
for AISI 304, 2750 €/ton for DSS 2205 and 2300 €/ton for LDSS
Stress corrosion cracking (SCC) stainless steel test specimens were simultane-
2001), values for the cost of stainless steel provided by supplier, ously subjected to mechanical stress and exposed to 8%wt. chloride contaminated
is about 3 to 5 times higher than carbon steel (700 €/ton), due to concrete pore solution (pH = 12.6) at room temperature. High Cl– concentration is
the nickel price fluctuation in the stock market; this fact has held used for SS rebars to accelerate pit nucleation, since in previous studies chloride
up the development of the stainless steel as reinforcement for con- corrosion threshold for SS rebars in concrete pore solution was found to be about
6–8%wt. Cl– [6]. Carbon steel B500SD was exposed to 3.5%wt. Cl– contained solution
crete structures. However, taking advance of stainless steel under SCC conditions. The samples were loaded up to 85% of their yield strength in
mechanical properties, the over cost can be only at about 20%, a creep machine. Table 2 shows the main mechanical properties data for both stain-
and, if considering the complete life-cycle cost, this solution can less steels: yield strength (fy), applied load, load induced stress (f) and yield stress-
cut down retrofitting cost in 20–25%, making it cost effective bearing stress ratio (fy/f).
The SCC monitoring was carried out using a simulated concrete pore solution
[16,17]. Austenitic stainless steel reinforcements, AISI 304 and AISI
[29] contaminated with chloride (8% wt. Cl–), initial pH solution was 12.6. A
316 were originally used and a duplex stainless steel was devel- three-electrode configuration electrochemical cell set-up was designed, including
oped (2205 DSS) later with the aim of reducing price. Nowadays, a saturated calomel electrode (SCE), an AISI304 austenitic stainless steel mesh as
current trends focus on the corrosion performance of lean–duplex reference electrode (RE) and counter electrode (CE) respectively, and the stainless
stainless steel, such as 2001 LDSS, which nickel content is lower steel reinforcement as working electrode (WE), as depicted in Fig. 1. Uniaxial con-
stant tensile load (Fa) was applied. Test specimen surface 5.65 mm2 was exposed,
than DSS. This low–nickel content need to be balance with higher being isolated to avoid triple interface between solution, air and electrode. SCC tests
amount of manganese to maintain the duplex austenite-ferrite of each SS specimens were carried out in triplicate.
microstructure as to perform high mechanical properties Linear polarization resistance method (LPR) was employed to evaluate SCC sus-
[11,18,19]. ceptibility of studied stainless steel reinforcements, following steps: first corrosion
potential, Ecorr, was measured; once Ecorr was stabilised, a polarization was imposed
Due to the lack of conclusive results of stainless steel reinforce-
at a scan rate of 0.1667 mV/s in an interval of ±15 mV vs Ecorr.; and finally, according
ments corrosion behavior, because of scatter tests driven, no regu- to Stern & Geary equation (icorr = B/Rp), icorr was calculated using a value of
lations have been developed for the specific use of stainless steel B = 26 mV [7,29]. In addition, and to quantify the corrosion damage, corrosion rate
(vcorr) was obtained by Faraday Law [29].

Table 1
Chemical composition of the stainless steel reinforcements (% wt. Fe balance).

SS grade C Si Mn P S Cr Ni Cu N Mo Ti
2205 DSS 0.021 0.338 1.617 0.028 0.001 22.245 4.77 0.217 0.184 3.299 0.021
2001 LDSS 0.028 0.65 4.19 0.023 <0.01 20.07 1.78 0.08 0.129 0.22 0.006

Table 2
Applied tensile load for SCC test.

