Journal of Cleaner Production 262 (2020) 121237

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Journal of Cleaner Production

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

Mechanical behavior degradation of recycled aggregate concrete after

simulated acid rain spraying
Caifeng Lu a, c, Wei Wang b, *, Qingsong Zhou a, Shenghuai Wei a, Chen Wang a
a
Jiangsu Key Laboratory of Environmental Impact and Structural Safety in Engineering, School of Mechanics and Civil Engineering, China University of
Mining & Technology, Xuzhou, 221116, China
b
Department of Architecture, Graduate School of Engineering, The University of Tokyo, Tokyo, 113-8654, Japan
c
JiangSu Collaborative Innovation Center for Building Energy Saving and Construct Technology, Xuzhou, 221008, China

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

Article history: To understand the degradation of mechanical properties of recycled aggregate concrete(RAC) after acid
Received 9 November 2019 rain exposure, the effect of recycled coarse aggregate (RCA) replacement ratios, the acidity (pH value) of
Received in revised form the simulated acid rain solution and mineral admixtures on compressive strength and elastic modulus of
23 February 2020
RAC are investigated in this study. The test results showed that elastic modulus and the compressive
Accepted 18 March 2020
Available online 23 March 2020
strength of RAC specimens may increase slightly at the beginning of acid rain spraying, then decreases
gradually with the continuous erosion of acid rain. The greater the acidity of acid rain solution is, the
Handling Editor: Baoshan Huang more obviously the mechanical properties of RAC decreases. Appropriately adding fly ash and silica fume
separately or together will effectively improve the strength and the acid rain resistance of RAC, whereas
Keywords: higher replacement rate of RCA may be unfavourable for RAC to resist acid rain. SEM/EDS observation
Mineral admixtures and analyses also further illustrated that the impact of acid rain and mineral admixtures on the mi-
Compressive strength crostructures of ITZ in RAC.
Elastic modulus © 2020 Elsevier Ltd. All rights reserved.
Interfacial transition zone
Recycled aggregate concrete
Acid rain

1. Introduction and stone (Abid et al., 2018). The total aggregate consumption
increased rapidly from twenty-one billion tons in 2007 to forty
With the acceleration of modern industrialization and new ur- billion tons in 2014 in the world (Tam et al., 2018). Therefore, from
banization in China, an increasing amount of concrete waste has the perspective of natural resources saving and environmental
been produced due to the demolition of existing buildings and the protection, concrete wastes can be utilized as recycled coarse
conctruction of new-built structures (Huang et al., 2018). Some aggregate (RCA) after crushing and sieving treatment. It can be
natural disasters including earthquake, typhoon and geologic capable of taking the place of natural coarse aggregate (NCA) used
hazards have also generated extensive concrete wastes (de Goyet in concrete to produce recycled aggregate concrete (RAC), which
et al., 2006). According to official statistics, approximately two meets the requirements of sustainable social development (Ali
hundreds million tons of concrete wastes will be newly added per et al., 2019; Bassani et al., 2019; Santos et al., 2019; Tam et al., 2018).
year in China (Shaban et al., 2019). A large part of concrete wastes Over the past few decades, a great quantity of extensive and in-
are still piled up or buried outdoors in the countryside. These depth researches have been carried out on various aspects of RAC,
concrete wastes are not properly disposed of or effectively utilized, such as manufacture and treatment techniques of RCA (Exteberria
which not only poses a great threat to the sustainable development et al., 2007; Pandurangan et al., 2016), micro- and meso-
of the environment but also causes waste of resources (Aljerf, structures (Lu et al., 2019; Tam et al., 2005), physical properties
2016). Meanwhile, a growing number of new-built concrete (Lu et al., 2019; Nazal and Ismael, 2019; Silva et al., 2018), me-
structures consume enormous natural aggregates including sand chanical properties (Emeka et al., 2018; Exteberria et al., 2007; Lu
et al., 2019; Mohammed and Abbas, 2019; Pandurangan et al.,
2016; Thomas et al., 2018), durability (Evangelista and De Brito,
2010; Thomas et al., 2018) and structural performance (Rahal and
* Corresponding author. Alrefaei, 2018; Sindy et al., 2018). Although it was found that
E-mail address: [email protected] (W. Wang).

