materials
Article
Strength and Durability Properties of Antimony Tailing Coarse
Aggregate (ATCA) Concrete
Long Li, Jianqun Wang * , Longwei Zhang *, Renjian Deng






Citation: Li, L.; Wang, J.; Zhang, L.;
Deng, R.; Zhou, S.; Wang, G. Strength
and Durability Properties of
Antimony Tailing Coarse Aggregate
(ATCA) Concrete. Materials 2021, 14,
5606. https://doi.org/10.3390/
ma14195606
Academic Editor: Yann Malecot
Received: 26 August 2021
Accepted: 23 September 2021
Published: 27 September 2021
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iations.
Copyright: © 2021 by the authors.
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This article is an open access article
distributed under the terms and
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Attribution (CC BY) license (https://
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4.0/).
Materials 2021, 14, 5606. https://doi.org/10.3390/ma14195606
, Saijun Zhou and Gongxun Wang
Hunan Provincial Key Laboratory of Structures for Wind Resistance and Vibration Control, School of Civil
Engineering, Hunan University of Science and Technology, Xiangtan 411201, China;
lilong15173271886@163.com (L.L.); 800912deng@sina.com (R.D.); sjzhou@hnust.edu.cn (S.Z.);
wanggx@hnust.edu.cn (G.W.)
* Correspondence: jqw@hnust.edu.cn (J.W.); zhanglongwei@hnust.edu.cn (L.Z.)
Abstract: Antimony (Sb) is a trace element applied widely in modern industry. A large number of
tailing solid wastes are left and accumulated in the mining area after purifying the precious antimony
from the antimony ores, causing serious pollution to the environment. The major aim of this study
is to investigate the feasibility of utilizing antimony tailing coarse aggregate (ATCA) as a complete
substitute for natural coarse aggregate (NCA) in high-strength concrete. Concrete specimens with
25%, 50%, 75%, and 100% ATCA replacing the NCA in conventional concrete were prepared for
evaluating the performance of ATCA concrete. The investigators find that ATCA concrete has good
workability, and the mechanical properties and long-term behavior (shrinkage and creep) of ATCA
concrete with all replacement levels are superior to those of NCA concrete. The durability indices
of ATCA concrete, such as the frost-resistant, chloride permeability, and resistance to carbonation,
are better than those of NCA concrete. While the alkali activity and cracking sensitivity behavior
of ATCA concrete seem to be decreased, nevertheless, the difference is not significant and can be
neglected. The researchers demonstrate that all of the control indices of ATCA concrete meet the
requirements of the current industry standards of China. Overall, ATCA can be used in concrete to
minimize environmental problems and natural resources depletion.
Keywords: antimony tailing waste rock (ATWR); antimony tailing coarse aggregate (ATCA); natu-
ral coarse aggregate (NCA); construction performance; mechanical property; long-term behavior;
durability performance
1. Introduction
Concrete is one of the most popularly used building and construction materials and
has been widely researched [1–3]. In recent years, the green and sustainable produc-
tion of concrete has received much attention [4–6]. Coarse aggregate (CA), as the largest
component of the concrete mix ratio, has continued to be increased in recent years. There-
fore, a large number of quarries are mined, negatively impacting the environment. The
traditional ways to produce CA are not sustainable. Therefore, researchers are actively
searching for substitutes for aggregates with minimum or no negative impact on the natural
resources [7,8]. Some new eco-friendly concrete, including tailing concrete, recycled aggre-
gate concrete, and waste ceramic aggregate concrete, have been extensively researched and
successfully applied in civil engineering [9].
China is the largest consumer and producer of concrete in the world. Meanwhile,
China has the richest antimony deposits in the world and produces millions of tons of
antimony ore tailing. Since the beginning of the 20th century, China has become the world’s
largest producer of antimony and its compounds [10]. A large number of tailing solid
wastes are accumulated in the mining area after purifying the precious antimony from the
antimony ores. To dispose these solid wastes, it is necessary to build large tailing dams
and take strict isolation measures, which require the use of additional land and cost [11].
https://www.mdpi.com/journal/materials
Materials 2021, 14, 5606 2 of 15