SS grade Specimen fy [N/mm2] Load [Kg] f [N/mm2] fy/f


2001 LDSS A 951 1604 785 1.21
B 946 1604 785 1.20
2205 DSS A 1004 1803 882 1.14
B 986 1803 882 1.12
E. Briz et al. / Construction and Building Materials 192 (2018) 1–8 3

High concentration of chloride can induce pits growth across exposed surface,
wherein cracks may nucleate and propagate on this particular location. For this rea-
son, pitting corrosion resistance was measured by cyclic anodic polarization tech-
nique using scan amplitude of 1.0 V vs Ecorr at a scan rate of 0.1667 mV/s after
SCC tests.
Test lasted for one year, to assess the damage, both non-destructive and
destructive methods were used. Visual inspection was made by taking images of
the exposed surface, after complete this, exposed specimens and as-received spec-
imens were loaded in a tensile test machine until failure, to analyze the fracture
surface to elucidate the crack path.

3. Results and discussion

An evolution of the pH of concrete pore solution with time dur-


ing SCC test for 2001 LDSS, 2205 DSS and BS500SD is presented in
Fig. 2 The electrochemical cell was not isolated from the environ-
ment in order to allow experiment simulates real exposure condi-
tions, considering that atmospheric CO2 may pollute the
electrolyte altering the pH. It has been observed a sharp pH change
after 40 days of test, where it decreased from 12.6 (pH value for
non-carbonated concrete) down to pH = 6. The sharp pH decrease
found is a consequence of the carbonation of the concrete pore
solution. In addition, Fe acid hydrolysis reaction, is responsible
for the local acidification and the H2 evolution related to cathodic
reaction. This pH decrease led to an accelerate corrosion initiation
process. Ecorr values showed a similar trend for both studied duplex
stainless steels, 2001 LDSS and 2205 DSS. Ecorr variation is shown in
Fig. 3. Comparing Figs. 2 and 3, it is evidenced the influence of pH
on the Ecorr values, as they fluctuate in the same way as pH does
[30].
According to Ecorr values, while pH > 9 probability of corrosion
Fig. 1. Stress corrosion cracking test set-up. Uniaxial applied load (Fa) and 3- in any case is less than 10%. After pH drops below pH < 9, elec-
electrodes configuration electrochemical cell, working electrode (WE), reference
trolyte solution it carbonates decreasing Ecorr values. For 2001
electrode (RE) and counter electrode (CE).
LDSS, Ecorr dropped at about 215 mV and 2205 DSS hardly
decreased 50 mV. This Ecorr decrease, led to corrosion probabilities

Fig. 2. Electrolyte pH evolution during the SCC test, for 2001 LDSS and 2205 DSS.
4 E. Briz et al. / Construction and Building Materials 192 (2018) 1–8

Fig. 3. Corrosion potential (Ecorr) evolution during SCC test in chloride contaminated concrete pore solution, at room temperature for carbon steel B500SD (3.5% Cl–), and
stainless steel reinforcements 2205 DSS, 2001 LDSS (8% Cl–).

