Journal Pre-proof

Corrosion behavior of concrete fabricated with lithium slag as corrosion inhibitor under
simulated acid rain corrosion action

Liqing Zhang, Yannian Pan, Kaicheng Xu, Liping Bi, Mengcheng Chen, Baoguo Han

PII: S0959-6526(22)03872-0
DOI: https://doi.org/10.1016/j.jclepro.2022.134300
Reference: JCLP 134300

To appear in: Journal of Cleaner Production

Received Date: 23 November 2021

Revised Date: 15 August 2022
Accepted Date: 19 September 2022

Please cite this article as: Zhang L, Pan Y, Xu K, Bi L, Chen M, Han B, Corrosion behavior of concrete
fabricated with lithium slag as corrosion inhibitor under simulated acid rain corrosion action, Journal of
Cleaner Production (2022), doi: https://doi.org/10.1016/j.jclepro.2022.134300.

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 Credit Author Statement
Liqing Zhang: Conceptualization, Resources, Writing - review & editing,
Supervision, Project administration, Funding acquisition.
Yannian Pan: Methodology, Investigation, Writing.
Kaicheng Xu: Methodology, Validation, Formal analysis, Investigation, Writing -
original draft, Project administration, Funding acquisition.
Liping Bi: Methodology, Investigation.
Mengcheng Chen: Methodology, Supervision.
Baoguo Han: Writing - review & editing, Supervision.

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 1 Corrosion Behavior of Concrete Fabricated with Lithium Slag as Corrosion

2 Inhibitor under Simulated Acid Rain Corrosion Action

3
4 Liqing Zhang a,b, Yannian Pan a,b, Kaicheng Xu *a,b, Liping Bi c, Mengcheng Chen a,b, Baoguo
5 Hand
6
7 a State Key Laboratory of Performance Monitoring and Protecting of Rail Transit

8 Infrastructure, East China Jiaotong University, Nanchang, 330013, China

9 b School of Civil Engineering and Architecture, East China Jiaotong University, Nanchang,

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10 330013, China

11 c School of Civil Engineering, Central South University, Changsha, 410075, China

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12 -p
d School of Civil Engineering, Dalian University of Technology, Dalian, 116024, China
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*
13 Corresponding author.
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14 Tel: 86-13879115766

15 Email address: xkcxj@ecjtu.edu.cn

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16
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17
18 Abstract: Concrete has great potential for local applications as a building material.

19 Utilization of lithium slag in concrete can effectively and quickly solve its stacking problem.

20 In this study, we used lithium slag to fabricate concrete and used a self-designed indoor dry-

21 wet cycle spraying equipment to explore its acid rain corrosion resistance properties to

22 promote its resource utilization because acid rain corrosion is very serious in Jiangxi Province.

23 First, we investigated the fresh properties and the hardened properties of the concrete with

24 lithium slag, and the mechanisms of acid rain corrosion resistance of concrete with lithium

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25 slag were studied. The study showed that lithium slag can accelerate the hydration reaction

26 and improve the acid rain resistance of concrete, with better appearance integrity, and the

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27
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lower decrease rate of compressive strength and mass loss of concrete. Unfortunately, lithium
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28 slag enhanced the neutralization depth of concrete. The compressive strength and mass loss of
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29 concrete with lithium slag are sensitive to the concentration of SO42-, and the neutralization

depth is sensitive to the concentration of H+. Adding lithium slag can decrease the tendency
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30

31 for formation of CH crystals in the matrix, increase the hydration degree of cement, improve
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32 the microstructural compactness of concrete and decrease the Ca/Si of C-S-H gel. Therefore,
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33 lithium slag is beneficial for resisting the acid rain corrosion of concrete, and can be used as

34 an acid rain corrosion inhibitor.

35 Keywords: Lithium Slag; Concrete; Acid Rain Corrosion; Properties; Mechanisms

36 1. Introduction

37 Concrete has become the most widely used building material because it has a wide range

38 of raw materials. The raw materials used in concrete include mainly cement, aggregate, water,

39 water reducer, and admixtures [1]. Among these raw materials, the admixtures can not only

40 replace part of the cement to reduce environmental pollution and the cost, but also improve

41 the properties of concrete [2]. The admixtures commonly used in concrete are divided into

42 natural types, artificial types, and industrial wastes. Using industrial wasters as admixtures

2
43 can quickly solve the environmental pollution and land occupation problems brought by

44 industrial waste, such as electric arc furnace dust [3], ferrochromium slag [4], electric arc

45 furnace slag [5], electric steelmaking slag [6], fluorescent lamp glass [7], wood ash [8], silica

46 fume [9-11] and fly ash [9,12]. A typical example of success is the application of silica fume

47 and fly ash as mineral admixtures in concrete. At present, due to the improved effect of silica

48 fume on the mechanical properties and durability of concrete [13-15], the silica fume has

49 become an essential high-quality admixture for the preparation of high-performance concrete

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50 and ultra-high-performance concrete (UHPC) [16-19]. Fly ash, as industrial waste from coal-

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51 fired power plants, has been widely used to prepare mass concrete [20] and engineered

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52 cementitious composites. Due to its widespread use, the fly ash has changed from a buyer’s
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53 market to a seller’s market in China.
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54 With the development of industry, new types of industrial waste continue to appear.
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55 Lithium slag is a new type of industrial waste caused by the production of lithium through
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56 sulfuric acid processing. One ton of lithium carbonate produces approximately ten tons of
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57 lithium slag [21]. In Yichun city of Jiangxi Province, the tantalum-niobium ore is rich, and the
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58 lithium battery industry is developing rapidly. As a result, the lithium slag piles up like a

59 mountain. The random piling of such large quantities of lithium slag not only wastes the land

60 resources, but also causes serious environmental pollution [22,23]. Can the successful cases

61 of silica fume and fly ash as concrete admixtures be transplanted to treat of the lithium slag,

62 and deal with the harm of the lithium slag quickly and effectively?

63 Recently, various studies have been carried out on the cementitious composites

64 fabricated with lithium slag as admixtures, such as the microstructure of cement paste [24]

65 and concrete [21,25], mechanical performance of cement paste [26-27] and cement mortar [28]

66 as well as concrete [29], durability of cement mortar [30] and concrete [31], and crack

67 resistance of concrete [32]. Some scholars have discussed the influence of lithium slag on the

3
68 properties of concrete from the aspects of the hydration process, hydration degree, hydration

69 products and microstructure, which was helpful to understand or explain the macroscopic

70 properties of concrete with different contents of lithium slag. He et al. [21] studied the effect

71 of lithium slag on the microstructure of UHPC. The results showed that the lithium slag could

72 enhance the degree of hydration of UHPC and improve the microstructure of UHPC in the

73 whole process due to the filling effect and pozzolanic reaction of lithium slag. However,

74 lithium slag cannot replace cement at a high ratio because of the high content of SO42- in

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75 lithium slag and the limitation on the optimum gypsum content [33]. An appropriate amount

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76 of lithium slag can improve the microstructure of concrete, reduce the internal pores, and

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77 -p
improve the performance of concrete. Tan et al. [27] studied the effect of lithium slag on the

78 early strength of sulfoaluminate cement paste. The results showed that lithium slag with a
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79 content less than 10% could accelerate the hydration of sulfoaluminate cement paste and
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80 increase the early strength of sulfoaluminate cement paste.

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81 At present, the effect of lithium slag on durability focuses mainly on the sulfate
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82 corrosion of cement mortar [30], chloride ion penetration and wear resistance of concrete [31].
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83 There are limited references focused on acid rain corrosion of concrete with lithium slag.

84 However, in recent years, acid rain pollution has become a more severe issue due to rapid

85 industrial development. Studies have shown that the rainwater of the southwestern parts of

86 China has been strongly acidified [34]. Jiangxi Province is one of the areas with the worst

87 acid rain in China. Acid rain is well known to cause physical and chemical reactions in

88 concrete [35,36], cause durability problems in concrete [37-40] and lead to the degradation of

89 concrete structures [41,42]. Therefore, it is necessary to study the durability of concrete with

90 different contents of lithium slag under acid rain corrosion conditions. In this study, a series

91 experiment of concrete with different contents of lithium slag was presented by using a self-

92 designed acid rain spraying device to simulate acid rain corrosion environment action, and

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 93 characterized indices, such as fresh properties (workability and setting time), appearance,

94 compressive strength, mass loss rate and neutralization depth were analysed. To evaluate the

95 mechanisms of concrete with different contents of lithium slag, the hydration products,

96 hydration degree and microstructure were characterized and analysed by using X-ray powder

97 diffraction (XRD), thermogravimetric and derivative thermogravimetry analyses (TG/DTG),

98 scanning electronic microscopy (SEM), and energy dispersive spectroscopy (EDS).

99 2. Experimental

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100 2.1. Raw Materials

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101 The raw materials used in this paper were cement, lithium slag, fine and coarse

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102 -p
aggregates, polycarboxylate superplasticizer, water, and chemical reagents to prepare

103 simulated acid rain solutions. The cement used in this study was P·O 42.5 R obtained from
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104 Jiangxi Yadong Cement Co., Ltd. (Jiangxi, China). The chemical composition of the cement is
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105 shown in Table 1, and its basic physical and mechanical properties are summarized in Table 2.
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106 Lithium slag was obtained by drying and grinding the white lithium mica slag collected from
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107 Jiangxi Yichun Silver Lithium New Energy Co., Ltd. (Jiangxi, China) as shown in Fig. 1. The

sieve balance of the 45 μm sieve and the specific surface area of lithium slag were less than
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108

109 7.5% and 895 m2/kg, respectively. Figs. 2 and 3 depict the XRD and TG/DTG test results for

110 lithium slag, respectively. As Fig. 2 shows, the main components of the lithium slag include

111 quartz (SiO2), tricalcium silicate (C3S), dicalcium silicate (C2S), tricalcium aluminate (C3A),

112 calcium sulfate (CaSO4) and gismondine. The chemical composition and fineness

113 characteristics of the lithium slag are tabulated in Tables 3 and 4, respectively. The fine

114 aggregate used was Ganjiang medium sand with a fineness modulus of 2.8 grading in zone II,

115 and its specific gravity was 2640 kg/m3. The mud content and the moisture content of the

116 Ganjiang medium sand were less than 1% and 3.1%, respectively. The size range of the

117 crushed stone used as coarse aggregates ranged from 5 mm to 25 mm. The polycarboxylate

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118 superplasticizer with a solid content of 19.8% and a water-reducing ability of 27% was added

119 to adjust the workability of concrete with different contents of lithium slag. To prepare the

120 simulated acid rain, some chemical reagents were used including nitric acid (HNO3),

121 ammonia sulfate ((NH4)2SO4), sodium sulfate (Na2SO4), magnesium sulfate (MgSO4) and

122 sodium chloride (NaCl). Nitric acid (HNO3) was analytically pure concentrated nitric acid

123 produced by Nanchang Xinguang Fine Chemical Plant with a net content of ≥ 65.0%.