https://doi.org/10.1016/j.jclepro.2020.121237
0959-6526/© 2020 Elsevier Ltd. All rights reserved.
2 C. Lu et al. / Journal of Cleaner Production 262 (2020) 121237

some mechanical properties such as flexural tensile strength, the performace degradation of RAC under the condition of acid rain
splitting tensile strength, compressive strength and elastic environment. Hence, the mechanical properties of RAC sprayed by
modulus of RAC decreased with the increase of substitution rate of simulated acid rain solution, mainly including failure modes, elastic
RCA replacing NCA (Kou et al., 2007; Thomas et al., 2018; Wang modulus and compressive strength, were investigated exper-
et al., 2019), it should be noted that the reduction extent is imently in this study. Moreover, the effects of RCA replacement
tightly associated with many factors, such as the production and ratios, acid rain acidity and erosion periods, and mineral admix-
treatment of RCA (Exteberria et al., 2007; Tabsh and Abdelfatah, tures on acid rain erosion restistance of RAC were mainly discussed.
2009), water-binder ratio (Li et al., 2006) and the substitution
rate of RCA replacing NCA (Tabsh and Abdelfatah, 2009).
2. Experimental material and methods
Additionally, the worldwide problems initiated by acid rain,
such as soil acidification, ecosystems destruction and building
2.1. Preparation of RCA
deterioration, have become more and more critical over the past
several decades (Du et al., 2012). Acid rain is a typical corrosive
RCA for concrete is produced according to GB/T25177-2010 in
mixed liquids mainly containing Hþ, SO2  þ
4 , NO3 , NH4 , Mg
2þ
etc.
China. RCA used in this study were sourced from some abandoned
(Aljerf, 2018). They will react chemically with cement hydration
concrete members (Fig. 1(a)) in the laboratory. After the concrete
products in concrete, which will gradually cause a decrease of
members were primarily broken by electric hammer (Fig. 1(b)),
concrete strength, concrete cracking and eventual structure failure.
collected concrete waste was subjected to secondary crushing using
Admittedly, many celebrated architectural relics including the
jaw crusher (Fig. 1(c)), and then screened by means of sieves with
Statue of Liberty in America and Leshan Giant Buddha in China have
square-hole aperture 20 mm and 5 mm respectively for the sake of
been sorely corroded by acid rain (Guo, 2013). Some scientific in-
collecting 5e20 mm diameter aggregates as RCA (Fig. 1(d)). RCA
vestigations have been devoted to the acid rain erosion on concrete
obtained was cleaned with water under pressure to get rid of any
structures, including acid rain erosion mechanism (Xie et al., 2004;
loose mortar, and then dried in the sun. The measured physical
Gao et al., 2016), simulating method of acid rain environment (Xie
indexes of RCA are presented in Tables 1 and 2, respectively, which
et al., 2004), mechanical properties (Xie et al., 2004; Fan et al., 2010;
conformed to relevant requirements of grade III RCA in the standard
Wang et al., 2017; Yuan et al., 2018) and durability of concrete
GB/T25177-2010.
corroded by acid rain (Tsouli et al., 2018; Mahdikhani et al., 2018),
but the unified understanding on some important aspects such as
the corrosion mechanism and evaluation methods of acid rain has 2.2. Mixtures for RAC
not been achieved. Although some mandatory measures have been
adopted to limit the emission of acidic substances into the atmo- As given in Table 3, primary concrete (type Q0) containing NCA
sphere, acid rain still occurs frequently in some zones. Therefore, alone as coarse aggregate was treated as the control mixture, while
the further studies on the mechanism of acid rain resistance of the remaining three kinds of mixtures (type Q1, Q2 and Q3) con-
concrete are still very necessary in order to limit more effectively or tained RCA replacing NCA. The replacement levels of RCA consid-
even clear up the impacts of acid rain attack on concrete structures. ered in the study were 20%, 35% and 50% by mass, respectively.
As mentioned above, although previous researches have focused Considering the water content and higher water absorption of RCA,
on various properties of RAC and acid rain attack on the concrete the quantity of extra mixing water (Dmw ) in RAC mixtures was
structure, few experimental works have been conducted to study determined on the basis of Eq. (1).

Fig. 1. Production process for RCA.

