Construction and Building Materials 188 (2018) 9–16

Contents lists available at ScienceDirect

Construction and Building Materials

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

Study on corrosion mechanism of alkali-activated concrete with biogenic

sulfuric acid
Yudong Xie, Xujian Lin ⇑, Weijie Pan, Tao Ji, Yongning Liang, Hongru Zhang
College of Civil Engineering, Fuzhou University, Fuzhou, Fujian Province 350108, China

h i g h l i g h t s

Biogenic sulfuric acid (BSA) corrosion of AAC was studied.

The effect of sulfuric acid type on the performance of AAC was studied.

The degradation mechanism of AAC eroded by BSA was analyzed.

The BSA had a more negative effect on the performance of AAC.

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

Article history: Two different types of sulfuric acid, chemical sulfuric acid (CSA) and biogenic sulfuric acid (BSA) pro-
Received 7 May 2018 duced by T.f bacteria (Thiobacillus ferrooxidans), were applied into the simulation of the corrosion of
Received in revised form 12 August 2018 alkali-activated concrete (AAC). Compared with CSA corrosion, three sulfuric acid concentrations
Accepted 17 August 2018
(pH = 1.1, 1.6 and 2.0) were used to study the degradation of AAC under the BSA corrosion. In this paper,
the change of appearance, compressive strength, Ca2+ emission, the environmental scanning electron
microscope-energy dispersive spectroscopy (ESEM-EDS), X-ray diffraction (XRD) and nuclear magnetic
Keywords:
resonance (NMR) respectively were used to study the deterioration mechanism of AAC under BSA attack.
Biogenic sulfuric acid
Alkali-activated concrete
The result of the experiment revealed that BSA was more corrosive to AAC than CSA. However, with the
Deterioration impact of different concentrations of CSA and BSA, the product of corrosion of the AAC was still mainly
Corrosion gypsum. Therefore, BSA merely accelerated the corrosion rate and did not transform the corrosion mech-
pH values anism. Additionally, AAC less affected by bacteria, the degree of corrosion of the AAC is mainly influenced
by the concentration of sulfuric acid.
Ó 2018 Elsevier Ltd. All rights reserved.

1. Introduction anaerobic environments, and then H2S is oxidized into BSA by

Microbes producing sulfuric acid exert a negative influence on
concrete materials [1]. Such corrosion damage often occurs in cer-
tain areas where are enriched with microorganisms, such as under-
ground structure, sewage systems as well as wastewater treatment
systems [2]. The percentage of corrosion due to microorganisms is
10–20% in the damage of German building materials and roughly
10% in American concrete sewage pipe [3,4]. It is imperative to
study the microbial corrosion of concrete for reduction in the hefty
cost of building maintenance.
Parker [5] has discovered that the biological sulfuric acid (BSA)
corrosion is one of the main reasons accountable for the concrete
corrosion. Sulfate and organic sulfur is turned into H2S by SRB in
⇑ Corresponding author.
E-mail address: xjlin@163.com (X. Lin).
SOB in aerobic environments.
Alkali-activated concrete (AAC) has much more advantages in
engineering than ordinary Portland concrete (OPC) such as acid
resistance and impermeability [6]. Therefore, it is imaginable that
the potentiality of AAC in marine application is huge [7].
Currently, compared to the studies about alkali-activated
cement paste under BSA corrosion, research on the corrosion of
AAC by BSA has been hardly conducted. Sun and Wu [8] immersed
alkali-activated fly ash cement paste in various concentrations of
H2SO4 solutions; as a result, slight damage on the surface was
found when immersed in 0.05% H2SO4 for 6 months; when
immersing specimens in a 3% H2SO4 solution for 1 week, the sur-
face was damaged. And when alkali-activated slag (AAS) concrete
was immersed in an acetic acid solution (pH = 4) for 6 months,
the change of compressive strength was very small [9].