124 Ammonium Sulphate ((NH4)2SO4) called analytically pure anhydrous ammonium sulphate

was obtained from Shanghai Test Reagent Co., Ltd. with a net content of ≥ 99.0%. Sodium

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125

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126 Sulphate (Na2SO4) was analytically pure anhydrous sodium sulfate provided by Xilong

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127 Chemical Co., Ltd. with a net content of ≥ 99.0%. Magnesium Sulphate (MgSO4) was
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128 analytically pure magnesium sulfate provided by Shanghai Qingxi Chemical Technology Co.,
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129 Ltd. (Shanghai, China) with a net content of ≥ 99.0%. Sodium chloride (NaCl) is also a deep
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130 well iodized edible salt produced by Jiangxi Salt Industry Group Company.
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131 Table 1 Chemical composition of cement (%).

SiO2 Al2O3 Fe2O3 CaO Na2O K2O MgO SO3 Loss
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21.47 5.80 4.04 56.64 0.05 0.64 3.24 2.08 2.44

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132
133 Table 2 Basic physical properties of cement.
Compressive
Setting time Flexural strength
strength
Cement (min) (MPa) Fineness
(MPa)
soundness (m2/kg)
Initial Final 3 28 3 28
setting setting days days days days
Qualified 129 179 6.4 8.8 34.2 60.4 368.9
134
135 Table 3 Chemical composition of lithium slag (%).
Li2O Al2O3 Fe2O3 K2O Na2O MgO Rb2O Cs2O SiO2 SO3 MnO
0.6 8.7 0.43 3.8 0.9 0.003 0.3 0.08 78.6 2.5 0.09
136
137 Table 4 Fineness characteristics of cementitious materials.
Fineness measurement method Lithium slag Cement
80 μm sieving residue (%) 0.85 1.42
45 μm sieving residue (%) 7.50 8.81

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Fig. 1. Lithium slag.
3500 100
Q:Quartz
0.00
3000

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QS C:CaSO4 98
G

DTG(mass %/℃)
-p
TG-mass loss(%)

A:C3A
Intensity(Cps)

2500 -0.02
S:C2S 96
2000 B:C3S
-0.04
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QG
B G:Gismondine 94
1500 C
92 -0.06
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G
1000 A
B
C S B
A Q QQ
B SS 90 -0.08
500 A A Q
S B Q
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0 88 -0.10
10 20 30 40 50 60 70 80 200 400 600 800 1000
2θ(°) Temperature(℃)
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Fig. 2. XRD pattern of lithium slag. Fig. 3. TG/DTG pattern of lithium slag.
138
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139 2.2 Simulated acid rain

140 The difference between the simulated acid rain and real acid rain includes two main

141 aspects: first, the pH values of real acid rain were constantly changing and varied from region

142 to region, while the pH values of the simulated acid rain could be adjusted and fixed; second,

143 the real acid rain contained more ions. To simulate the composition of the real acid rain in

144 Jiangxi Province, three types of simulated acid rain solutions were prepared, as shown in

145 Table 5. The pH values of the solution were determined to be 2.5 and 3.5, and the

146 concentrations of SO42- were selected to be 0.01 mol/L and 0.06 mol/L. The simulated acid

147 rain solutions were designed as follows：(1) pH value = 2.5 and SO42- = 0.01 mol/L (Class

148 S1). (2) pH value = 3.5 and SO42- = 0.01 mol/L (Class S2). (3) pH value = 2.5 and SO42- =

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149 0.06 mol/L (Class S3). The acid rain corrosion ages were designed as 20 days, 40 days, 60

150 days, 80 days, and 100 days.

151 Table 5 Chemical composition of the main ions in the simulated acid rain solutions (mol/L).
Types Mg2+ NH4+ Na+ SO42- H+ NO3-
S1 0.01 0.0032 0.0032
S2 0.002 0.002 0.014 0.01 0.0003 0.0003
S3 0.06 0.0032 0.0032
152

153 2.3 Specimen preparation

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154 Three types of concrete with lithium slag were manufactured. The mass ratio of the raw

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155 materials of the blank specimens (L00) was cement : lithium slag : sand : gravel : water = 1 :

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156 0 : 2.14 : 2.72 : 0.466. L20 and L40 represent the lithium slag replacing 20% and 40% cement
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157 by mass, respectively. A constant water-to-binder material ratio of 0.446 was adopted. To
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158 ensure that the concrete had a similar workability, the dosage of the water reducer increased
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159 with increasing lithium slag. The masses of the water reducer of L00, L20 and L40 were
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160 0.80%, 1.40% and 1.85% by mass of binder, respectively.

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161 The design and grouping of specific specimens for tests are presented in Table 6. As
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162 shown in Table 6, the dimensions of the samples used for measuring the neutralization depth

163 were 100 mm × 100 mm × 400 mm, whereas those used for measuring the compressive

164 strength and mass were 100 mm × 100 mm × 100 mm cube specimens. In total, 5 × 3 = 15

165 concrete prismatic specimens (5 groups and 3 specimens in each group) and 5 × 5 × 3 = 75

166 concrete cube specimens (5 groups, 5 ages and 3 specimens for each curing age in each group)

167 were fabricated and tested. In Table 6, the group was represented by Sn-Lx, where S refers to

168 simulated rain acid, n represents the code of different corrosion action, and x represents the

169 lithium slag content. For example, S1-L20 represents the group of the concrete specimens

170 with 20% lithium slag under Class S1 simulated acid rain corrosion action.

171

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172 Table 6 The design and grouping of specific specimens.
Number of specimens of different corrosion
Curing ages
Specimen
Tests No. ages
size 20 40 60 80 100
days days days days days
S1-L00 3
S1-L20 100 × 3
Neutralized 110 days
S1-L40 100 3
specimens (30 days
S2-L20 × 400 mm 3
Standard
S3-L20 3
curing
S1-L00 +80 days 3 3 3 3 3
Compressive S1-L20 3 3 3 3 3
100 × natural
strength and

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S1-L40 100 curing) 3 3 3 3 3
Mass

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S2-L20 × 100 mm 3 3 3 3 3
specimens
S3-L20 3 3 3 3 3

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173
174 2.4. Experimental methods -p
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175 2.4.1. Acid rain corrosion
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176 In this study, the simulated acid rain corrosion test adopted the periodic dry-wet cycle

177 spraying method (as shown in Fig. 4) for each lithium slag mixture sample with acid rain
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178 spraying for 4 hours and was then dried at room temperature for 4 hours. This process is
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179 referred to as a period; three periods comprised one day. Since the pH values of the solutions
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180 changed as the conditioning continued, the acidity of the solution was recorded by a Nishima

181 PSH-25 Sartorius Acidometer every day. To maintain the pH of the acid rain corrosion

182 solutions, the required amount of nitric acid was added to the original solution after each

183 period, and a new simulated acid rain solution was used at the end of every 7 days.

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(a) Sketch of the acid rain spray device. (b) Picture of acid rain spray device.

184
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Fig. 4. Self-designed acid rain spray device.
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185 2.4.2. Fresh properties
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186 Slump and setting time were measured to characterize the fresh properties of concrete

187 with different contents of lithium slag according to the GB/T50080-2016 [43] and GB/T1346-
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188 2011 [44] standards in China.

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189 2.4.3. Compressive strength

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190 Compressive strength was measured at a speed of 0.7 MPa/s after different acid rain

191 corrosion action ages according to the GB/T50081-2002 standard in China [45].

192 2.4.4. Mass

193 In the test, the objective of the mass of specimens is to evaluate the degree of acid rain

194 corrosion. The initial mass of the specimens was measured before the acid rain corrosion test.

195 At the end of each acid rain corrosion age, each specimen was dried at room temperature to a

196 constant mass, and the mass loss of the specimens was measured.

197 2.4.5. Neutralization depth

198 1) When the acid rain corrosion ages were 20 days, 40 days, 60 days, 80 days, and 100

199 days, a group of the prismatic specimens of 100 mm × 100 mm × 400 mm was removed. The

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200 specimens were then cut using a cutting machine and dried at 60℃ for 48 hours. After drying,

201 other surfaces were sealed with heated paraffin wax, except that one or two opposite sides

202 were left. A parallel line with a distance of 10 mm perpendicular to the forming surface was

203 drawn on the exposed side of the specimens as the prediction point of the neutralization depth

204 according to GB/T 50082-2009 [46].

205 2) Then, 1% phenolphthalein in ethanol was sprayed. After approximately 30 seconds,

206 the neutralization depth was measured with Vernier callipers per 10 mm measuring point

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207 based on the original mark. If coarse aggregate particles happened to be in the neutralization

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208 boundary of the measurement point, the depth value of the measurement point was acquired

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209 -p
based on the average neutralization depth on both sides of the particle. The average

210 neutralization depth was accurate to 0.1 mm.

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211 2.4.6. XRD
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212 The XRD test used paste specimens to qualify the phase composition of concrete with
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213 different contents of lithium slag. Before XRD observation, the specimens were immersed in
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214 absolute alcohol to terminate the hydration. The samples were then ground to a fine powder
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215 with a diameter no more than 45 µm sieve and dried at 50℃ to reach a constant mass. Finally,

216 the XRD test using an XRD-6100 X-ray powder diffractometer was used to identify the phase

217 compositions of the hydrated product and was applied to study the change tendency of CH

218 crystals which caused by lithium slag under different acid rain corrosion actions.

219 2.4.7. TG/DTG

220 The TG/DTG analysis was performed using paste specimens to obtain the amount of

221 other hydration products of concrete with different contents of lithium slag. Typical

222 specimens were selected to conduct TG/DTG tests using a Perkin Elmer TGA 4000 system

223 (Perkin Elmer, Waltham, MA, USA) under a nitrogen atmosphere at a heating rate of

224 10 ℃/min up to 1000℃.

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225 2.4.8. SEM

226 The purpose of the SEM test is to investigate the microstructure and product

227 morphological characteristics of concrete with different contents of lithium slag under

228 different simulated acid rain corrosion action. Therefore, the concrete specimens are used in

229 the SEM test [47-48]. The samples were selected from the concrete surface of 10-mm

230 thickness and the outer surface (eroded surface) was taken as the observation surface. The

231 characteristics and differences in the corrosion products of concrete with different contents of

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232 lithium slag under different simulated acid rain corrosion actions can be analysed intuitively

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233 through SEM. The device used in the SEM test was a QUANTA 200F SEM (FEI Company,

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234 Hillsboro, OR, USA). -p
235 2.4.9. EDS
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236 To perform EDS tests, small cement paste samples were immersed in anhydrous ethanol
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237 in brown sealed jars for 3 days to stop hydration and dried at 50℃ for 24 hours to a constant
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238 weight before the SEM test. The samples were coated with a Au conductive film. The SEM
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239 test was performed by a HITACHI SU8010 microscope (HITACHI, Tokyo, Japan). Under a
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240 15 kV acceleration voltage, SE mode was used to test the Ca/Si of the C-S-H gels. During the

241 test, 5 fields of view were selected for each sample, and 12 hydration product points were

242 selected for every field of view. Finally, the average value of 60 data points was taken to

243 characterize the Ca/Si.