Metal tailing has long been considered a worldwide environmental problem for the
earth and aquatic pollution [12,13]. These solid wastes release harmful elements under
the action of alternation of dry and wet conditions, high and low temperatures, and even
freeze and thaw conditions. These hazard elements enter into the soil and surrounding
rivers via the runoff and infiltration of rainwater [14,15], which not only cause pollution to
the surrounding environment of the mining area but also move to other living areas [16].
In order to deal with these solid waste materials, extensive research has been conducted
around the world, and some treatment methods have been developed. A feasible method
is to utilize the metal tailing in concrete as a partial or complete substitution for aggregate.
In this way, low-cost green concrete is obtained, and meanwhile, harmful substances can
be solidified in the concrete [17,18].
Onuaguluchi and Eren [19,20] investigated the feasibility of using copper tailing as
a partial substitute of cement for mortars material. It was demonstrated that the copper
tailing led to an improvement in mechanical strength, abrasion resistance, and resistance
to chloride penetration. Blessen et al. [21] conducted an experiment on concrete containing
copper tailing as fine aggregate, which indicated that the maximum replacement amount
was 60%. Sharma et al. [22] reported the reuse of copper tailing as a substitute for natural
sand in self-compacting concrete. It was shown that, compared with controlled samples,
even with 100% copper slag reused as a substitute for natural sand, the concrete possessed
a better mechanical strength and absorption properties. Huang et al. [23] utilized copper
tailing in autoclaved aerated concrete and proposed an effective method to decrease the
CO2 emission in the concrete production process.
Zhao et al. [24] studied different substitute levels of iron ore tailing (IOT) for natural
sand in ultra-high-performance concrete. Test results showed that the mechanical behavior
of concrete with no more than 40% natural sand replaced was nearly the same with the
controlled sample. Shettima et al. [25] evaluated the performance of concrete with different
substitute amount of IOT as natural sand. Test results indicated that IOT had little negative
effect on the construction performance, while mechanical strength was superior to the
control specimen. Lv et al. [26] carried out a series of experiments to investigate the behavior
of dam concrete with IOT as natural aggregate. It was demonstrated that the tailing
aggregate concrete could possess a comparable mechanical behavior and frost-resistant
performance with superior thermal performance. Liu et al. [27] studied the sprayed
concrete containing IOT substituted for the natural sand and suggested the best substitution
was 20%. IOT was also utilized in green engineered cementitious composites [28], metal
tailing porous concrete [29], and steam-cured precast concrete [30]. In addition, tungsten
ore tailing [31], gold ore tailing [32], zinc ore tailing [33], and molybdenum ore tailing [34]
were also reported for reusing in concrete. Wang investigated the feasibility of utilizing
antimony tailing waste rock (ATWR) for a practical project, providing a new way for
utilizing ATWRs [35]. It is demonstrated that all of the quality control indices of antimony
tailing coarse aggregate (ATCA) meet the requirements of the current industry standards
of China.
As mentioned above, although the literature on other metal ore tailing utilizing in
concrete is relatively rich, little investigation on the utilization of antimony ore tailing as
CA has been reported. The goal of this research is to study the feasibility of ATCA as
a complete substitute for natural coarse aggregate (NCA). The workability, mechanical
property, long-term performance, and durability of ATCA concrete and NCA concrete are
studied and compared in the present work.
The rest of this paper is organized as follows. Section 2 introduces the materials and
mix ratio of ATCA concrete. Section 3 describes the workability of fresh ATCA concrete,
such as slump, air content, setting time, and apparent density and so on. Section 4 illustrates
the mechanical property of ATCA concrete, including cubic compressive strength, splitting
tensile strength, prism compressive strength, and elasticity modulus. Section 5 shows the
long-term behavior of ATCA concrete, including drying shrinkage and creep. Section 6
researches the durability performance of ATCA concrete, involving freezing and thawing,
 shows the long-term behavior of ATCA concrete, including drying shrinkage and c
Section 6 researches the durability performance of ATCA concrete, involving freezing
thawing, alkali activity, chloride ion penetration, cracking sensitivity, and carbona
Materials 2021, 14, 5606 Finally, Section 7 concludes the article and gives some recommendations3forof 15future w