https://doi.org/10.1016/j.conbuildmat.2018.08.105
0950-0618/Ó 2018 Elsevier Ltd. All rights reserved.
10 Y. Xie et al. / Construction and Building Materials 188 (2018) 9–16
There has been little research on the corrosion of AAC by BSA
compared to studies about sewer pipe made by concrete under
BSA corrosion [10,11]. It is improper to investigate the corrosion
of concrete merely by chemical sulfuric acid (CSA) in that the pro-
cess of BSA corrosion is a complex and long-term. Thus, the differ-
ences between BSA and CSA were of significance [12–15]. What’s
more, there is no study on the effect of BSA of different concentra-
tions on the behavior of AAC. This paper studies the behavior of
AAC under BSA with three different concentration levels. T.f bacte-
ria (Thiobacillus ferrooxidans, T.f) was used to simulate the BSA
corrosion in this paper. CSA was applied to study the corrosion
effect of BSA on AAC as a contrast, which revealed the mechanism
of AAC by BSA corrosion.
2. Materials
All materials used in the experiment were produced in China. The chemical
composition of Fuzhou slag and fly ash is shown in Table 1. Analytical Reagent
NaOH (the solid content is 96%) was used as activator. The coarse aggregate was
ordinary stone, which was selected in accordance with GB/T 14685-2001 [16]; Fine
aggregate was river sand, and its each performance index measured according to
GB/T 14684-2001 [17] is listed in Table 2. Water used in AAC was the tap water
of the Fuzhou municipal area. According to the Berger Bacteria Identification Man-
ual [18], Thiobacillus ferrooxidans (T.f) from Xiamen Ocean Institute selected as the
representative bacterium of ASOM was used in this study. Specifically, 10% T.f
bacteria solution inoculated with 9 K medium (a medium specially used for cultur-
ing T.f bacterium [19]) was used as a medium erosion solution for simulating BSA
corrosion. 9 K cultured medium contained 3 g (NH4)2SO4, 0.1 g KCl, 0.5 g K2HPO4,
0.5 g MgSO47H2O, 0.01 g Ca(NO3)2, 44.78 g FeSO47H2O and 1000 ml H2O.
3. Experimental
3.1. Mix proportion
Because the superplasticizer is generally not suitable for AAC,
and the current has not developed a water-reducing agent widely
used for AAC. Thus, no water-reducing agent was added in this
experiment.
Puertas et al. [20] reported that the ratio of fly ash-slag and the
activator concentration always turn out to be critical factors. They
have found that the mixture 50% fly ash-50% slag activated with
10 M NaOH solution develops compressive strength of 50 MPa.
After repeated trial, the mixture 20% fly ash-80% slag by mass acti-
vated with 5.44 M NaOH solution was proportioned in this study,
and the compressive strength at 28 days can reach 65.5 MPa. The
final mix proportion is shown in Table 3.
Table 1
Chemical composition (% wt.).
SiO2 Al2O3 Fe2O3
Slag 32.85 13.01 0.29
Fly ash 50.02 24.96 4.46
Table 2
Performance index of the river sand.
Fineness modulus Bulk density (kg/m3) Apparent density (kg/m3)
2.5 1480 2591
Table 3
Mix proportion of alkali-activated concrete (AAC) (kg/m3).
Water Slag Fly ash
170 369.19 92.30
3.2. Specimen preparation
To prepare the concrete specimens, NaOH was dissolved first in
the water to form a solution. The slag, fly ash, sand and crushed
stone were mixed in a mixer for 1 min and then the NaOH solution
was added and stirred thoroughly for 1 min. Afterwards, the mix-
tures were poured into inner surface-oiled moulds (100 mm 
100 mm  100 mm) and were carefully compacted to minimize
the amount of entrapped air. Then, the specimens were cured in
a fog room (20 ± 2 °C, RH > 95%) for one day. The specimens were
then demoulded from the moulds and were transferred into steam
pressure equipment and then experienced an autoclaved curing
(had a vacuum pumping for 30 min first, and then increased tem-
perature to 195 °C and pressure to 1.2 MPa for 1 h, the temperature
and pressure should be maintained for 6 h, and then reduced the
pressure in 2 h). Subsequently, the specimens were cured in stan-
dard for 28 days. After that, the specimens were placed in the pre-
pared CSA solution and BSA solution for corrosion test.
3.3. Biogenic sulfuric acid corrosion device
The BSA corrosion simulation device is schematically shown in
Fig. 1, which has been performed as previously described in litera-
ture [21]. The experiment was carried out by changing the concen-
tration of H2S and keeping the other parameters unchanged so that
obtained three different pH values (pH = 1.1, 1.6 and 2.0) of the
bacterial broth in the course of the experiment to consider the
effect of different bacterial growth conditions on the concrete
specimen. The following is a brief description of the simulated
BSA corrosion device, which is as follows:
H2S is produced in part 1 while part 2 conducts the BSA corro-
sion. H2S was produced by Na2S (0.086 M) and HCl (0.042 M). Vol-
umetric flow of Na2S and HCl was kept at 1.4 ml/min while certain
oxygen input quantity of 30 ml/min was maintained in the med-
ium. H2S was transformed into BSA due to the T.f bacteria in the
cultured medium [22,23]. The change of pH within the cultured
medium is shown in Fig. 2. Laboratory temperature was kept at
25 ± 2 °C to ensure an identical test condition. A period of 14 days
was used as a cycle in this experiment and the solution of cultured
medium was adjusted every other cycle.
In order to make a comparison of the CSA and BSA, the samples
were placed in a simulated acid rain corrosion test chamber with
CSA solution in the course of the experiment on CSA corrosion.
Due to the large acid consumption of CSA during the test, the sul-
CaO MgO SO3 TiO2 Na2O LOI
37.44 10.78 1.91 2.15 0.32 0.2
7.52 1.47 1.06 1.57 0.78 4.01
Water absorption (%) Mud content (%)
0.1 3.53
NaOH Stone River sand
38.51 1233 527
 Y. Xie et al. / Construction and Building Materials 188 (2018) 9–16 11