244 2.5. The performance indices

245 2.5.1. Mass loss and mass loss rate

246 During the test, the mass of each specimen dried at room temperature and the mass loss

247 of the specimens with the same corrosion time was measured. The average mass loss rate of

248 three specimens was acquired as a group of concrete specimens to simulate the mass loss rate

249 after corrosion. The mass loss rate was calculated according to Equation (1):

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 W0i − Wni
250 Wni = 100% (1)
W0i

251 where ∆Wni is the mass loss rate (%) of the concrete specimen after n days of simulated acid

252 rain corrosion, W0i is the mass (kg/m3) of the concrete specimen before simulated acid rain

253 corrosion, and Wni is the mass (kg/m3) of the concrete specimen after n days of simulated acid

254 rain corrosion.

255 2.5.2. The decrease rate of compressive strength

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256 During the curing ages, the specimens were periodically dried, and then compressive

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257 strength tests were carried out. The compressive strength and the decrease rate of the

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258 -p
compressive strength were calculated. In this paper, the decrease rate of the uniaxial

259 compressive strength of concrete specimens was calculated according to Equation (2). Finally,
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260 the average decrease rate of compressive strength of the three specimens in a group was taken
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261 to characterize the decrease rate:

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f c 0 − f cn
262 f c = 100% (2)
fc0
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where ∆fc is the change rate (%) of the concrete compressive strength after n days of
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263

264 simulated acid rain corrosion, fc0 is the value (MPa) of the compressive strength of a group of

265 concrete specimens before acid rain corrosion, and fcn is the value (MPa) of the compressive

266 strength of a group of concrete specimens after n days of simulated acid rain corrosion.

267 2.5.3. Neutralization depth

268 In the test, the measured value of neutralization depth of every group was acquired based

269 on the average neutralization depth of 3 specimens. The average neutralization depth of every

270 specimen can be calculated with Equation (3) according to GB/T 50082-2009 [46]. The

271 average neutralization depth of three specimens was taken to characterize the neutralization

272 depth of a group of concrete specimens after simulated acid rain corrosion:

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 1 m
273 d nj =  di
m i =1
(3)

274 where dnj is the average neutralization depth (mm) of the jth specimen after n days of the

275 simulated acid rain corrosion, di is the neutralization depth (mm) of the ith measurement point

276 on the jth specimen, and m is the total measurement point (m is 10 in this test).

277 2.5.4. CH orientation

278 According to XRD analysis and the literature [49], the CH orientation was calculated:

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I 001
I CH =

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279 (4)
( I101  0.74)

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280 -p
where ICH is the orientation of CH, I001 is the diffraction peak intensity of the CH (001) crystal

281 surface, and I101 is the diffraction peak intensity of the CH (101) crystal surface.
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282 2.5.5. Hydration degree
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283 The hydration degree was calculated according to TG/DTG curves and the literature [50]:
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M 105 − M 1000 − M CaCO 3

284 t = (5)
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M Water-Full
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285 where βt is the hydration degree of specimens, M105 is the mass of paste after 105℃ heat

286 treatment for 2 h (g), M1000 is the mass of paste after 1000℃ heat treatment for 2 h (g), MCaCO3

287 is the mass change of paste caused by CaCO3 decomposition during heating (g), MWater-Full is

288 the water assumption required for full hydration of 1 g cement, according to the literature [51],

289 and Mwater-Full adopted in this paper is 0.23.

290
291 3. Results and discussion

292 3.1. Fresh properties

293 All the test data of fresh concrete with different contents of lithium slag are presented in

294 Table 7. As seen in Table 7, the setting time of the concrete prepared by lithium slag

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295 decreased as the lithium slag content increased from 0% to 40%. The initial setting time and

296 final setting time of concrete prepared by lithium slag shortened from 604 min to 63 min and

297 from 701 min to 180 min, respectively, with a lithium slag content of 0%-40%. The decrease

298 rates of the initial setting time and final setting time were from 26.8% to 89.6% and 25.5% to

299 74.3%, respectively, compared with the control samples without lithium slag. Accordingly, the

300 setting time results showed that lithium slag can distinctly promote the hydration reaction rate

301 and reduce the setting time of concrete. Thus, the addition of 40% lithium slag noticeably

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302 reduced the setting time value of the concrete with lithium slag compared with the control

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303 samples without lithium slag. In addition, Table 7 also shows that the slump values of

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304 -p
concrete prepared by the lithium slag increased first and then decreased with increasing

305 lithium slag content from 0% to 40%. The objective of the slump test was to ensure that
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306 slump remained constant throughout the whole test.
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307 Table 7 The influence of lithium slag content on the fresh properties of concrete
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No. Lithium Setting time Slump

Slag (%) Initial setting time (min) Final setting time (min) (mm)
L00 0 604 701 41
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L20 20 442 522 42

L40 40 63 180 40
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308
309 3.2. Appearance

310 3.2.1 Effect of lithium slag content on concrete appearance damage

311 The appearance of the concrete with different contents of lithium slag after 20 days, 60

312 days, 80 days and 100 days of dry-wet spraying under Class S1 simulated acid rain action (pH

313 value = 2.5 and SO42- = 0.01 mol/L) are illustrated in Fig. 5. As shown in the figure, the

314 concrete specimens with lithium slag exhibited the smallest appearance damage. With

315 increasing corrosion ages, the control specimens without lithium slag suffering from acid rain

316 corrosion were observed to have a deep yellow appearance, while the surface colour of the

317 concrete with lithium slag was whiter than the surface colour of the control concrete without

15
318 lithium slag. At an acid rain corrosion age of 100 days, the concrete specimen with 40%

319 lithium slag showed a relatively intact appearance, and only a few etch pits appeared on its

320 surface, whereas the other specimens had obvious spalling. As a result, the lithium slag was

321 beneficial for resisting acid rain corrosion of concrete, and 40% was the optimum content of

322 lithium slag.

f
oo
S1-L00 S1-L20 S1-L40
(a) Corrosion for 20 days

r
-p
re
S1-L00 S1-L20 S1-L40
lP

(b) Corrosion for 60 days

na
ur

S1-L00 S1-L20 S1-L40

Jo

(c) Corrosion for 80 days

S1-L00 S1-L20 S1-L40

(d) Corrosion for 100 days
Fig. 5. Surface of concrete with different contents of lithium slag under Class S1 simulated
acid rain corrosion action at different corrosion ages.
323 3.2.2 Effect of pH values of acid rain on appearance damage of concrete

324 Fig. 6 shows that the appearance of concrete with 20% lithium slag after 20 days, 60

325 days, 80 days and 100 days of the dry-wet spraying under Class S2 simulated acid rain

326 corrosion action (pH value = 3.5 and SO42- = 0.01 mol/L). Fig. 6 shows that the concrete

327 specimens with 20% lithium slag of the dry-wet spraying with pH value = 3.5 suffered the

16
328 smallest acid attack compared to the specimens with pH value = 2.5. Among these specimens,

329 the concrete with 20% lithium slag showed fewer pockmarks and smaller holes. Under Class

330 S2 simulated acid rain action, the concrete with lithium slag also exhibited good resistance to

331 acid attack. The simulated acid solution with pH value = 3.5 had a weak attack on the

332 concrete. Therefore, the acid resistance of concrete with 20% lithium slag increased with

333 increasing pH value.

f
r oo
-p
re
lP

20 days 60 days 80 days 100 days

Fig. 6. Surface of concrete with 20% lithium slag under Class S2 simulated acid rain
na

corrosion action at different corrosion ages.

334
335 3.2.3 Effect of the concentration of SO42- on the appearance damage of concrete
ur

336 The appearance of the concrete with 20% lithium slag after 20 days, 60 days, 80 days
Jo

337 and 100 days of the dry-wet spraying under Class S3 simulated acid rain corrosion action (pH

338 value = 2.5 and SO42- = 0.06 mol/L) is illustrated in Fig. 7. The concrete specimens with 20%

339 lithium slag of the dry-wet spraying with SO42- = 0.06 mol/L suffered the most serious acid

340 attack compared to specimens with SO42- = 0.01 mol/L. Among these specimens, the concrete

341 with 20% lithium slag showed a quantity of sand grain exfoliation. Under the simulated acid

342 rain action, the concrete with lithium slag also exhibited good resistance to acid attack. The

343 simulated acid solution with SO42- = 0.01 mol/L had a weak attack on the concrete. Therefore,

344 the acid resistance of concrete with 20% lithium slag decreased with increasing SO42-.

17
 20 days 60 days 80 days 100 days
Fig. 7. Surface of concrete with 20% lithium slag under Class S3 simulated acid rain
corrosion action at different corrosion ages.

f
345

oo
346 3.3. Compressive strength

r
347 3.3.1 Effect of lithium slag content on compressive strength

348
-p
The compressive strength of concrete with different contents of lithium slag under Class
re
349 S1 simulated acid rain action is shown in Fig. 8(a), and the corresponding relative decrease
lP

350 rate in compressive strength is shown in Fig. 8(b). In this study, the corrosion process in
na

351 simulated acid rain corrosion was divided into two stages according to the decreasing range of

352 the compressive strength, in which the first stage was when the compressive strength
ur

353 decreased rapidly, while the compressive strength declined slowly in the second stage. Fig.
Jo

354 8(a) shows that the addition of lithium slag to the concrete not only increased the initial

355 strength but also increased its residual strength significantly under Class S1 simulated acid

356 rain action. In the early stage, the compressive strength of concrete with different contents of

357 lithium slag declined rapidly with increasing corrosion age. However, the compressive

358 strength decrease rate of the concrete with 40% lithium slag was the lowest in all of the

359 concrete specimens. In the middle-later stage, the reduction of the compressive strength of

360 concrete with different contents of lithium slag was similar, increased slightly and then

361 decreased slowly throughout the whole corrosion ages. At a corrosion age of 100 days, the

362 compressive strength of concrete with lithium slag was higher than the compressive strength

18
363 of control concrete without lithium slag. Among these specimens, the compressive strength of

364 concrete with 40% lithium slag was 35.9 MPa and was the largest. Because lithium slag can

365 fill the pores in the concrete and increase the microstructural compactness of concrete, the

366 compressive strength of concrete with lithium slag increased. According to Fig. 8(b), for the

367 specimens with lithium slag suffering from acid rain attack accompanied with or without acid

368 rain attack, the compressive strength decrease rate slightly decreased vs the increase in

369 corrosion ages. The compressive strength decrease rate of control concrete without lithium

f
370 slag was 43.4% and larger than concrete with lithium slag. From the compressive strength

oo
371 decrease rate results, the acid resistance of concrete from the best to the worst is as follows:

r
372 -p
concrete with 40% lithium slag > concrete with 20% lithium slag > control concrete without

373 lithium slag. Therefore, the compressive strength of concrete increased and the compressive
re
374 strength decrease rate of concrete declined when the content of lithium slag increased. Among
lP

375 these specimens, the best content of lithium slag was 40%. Due to the pozzolanic reactivity
na

376 [52], concrete with lithium slag has more hydration products and the addition of lithium slag
ur

377 can consume the CH content and improve the microstructural compactness of concrete, thus
Jo

378 enhancing the compressive strength of concrete.