 C. Lu et al. / Journal of Cleaner Production 262 (2020) 121237 3

Table 1 Table 4
Physical indexes of RCA. Chemical compositions of cementitious materials (%).

Apparent Density (kg/m3) Crushing index (%) Water absorption (%) Ingredients Cement Fly ash Silica fume

10 min 1h 24 h CaO 59.0 5.98 0.58

SiO2 22.5 46.52 93.7
2463 23.90 5.49 6.50 6.89
Al2O3 7.0 22.95 1.54
Fe2O3 3.3 12.37 0.89
MgO 2.5 2.34 0.67
Table 2 Na2O 0.17 1.13 0.47
Particle size distribution of RCA. K2O 0.78 0.94 e
MnO 0.33 0.07 e
Size in square-hole sieve (mm) 19 9.5 4.75 2.36 TiO2 0.31 2.07 e
P2O5 0.1 0.15 e
Residual ratio after sieving (%) 7 75 100 100
SO3 1.8 0.4 e

Dmw ¼ mRCA ðu1  u2 Þ (1) Table 5

Physical indexes of cementitious materials.
Here Dmw (kg) is the quantity of extra mixing water, mRCA (kg) is
Indexes Cement Fly ash Silica fume
the quality of RCA used, u1 (%) and u2 (%) are the water absorption
and water content of RCA, respectively. Specific gravity 3.1 2.4 e
Specific surface area (m2/kg) 352 308 e
For recycled concrete with 50% RCA replacement ratio (type Q3), Loss on ignition (%) 7.0 6.2 2.6
three kinds of fly ash content 15%, 30% and 45% (type Q3F1、Q3F2 Fineness (% retain in 45 mm) e 7% e
and Q3F3, respectively) and 10% replacement ratio of silica fume Water demand (%) e 84 106
(type Q3SF10) were also considered. In addition, the double influ-
ence of silica fume and fly ash on the performance of RAC was taken
into account, namely Q3F1SF10、Q3F2SF10 and Q3F3SF10 respec- Table 6
tively. Among them, fly ash as a replacement for cement is replaced Physical indexes of fine aggregate.
by excessive substitution method, while silica fume is replaced by Indexes Magnitude
equivalent substitution method, according to GB/T27690-2011 and
Fineness modulus 2.52(medium sand)
GB/T50146-2014. Water absorption (%) 1.22
According to Chinese standards (JGJ55-2011; JGJ/T443-2018), Specific gravity 1.69
the material composition for all concrete mixtures are designed
(Table 3). Superplasticizer accounting for 0.16% of the cement
quality were added to the mixtures. Cementitious materials Table 7
including ordinary Portland cement 42.5 (P.O42.5), fly ash and silica Physical indexes of natural coarse aggregate.
fume conformed to the Chinese standards (GB/T486-2005; GB175- Indexes Magnitude
2007; GB/T486-2015; GBT50146-2014). Their chemical composi-
nominal maximum size (mm) 20
tions and physical properties were obtained from laboratory tests,
Water absorption (%) 0.12
as reported in Tables 4 and 5, respectively. Specific gravity 2.77
Natural river sand conforming to GBT14684-2011 and crushed
stone conforming to GBT14685-2011 were used as fine aggregate
and NCA, respectively. Their physical properties are given in
account more practical affecting factors including illumination,
Tables 6 and 7 respectively.
rainfall and scouring of acid rain, it can better simulate the actual
attack of acid rain on concrete structures. Therefore, the self-made
2.3. Acid rain spraying simulator simulator of acid rain spraying was designed, mainly including
solution pool, spraying device and specimen holders, as shown
Two major accelerated test methods, i.e. periodic soaking and schematically in Fig. 2.
spraying, are generally adopted in the experimental study on acid A solution pool made of stainless steel was used to store the
rain resistance of concrete. Whereas acid rain spraying takes into

Table 3
Mixture of RAC.