Part 1 Part 2
Fig. 1. Setup of the BSA corrosion tests (adapted from [21]).

corrosion ages (i.e., 28, 84 and 140 days in this study), their appear-
ances were significantly degenerated. A Canon EOS 6D camera was
2.5 used to record the change in appearance.
Compressive strength of the concrete specimens was measured
2.0 in accordance with China’s standard, GB/T50081-2002 [24]. The
compressive strength of the specimens under the corrosion of
CSA and BSA was tested for every 28 days. The average of three
1.5
pH

specimens’ compressive strength was taken as the representative

1.0
S2.0
S1.6
0.5
S1.1
0.0
0 2 4 6 8 10 12 14
t (d)
Fig. 2. pH value of cultured medium in function of time.
furic acid solution was replaced once a week. The pH value of the
solution was monitored daily with a pH meter.
In the following test results, the first letter H in all figures rep-
resents the CSA corrosion, S represents the BSA corrosion; the sec-
ond letter A represents alkali-activated concrete; 1.1, 1.6, 2.0
represents different pH value; SA1.1 represents that concrete spec-
imens were corroded in BSA solution which pH value is 1.1; SA1.6
represents that concrete specimens were corroded in BSA solution
which pH value is 1.6; SA2.0 represents that concrete specimens
were corroded in BSA solution which pH value is 2.0; HA1.1 repre-
sents that concrete specimens were corroded in CSA solution
which pH value is 1.1; HA1.6 represents that concrete specimens
were corroded in CSA solution which pH value is 1.6; HA2.0 repre-
sents that concrete specimens were corroded in CSA solution
which pH value is 2.0.
3.4. Test methods
compressive strength of each concrete.
3.4.2. The leaching amount of calcium
Since the Ca2+ emission from the concrete is an indicator for
structural failure, the dissolved calcium concentration is measured
in the bulk phase of the chemical and biological set-ups were of
importance. Thus, calcium measurements in the corrosion solu-
tions were taken to monitor calcium leaching from the concrete;
the specific experiment process is as follows:
The medium speed filter was used to filter the corrosion liquid,
and 50 ml of the filter solution was placed in the 250 ml conical
bottle, then 3 drops of the mixture 50% analytical pure hydrochlo-
ric acid-50% distilled water were added to the conical bottle, and
the mixed solution was heated to boil for 30 s and then cooled to
below 50 °C; after that, 5 ml potassium hydroxide solution (20%
wt.), 80 mg calcein and phenolphthalein mixture indicator (0.2 g
calcium chlorotolein, 0.07 g phenolphthalein and 20 g potassium
chloride) were added into the conical bottle. After the solution in
the conical bottle was shaken evenly, 2 ml of triethanolamine
was added into conical bottle to screen the Fe ions in corrosion
solution. Finally, titration of the amount of Ca2+ was carried out
using a 0.01 mol/L EDTA standard solution. When the yellow-
green color disappeared, the solution was red and there was no
color return, the titration was completed, and the EDTA usage
was recorded at this time. The average of two specimens’ leaching
amounts of calcium was taken as the representative emission
quantity of Ca2+ of each concrete, and the deviation of two mea-
surements should not exceed 2 mg/L. The leaching amount of cal-
cium is calculated according to Eq. (1):