80 Early Middle-later 70
Early Middle-later
Compressive strength (MPa)

70 stage stage 60 stage stage

Decrease rate (%)

58.4
60 55.1 50
43.4
50 48.6 40 39.9
40 35.9 34.7
30
35.1
30
27.5 20 S1-L00
20 S1-L00 S1-L20
S1-L20 10 S1-L40
10 S1-L40 0.0
0
0
0 20 40 60 80 100 0 20 40 60 80 100
Corrosion ages (days) Corrosion ages (days)
(a) Compressive strength (b) Compressive strength decrease rate
Fig. 8. Compressive strength and compressive strength decrease rate of concrete with
different contents of lithium slag under Class S1 simulated acid rain action.
379
380 3.3.2 Effect of pH values of acid rain solution on compressive strength

381 Figs. 9(a) and (b) show the compressive strength and the compressive strength decrease

19
382 rate of the concrete with 20% lithium slag under simulated acid rain conditions with different

383 pH values, respectively. Fig. 9(a) shows that the initial strengths of concrete with 20% lithium

384 slag under simulated acid rain conditions with different pH values were almost the same, but

385 with the increase in corrosion ages, the compressive strength of the concrete with 20% lithium

386 slag with pH value = 3.5 more than doubled over the compressive strength of specimens with

387 pH value = 2.5. In the early stage, the compressive strength of concrete with 20% lithium slag

388 with pH value = 2.5 decreased more than the compressive strength of concrete with pH value

f
389 = 3.5. In the middle-later stage, the compressive strength of concrete with 20% lithium slag

oo
390 with different pH values decreased slowly with increasing of corrosion age. At 100 days, the

r
391 -p
compressive strength of concrete with 20% lithium slag with pH value = 3.5 was 35.7 MPa

392 larger than that of concrete with pH value = 2.5. According to Fig. 9(b), the compressive
re
393 strength decrease rate of concrete with 20% lithium slag decreased with increasing pH values.
lP

394 The compressive strength decrease rate of concrete with 20% lithium slag with pH value = 3.5
na

395 was reduced by 2.5% compared to the compressive strength of concrete with 20% lithium
ur

396 slag with pH value = 2.5. Generally, the simulated acid rain corrosion action with a low pH
Jo

397 value is more corrosive to concrete with lithium slag. However, within the design pH values

398 of this study, the pH values have little effect. The concrete with lithium slag may not be

399 sensitive to the effect of the pH value on the compressive strength of concrete.

80 70
Early Middle-later Early Middle-later
Compressive strength (MPa)

70 stage stage 60 stage stage

58.4
Decrease rate (%)

60 50
58.4
50 40 39.8
38.8
40 35.7 30
35.1
30
20
20 S1-L20(pH=2.5,SO42-=0.01)
S1-L20(pH=2.5,SO42-=0.01)
2-
S2-L20(pH=3.5,SO4 =0.01) 10
10 S2-L20(pH=3.5,SO42-=0.01)
0.0
0
0
0 20 40 60 80 100 0 20 40 60 80 100
Corrosion ages (days) Corrosion ages (days)
(a) Compressive strength (b) Compressive strength decrease rate
Fig. 9. Compressive strength and compressive strength decrease rate of concrete with 20%

20
 lithium slag with different pH values.
400
401 3.3.3 Effect of the concentration of SO42- on compressive strength

402 The compressive strength and the compressive strength decrease rate of concrete with

403 20% lithium slag under simulated acid rain corrosion action with different concentrations of

404 SO42- are shown in Figs. 10(a) and (b), respectively. Fig. 10(a) shows that the initial strengths

405 of concrete with 20% lithium slag under simulated acid rain conditions with different

406 concentrations of SO42- were the same, but with the increase in corrosion ages, the

compressive strength of the concrete with 20% lithium slag with SO42- = 0.01 mol/L more

f
407

oo
408 than doubled the compressive strength of specimens with SO42- = 0.06 mol/L. In the early

r
409 stage, the compressive strength of concrete with 20% lithium slag with SO42- = 0.01 mol/L
-p
410 decreased more than the compressive strength of concrete with SO42- = 0.06 mol/L. In the
re
411 middle-later stage, the compressive strength of concrete with 20% lithium slag with SO42- =
lP

412 0.01 mol/L basically remained unchanged, while the compressive strength of concrete with
na

413 20% lithium slag with SO42- = 0.06 mol/L decreased quickly. At 100 days, the compressive
ur

414 strength of concrete with 20% lithium slag with SO42- = 0.01 mol/L was 35.1 MPa larger than
Jo

415 the compressive strength of concrete with SO42- = 0.06 mol/L. According to Fig. 10(b), the

416 compressive strength decrease rate of concrete with 20% lithium slag increased with

417 increasing concentrations of SO42-. The compressive strength decrease rate of concrete with

418 20% lithium slag with SO42- = 0.06 mol/L was increased by 43.7% compared to the

419 compressive strength decrease rate of concrete with 20% lithium slag with SO42- = 0.01 mol/L.

420 Generally, a simulated acid rain solution with a low pH value is more corrosive to the

421 concrete with lithium slag. However, within the design of the concentration of SO42- of this

422 study, the concentration of SO42- has an obvious effect on the compressive strength of

423 concrete. Ca2+ dissolved in concrete can react with SO42- in acid rain solution to produce more

424 expansive products (such as gypsum and ettringite) at an early stage, thus enhancing the

21
425 compactness and compressive strength. However, with increasing of corrosion age, a large

426 amount of ettringite was generated, thus producing expansion stress. When the tensile stress

427 from the corrosion products is greater than the ultimate tensile stress of concrete, cracks will

428 occur in the concrete, thus leading to the rapid decline of the compressive strength of concrete

429 [53].

80 Early Middle-later 70 Early Middle-later

Compressive strength (MPa)

70 stage stage stage stage

60 57.2

Decrease rate (%)

60 58.4
58.4 50

f
50 39.8

oo
40
40 35.1 30
30 25.0
20

r
20 2- S1-L20(pH=2.5,SO42-=0.01)
10
0
S1-L20(pH=2.5,SO4 =0.01)
S3-L20(pH=2.5,SO42-=0.06)
-p 10
0
0.0
S3-L20(pH=2.5,SO42-=0.06)
re
0 20 40 60 80 100 0 20 40 60 80 100
Corrosion ages (days) Corrosion ages (days)
(a) Compressive strength (b) Compressive strength decrease rate
lP

Fig. 10. Compressive strength and compressive strength decrease rate of concrete with 20%
lithium slag with the different concentrations of SO42-.
na

430
431 3.4. Mass
ur

432 3.4.1 Effect of lithium slag content on the concrete mass

Jo

433 The mass change values of the concrete exposed to acidic solutions were determined by

434 comparing the masses of the concrete with different contents of lithium slag under Class S1

435 simulated acid rain action (pH value = 2.5 and SO42- = 0.01 mol/L) with the initial

436 noncorroded concrete specimens. The results are shown in Figs. 11(a) and (b), respectively.

437 The results reported in Fig. 11(a) demonstrate that the mass of all specimens gradually

438 decreased with increasing of corrosion age. The mass of control samples without lithium slag

439 under Class S1 simulated acid rain action was 2400 kg/m3, which was greater than the mass

440 of concrete with lithium slag before corrosion. In the early stage, the mass of concrete with

441 different contents of lithium slag all remained the same. In the middle-later stage, the mass of

442 control samples without lithium slag decreased rapidly with increasing of corrosion age, while

22
443 the mass of concrete with lithium slag gradually declined. At 100 days, the mass of the control

444 samples without lithium slag was 2350 kg/m3, which was larger than the mass of the

445 specimens with lithium slag. However, the mass of control samples without lithium slag

446 decreased 500 kg/m3. Fig. 11(b) shows that the mass loss rate of the specimens gradually

447 increased with increasing corrosion age. The mass loss of concrete with 40% lithium slag

448 showed the lowest decrease rate and it was 0.86%, which correspondingly decreased by

449 58.7% compared with the mass loss of the control samples without lithium slag. The mass

loss rate of concrete declined with increasing lithium slag content because SiO42- and

f
450

oo
451 amorphous alumina in lithium slag had secondary hydration reactions with hydration products,

r
452 -p
which filled the internal pores and increased the compactness of the concrete [24]. The dense

453 structure of concrete with lithium slag can hinder the penetration of H+ and SO42- and reduce
re
454 the mass loss of the concrete with lithium slag, once again demonstrating that the lithium slag
lP

455 has significant resistance to acid rain corrosion.

na

2480 2.80
Early Middle-later Early Middle-later
stage stage 2.40 stage stage
2440
ur

2.08
Mass loss rate (%)

2400 2.00
Mass (kg/m3)

2400
1.60
Jo

1.28
2360 2350
1.20
2340
2330 0.86
2320 2310 0.80
2310 S1-L00
S1-L00 0.40
2280 S1-L20 S1-L20
0.0 S1-L40
S1-L40 0.00
2240
0 20 40 60 80 100 0 20 40 60 80 100
Corrosion ages (days) Corrosion ages (days)
(a) Mass (b) Mass loss rate
Fig. 11. Mass and mass loss rate of concrete with different contents of lithium slag
under Class S1simulated acid rain action.
456
457 3.4.2 Effect of pH values of acid rain solution on concrete mass change

458 Figs. 12(a) and (b) illustrate that the mass loss and the mass loss rate of concrete with

459 20% lithium slag under simulated acid rain solutions with different pH values, respectively.

460 Fig. 12(a) shows that the initial mass of concrete with 20% lithium slag with pH value = 2.5

23
461 was larger than the initial mass of specimens with pH value = 3.5, but with the increase in

462 corrosion ages, the masses of the concrete with 20% lithium slag under different simulated

463 acid rain solutions were almost the same. In the early stage, the mass of concrete with 20%

464 lithium slag with different pH values showed a similar trend and the mass curve was a straight

465 horizontal line. The straight line was a dynamic equilibrium process. The acid corrosion of H+

466 resulted in a mass decrease, while the continuous hydration of the cementitious materials

467 promoted an increase in the mass of the specimens, therefore reaching a balance [54]. In the

f
468 middle-later stage, the mass of specimens with 20% with different pH values declined with

oo
469 increasing corrosion age, and the mass of concrete with 20% lithium slag with pH value = 2.5

r
470 -p
decreased more quickly than the mass of specimens with pH value = 3.5. In the whole

471 corrosion process, the mass of concrete with 20% lithium slag with pH value = 2.5 decreased
re
472 by 30 kg/m3, while the concrete with pH value = 3.5 decreased by 20 kg/m3. According to Fig.
lP

473 12(b), the mass loss rate of concrete with 20% lithium slag decreased along with increasing
na

474 pH values. The mass loss rate of concrete with pH value = 2.5 was 1.28%, which
ur

475 correspondingly increased by 32.8% compared with the mass loss rate of the concrete with
Jo

476 20% lithium slag with pH value = 3.5. Within the design of the pH values of this study, the

477 concentration of H+ has an obvious effect on the mass of concrete with lithium slag.