Types Cement (kg/m3) NCA (kg/m3) RCA (kg/m3) Sand (kg/m3) Water (kg/m3) Fly ash (kg/m3) Silica fume (kg/m3)

Q0 405 1108 e 679 207 e e

Q1 427 886 222 679 218 e e
Q2 442 720 388 679 226 e e
Q3 458 554 554 679 234 e e
Q3F1 389 554 554 667 234 83 e
Q3F2 321 554 554 655 234 165 e
Q3F3 252 554 554 643 234 247 e
Q3SF10 412 554 554 679 234 e 46
Q3F1SF10 344 554 554 667 234 83 46
Q3F2SF10 275 554 554 655 234 165 46
Q3F3SF10 206 554 554 643 234 247 46

Notes: The letters Q, F and SF represent RCA, fly ash and silica fume, respectively. Type Q0、Q1、Q2 and Q3 refer to RAC with RCA replacement ratio 0%, 20%, 35% and 50%. F1,
F2 and F3 indicate fly ash content 15%, 30% and 45%, and SF10 means 10% silica fume in concrete, respectively.
4 C. Lu et al. / Journal of Cleaner Production 262 (2020) 121237

Fig. 2. Schematic diagram of acid rain spraying simulator.

simulated acid rain solution. The solution is periodically sprayed on ensure adequate hydration reactions of cement-based materials.
the specimens (Countless small raindrops with less than 3 mm Concrete specimens with the same mixture were divided into three
diameter through spraying pipe and punched-plate above the groups, one of which maintained in water as the control group, the
specimen.) by clock controllers for switching the water pumps at other two groups were sprayed by simulated acid rain solution with
the expected time. During the test, the concrete specimen un- pH ¼ 2.5 and pH ¼ 3.5, respectively.
dergoes predetermined wet-dry cycles. The vertical distance between the punched-plate and the upper
In this paper, only the China’s typical sulfuric acid rain was surface of specimens shall not less than 2 m. The upper and lower
considered, so the simulated acid rain solution was made up by concrete specimens shall be staggered, and the adjacent ones shall
mixing (NH4)2SO4 and HNO3. Two kinds of pH values, 2.5 and 3.5, be separated at least 10 cm to achieve more effective simulation of
were designed, in which the weight ratio of (NH4)2SO4 and HNO3 falling rain. During the spraying tests, the pH value of acid solution
was kept at 6:1. The specified spraying time and simulated illu- was recorded at regular time with the help of a pH meter, and if
mination time are 10h and 3h, respectively. The flow rate of sprayed necessary, adjusted by adding HNO3 solution irregularly to main-
solution was controlled at 1.653 m3/h by flowmeter, denoting that tain constant pH value. The scene photos of acid rain spraying test
the total amount of solution passing through spraying pipe every was presented in Fig. 3.
day roughly corresponding to that of therainfall of a city in China for After prescribed days exposure, the specimens were take out
a year. and dried by towels. Among them, the 100 mm cubic specimens
were used to measure the cubic compressive strength, whereas
elastic modulus and axial compressive strength were determined
2.4. Test procedure and methods
on 100 mm  100 mm  300 mm prism specimens, following the
test procedure described in GB/T50081-2016.
All concrete specimens were cast according to the specification
Besides, a Quanta 250 scanning electron microscope equipped
GB/T50081-2016 and removed from moulds 3 days later, and then
with energy dispersive spectroscopy (SEM/EDS) was adopted to
put into the water for curing for at least three months (Wang et al.,
study the microstructure of the interfacial transition zone (ITZ) of
2017), especially for specimens containing mineral admixtures to

Fig. 3. Scene photos of acid rain spraying test.

 C. Lu et al. / Journal of Cleaner Production 262 (2020) 121237 5

Fig. 4. Flowchart of the experimental procedures.

Fig. 5. Failure modes of cube specimens with 0%, 20%, 35% and 50% RCA under acid rain environment.
6 C. Lu et al. / Journal of Cleaner Production 262 (2020) 121237

RAC after acid rain erosion. The specimes were cut into small pieces These pictures were taken from crushed concrete samples main-
and immersed in alcohol for 7 days to stop hydration, followed by tained in water (reference group) or sprayed by simulated acid rain
vacuum drying for 2 days. Before testing, the samples were gold solution (pH value of 2.5 and 3.5) for 10 and 50 days.
coated to increase its electrical conductivity. Fig. 4 provides a For cube concrete samples not corroded by acid rain, more
flowchart of the experimental procedures and methods used in this mortar is wrapped after compression failure with the increase of
study. RCA substitution level due to the changes given by rheology of
mortar (Silva et al., 2018; Santos et al., 2019). However, encapsu-
lated mortar decreases for RAC specimens exposed to acid rain
3. Results and analysis solution, and cuts down obviously with the increase of acidity or
erosion days, This may be attributed to the lower the pH value is,
3.1. Failure mode of RAC after acid rain erosion the more severely the acid rain erodes the concrete. Under the
action of axial compression, prism specimens are less prone to spall
Figs. 5 and 6 indicate the failure situations of cube and prism and crack with the increase of RCA substitutive level. However,
specimens containing 0%, 20%, 35% and 50% RCA, respectively.