V  M  100:8  1000
3.4.1. Surface images and compressive strength X¼ ð1Þ
Vw
The most direct way to judge the degree of sulfuric acid corro-
sion is to observe the appearance of concrete specimen. After con- where Xis the emission quantity of Ca2+ (mg/L); Vis the usage of
crete specimens were exposed to BSA and CSA at the specified EDTA solution (ml);M is the concentration of EDTA standard solu-
12 Y. Xie et al. / Construction and Building Materials 188 (2018) 9–16

tion (mol/L); V w is the volume of test solution (ml); 100.8 is the

molar mass of CaCO3 (g/mol). HA1.1-28 days SA1.1-28 days

3.4.3. XRD, NMR and ESEM-EDS analyses

In this study, the hydration products of concrete cured for 28
days and the corrosion products at the specified corrosion ages
were tested by the Philips X/Pert Pro MPD X-ray diffraction
(XRD), Netherlands. XRD used Cu Kɑ radiation in the 2h region
between 5°and 80°, with a 0.02°step size and 2 s/step count time.
A XL30 ESEM-TMP environmental scanning electron microscope-
energy dispersive spectroscopy (ESEM-EDS) was used for examin-
ing the localized morphology and chemical composition of the cor-
rosion products which were exposed to BSA and CSA at the
specified corrosion ages. Nuclear magnetic resonance spectroscopy HA1.1-84 days SA1.1-84 days
(NMR) gives detailed structural information on materials contain-
ing atoms, which possess a magnetic moment, e.g. 27Al, 29Si. Before
using NMR, all the specimens were finely ground in agate mortar
and through a 100-mesh sieve. Then, the spectra were recorded
by a Bruker Avance III 500 spectrometer in magic-angle spinning
(MAS) with the single pulse technique. The 29Si and 27Al NMR spec-
tra were deconvoluted using the Bruker WINNMR software. The
samples of microstructure measurements (ESEM-EDS, XRD and
NMR) were immersed in acetone to stop hydration as fast as pos-
sible until being put in an oven for drying.

HA1.1-140 days SA1.1-140 days

4. Results and discussion

4.1. Surface images

The surface images of AAC corroded by BSA and CSA at the 28th,
84th and 140th day in the case of pH = 1.1 are shown in Fig. 3.
Under the CSA corrosion, the surface of AAC appeared to be soft-
ened with some pores at the 28th day. After 84 days, the surface
layer has completely fallen off and part of the coarse aggregate
was exposed. Coarse aggregate protruding corrosion surface 2
mm was not presented until 140 days’ exposure to CSA, while Fig. 3. Surface images of AAC attacked by CSA and BSA at the 0, 28th, 84th and
there was no gap between aggregate and mortar. Observationally, 140th day in the case of pH = 1.1.

it can be concluded that the internal structure of AAC affected by

acid long-termly will not suffer serious damage. Throughout the
corrosion process, the color of concrete specimens shifted from 65
grayish black to yellow and eventually became beige.
In the BSA corrosion, the mortar matrix of the specimen began 60
to soften and coarse aggregate was exposed due to the dissolution
of adhering mortar, and the surface of AAC appeared beige with
fc(MPa)

55
many small pores after the 28 days. Compared with CSA corrosion, SA1.1
there was a gap between the aggregate and the mortar at the 84th SA1.6
50 SA2.0
days. Coarse aggregate protruding corrosion surface 3 mm was not
HA1.1
presented until 140 days’ exposure to BSA, and there was a clear HA1.6
gap between aggregate and mortar. It can be seen that compared 45
HA2.0
to the CSA corrosion, BSA caused more serious corrosion on AAC
due to the presence of bacteria. 40
0 20 40 60 80 100 120 140
4.2. Variation of compressive strength t (d)

The compressive strength of AAC corroded by BSA and CSA is Fig. 4. The compressive strength of AAC corroded by BSA and CSA.