Early Middle-later
2.40
S1-L20(pH=2.5,SO42-=0.01)
2360 stage stage
2.00 S2-L20(pH=3.5,SO42-=0.01)
Mass loss rate (%)

Early Middle-later
2340 1.60
Mass (kg/m3)

2340 stage stage

2330 1.28
1.20
2320 0.86
2310 0.80
2310
2300 S1-L20(pH=2.5,SO42-=0.01) 0.40
S2-L20(pH=3.5,SO42-=0.01) 0.0
0.00
2280
0 20 40 60 80 100 0 20 40 60 80 100
Corrosion ages (days) Corrosion ages (days)
(a) Mass (b) Mass loss rate
Fig. 12. Mass and mass loss rate of concrete with 20% lithium slag with different pH values.
478

24
479 3.4.3 Effect of the concentration of SO42- on concrete mass change

480 The mass loss and the mass loss rate of concrete with 20% lithium slag under simulated

481 acid rain with the different concentrations of SO42- are shown in Figs. 13(a) and (b),

482 respectively. Fig. 13(a) shows that the initial mass of concrete with 20% lithium slag with

483 SO42- = 0.01 mol/L was larger than the initial mass of specimens with SO42- = 0.06 mol/L, and

484 with increasing corrosion age, and the mass of the concrete with 20% lithium slag with SO42-

485 = 0.06 mol/L was also the smallest. In the early stage, the mass of concrete with 20% lithium

slag with different concentrations of SO42- showed a similar trend and remained constant. In

f
486

oo
487 the middle-later stage, the mass of concrete with 20% lithium slag with SO42- = 0.06 mol/L

r
488 declines more rapidly than that with SO42- = 0.01 mol/L. After 100 days of corrosion, the
-p
489 mass of the concrete with 20% lithium slag with SO42- = 0.01 mol/L was 2310 kg/m3 and
re
490 larger than the mass of the concrete with SO42- = 0.06 mol/L. There appears to be tensile
lP

491 stress inside concrete due to more expansive ettringite formed with increasing of corrosion
na

492 age [52]. When it exceeded the tensile strength of concrete, cracks appeared and provided
ur

493 new diffusion pathways for H+ and SO42-. The higher the concentration of SO42-, the more
Jo

494 expansive products will be generated, and the concrete cracks will gradually widen. Therefore,

495 the amount of soluble salts generated by the concrete reaction also increased greatly, resulting

496 in the rapid decline of the concrete mass. According to Fig. 13(b), the mass loss rate of

497 concrete with 20% lithium slag increased with increasing concentration of SO42-. The mass

498 loss rate of concrete with SO42- = 0.06 mol/L was 5.17%, which correspondingly was

499 approximately 4 to 5 times compared with the mass loss rate of concrete with 20% lithium

500 slag with SO42- = 0.01 mol/L. SO42- in acid rain can react with cement hydration products to

501 form expansive products. The higher the concentration of SO42-, the more expansive products

502 were generated to prevent H+ and SO42- from diffusing into the concrete. Therefore, the

503 smaller the concentration of SO42- is, the smaller the mass loss rate of concrete with 20%

25
504 lithium slag.

2400 Early Middle-later 10.00

S1-L20(pH=2.5,SO42-=0.01)
stage stage
2350 2340 8.00 S3-L20(pH=2.5,SO42-=0.06)
Early Middle-later

Mass loss rate (%)

Mass (kg/m3)

2310 stage stage

2300 2320 6.00 5.17

4.00
2250
2.00 1.28
S1-L20(pH=2.5,SO42-=0.01) 2200
2200
S3-L20(pH=2.5,SO42-=0.06) 0.00
0.0

0 20 40 60 80 100 0 20 40 60 80 100
Corrosion ages (days) Corrosion ages (days)

f
(a) Mass (b) Mass loss rate

oo
Fig. 13. Mass and mass loss rate of concrete with 20% lithium slag with the different
concentrations of SO42-.
505

r
506 3.5. Neutralization depth -p
re
507 The neutralization depth is the diffusion depth of H+, which is a direct reflection of the
lP

508 degree of corrosion of acid rain and the acid rain corrosion resistance of concrete. The

509 influence of lithium slag content, different pH values, and the concentration of SO42- in acid
na

510 rain on the neutralization depth of concrete were considered.

ur

511 3.5.1 The phenomenon of neutralization

Jo

512 Fig. 14 shows the fracture surface appearance of the corroded concrete specimens with

513 different contents of lithium slag under Class S1 simulated acid rain action after

514 phenolphthalein spraying. The neutralization depth of concrete increased under the same

515 simulated acid rain corrosion action with increasing of lithium slag content. The neutralization

516 depth of control samples without lithium slag increased rapidly and then increased slowly

517 under Class S1 simulated acid rain action. The neutralization depth of concrete with 20%

518 lithium slag increased rapidly and then decreased slowly. The width of the yellow strip around

519 the specimens and the neutralization depth were greater than those parameters of the control

520 samples without lithium slag. For the concrete with 40% lithium slag, the change trend of the

521 neutralization depth of concrete was similar to the change trend of concrete with 20% lithium

26
522 slag but was largest among the concrete specimens with other contents of lithium slag.

523 Therefore, under the same acid rain corrosion action, the increase in lithium slag content is

524 accompanied by an increase in the neutralization depth.

20 days 60 days 80 days 100 days

S1-L00

f
S1-L20

r oo
S1-L40
-p
re
lP

Fig. 14. Fracture surface appearance of concrete with different contents of lithium slag
under Class S1 simulated acid rain corrosion action.
na

525
526 Fig. 15 shows that the fracture surface appearance of concrete with 20% lithium slag
ur

527 under different simulated acid rain corrosion actions. For the concrete with 20% lithium slag
Jo

528 under Class S2 simulated acid rain corrosion action, with the increase in corrosion ages, a red

529 colour appeared on the fracture surfaces after spraying phenolphthalein, indicating that the

530 neutralization depth was not obvious. Compared with concrete with 20% lithium slag with a

531 pH value = 2.5, the neutralization depth of concrete with 20% lithium slag was smaller.

532 Therefore, the neutralization depth of concrete with 20% lithium slag declined with increasing

533 pH value.

534 For the concrete with 20% lithium slag under Class S3 simulated acid rain corrosion

535 action, the width of the yellow strip slightly increased with increasing corrosion age. The

536 depth of neutralization increased rapidly at first, and then the rate slowed down. Obviously,

537 the neutralization depth of the concrete with 20% lithium slag with SO42- = 0.06 mol/L was

27
538 larger than that of concrete with 20% lithium slag with SO42- = 0.01 mol/L, moreover, the

539 neutralization depth of concrete with 20% lithium slag increased with increasing

540 concentration of SO42-.

20 days 60 days 80 days 100 days

S2-L20

f
S3-L20

r oo
Fig. 15. Fracture surface appearance of concrete with 20% lithium slag under different

541
-p
simulated acid rain corrosion actions.
re
542 3.5.2 Effect of lithium slag content on neutralization depth
lP

543 Fig. 16 verifies the variations in the neutralization depth of concrete with different
na

544 contents of lithium slag under Class S1 simulated acid rain corrosion action (pH value = 2.5

545 and SO42- = 0.01 mol/L). According to Fig. 16, the neutralization depth of concrete with
ur

546 lithium slag suffering from acid rain attack was higher than the neutralization depth of
Jo

547 concrete without lithium slag. In the early stage, the neutralization depth of concrete with

548 40% lithium slag under Class S1 simulated acid rain corrosion action increased more than the

549 neutralization depth of concrete with other contents of lithium slag. The smallest

550 neutralization depth was observed for the control samples without lithium slag, while the

551 largest neutralization depth was observed in the concrete with 40% lithium slag. In the

552 middle-later stage, the neutralization depth of concrete with 40% lithium slag increased

553 rapidly, while the neutralization depth of concrete with other contents of lithium slag

554 increased gradually. At 100 days, for the specimens exposed to acetic acid under Class S1

555 simulated acid rain corrosion action, the largest neutralization depth was 2.27 mm, that is, the

28
556 neutralization depth of the concrete with 40% lithium slag, followed by the concrete with

557 20% lithium slag, which was approximately 1.96 mm, and the neutralization depth of control

558 samples without lithium slag was the smallest, i.e., only 1.43 mm. Obviously, the

559 neutralization depths of concrete with lithium slag were greater than the neutralization depths

560 of control samples without lithium slag; moreover, the neutralization depths of concrete

561 increased with an increase in their lithium slag content due to the lower content of CH.

562 Adding lithium slag can reduce the content of CH to decrease the content of alkaline

f
563 substances that can be neutralized in concrete, leading to a greater neutralization depth of

oo
564 concrete corroded by the acid rain solution [52]. Therefore, the neutralization depth increased

r
565 -p
with increasing lithium slag content. However, the maximum value of the neutralization depth

566 of concrete with 40% lithium slag was also far less than the general structural design of
re
567 reinforced concrete protective layer thickness.
lP

3.00 Early Middle-later

Neutralization depth (mm)

na

stage stage
2.50 2.27
1.96
2.00
ur

1.43
1.50
Jo

1.00
0.50 S1-L00
S1-L20
0.0 S1-L40
0.00
0 20 40 60 80 100
Corrosion ages (days)

Fig. 16. The neutralization depth of concrete with different contents of lithium slag under
Class S1 simulated acid rain corrosion action.
568

569 3.5.3 Effect of pH values of acid rain solution on neutralization depth

570 The changing trend of the neutralization depth of concrete with 20% lithium slag with

571 different pH values is presented in Fig. 17. Fig. 17 shows that with increasing corrosion age,

572 the neutralization depth of concrete with 20% lithium slag at different pH values increased. In

29
573 the early stage, the neutralization depth of concrete with 20% lithium slag with pH value = 2.5

574 increased more than the neutralization depth with pH value = 3.5. In the middle-later stage,

575 the neutralization depth of concrete with 20% lithium slag with pH value = 2.5 increased

576 gradually while the neutralization depth of concrete with 20% lithium slag with pH value =

577 3.5 was basically unchanged. At 100 days, for the specimens under simulated acid rain

578 solution with a pH value = 3.5, the neutralization depth of concrete with 20% was the smallest,