Fig. 6. Failure modes of prism specimens with 0%, 20%, 35% and 50% RCA under acid rain environment.
 C. Lu et al. / Journal of Cleaner Production 262 (2020) 121237 7

even for the prism specimens which have been eroded by acid rain actually decreases with the increase of RCA content (0.51, 0.485,
for a short time, concrete spalling after failure under axial 0.467, 0.451 for Q0, Q1, Q2, Q3, respectively) after considering the
compression is more serious, especially for RAC containing 50% RCA water absorption and moisture content of RCA, which gives rise to
(Q3). the improvement of mechanical indexes of RAC with increasing
RCA replacement level. Whereas the interfacial transition zone(ITZ)
3.2. The influences of RCA and mineral admixtures on mechanical between the RCA and the old cemet mortar adhered, as the weakest
properties point in RAC due to the existence of many voids and cracks, will
weaken the performance of RAC(Tam et al., 2005; Etxeberria et al.,
After water curing for 3 months, the elastic modulus and 2006). Therefore, the actual influences of RCA replacement on
compressive strength of primary concrete (Q0) and RAC (Q1, Q2 and mechanical properties of RAC are a combined action of the above
Q3) are obtained experimentally, as reported in Fig. 7, and Fig. 8 two aspects.
illustrates the strength values of RAC with mineral admixtures Additionally, as can be seen from Fig. 8, replacing cement with
including silica fume and fly ash. fly ash excessively will enlarge the strength of RAC. 30% replace-
Fig. 7 demonstrated that the mechanical indexes of RAC, such as ment rate of fly ash will result in a 17% increase in the strength of
the elastic modulus and compressive strength, wouldn’t be signif- RAC (Q3F2), and the strength of RAC doesn’t decrease even when
icantly affected by the addition of RCA. For RAC containing 20%, 35% the content of fly ash reaches 45% (Q3F3). Moreover, adding 10%
and 50% RCA replacing NCA, their cube strengths were 96%, 107% silica fume alone will largely increase the strength of RAC by 33%
and 103% of the control concrete (Q0), and the elastic modulus were (Q3SF10), and the strength of RAC mixed with silica fume and fly
93%, 103% and 102% of that, respectively. Here, the influence of RCA ash together (Q3SF10, Q3F1SF10 and Q3F2SF10) was not higher
on the mechanical indexes of RAC can be interpreted from two than that with silica fume alone. The strength variation of RAC
perspective of water-binder ratio and inherent defects in RCA containing mineral mixtures is mostly due to the pozzolanic reac-
(Exteberria et al., 2007). In this study, although the water-binder tion (Aljerf, 2015), that is, the secondary hydration reaction taking
ratio of RAC containing RCA replacing NCA is the same as that of place between portlandite(CH) produced during cement hydration
primary concrete (all equal to 0.51), the effective water-binder ratio and mineral admixtures (such as silica fume or fly ash) to generate

Fig. 7. Effect of RCA on strength and elastic modulus of RAC.

Fig. 8. Effect of fly ash and silica fume on the cubic compressive strength of RAC.
8 C. Lu et al. / Journal of Cleaner Production 262 (2020) 121237