shown in Fig. 4. It can be seen from the figure that SA1.1 >
HA1.1 > SA1.6 > HA1.6 > SA2.0 > HA2.0 on strength loss, therefore,
that reveals that the concentration of sulfuric acid solution domi-
nates. The compressive strength of HA1.1 and SA1.1 decreased
slowly in the first 28 days, and the strength loss rate accelerated
greatly after the 28th day. The slope of SA1.1 decline is greater than
that of HA1.1. SA1.1 produced gypsum due to surface dissolution,
which provided a good living condition for bacteria. Therefore,
the strength also decreased rapidly. Under the condition of pH =
1.1, the loss of compressive strength of AAC at 140 days under
the BSA and CSA is 36% and 24%, respectively; the loss of AAC
strength under the BSA is 1.5 times that of CSA. The variation of
compressive strength curve in Fig. 4 is basically a linear relation-
ship, which indicated that the internal structure of the concrete
specimen during the corrosion process is not destroyed, and acid
corrosion is limited to the surface layer. Bacteria only accelerated
corrosion and did not change the corrosion process throughout
the corrosion process.
 Y. Xie et al. / Construction and Building Materials 188 (2018) 9–16
4.3. Calcium concentration in the bulk phase
Fig. 5 shows the change of Ca2+ emission of AAC corroded by
BSA and CSA. Under the CSA corrosion, the amount of Ca2+ emis-
sion has been decreased and the emission rate is linear with time
when pH = 1.6 and 2.0. The dissolution of Ca2+ originates from
the destruction of the free Ca2+ in the surface and the internal
Ca-O inside the structure. However, it has been known from previ-
ous analysis that the internal structure of specimen exposed to CSA
when pH = 1.6 and 2.0 has not been severely damaged, so the Ca2+
from the damage derived from Ca-O is very limited, and the free
Ca2+ gradually decreases with the dissolution of the surface. Thus,
the emission of Ca2+ from concrete specimen was exposed to CSA
when pH = 1.6 and 2.0 had been decreasing over time.
In the BSA corrosion, the Ca2+ overall emission level is higher
than the CSA corrosion at corresponding pH value; BSA was more
corrosive to AAC than CSA. In the case of pH = 1.1, since the bacte-
ria have not been fully adapted in the initial period, the emission
amount was low; afterwards, with the dissolution of the surface
of the specimen, the release of Ca2+ began to increased, and then
maintained at a stable level. However, when pH = 1.6 and 2.0, sur-
face layer protects the interior part of structure because of its slow
deterioration. Thus, the release of Ca2+ increased first and then
decreased. In addition, it can be found that the amount of Ca2+
emission of concrete specimen corroded by BSA is 1.17 times that
of CSA corrosion when pH = 1.1; however, the Ca2+ emission of
specimen corroded by BSA is 1.67 times that of CSA corrosion when
pH = 2.0. It was found that the accelerated corrosion of bacteria
decreased with increasing concentration of Ca2+. However, Fig. 5
shows the difference of the amount of Ca2+ emission between
SA1.1 and HA1.1 is obviously larger than that of SA2.0 and
HA2.0. The explanation for this is that the overall level of Ca2+
emission in each group is too high, while the acceleration effect
of bacteria is limited, and the acceleration of bacteria in the
SA1.1 group with higher average level is less obvious. However,
the bacterial acceleration effect of the SA2.0 group with the lowest
overall level is more obvious.
4.4. ESEM-EDS analysis
Fig. 6 shows the corrosion appearance and corrosion products of
AAC corrosion layer corroded by BSA for 84 days in the case of pH
= 1.1. It can be found that gypsum crystal is the main corrosion
product which can be seen everywhere in the erosion loose layer.
The EDS spectrum of the corrosion layer is shown in Fig. 7, in which
0–2 mm is a loose area of corrosion. It can be observed that more S
elements appear in this area, but few S elements are found after
600
550
500
450
CCa2+(mg/L)
400
SA1.1 HA1.1
350
SA1.6 HA1.6
300 SA2.0 HA2.0
250
200
150
100
50
0 group after the decomposition of Al-O structure. All in all, the
2 4 6 8 10 12 14 16 18
t (week)
Fig. 5. The Ca2+ emission of AAC corroded by BSA and CSA.
13
more than 2 mm. It also proves that the corrosion products pro-
duced in the corrosion zone are gypsum. In addition, Al and Si will
be dissolved after acid corrosion, and the acid resistance of Al is
worse than Si, so the dissolution depth of Al is larger than Si. Most
of Na+ comes from free alkali; at the same time, according to pre-
vious analysis, Ca2+ is in the presence of Ca-O bond, so Ca2+ can be
dissolved after destroying the hydrated calcium silicate. Precisely,
it is because of the exchange of cation such as Na+, Ca2+ and H+ that
results in acidification of AAC.
4.5. XRD analysis
The XRD comparison between the concrete specimens cured for
28 days and the corrosion layer corroded by BSA for 84 days in the
case of pH = 1.1 is shown in Fig. 8. Given the previous analysis,
SA1.6 and SA2.0 is corroded to a very small extent. Only SA1.1 is
severely corroded and the surface is dissolved in large amounts.
Therefore, the corrosion layer on the surface of SA1.1 is sampled
for XRD. It can be seen that the hydration products of AAC were
mainly Xonotlite, Tobermorite, and CSH (B); the aluminosilicates
are dominated by Gmelinite. After AAC is corroded by BSA when
pH = 1.1, the dispersion peak of calcium silicate hydrate has disap-
peared and been replaced by gypsum peak. The diffraction peak of
sodium siderite is obviously weakened. At the same time, it is a
dispersion peak between 27 and 35° disappeared basically under
the BSA corrosion, and the original dispersion peak is supplanted
by a strong plaster peak. In other words, AAC is seriously corroded.
All in all, the hydration products of AAC are severely damaged, and
the main corrosion product is gypsum, which is consistent with the
results obtained in ESEM-EDS.
4.6. NMR analysis
In recent researches, a substantial amount of Al was found to be
the major corrosion product of AAC by using ESEM-EDS and XRD.
This solid state NMR study was designed to understand that
whether the aluminum in solid solution would replace Si tetrahe-
dron and to analyze the cause of the destruction of the structure.
29
Si (a) and 27Al (b) MAS NMR spectrum between the concrete
specimens cured for 28 days and the corrosion layer corroded by
BSA for 84 days in the case of pH = 1.1 are shown in Fig. 9. It can
be observed that the hydration products of AAC mainly include cal-
cium silicate hydrates and silicates; hydrated calcium silicates
include Xonotlite, Tobermorite, and CSH (B), [SiO4]4 tetrahedron
is its main architecture; the aluminosilicates are dominated by
Gmelinite, and the internal structure is dominated by [AlO4]5
tetrahedron. From Fig. 9(a), it is obvious to perceive that the two
main peaks of 85.5 and 83.1 ppm disappear completely, being
taken the place of the two new peaks of 102.2 and 110.7
ppm. 85.5 and 83.1 ppm as Q02 s two different [SiO4]4 tetrahe-
dron, 102.2 and 110.7 ppm belong to the [SiO4]4 three-
dimensional networks of Q4, which indicates that the Si-O struc-
ture has undergone major changes and new structures have been
created. From Fig. 9(b), it can be observed that the main peak of
AlO4 tetrahedron at 60 ppm after corrosion fell rapidly, and the
peak value of six coordination Al at 7.9 ppm is also very weak,
which indicates that the two structures are seriously damaged
after BSA corrosion. After BSA corrosion, the Al-O structure disap-
peared, but no new peaks are generated. It indicates that Al has not
formed a new functional group with other Oxygen functional
20 hydrated calcium silicates, such as the hard silica calcareite, the
CSH (B), and so on, are destroyed and the original Q2 type of SiO4
tetrahedron structure is destroyed and the new Q4 type of SiO4
tetrahedron structure is formed. But these structures do not form
14 Y. Xie et al. / Construction and Building Materials 188 (2018) 9–16