579 i.e., 0.64 mm, while the neutralization depth of the concrete with 20% lithium slag with pH

f
580 value = 2.5 was the greatest, i.e., 1.96 mm. Replacing cement with an equal content of lithium

oo
581 slag can reduce the alkaline hydration products in concrete. At the same ages, the pH value of

r
582 acid rain was very low, and the concentration of H+ was very high. H+ reacted violently with
-p
583 the alkaline hydration products, which increased the neutralization depth of concrete with
re
584 lithium slag. Therefore, when the pH value increased, the neutralization depth in the corroded
lP

585 concrete with lithium slag decreased.

na

3.60
S1-L20(pH=2.5,SO42-=0.01)
Neutralization depth (mm)

ur

3.00 S2-L20(pH=3.5,SO42-=0.01)

2.40 Early Middle-later

stage stage
Jo

1.96
1.80
1.20
0.64
0.60
0.0
0.00

0 20 40 60 80 100
Corrosion ages (days)
Fig. 17. The neutralization depth of concrete with 20% lithium slag with different pH values.
586

587 3.5.4 Effect of the concentration of SO42- on concrete neutralization depth

588 The neutralization depth of concrete with 20% lithium slag with different concentrations

589 of SO42- is shown in Fig. 18. The changing trend of the neutralization depth of concrete with

590 20% lithium slag with different concentrations of SO42- was similar to the changing trend of

30
591 the neutralization depth with different pH values, and the neutralization depth of concrete with

592 20% lithium slag increased with increasing concentrations of SO42-. In the early stage, the

593 degree of increase in the neutralization depth of concrete with 20% lithium slag with SO42- =

594 0.01 mol/L was larger than the degree of increase in the neutralization depth of concrete with

595 20% lithium slag with SO42- = 0.06 mol/L. In the middle-later stage, the neutralization depth

596 of concrete with 20% lithium slag with SO42- = 0.06 mol/L increased faster and was larger

597 than the neutralization depth with SO42- = 0.01 mol/L. In all corrosion ages, the smallest

f
598 neutralization depth of concrete was 1.96 mm, that is the neutralization depth of concrete with

oo
599 20% lithium slag with SO42- = 0.01 mol/L, and that of concrete with 20% lithium slag with

r
600 SO42- = 0.06 mol/L was the largest, i.e., 2.13 mm. Because SO42- diffuses to the inside of the
-p
601 concrete, SO42- can react with Ca2+ in concrete to form insoluble and expansive products such
re
602 as ettringite. These products can fill the pores of concrete and enhance the density of concrete.
lP

603 With the increase in the concentration of SO42-, the cracks in concrete increased. Moreover,
na

604 the cracks are conducive to the diffusion of SO42- ions, resulting in serious concrete damage
ur

605 and the neutralization depth of concrete with lithium slag increased. Compared with the pH
Jo

606 value, the effect of the concentration of SO42- on the concrete neutralization depth was large.

2.80 Early Middle-later

Neutralization depth (mm)

2.40 stage stage

2.13
2.00 1.96

1.60
1.20
0.80
0.40 S1-L20(pH=2.5,SO42-=0.01)
0.0
0.00 S3-L20(pH=2.5,SO42-=0.06)

0 20 40 60 80 100
Corrosion ages (days)
Fig. 18. The neutralization depth of concrete with 20% lithium slag with different
concentrations of SO42-.
607
608

31
609 3.6. Microscopic analysis

610 3.6.1 XRD analysis

611 (1) Effect of lithium slag content

612 The effect of lithium slag on the hydration products of concrete before corrosion was

613 studied by XRD, as shown in Fig. 19. Fig. 19(a) shows that the calcium sulfoaluminate

614 (C4A3S), belite (C2S) and quartz (SiO2) from concrete with different contents of lithium slag

615 were clearly observed. Typical hydration products such as ettringite, gypsum and CaCO3 can

f
616 be clearly observed. With increasing of lithium slag content, the peak intensities of SiO2 and

oo
617 ettringite increased slightly, and the peak intensity of C2S decreased. The results demonstrated

r
618 -p
that lithium slag was able to accelerate the hydration reaction of concrete and facilitate the

619 formation of hydration products due to the pozzolanic reaction. This was the main factor why
re
620 lithium slag can enhance the compressive strength of concrete. The CH orientation of
lP

621 concrete with different contents of lithium slag is shown in Fig.19(b). The CH orientation of
na

622 concrete obviously presented a decreasing trend with increasing lithium slag content before
ur

623 corrosion. The CH orientation of control samples without lithium slag was 1.32, and adding
Jo

624 20% and 40% lithium slag decreased the CH orientation by 4.23% and 10.56%, respectively,

625 compared with control samples without lithium slag.

626 The hydration products of concrete with different contents of lithium slag after corrosion

627 under Class S1 simulated acid rain corrosion action (pH value = 2.5 and SO42- = 0.01 mol/L)

628 were analysed by XRD, as shown in Fig. 20. CH was almost exhausted, but gypsum also

629 exhibited characteristic peaks. The amount of gypsum increased with increasing corrosion age,

630 which led to a decrease in the compressive strength of concrete with lithium slag. According

631 to XRD data, the CH orientation of concrete after corrosion was calculated as shown in Fig.

632 20(b). The CH orientation of concrete with lithium slag after corrosion presented an

633 increasing trend that increased with increasing lithium slag content under Class S1 simulated

32
634 acid rain corrosion action, which means that the incorporation of lithium slag can also

635 obviously affect the CH orientation.

G:Gypsum P:Ca(OH)2 L00 1.6

A:CaCO3 E:Ettringite 1.42
L20 1.36
C:C4A3S G 1.27
S:SiO2 L40
1.2
Intensity(a.u.)

CH orientation
B:C2S S E
A E C C
G E GE E BP S S

0.8

0.4

0.0

f
10 20
40 50 60 70 30 0 20 40

oo
2θ(˚) Lithium slag content (%)
(a) XRD pattern of concrete with different (b) CH orientation
contents of lithium slag

r
B
before corrosion.
-p
Fig. 19. XRD pattern and CH orientation of concrete with different contents of lithium slag
re
G:Gypsum P:Ca(OH)2 S1-L00 1.6
A:CaCO3 E:Ettringite 1.42
S1-L20
C:C4A3S G S1-L40
lP

S:SiO2 1.20 1.21

1.2
Intensity(a.u.)

CH orientation

B:C2S
S
G E GEE A E BPE C C S
S
na

0.8

0.4
ur
Jo

0.0
10 20
40 50 60 70 30 0 20 40
2θ(˚) Lithium slag content (%)
(a) XRD pattern of concrete with different (b) CH orientation
contents of lithium slag
Fig. 20. XRD patterns and CH orientation of concrete with different contents of lithium slag
under Class S1 simulated acid rain corrosion action.
637
638 (2) Effect of simulated acid rain types

639 Hydration products were analysed by XRD under Class S2 simulated acid rain corrosion

640 action (pH value = 3.5 and SO42- = 0.01 mol/L) and Class S3 simulated acid rain corrosion

641 action (pH value = 2.5 and SO42- = 0.06 mol/L), and the CH orientation was calculated as

642 shown in Fig. 21(a). From Fig. 21(a), there are no new hydration products generated

643 compared with concrete with 20% lithium slag before corrosion. With increasing pH values,

33
644 the peak intensity of CH decreased. Under simulated acid rain corrosion action, CH can be

645 assumed; therefore, the peak intensity of CH was weak. According to Fig. 21(b), the CH

646 orientation showed a decreasing trend with increasing pH values. Compared with Fig. 19(b)

647 and Fig. 20(b), the CH orientation of concrete with 20% lithium slag with pH value = 2.5 at

648 the same concentration of SO42- was 19.8% smaller than the CH orientation with pH value =

649 3.5. This result indicated that the pH value had a great influence on the hydration products

650 and CH orientation.

In addition, Fig. 21(a) also shows that with the increase in the concentration of SO42-, the

f
651

oo
652 peak intensity of ettringite and gypsum of concrete with 20% lithium slag increased. The

r
653 amount of gypsum produced in concrete with 20% lithium slag with SO42- = 0.06 mol/L was
-p
654 obviously greater than the amount of gypsum produced in concrete with SO42- = 0.01 mol/L.
re
655 Ca2+ can react with SO42− in the acid solution, resulting in the formation of CaSO4·2H2O,
lP

656 which precipitates as gypsum after saturation. With increasing corrosion age, a large amount
na

657 of ettringite and gypsum destroyed the internal structure and reduced the compactness of the
ur

658 concrete to affect the compressive strength. Therefore, at the same pH value, the compressive
Jo

659 strength of concrete with 20% lithium slag with SO42- = 0.06 mol/L was lower than that with

660 SO42- = 0.01 mol/L. From Fig. 21(b), with the increase in the concentration of SO42-, the CH

661 orientation of concrete with 20% lithium slag at the same pH value exhibited an increasing

662 trend. The CH orientation of concrete with 20% lithium slag with SO42- = 0.06 mol/L was

663 12.4% larger than that with SO42- = 0.01 mol/L. It indicated that the concentration of SO42-

664 can obviously affect the hydration products and CH orientation of concrete with 20% lithium

665 slag.

34
 G:Gypsum S2-L20(pH=3.5, SO42-=0.01) 1.5 1.45
A:CaCO3 1.36
2-
C:C4A3S S3-L20(pH=2.5, SO4 =0.06)
S:SiO2 1.2

CH orientation
G
Intensity(a.u.)

P:Ca(OH)2
E:Ettringite
0.9

0.6
S A C
E E PES C S
0.3

0.0
10 20 3040 50 60 70 pH value=3.5 pH value=2.5
2θ(˚) SO42-=0.01mol/L SO42-=0.06mol/L
(a) XRD pattern of concrete with 20% (b) CH orientation of concrete with 20%
lithium slag lithium slag

f
Fig. 21. XRD patterns and CH orientation of concrete containing 20% lithium slag under

oo
different simulated acid rain corrosion action.
667
3.6.2 TG/DTG analysis

r
668

669 (1) Effect of lithium slag content

-p
re
670 The effect of lithium slag on hydration products before corrosion was analysed by
lP

671 TG/DTG, as shown in Fig. 22. Figs. 22(a) and (b) show two endothermic peaks of concrete
na

672 with different contents of lithium slag before corrosion located at 50-200℃ and 600-800℃

673 were observed. The endothermic peak at approximately 50-200℃ corresponded to the
ur

674 dehydration of C-S-H gel, ettringite and physically-bonded water. The amounts corresponding
Jo

675 to the C-S-H gel, ettringite and physically bonded water in the powder specimens were

676 calculated and are tabulated in Table 8. As shown in Table 8, the amount of C-S-H gel,

677 ettringite and physically bonded water increased with increasing lithium slag content. The

678 amount of C-S-H gel, ettringite and physically bonded water in concrete with 40% lithium

679 slag increased by 42.3% compared with the blank. The endothermic peak at 600-800℃ was

680 the endothermic decomposition of CaCO3. Based on the TG/DTG data, the hydration degree

681 of concrete with different contents of lithium slag before corrosion is shown in Fig. 22(c). The

682 hydration degree increased with increasing lithium slag at the same curing age, which

683 illustrated that more C-S-H gel was produced in concrete with lithium slag than in control

35
684 samples without lithium slag. With 20% lithium slag, the hydration degree of concrete

685 increased by 38.8%. Compared with the hydration degree of the control samples without

686 lithium slag, the hydration degree of concrete with 40% lithium slag was higher,

687 corresponding to a higher mechanical strength, illustrating that the addition of lithium slag

688 can promote the hydration degree, increase the hydration products and enhance the

689 compressive strength.