higher than 90% and uncertain range of corrosion for 2001 LDSS mechanical resistance considering safety factors for material and
and 2205 DSS, respectively [31,32]. These results are in good agree- loads defined in different directives [22,36]. The reduction of
ment with those reported by other researchers [33,34]. cross–section diameter of 2205 DSS is 3.86% for 100 years of lifes-
In addition to duplex stainless steel, carbon steel B500SD rein- pan, value even lower than the one obtained for 2001 LDSS. How-
forcements were tested, for comparative purpose. SCC test was ever, 2001 LDSS cross-section reduction is 11.4%, this value is
performed under load equal to 85% of their yield strength in simu- higher than the safety coefficient (1.15) applied to the yield stress
lated concrete pore solution with 3.5% chloride content, in order to for structural design. It must be pointed out that this analysis has
compare SCC susceptibility. been done without evaluating the detrimental of mechanical
Fig. 4 summarizes the evolution of corrosion current density properties.
(icorr) with time test. Initial icorr values (0.01 lA/cm2), were similar Ecorr is not a quantitative parameter; however, its measurement
for both duplex stainless steel. Thus indicating a negligible corro- allows gathering information about corrosion level in a simple
sion probability during the early 40 days of test. After this time, way. Ecorr limits provided by different directives have been defined
pH decreased down to pH < 9, while icorr values increased. In the for carbon steel B500SD reinforcements. Considering Ecorr and icorr
case of 2205 DSS, icorr values stabilised below 0.1 lA/cm2 while results, it can be confirmed that these limits are not suitable for
for 2001 LDSS recorded icorr was above 0.1 lA/cm2. According to stainless steels rebars, this makes it necessary to establish and
corrosion threshold limits defined in UNE 112072 [29], 2001 LDSS define new corrosion thresholds for stainless steel reinforcements.
corrosion risk is very low, while 2205 DSS corrosion risk is negligi- A cyclic polarization curve was recorded to measure pitting cor-
ble. B500SD carbon steel reinforcements present SCC susceptibility rosion resistance once SCC test was finished (315 days). Fig. 5
higher than duplex stainless steels, leading to a high corrosion risk shows anodic polarization curves of 2001 LDSS and 2205 DSS.
since the very beginning of SCC test. According to cyclic anodic polarization curve, no pit nucleated on
Obtained maximum icorr values have been 0.1 µA/cm2 and 2205 DSS, only metastable pitting was observed (Emetpit =
0.295 µA/cm2 for 2205 DSS and 2001 LDSS respectively. These 14.09 mV). More noble Ecorr was defined after reverse scan
inform about a higher corrosion level of 2001 LDSS in relation (Ecorr = 24.25 mV), this can be explained as passive layer developed
2205 DSS, close to factor of 3. Reduction of the cross-sections, in the simulated pore solution during the polarization process.
obtained by Faraday equation, were 1.16 µm/year and 3.42 µm/year However, a sharp increase of the icorr is observed for 2001 LDSS,
for 2205 DSS and 2001 LDSS, respectively. The obtained values were pits nucleation occurs (Epit = 178.9 mV), and afterwards pits
for SS, are two orders of magnitude smaller than corrosion rate grow, thus producing a hysteresis loop after reverse scan. At this
result 711.15 µm/year, obtained for carbon steel B500SD. point 2001 LDSS, present high risk of developing cracks in these
Current directives define two nominal service lifetime limits, 50 pits.
and 100 years [35], depending on the application of the structure. The crack propagation rate can be estimated by Galvelés theory
Table 3 summarizes diametrical reinforcement reduction of 2001 as defined in (Eq. (1)). Crack propagation rate (cpr) values for LDSS
LDSS and 2205 DSS applying maximum icorr values. Dissolution 2001, at 25 °C, range between 4  10–7 and 4  10–3 m/s consider-
processes strongly influenced sample diameter, 2001 LDSS diame- ing FeCl2 or FeCl3, respectively, as chemical species formed on sur-
ter reduction values are higher than 2205 DSS. Lean-duplex 2001 face during corrosion reaction, [37], at yield stress (950 N/mm2) as
LDSS shows a reduction of 5.7% cross–section diameter for 50 years is showed in Fig. 6. The cpr values directly depend on the elastic
of service life. This corrosion rate is acceptable with no detrimental surface stress at the tip of the crack (r), therefore, the higher the
E. Briz et al. / Construction and Building Materials 192 (2018) 1–8 5

Fig. 4. Corrosion current density (icorr) evolution during SCC test in chloride contaminated concrete pore solution of carbon steel B500SD (3.5% Cl–), and stainless steel
reinforcements 2205 DSS, 2001 LDSS (8% Cl–).

Table 3
Cross-section reduction as a function of service lifetime prediction.