(a) SA1.1 Corrosion appearance (b) SA1.1 Corrosion products

Fig. 6. The corrosion appearance (a) and corrosion products (b) of AAC corrosion layer corroded by BSA for 84 days in the case of pH = 1.1.

other materials which are beneficial to the structure. And these

materials have no structural strength, in other words, the structure
Al is destroyed. The original [AlO4]5 tetrahedron and six coordina-
tion Al is severely weakened, and no new Al-O structure is gener-
ated. While not does it produce materials that are beneficial to the
structure, in other words, the structure is destroyed.
Si

4.7. Mechanism analysis

Na
From the above results, the corrosion degree of AAC under the
Ca BSA corrosion was the most serious when pH = 1.1. The deteriora-
tion mechanism of AAC under the action of BSA may be different
from CSA. When pH = 1.1, for example, the analyses are as follows:
From the results shown in Figs. 3–5: compared with CSA corro-
S
sion, BSA is only used to accelerate the corrosion process of AAC in
0 1000 2000 3000 4000 5000 terms of appearance loss, Ca2+ emission, etc., and does not change
the corrosion law, which can be verified from the following analy-
x (um)
ses: First, there are many bacteria on the surface of the concrete
Fig. 7. The EDS spectrum of the distribution of elements of corrosion products in specimen. Fig. 10 is the distribution of bacteria on the surface of
SA1.1. SA1.1. It can be seen that the bacteria are not evenly distributed
on the surface of the specimen, but selectively gather on some pro-
truding aggregates. This phenomenon also provides a basis for the

- Xonotlite
- CSH(B)
- Reinhardbraunsite
- 11A Tobermorite
- Qaurtz
- Gismondine
- Aluminum tobermorite
- Margarite
- Gmelinite
- Gypsum

SA1.1

AAC

10 20 30 40 50 60 70 80
2θ/(°)