690 Two stages of concrete with different contents of lithium slag after corrosion under Class

S1 simulated acid rain corrosion action (pH value = 2.5 and SO42- = 0.01 mol/L) still existed,

f
691

oo
692 as shown in Figs. 23(a) and (b). As shown in Table 8, the amount of C-S-H, ettringite and

r
693 -p
physically bonded water in concrete with different contents of lithium slag decreased with

694 increasing corrosion age. The maximum decrease rate of concrete was 28.3%, that is, the
re
695 concrete with 40% lithium slag, corresponding to that the compressive strength of concrete
lP

696 with lithium slag decreasing with increasing corrosion age. From Fig. 23(c), the hydration
na

697 degree of concrete after corrosion increased with increasing lithium slag content. The
ur

698 hydration degree of concrete with 40% lithium slag was the highest among the other contents
Jo

699 of lithium slag, but the hydration degree of concrete after corrosion was lower than the

700 hydration degree before corrosion, which was related to the decrease in compressive strength

701 after corrosion.

100 0.00
L00
95 -0.05
DTG(mass %/℃)

L20
TG-mass loss(%)

L40
90 -0.10
85 -0.15
80 -0.20
75 -0.25 L00
L20
70 -0.30 L40

65 -0.35
200 400 600 800 1000 200
400 600 800 1000
Temperature(℃) Temperature(℃)
(a) TG pattern of concrete with different (b) DTG pattern of concrete with different

36
 contents of lithium slag contents of lithium slag
90 83.2%
80
79.9%

Hydration degree(%)
70 64.1%
60
38.8%
50
40
30
20
10
0
0 20 40
lithium slag content(%)
(c) Hydration degree of concrete with different contents of lithium slag

f
oo
Fig. 22. TG/DTG patterns and hydration degree of concrete with different contents of lithium
slag before corrosion.
100 0.00

r
S1-L00
95 S1-L20 -p-0.05
DTG(mass %/℃)
TG-mass loss(%)

S1-L40
90 -0.10
re
85 -0.15
80 -0.20
lP

-0.25 S1-L00
75
-0.30 S1-L20
70
na

S1-L40
-0.35
65
200 400 600 800 1000 200 400 600 800 1000
ur

Temperature(℃) Temperature(℃)
(a) TG pattern of concrete with different (b) DTG pattern of concrete with different
Jo

contents of lithium slag contents of lithium slag

90
79.7%
80
Hydration degree(%)

70 73.1% 66.4%
60
44.1%
50
40
30
20
10
0
0 20 40
lithium slag content(%)
(c) Hydration degree of concrete with different contents of lithium slag
Fig. 23. TG/DTG patterns and hydration degree of concrete with different contents of lithium
slag under Class S1 simulated acid rain corrosion action.
704
705
706

37
707 Table 8 The amount of C-S-H gel, ettringite and physically bonded water in the concrete
Lithium The amount of C-S-H gel, ettringite and physically bonded Decrease
No. Slag water (%) rate (%)
(%) Before corrosion After corrosion
L00 0 3.7 3.5 5.4
L20 20 4.2 3.6 14.3
L40 40 5.3 3.8 28.3
708
709 (2) Effect of simulated acid rain types

710 The hydration products of concrete with 20% lithium slag under Class S2 simulated acid

711 rain corrosion action (pH value = 3.5 and SO42- = 0.01 mol/L) and Class S3 simulated acid

f
712 rain action (pH value = 2.5 and SO42- = 0.06 mol/L) were evaluated via TG/DTG. From the

oo
713 results shown in Figs. 24(a) and (b), two major mass loss steps can also be seen. C-S-H,

r
714 -p
ettringite and CaCO3 were still the main hydration products. At the same concentration of
re
715 SO42-, the amount of C-S-H gels, ettringite and physically bonded water of concrete with 20%
lP

716 lithium slag increased with increasing pH values. The amount of C-S-H gels, ettringite and

717 physically bonded water in concrete with 20% lithium slag with pH value = 3.5 was 13.9%
na

718 higher than those parameters with pH value = 2.5, as shown in Table 9. According to Fig.
ur

719 24(c), the hydration degree of concrete with 20% lithium slag decreased with increasing pH
Jo

720 values. The hydration degree of concrete with 20% lithium slag with pH value = 3.5

721 decreased by 9.2% compared with the degree of hydration of concrete with pH value = 2.5.

722 The pH value has been proven to obviously affect the amount of hydration products through

723 the influence on the degree of hydration, thus affecting the corrosion resistance of concrete

724 with 20% lithium slag.

725 Fig. 24 shows that with the increase in the concentration of SO42-, the mass loss steps of

726 C-S-H gels, ettringite and physically bonded water presented an increasing trend. The amount

727 of C-S-H gels, ettringite and physically bonded water was calculated, as shown in Table 9.

728 The amount of C-S-H gels, ettringite and physically bonded water of concrete with 20%

729 lithium slag with SO42- = 0.06 mol/L increased by 36.1% compared with that with SO42- =

38
730 0.01 mol/L. According to Fig. 20(c), the hydration degree of concrete with 20% lithium slag

731 decreased with increasing the concentration of SO42-. The hydration degree of concrete with

732 20% lithium slag with SO42- = 0.06 mol/L decreased by 14.9% compared with the hydration

733 degree with SO42- = 0.01 mol/L, illustrating that the concentration of SO42- can obviously

734 affect the hydration degree of concrete with 20% lithium slag, further affecting the corrosion

735 resistance of concrete with 20% lithium slag.

100 0.00
95 -0.05

DTG(mass %/℃)

f
TG-mass loss(%)

-0.10

oo
90
85 -0.15
-0.20

r
80
75
S2-L20(pH=3.5, SO42-=0.01)
-p -0.25
-0.30 S2-L20(pH=3.5,SO42-=0.01)
re
70 S3-L20(pH=2.5,SO42-=0.06)
S3-L20(pH=2.5, SO42-=0.06) -0.35
65
200 400 600 400 200
600 800 1000
lP

800 1000
Temperature(℃) Temperature(℃)
(a) TG pattern of concrete with 20% lithium (b) DTG pattern of concrete with 20%
na

slag under different simulated acid rain lithium slag under different simulated acid
corrosion action rain corrosion action
60.3
60
ur

56.5
Hygdration degree(%)

50
Jo

40
30
20
10
0
pH value=3.5 pH value=2.5
SO42-=0.01mol/L SO42-=0.06mol/L
(c) Hydration degree decrease rate of concrete
Fig. 24. TG/DTG patterns and hydration degree of concrete with 20% lithium slag under
different simulated acid rain corrosion action.
737
738 Table 9 The amount of C-S-H gel, ettringite and physically bonded water in the concrete
No. pH Concentration of The amont of C-S-H gels, ettringite and
value SO42- (mol/L) physically bonded water (%)
S2-L20 3.5 0.01 4.1
S3-L20 2.5 0.06 4.9

39
739 3.6.3 SEM analysis

740 (1) Effect of lithium content

741 Fig. 25 shows the SEM images of specimens with different contents of lithium slag

742 under Class S1 simulated acid rain corrosion action (pH value = 2.5 and SO42- = 0.01 mol/L)

743 at different magnifications. Figs. 25(a), (b) and (c) present the SEM images of control samples

744 without lithium slag, with 20% and 40% lithium slag, respectively. Fig. 25(a) show that the

745 internal porosity of control concrete without lithium slag was large, and a large number of

microcracks appeared in concrete to accelerate the secondary diffusion of H+ and SO42-.

f
746

oo
747 Therefore, the internal porosity brought potential hidden dangers to the concrete structure,

r
748 -p
increased the mass loss and decreased the compressive strength on the macrolevel. Fig. 25(b)

749 show that the microstructure of specimens with 20% lithium slag was relatively dense, the
re
750 number of microcracks was few, and small amounts of ettringite appeared on the surface of
lP

751 concrete with 20% lithium slag. Fig. 25(c) show that the internal structure of concrete with
na

752 40% lithium slag was dense because lithium slag has a certain pozzolanic effect and fill effect,
ur

753 and adding lithium slag into concrete can refine the holes in concrete to improve the
Jo

754 compactness. Meanwhile, lithium slag replacing part of the cement can reduce the generation

755 of hydration products CH to decrease the alkaline hydration products and C-S-H gels are

756 converted into nongelling products, resulting in a decrease in concrete strength and stability.

757 Therefore, the mass loss and compressive strength decrease rate of concrete with lithium slag

758 declined, and the neutralization depth of concrete with lithium slag increased with increasing

759 corrosion age. However, the neutralization depth of concrete with 40% lithium slag is still less

760 than 2.25 mm.

40
 f
(a) SEM image of control samples without (b) SEM image of concrete with 20% lithium

oo
lithium slag slag

r
-p
re
lP
na
ur
Jo

(c) SEM image of concrete with 40% lithium slag

Fig. 25. SEM images of concrete with different contents of lithium slag under Class S1
simulated acid rain corrosion action.
761
762 (2) Effect of simulated acid rain types

763 The microstructure of corrosion products of concrete with different contents of lithium

764 slag under simulated acid rain corrosion action with different pH values and different

765 concentrations of SO42- can be analysed intuitively through SEM.

766 Fig. 26 shows the SEM images of specimens with 20% lithium slag under different

767 simulated acid rain corrosion actions. Figs. 26(a) and (b) present the SEM images of concrete

768 with 20% lithium slag under Class S2 simulated acid rain corrosion action (pH value = 3.5

769 and SO42- = 0.01 mol/L) and Class S3 simulated acid rain corrosion action (pH value = 2.5

41
770 and SO42- = 0.06 mol/L), respectively. Fig. 26(a) show the quantity of large holes and cracks

771 in concrete with 20% lithium slag under Class S2 simulated acid rain corrosion action. A

772 number of large cracks in concrete with 20% lithium slag under Class S3 simulated acid rain

773 corrosion action were observed, according to Fig. 26(b). In the early corrosion ages, the low

774 pH value, i.e., high concentration of H+, played a major role. The increase in microcracks and

775 porosity provided a new channel for H+ and SO42- and accelerated the diffusion rate of H+ and

776 SO42-. The low concentration of H+ can decrease the reaction between H+ and CH. Few C-S-H

f
777 gels were converted into silica gel to ensure the strength and stability of the concrete.

oo
778 Moreover, with increasing concentration of SO42-, ettringite was produced to fill the cracks

r
779 -p
and micropores of concrete and to enhance the density of the concrete. With the increase in

780 the number of dry-wet cycles, cracks and exfoliation were caused by the expansion products,
re
781 such as ettringite. Finally, the increase in the number of cycles led to a decrease in concrete
lP

782 strength and deterioration of durability. Therefore, macroscopically, the mass loss,
na

783 compressive strength decrease rate, and neutralization depth increased.

ur
Jo

(a) SEM image under Class S2 simulated acid (b) SEM image under Class S3 simulated
rain corrosion action acid rain corrosion action
Fig. 26. SEM images of concrete with 20% lithium slag under different simulated acid rain
corrosion action.
784
785 3.6.4 EDS analysis

786 (1) Effect of lithium slag content

42
787 The EDS test was used to analyse the chemical components of the C-S-H gels before

788 corrosion, as shown in Fig. 27. Based on the Figs. 27(a), (b) and (c), the effect of lithium slag

789 on the Ca/Si of the C-S-H gels can be evaluated before corrosion. The Ca/Si of the C-S-H gels

790 of concrete with different contents of lithium slag before corrosion is shown in Fig. 27(d).