additional calcium silicate hydrated (CSH). The additional CSH, as

the most important compound that contributes to concrete fc;water  fc;acid
strength, also ameliorates the meso- and micro-microstructure of Rc ð%Þ ¼  100% (3)
fc;water
concrete by pores filling, which further enhances the strength of
concrete (Jung et al., 2018). Therefore, although the content of Where, Eacid (MPa) and fc;acid (MPa) are the elastic modulus and
cement used in concrete is less (a certain amount of cement is strength values of test samples sprayed by simulated acid rain so-
replaced by mineral mixtures), the strength of RAC mixed with fly lution for designated days, Ewater (MPa) and fc;water (MPa) are the
ash alone or with silica fume and fly ash together will not decrease elastic modulus and strength values of test samples left in water for
but increase (Lam et al., 1998). Of course, too high replacement rate corresponding days.
of mineral admixture (Q3F3SF10) will also reduce the strength of Fig. 9 presented the strength reduction rate (Rc ) of concrete
RAC due to less hydration products generated. specimens after sprayed by simulated acid rain solutions (pH values
of 2.5 or 3.5) for 10,30 and 50 days, and the reduction rate of elastic
modulus (Re ) after acid rain spraying for 20 and 40 days was re-
ported in Fig. 10. In Figs. 9 and 10, if the Rc (Re ) is positive, it
3.3. The influence of acid rain erosion on mechanical indexes of RAC
represent the concrete strength (elastic modulus) decrease after
acid rain exposure, otherwise they increase.
For primary concrete (Q0) and RAC with three substitution
According to the results, for both primary concrete and RAC, the
levels of RCA (Q1, Q2 and Q3) after acid rain spraying for specified
compressive strength is lilely to increase in the initial stage of acid
days, their elastic modulus and compressive strength were deter-
rain erosion. However, the strength values of all mixtures will
mined through tests, respectively. By comparing with the elastic
decrease gradually with the continuous erosion of acid rain, and the
modulus and strength values of appropriate concrete samples left
lower the pH value in acid rain is (i.e., the greater the acidity is), the
in water for corresponding days, the reduction rates of the elastic
more obviously concrete strength decreases. This was also the case
modulus (Re ) and strength (Rc ) were calculated using Eqs. (2) and
with the variation of elastic modulus. For example, the strength of
(3) (Fan et al., 2010)
Q0, Q1, Q2 and Q3 increased by 3.9%, 6.4%, 6.9% and 11.9% respec-
tively after being sprayed by acid rain solution with pH ¼ 3.5 for 10
Ewater  Eacid
Re ð%Þ ¼  100% (2) days. When the specimens were sprayed acid rain solution with
Ewater
pH ¼ 2.5 or 3.5 for 50 days, the strength of Q0 is reduced by 16.8%
and 10%, respectively. Meanwhile, the strength of Q3 is reduced by

Fig. 9. Strength reduction rate of concrete specimens sprayed by acid rain for 10, 30 and 50 days.

Fig. 10. Elastic modulus variations of RAC specimens after acid rain spraying for 20 and 40 days.
 C. Lu et al. / Journal of Cleaner Production 262 (2020) 121237 9

Fig. 11. Strength variations of RAC (Q3) with fly Ash or silica fume under acid rain environment.

25.1% and 8% respectively. complexity, some existing researches have demonstrated that the
This evolution law of the mechanical properties under acid rain acid rain erosion on concrete primarily includes two aspects,
environment is mostly caused by the chemical reaction between namely, acid attack caused by Hþ ions and sulfate attack caused by
the hydration products of cement-based materials and the ions SO2
4 ions (Xie et al., 2004; Mahdikhani et al., 2018), which will
contained in acid rain solution. Although the mechanism of con- generate the expansive products such as AFt and CaSO42H2O.
crete damages caused by acid rain is not very distinct due to its These expansive erosion products can absorb the pore water in

Fig. 12. SEM images of concrete after 40 days of acid rain exposure with different pH.
10 C. Lu et al. / Journal of Cleaner Production 262 (2020) 121237

Fig. 13. EDS patterns of gel in the ITZ of RAC.

Table 8 concrete, and their volume will increase. Consequently, they can
Relative content of calcium element (%). improve the microstructure of concrete by pore filling, and enhance
RAC types pH ¼ 2.5 pH ¼ 3.5 mechanical properties of concrete to a certain extent (Guo et al.,
Q2 13.03 23.32
2019). Of course, with the continuous erosion of acid rain, the
Q3 18.99 30.90 increasing internal stress caused by more and more expansive
products will give rise to internal cracking of the concrete, which