Fig. 8. The XRD comparison between the concrete specimens cured for 28 days and the surface of corrosion layer corroded by BSA for 84 days in the case of pH = 1.1.
 Y. Xie et al. / Construction and Building Materials 188 (2018) 9–16
29
Fig. 9. Si (a) and 27Al (b) MAS NMR spectrum between the concrete specimens cured for 28 days and the corrosion layer corroded by BSA for 84 days in the case of pH = 1.1.
Fig. 10. Distribution of bacteria on the surface of SA1.1 concrete specimen.
existence of cracks between the aggregate and paste on the surface
of the SA1.1. Bacteria only accelerate the corrosion on the surface
of the concrete specimens. Secondly, in the permeability of bacte-
15
ria, the volume of bacteria is about 10,000 Å [25], and the pore size
of AAC is basically below 10,000 Å [26]. Therefore, bacteria are
unlikely to infiltrate inside the AAC unless the holes become very
large on account of severe corrosion. It can be concluded that bac-
teria can only exist on the surface of concrete blocks, but can not
penetrate into the concrete specimens. Most of the bacteria can
only accelerate the effect of the surface corrosion of the specimen
and will not make a substantial change to the failure law of the
internal structure of the specimen, and Fig. 10 proves that because
they can only exist on the surface of the specimen.
In the microcosmic experiment, the structure of products such
as gmelinite was damaged, and the most obvious change was that
the dispersion peak of the AlO4 tetrahedron in NMR four and six
coordination Al was greatly reduced, in other words, the structure
of AlO4 tetrahedron was seriously damaged, which supported the
evidence that Al was dissolved in the aluminum tetrahedron.
Allahverdi et al. [27,28] reported that the corrosion of hardened
paste of geopolymeric cements in solutions of nitric acid starts
from a leaching process in which the soluble contents of the mate-
rial (i.e. Na+ and Ca2+) are depleted and replaced by H+ or H3O+ ions
from solution; and an electrophilic attack of acidic protons on
polymeric Si-O-Al bonds results in the formation of a partially
dealkalized and decalcified Si, Al-rich residue. In addition, it can
16 Y. Xie et al. / Construction and Building Materials 188 (2018) 9–16
be seen from the EDS spectrum that Ca2+ and Na+ in the corrosion
loose layer decrease significantly, which supports the evidence
that H+ and Ca2+ are exchanged by H+. In addition to the weakening
of the 4, 6-coordinated AlO4 tetrahedron signal in NMR, no new
peaks were generated, i.e., no significant Al-O structure was
formed or the amount generated was very small. However, the
concrete specimen was only corroded on the surface layer; its
internal structure was less vulnerable to acid attack. It is expected
that a decrease in the soluble content (sodium and calcium) of AAC
will bring about a higher acid resistance. In addition, the main cor-
rosion product of AAC under different concentrations of CSA and
BSA is gypsum. In other words, BSA only accelerated the corrosion
rate of AAC, and scarcely changed the corrosion mechanism of AAC.
5. Conclusions
1. BSA was more corrosive to AAC than CSA. Under the corrosion
of CSA, gypsum impedes the penetration of CSA; for BSA, gyp-
sum facilitates the attachment of bacteria and thus accelerates
the progress of corrosion.
2. Because the volume of bacteria is usually larger than the pore
size of the AAC, the bacteria can only exist on the surface of
the specimen. The bacteria only play the role of accelerating
the corrosion of the AAC, and there is no essential difference
between the law of corrosion of AAC by CSA and BSA. Under
the BSA corrosion, AAC is less affected by bacteria, and the
degree of corrosion is chiefly affected by sulfuric acid
concentration.
The softening of AAC after corrosion by CSA and BSA is limited
to the surface of the concrete specimens, and its internal structure
remains intact.
Conflict of interest
None.
Acknowledgement
The financial support under the NSFC (National Nature Science
Foundation of China) (Grant Number 51479036, 51708120,
51708119).
References
[1] M. Diercks, W. Sand, E. Bock, Microbial corrosion of concrete, Experientia 47