2. Materials and Mix Ratio of Concrete

2.1. Materials
alkali activity, chloride ion penetration, cracking sensitivity, and carbonation. Finally,
Section 7 concludes the article and gives some recommendations for future work.
2.1.1. Cement
2. Materials
In thisand Mix Ratio of Concrete
investigation, Ordinary Portland cement with a strength class of 42.5, i
2.1. Materials
cordance with Chinese Standard GB 175-2007 was used [36]. For the cement, the sp
2.1.1. Cement
gravity was 3130 kg/m3, the specific surface area was 312 m2/kg, the normal consistency
In this
27.7%, andinvestigation,
the initial andOrdinary Portland
final setting timecement with
was 168 mina and
strength class respectively.
207 min, of 42.5, in The
accordance with Chinese Standard GB 175-2007 was used [36]. For the cement, the specific
pressive strength of cement mortar at 3 days, 7 days, and 28 days iwas 26.7 MPa, 38.5
gravity was 3130 kg/m3 , the specific surface area was 312 m2 /kg, the normal consistency
and 52.8 MPa, respectively. The main chemical composition of cement is shown in Tab
was 27.7%, and the initial and final setting time was 168 min and 207 min, respectively.
The compressive strength of cement mortar at 3 days, 7 days, and 28 days iwas 26.7 MPa,
Table
38.5 MPa and1.52.8
TheMPa,
mainrespectively.
chemical composition of cement
The main chemical (%).
composition of cement is shown
in Table 1. −
CaO SiO2 Al2O3 Fe2O3 MgO SO3 Cl Los
56.1 34.6 The main chemical composition
Table 1.0.8 1.1 of cement3.25
(%). 2.3 0.024 4.35
CaO SiO2 Al2 O3 Fe2 O3 MgO SO3 Cl− Loss
2.1.2.
56.1Aggregate
34.6 0.8 1.1 3.25 2.3 0.024 4.35
The ATWR was obtained by 5-point sampling method in the antimony wast
stacking
2.1.2. area in Xikuangshan (XKS). The XKS Sb mine, located near Lenshuijiang
Aggregate
Hunan Province,
The ATWR was China,
obtainedisbythe5-point
largest Sb mines
sampling in the
method world
in the [37–39].
antimony Due
waste oreto Sb m
stacking area in Xikuangshan (XKS). The XKS Sb mine, located near Lenshuijiang
and smelting processes, a large number of tailing solid wastes are left and accumulat City,
Hunan Province,
the mining areaChina, is the
[40,41]. largestthe
During Sb field
minesinvestigation,
in the world [37–39]. Due to found
the authors Sb mining
that there
and smelting processes, a large number of tailing solid wastes are left and accumulated in
millions of tons of ATWRs in XKS (Figure 1). These ATWRs occupy valuable lan
the mining area [40,41]. During the field investigation, the authors found that there were
sources,
millions of resulting in serious
tons of ATWRs in XKS Sb contamination
(Figure of the
1). These ATWRs localvaluable
occupy environments [42,43]. The
land resources,
pled ATWR was mixed and crushed into ATCA, of which the particle
resulting in serious Sb contamination of the local environments [42,43]. The sampled ATWRsize was 5 mm
mm.
was mixed and crushed into ATCA, of which the particle size was 5 mm–20 mm.

Figure1. 1.
Figure TheThe ATWRs
ATWRs in Xikuangshan
in Xikuangshan (XKS)
(XKS) Sb mine.Sb mine.

2.2. Mix Ratio of Concrete

2.2. Mix Ratio of Concrete
The concrete mix proportion was determined through multiple trial mixes with the
The
absolute concrete
volume mix Poly-carboxylate
method. proportion wassuperplasticizer
determined through
was added multiple trialwith
to concrete mixes wit
absolute
0.2% by thevolume
weight ofmethod. Poly-carboxylate
cementitious materials. Tablesuperplasticizer was added
2 shows the five batches to concrete
of mixture
proportions.
0.2% by theT0weight
was theofcontrol mix with NCA.
cementitious While Table
materials. in the other 4 mixes,
2 shows theT25,
fiveT50, T75, of mi
batches
T100, the NCA in the samples was substituted by ATCA, with different levels of
proportions. T0 was the control mix with NCA. While in the other 4 mixes, T25, T50,25%, 50%,
75%, and 100%, respectively.
T100, the NCA in the samples was substituted by ATCA, with different levels of 25%,
75%, and 100%, respectively.
Materials 2021, 14, 5606 4 of 15

Table 2. Mix ratio of the concrete (unit: kg/m3 ).