Fig. 14. SEM images of Q3 with admixtures after 40 days of acid rain exposure (pH 2.5).
 C. Lu et al. / Journal of Cleaner Production 262 (2020) 121237 11

will constantly reduce the mechanical properties of concrete. of the acidity and erosion time of acid rain, more soluble substances
In addition, replacing NCA with more RCA may not be beneficial are generated through the chemical reactions between acid rain
to the acid rain resistance of concrete in the later stage of erosion. solution and hydration products, which will lead to the continuous
For instance, after spraying acid rain solution with pH ¼ 2.5 for 50 loss of calcium in RAC.
days, the strength of primary concrete (Q0) decreases by 16.8%, and The SEM images of the ITZs in RAC (Q3) with different amount of
the strength of RAC containing 20%, 35% RCA (Q1, Q2) decreases by mineral additions (silica fume and fly ash) are presented in Fig. 14.
15.9%, 13.5% respectively, whereas the strength with 50% RCA (Q3) Here it is easy to see the CSH gel in the matrix, but only a small
decreases by 25.1%. amount of ettringite and gypsum crystals, which proved that the
erosion caused by acid rain was very slight. The microstructures in
3.4. The influence of mineral additions on acid rain resistance of Fig. 14a and c were much denser, and the ITZ is hard to distinguish,
RAC whereas it is easy to see the obvious ITZ in Fig. 14b and d, which is
consistent with the results as shown in Fig. 10. This suggests that an
The compressive strength of RAC (Q3) mixed with different appropriate amount of silica fume or fly ash can improve the
proportion of fly ash or silica fume was determined after acid rain microstructure of concrete (Chu et al., 2019; Hilal, 2016), and
spraying experiments for 10, 30, 50 days, as reported in Fig. 11. thereby enhancing the acid rain resistance of concrete.
Herein, only pH ¼ 2.5 for simulated acid rain solution is considered.
According to the results, replacing cement with fly ash in a 4. Conclusions
certain range is advantageous to the acid rain resistance of RAC,
whereas the higher content of fly ash is unfavourable. For an To provide a suggestion for solving the problems caused by the
example, the compressive strength of RAC with 15% and 30% fly ash concrete waste and acid rain, this paper analyzed the mechanical
(Q3F1 and Q3F2) has not decreased even after acid rain erosion for properties of RAC after acid rain exposure. The following conclu-
50 days, while the strength of RAC containing 45% fly ash (Q3F3) is sions can be derived on the basis of the experiment results:
reduced by 12.4%. Nevertheless, adding 10% silica fume alone
(Q3SF10) caused 15.4% decrease in strength of RAC sprayed by acid (1) With a certain water-cement ratio, RCA replacement only has
rain solution for 50 days. Meanwhile, the strength of RAC mixed a slight influence on the elastic modulus and strength of RAC.
with silica fume and fly ash together (Q3F1SF10, Q3F2SF10 and This might be related to the bilateral effect of RCA replace-
Q3F3SF10) did not change significantly with the erosion time. ment. One hand, the inherent defects of RCA will redeuce the
Therefore, although mineral admixtures may effectively enhance bond strength of ITZ between RCA and paste. On the other
the acid rain resistance of RAC by improving the microstructure of hand, the effective water-cement ratio decreased with RCA
concrete (Golewski, 2018), the actual effect is bound up with the due to the water absorption of RCA which can enhance the
substitution methods and replacement levels of mineral admix- mechanical properties of RAC. Therefore, the real influence of
tures replacing cement. RCA replacement is a co-existing result of both.
(2) The mechanical properties of RAC may increase slightly in
3.5. Microstructure analysis of RAC after acid rain erosion the initial stage of acid rain spraying, then decreases gradu-
ally with the continuous erosion of acid rain. In the initial
In order to better investigate the influence of acid rain erosion stage, less amount of expansive products can act as the role
on the microstructure of RAC, SEM/EDS techniques were applied to of pores filling, while with time goes, the continually accu-
observe various substances at the ITZs and analyze the distribution mulating products will induce internal cracks and thereby
changes of various elements, respectively. Fig. 12 shows the SEM lead to the reduction of mechanical properties of RAC.
micrographs of primary concrete(Q0) and RAC(Q2 and Q3) samples (3) The greater the acidity of acid rain solution is, the more
after 40 days of acid rain exposure, and the corresponding EDS test obviously the mechanical properties of RAC decreases. Be-
results of products shown in SEM micrograph are presented in sides, higher replacement rate of RCA may be detrimental to
Fig. 13, respectively. the acid rain resistance of RAC, expecially after long term
It can be observed from the SEM micrographs that obvious errosion. This suggests that special attention should be given
variation occurs in the interface microsturcture with the change of in utilizing RAC in severe acid rain region.
pH values of simulated acid rain solution and RCA replacement (4) Appropriate amount of silica fume/fly ash addition not only
ratios. During the process of acid rain exposure, CH crystal and CSH can ameliorate the strength of RAC, but also can preferably
gel gradually decrease, and more ettringites and gypsums will be improve the acid rain resistance of RAC. This may provide a
generated and filled the ITZ as the acidity of simulated acid rain way to solve the problems caused by both.
solution increases (pH value decreases). Compared to primary
concrete(Q0), the ITZ of RAC (Q2 and Q3) are more obvious, and Additional cross-checking works and state-of-the-art methods
there are some micro-cracks in Fig. 12(e). That is related to the are needed to better understand the mechanism behind the
inherent defects of RCA and the expansibility of ettringites, which behavior. Moreover, it is necessary to further investigate the
would cause more weak ITZs. structural performace and durability of RAC after acid rain.
Similarly, as shown in Fig. 13, the EDS patterns of the gels in ITZ
also illustrate the content variation of the principal elements Declaration of competing interest
including calcium and silicon under acid rain erosion. It is clear that
there is less calcium but more silicon in the gels generated in RAC The authors declare that they have no conflict of interest.
under pH 2.5 acid rain than under pH 3.5 acid rain. For examples,
the relative content of the calcium element is calculated after CRediT authorship contribution statement
normalization as shown in Table 8. This phenomenon is very
consistent with the erosion mechanism of acid rain on concrete. Caifeng Lu: Conceptualization, Methodology, Investigation,
Originally, the relative content of calcium element mainly con- Writing - original draft, Writing - review & editing. Wei Wang:
tained in cement hydration products such as CH and CSH is the Conceptualization, Methodology, Investigation, Writing - original
highest in the concrete (Morandeau et al., 2014). With the increase draft, Writing - review & editing. Qingsong Zhou: Methodology,
12 C. Lu et al. / Journal of Cleaner Production 262 (2020) 121237