(6) (1991) 514–516.
[2] S. Wei, Z. Jiang, H. Liu, et al., Microbiologically induced deterioration of
concrete–a review, Braz. J. Microbiol. 44 (4) (2014) 1001–1007.
[3] R. Sydney, E. Esfandi, S. Surapaneni, Control concrete sewer corrosion via the
crown spray process, Water Environ. Res. 68 (3) (1996) 338–347.
[4] B.R. Hou, Marine Corrosive Environment Theory and Its Application (in
Chinese), Science Press, 1999.
[5] C.D. Parker, Mechanics of corrosion of concrete sewers by hydrogen sulfide,
Sewage. Ind. Waste. 23 (12) (1951) 1477–1485.
[6] C. Shi, P. Krivenko, D. Roy, Alkali-Activated Cement and Concrete, Taylor &
Francis, London and New York, 2006.
[7] E. Heitz, H.C. Flemming, W. Sand, Microbially Influenced Corrosion of
Materials, Springer, Berlin, 2013.
[8] P. Sun, H.C. Wu, Chemical and freeze–thaw resistance of fly ash-based
inorganic mortars, Fuel 111 (9) (2013) 740–745.
[9] T. Bakharev, J.G. Sanjayan, Y.B. Cheng, Resistance of alkali-activated slag
concrete to acid attack, Cem. Concr. Res. 33 (10) (2003) 1607–1611.
[10] M.G.D. Gutiérrez-Padilla, A. Bielefeldt, S. Ovtchinnikov, et al., Biogenic sulfuric
acid attack on different types of commercially produced concrete sewer pipes,
Cem. Concr. Res. 40 (2) (2010) 293–301.
[11] N.D. Belie, J. Monteny, A. Beeldens, et al., Experimental research and prediction
of the effect of chemical and biogenic sulfuric acid on different types of
commercially produced concrete sewer pipes, Cem. Concr. Res. 34 (12) (2004)
2223–2236.
[12] M.G. Alexander, C. Fourie, Performance of sewer pipe concrete mixtures with
portland and calcium aluminate cements subject to mineral and biogenic acid
attack, Mater. Struct. 44 (1) (2011) 313–330.
[13] S. Ehrich, L. Helard, R. Letourneux, et al., Biogenic and chemical sulfuric acid
corrosion of mortars, J. Mater. Civ. Eng. 11 (4) (1999) 340–344.
[14] J. Monteny, N.D. Belie, E. Vincke, et al., Chemical and microbiological tests to
simulate sulfuric acid corrosion of polymer-modified concrete, Cem. Concr.
Res. 31 (9) (2001) 1359–1365.
[15] J. Monteny, E. Vincke, A. Beeldens, et al., Chemical, microbiological, and in situ
test methods for biogenic sulfuric acid corrosion of concrete, Cem. Concr. Res.
30 (4) (2000) 623–634.
[16] GB/T14685-2001, Pebbie and crushed stone for building, General
Administration of Quality Supervision, Inspection and Quarantine of the PRC,
2001.
[17] GB/T14684-2001, Sand for construction, General Administration of Quality
Supervision, Inspection and Quarantine of the PRC, 2001.
[18] R.E. Buchanan, N.E. Gibbons, Bergey’s Manual of Determinative Bacteriology,
nineth ed., Williams and Wilkins, Baltimore, Maryland, 1994.
[19] A. Kumari, K.A. Natarajan, Electrobioleaching of polymetallic ocean nodules,
Hydrometallurgy 62 (2) (2001) 125–134.
[20] F. Puertas, S. Martı´ Nez-Ramı´Rez, S. Alonso, et al., Alkali-activated fly ash/slag
cements: strength behaviour and hydration products, Cem. Concr. Res. 30 (10)
(2000) 1625–1632.
[21] Y. Yang, T. Ji, X. Lin, et al., Biogenic sulfuric acid corrosion resistance of new
artificial reef concrete, Constr. Build. Mater. 158 (2018) 33–41.
[22] R.L. Islander, J.S. Devinny, F. Mansfeld, et al., Microbial ecology of crown
corrosion in sewers, J. Environ. Eng. 117 (6) (1991) 751–770.
[23] T. Maeda, A. Negishi, H. Komoto, et al., Isolation of iron-oxidizing bacteria from
corroded concretes of sewage treatment plants, J. Biosci. Bioeng. 88 (3) (1999)
300–305.
[24] Ministry of Construction, The state administration of quality supervision, in:
Inspection and Quarantine People’s Republic of China. GB/T50081-2002
Standard for test method of mechanical properties on ordinary concrete.
[25] A.R. Colmer, M.E. Hinkle, The role of microorganisms in acid mine drainage: a
preliminary report, Science 106 (2751) (1947) 253–256.
[26] C. Shi, Strength, pore structure and permeability of alkali-activated slag
mortars, Cem. Concr. Res. 26 (12) (1996) 1789–1799.
[27] A. Allahverdi, F. Škvára, Nitric acid attack on hardened of geopolymeric
cements Part I, Ceram. Silik. 45 (3) (2001) 81–88.
[28] A. Allahverdi, F. Škvára, Nitric acid attack on hardened paste of geopolymeric
cement; Part 2, Ceram. Silik. 4 (45) (2001) 143–149.