Type vcorr [µm/year] 50 years nominal service life 100 years nominal service life
Ø Reduction [µm] Ø Reduction [%] Ø Reduction [µm] Ø Reduction [%]
2001 LDSS 3.42 342 5.7 342 11.4
2205 DSS 1.16 116 2 116 3.86

Fig. 5. Anodic polarization curve of 2205 DSS and 2001 LDSS after SCC, in chloride contaminated concrete pore solution LDSS (8% Cl–).
6 E. Briz et al. / Construction and Building Materials 192 (2018) 1–8

Fig. 6. Crack propagation rate (cpr) values for 2001 LDSS after SCC test.

fy the lower the r. Thus, LDSS 2001 will present high cpr values,
since fy value is 951 N/mm2 rather than the 1004 N/mm2 obtained
for DSS 2205, as reported in Table 2. This is also in good agreement
with the electrochemical results obtained in Fig. 5.
  3  
Ds ra þ aEb
cpr ¼ exp 1 ð1Þ
L kT
where:

cpr: crack propagation rate, m s1


Ds: surface self-diffusion coefficient, 10–16 m2 s1 (FeCl2)
or 10–12 m2 s1 (FeCl3)
L: diffusion length, 10–8 m
r: elastic surface stress at the tip of the crack
a: atom size, 2.5  10–10 m
a: hydrogen saturation degree of vacancies, amax = 1,
dimensionless
Fig. 8. 2205 DSS fracture surface micrographs 750, after SCC test.

Fig. 7. Surface appearance of specimens after SCC test in chloride contaminated concrete pore solution (8% Cl–). (a) 2001 LDSS and (b) 2205 DSS.
E. Briz et al. / Construction and Building Materials 192 (2018) 1–8 7

Fig. 9. 2001 LDSS fracture surfaces micrograph after SCC test. (a) 750 and (b) 5000.

Eb (H-Fe): binding energy for hydrogen monovacancies in Fe,  The experimental results demonstrated suitable SCC behaviour
0.53 eV = 8.5915  10–24 J of 2205 DSS and 2001 LDSS. It is evidenced a better performance
k: Boltzman constant, 1.38066  10–23 J K1. of 2205 DSS than 2001 LDSS. However, it is found 2001 LDSS
T: temperature, 298 K (25 °C) stands as an outstanding reinforcement, in such conditions
wherein high corrosion material is needed. This considers safety
Surface morphology after SCC test of tested stainless steel rein-
factor of 1.15 related to yield strength of the SS rebar, as
forcements included in Fig. 7 shows 2001 LDSS (Fig. 7a) and 2205
required by different directives [22,36],
DSS (Fig. 7b) stainless steel surfaces that have been exposed to the
 Obtained results demonstrate cost saving across the service life-
electrolyte during SCC test and also to cyclic polarization test. 2001
time, in particular for 2001 LDSS as for maintenance and retro-
LDSS pits nucleated around the notch, in a size range between
fitting cost, but also construction cost by taking advantage of
1.5 mm and 2.3 mm. On the other hand, it is worth mentioning
the better SCC performance of stainless steel. These advantages,
that no pits have been detected on 2205 DSS surface.
evidence the need of a specific directives for the use of stainless
Fracture surface of SCC 2205 DSS specimens is shown in Fig. 8;
steel reinforcement, where RC structures service lifetime could
coalescence of microvoids was evidenced, thus leading to the dim-
be extended [2,40].
ple character of a ductile fracture; it is worth to note dimple den-
sity increased after SCC exposure. 2001 LDSS specimens, show
microvoids coalescence, related to system of dimples on ductile
fracture of non-exposed specimen. Acknowledgements
Cracked surface of 2001 LDSS is shown in Fig. 9. The SCC tested
specimen showed a 60% reduction in dimple diameter (Fig. 9a) and E. Briz thanks Research Group IT781-13 ‘‘Comprehensive
brittle failure was detected. In Fig. 9b, the combination of quasi- sustainability in building systems and materials” support, at the
cleavage fracture and ductile fracture it can be observed; which University of the Basque Country. D. M. Bastidas gratefully
means that brittle failure was detected. These results support bet- acknowledges funding from The University of Akron.
ter corrosion behavior for 2205 DSS than 2001 LDSS, under SCC
conditions. This is because 2001 LDSS showed brittle fracture evi- Conflict of interest
dence [10,26,38,39]. In addition, the growth of dimples density
during SCC test, confirms the reduction of toughness for both stud- The authors declare that they have no conflict of interest.
ied stainless steels, 2205 DSS and 2001 LDSS.
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