Investigation, Writing - review & editing. Shenghuai Wei: Meth- characteristics of fly ash concrete with rice husk ash and lime stone powder. Int.
J. Concre. Struct. Mater. 12 (1), 1e9. https://doi.org/10.1186/s40069-018-0257-4.
odology, Investigation, Writing - review & editing. Chen Wang:
Kou, S.C., Poon, C.S., Dixon, C., 2007. Influence of fly ash as cement replacement on
Conceptualization, Methodology, Investigation, Writing - review & the properties of recycled aggregate concrete. J. Mater. Civ. Eng. 19 (9), 709e717.
editing. https://doi.org/10.1061/(ASCE)0899-1561(2007)19:9(709).
Lam, L., Wong, Y.L., Poon, C.S., 1998. Effect of fly ash and silica fume on compressive
and fracture behaviors of concrete. Cement Concr. Res. 28 (2), 271e283. https://
Acknowledgement doi.org/10.1016/S0008-8846(97)00269-X.
Li, J.B., Xiao, J.Z., Huang, J., 2006. Influence of recycled coarse aggregate replacement
percentage on compressive strength of concrete. J. Build. Mater. 9 (3), 297e301
The authors gratefully acknowledge the financial support from (in Chinese) DOI: 1007- 9629(2006)03 - 0297 - 05.
JiangSu Collaborative Innovation Center for Building Energy Saving Lu, B., Shi, C.J., Cao, Z.J., Guo, M.Z., Zheng, J.L., 2019. Effect of carbonated coarse
and Construction Technology (SJXTBS 1715). The authors also want recycled concrete aggregate on the properties and microstructure of recycled
concrete. J. Clean. Prod. 233, 421e428. https://doi.org/10.1016/
to thank Mr. OMER Mohamed Ahmed who helped improve the j.jclepro.2019.05.350.
English writing of this paper. Mahdikhani, M., Bamshad, O., Shirvani, M.F., 2018. Mechanical properties and
durability of concrete specimens containing nano silica in sulfuric acid rain
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