791 With the increase in lithium slag content, the Ca/Si decreased. The Ca/Si of concrete with

792 20% lithium slag was 35.2% lower than the Ca/Si of control samples without lithium slag,

793 The Ca/Si of concrete with 40% lithium slag decreased 75.2% compared with control samples

f
794 without lithium slag. The addition of lithium slag replacing part of the cement can form C-S-

oo
795 H gels with low Ca/Si, which has a positive effect on the compressive strength.

r
796 -p
The Ca/Si of concrete with different contents of lithium slag after corrosion under Class

797 S1 simulated acid rain corrosion action (pH value = 2.5 and SO42- = 0.01 mol/L) was studied
re
798 by EDS, as shown in Fig. 28. The Ca/Si of concrete decreased with increasing lithium slag
lP

799 content. Among these values, the smallest Ca/Si of concrete was 0.76, that is, the Ca/Si of
na

800 concrete with 40% lithium slag, followed by the concrete with 20% lithium slag, which was
ur

801 1.17, and the Ca/Si of control concrete without lithium slag was the largest, i.e., 1.65.
Jo

802 Obviously, the Ca/Si of concrete with lithium slag was smaller than the Ca/Si of control

803 concrete without lithium slag. Moreover, the Ca/Si of concrete decreased with increasing

804 lithium slag content after corrosion, once again demonstrating that lithium slag has significant

805 resistance to acid rain corrosion.

(a) EDS image of control concrete without (b) EDS image of concrete with 20% lithium

43
 lithium slag slag
1.6
1.45

1.2 -35.2%

0.94 -75.2%

Ca/Si
0.8

0.4 0.36

0.0
10 20 40
Lithium slag content (%)
(c) EDS image of concrete with 40% lithium (d) The Ca/Si of concrete with different
slag contents of lithium slag

f
Fig. 27. EDS images and the Ca/Si of concrete with different contents of lithium slag before

oo
corrosion.

r
-p
re
lP
na

(a) EDS image of control concrete without (b) EDS image of concrete with 20% lithium
ur

lithium slag slag

1.8
Jo

1.65
1.5 -29.1%
1.17 -53.9%
1.2
Ca/Si

0.9 0.76
0.6
0.3
0.0
10 20 40
Lithium slag content (%)
(c) EDS image of concrete with 40% lithium (d) The Ca/Si of concrete with different
slag contents of lithium slag
Fig. 28. EDS images and the Ca/Si of concrete containing different lithium slag content under
Class S1 simulated acid rain corrosion action .
809
810 (2) Effect of simulated acid rain types

811 The EDS images of concrete with 20% lithium slag under Class S2 simulated acid rain

44
812 corrosion action (pH value = 3.5 and SO42- = 0.01 mol/L) and Class S3 simulated acid rain

813 corrosion action (pH value = 2.5 and SO42- = 0.06 mol/L) were illustrated the content

814 variation of the principal elements including Ca and Si of C-S-H gels under different

815 simulated acid rain corrosion action, as shown in Figs. 29(a) and (b). Clearly there is less Ca

816 but more Si in the C-S-H gels generated in lithium slag with pH value = 2.5. The Ca/Si was

817 calculated as shown in Fig. 29(c). With the increase in the concentration of H+, the Ca/Si of

818 concrete with 20% lithium slag decreased. The Ca/Si of C-S-H gels of concrete with 20%

f
819 lithium slag with pH value = 2.5 was 32.8% lower than the Ca/Si of C-S-H gels with pH value

oo
820 = 3.5. This phenomenon is consistent with the corrosion mechanism of simulated acid rain on

r
821 concrete with 20% lithium slag. With the increase in the concentration of H+, more H+ can
-p
822 react with CH to reduce the content of Ca in C-S-H. This result indicated that the pH values
re
823 have an obvious effect on the Ca/Si of C-S-H gels, which was related to the decrease in
lP

824 compressive strength after corrosion.

na

825 Fig. 29 also shows that with increasing concentration of SO42-, the Ca/Si of the C-S-H
ur

826 gels increased. The Ca/Si of C-S-H gels of concrete with 20% lithium slag with SO42- = 0.06
Jo

827 mol/L was 16.2% higher than the Ca/Si of C-S-H gels with SO42- = 0.01 mol/L. SO42- can

828 react with the component (unhydrated C3A, AFm, CH, etc.) to produce gypsum to fill the

829 pores and cracks, which led to an increase in Ca/Si. The increase in the Ca/Si of concrete with

830 20% lithium slag represented the decrease in compressive strength with increasing corrosion

831 age.

45
 (a) EDS image of concrete with 20% lithium (b) EDS image of concrete with 20% lithium
slag under Class S2 simulated acid rain slag under Class S3 simulated acid rain
corrosion action corrosion action

f
oo
1.8 1.74

1.5

r
1.36
1.2 -p
Ca/Si

0.9
re
0.6
lP

0.3
0.0
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pH value=3.5 pH value=2.5
SO4 =0.01mol/L SO42-=0.06mol/L
2-
(c) The Ca/Si of concrete with 20% lithium slag
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Fig. 29. EDS images and the Ca/Si of concrete with 20% lithium slag under different
simulated acid rain corrosion action
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832
833 4. Conclusions

834 This study explored the fresh properties (setting time and workability), appearance, mass,

835 compressive strength and the neutralization depth of concrete with lithium slag under

836 different simulated acid rain corrosion actions. In addition, the microscopic mechanisms have

837 been analysed to examine the effect of lithium slag content, pH values and the concentration

838 of SO42- on the corrosion degree of concrete. From this study, the following conclusions can

839 be drawn.

840 (1) The addition of lithium slag can decrease the workability of concrete. By adding

46
841 1.05% of SP, the concrete with 40% lithium slag can achieve a slump value similar to the

842 control concrete without lithium slag. With the increase of lithium slag content, the setting

843 time of concrete was shortened. The initial and final setting time of concrete with 40% lithium

844 slag were 89.6% and 74.3% lower than the control samples without lithium slag, indicating

845 that the lithium slag can accelerate the cement hydration.

846 (2) The appearance damage of concrete was effectively reduced as the lithium slag was

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847 incorporated into concrete. A small number of corrosion holes appeared in the concrete with

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848 40% lithium slag and the apparent damage was relatively low. The low pH value and the high

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849
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concentration of SO42- made the microcracks exhibited on the surface of the concrete and
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850 aggravated the appearance damage of concrete. However, the appearance damage of concrete
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851 is more sensitive to the concentration of SO42-.

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852 (3) The appropriate content of lithium slag in concrete can not only increase the
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853 compressive strength but also improve the acid rain resistance property. Before the corrosion,
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854 the compressive strength of concrete with 40% lithium slag was 13.37% higher than the

855 compressive strength of concrete without lithium slag. At the corrosion ages of 100 days

856 under Class S1 simulated acid rain corrosion action, the compressive strength of concrete with

857 40% lithium slag was 23.40% higher than the compressive strength of control concrete

858 without lithium slag. High concentration of H+ or SO42- increased the compressive strength

859 decrease rate. However, within the research scope of this study, the concentration degradation

860 of compressive strength is more sensitive to the concentration of SO42- than H+.

861 (4) During the corrosion process, the addition of lithium slag can effectively reduce the

862 mass loss of concrete. The mass loss rate of concrete with 40% lithium slag was only 0.86%

47
863 and 58.65% less than the mass loss of control concrete without lithium slag under Class S1

864 simulated acid rain corrosion action. In the simulated acid rain corrosion action, with

865 increasing concentration of H+ or SO42-, the mass loss rate of concrete with 20% lithium slag

866 increased. Moreover, the mass loss rate was also more sensitive to the concentration of SO42-.

867 (5) The neutralization depth of concrete increased with the increase of the lithium slag

868 content. The neutralization depth of concrete with 40% lithium slag was 2.27 mm and

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869 increased by 37% under Class S1 simulated acid rain corrosion action. However, the

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870 maximum value of the neutralization depth of the concrete was also far less than the general

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871
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structural design of reinforced concrete protective layer thickness. With increasing
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872 concentration of H+ or SO42-, the neutralization depth of concrete containing lithium slag
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873 enlarged. However, the concentration of H+ has more obvious effect on the neutralization
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874 depth than concentration of SO42-.

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875 (6) Through microscopic analysis, the lithium slag can assume CH, decrease the CH
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876 orientation, form more hydration products, promote the hydration degree, improve the

877 compactness of the matrix and decrease the Ca/Si of C-S-H gels, thus enhancing the

878 compressive strength. In simulated acid rain corrosion action, the corrosion of the concrete

879 with lithium slag by acid rain is a coordinate effect of the concentration of H+ and SO42-. The

880 concentration of H+ and SO42- did not affect the types of erosion products, but increased the

881 hydration products and the hydration degree, decreased the Ca/Si of C-S-H gels, with the

882 increase of corrosion ages. Because of the above mechanisms, the corrosion resistance of

883 concrete was improved.

884 The concrete with lithium slag has good acid rain corrosion resistance property and

48
885 lithium slag can be used as an acid rain corrosion inhibitor. This research can not only provide

886 a way to solve the problem of lithium slag accumulation and pollution but also develop a

887 promising cement-based material used in acid rain corrosion areas.

888

889 Acknowledgments

890 The authors thank funding from the National Science Foundation of China (51968021),

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891 National Science Foundation for Post-doctoral Scientists of China (2022M713497), Jiangxi

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892 Provincial Natural Science Foundation (20202BAB204031 and 20202BABL214042),

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Department of Education of Jiangxi Province (GJJ210656).
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894
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55
Research highlight

1 Lithium slag can act as an acid rain corrosion inhibitor in concrete.

2 A self-designed indoor dry-wet cycle spraying equipment is used to simulate acid

rain corrosion.

3 Acid rain resistance performance of concrete is significantly enhanced by 40%

lithium slag.

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4 Concrete containing lithium slag can effectively solve environment pollution and

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stocking problem.

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Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal

relationships that could have appeared to influence the work reported in this paper.

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