ATCA Proportion
Description
T0 T25 T50 T75 T100
Cement 485 485 485 485 485
NCA 1047 785.3 523.5 261.8 0
ATCA 0 261.8 523.5 785.3 1047
Manufactured sand 758 758 758 758 758
Water 160 160 160 160 160
Superplasticizer 5.8 5.8 5.8 5.8 5.8

3. The Workability of Fresh Concrete

3.1. Experiment Methodology
The workability of fresh concrete is a key factor in assessing whether it can be applied
to construction projects. CA is the largest component of the concrete mix ratio, playing an
important role as the skeleton. The shape and particle size of CA will affect the construction
performance of concrete. The slump, air content, setting time, and apparent density was
tested based on the Chinese Standard GB/T 50080-2016 [44]. The workability of fresh
concrete is illustrated and assessed in the following subsection.

3.2. Results and Discussion

The workability of fresh concrete, such as the slump, setting time, air content, and
apparent density, is listed in Table 3. It is demonstrated that all indexes meet specification
requirements [44–46]. The apparent density of ATCA concrete was slightly higher than that
of NCA concrete, and the value was only 1%. Other indices decrease with the increasing
replacement amount of ATCA. Nevertheless, it was explicitly found that the difference in
workability between ATCA and NCA concrete was very small. It can be inferred that the
influence of CA on concrete construction performance was negligible.

Table 3. The test results of fresh concrete.

Slump (mm) Air Content (%) Setting Time (min) Apparent Density
Series
0h 1h 0h 1h Initial Final (kg/m3 )

T0 198 187 3.8 2.9 398 570 2445

T25 195 183 3.7 2.8 389 565 2451
T50 192 182 3.7 2.7 380 556 2461
T75 188 179 3.4 2.7 372 547 2468
T100 185 175 3.3 2.6 365 540 2475

4. Mechanical Property Experiments

4.1. Specimen Design
It is important to understand the development of strength, especially at the early
age of concrete structures [47,48]. The mechanical properties, such as cubic compressive
strength, splitting tensile strength, prism compressive strength, and elasticity modulus,
were conducted to investigate the ATCA as a complete substitute for NCA in high strength
concrete in this study. The early age and long-term mechanical properties were tested at the
curing age of 3, 7, 28, 90, and 180 days. The test methods were based on Chinese Standard
GB/T 50081-2019 [49]. The dimensions of the specimens used for the experimental study
are listed in Table 4.
No. Experiments Sample Shape Sampl
1 Cubic compressive strength Cube 150 ×
2 Splitting
Materials 2021, 14, 5606 tensile strength Cube 5 of 15 150 ×
3 Prism compressive strength Prism 150 ×
4 Elasticity modulus Prism 150 ×
Table 4. Dimensions of the concrete specimens for mechanical property experiments.

No. Experiments Sample Shape Sample Size (mm)

4.2. Results and Discussion
1 Cubic compressive strength Cube 150 × 150 × 150
4.2.1. 2Compressive Strength
Splitting tensile strengthof CubicCube
Sample 150 × 150 × 150
3 Prism compressive strength Prism 150 × 150 × 300
As
4 illustrated it inmodulus
Elasticity Figure 2,
seen canPrism
be that150the difference
is v
× 150 × 300

first 3 days. However, the measured values of compressive strength o

4.2. Results and Discussion
at theCompressive
4.2.1. 28th dayStrength
were of 58.9
CubicMPa,
Sample61.5 MPa, 63.5 MPa, and 64.5 MPa, whi
110%, and 112%
As illustrated of the
in Figure controlled
2, it can be seen thatsample (T0),
the difference respectively.
is very small during theMoreov
first 3 days. However, the measured values of compressive strength of T25, T50, T75, T100
age was 180 days, the results of compressive strength of T25, T50, T
at the 28th day were 58.9 MPa, 61.5 MPa, 63.5 MPa, and 64.5 MPa, which were 102%, 108%,
107%,
110%, and 110%,
112% ofand 116% of
the controlled the(T0),
sample controlled
respectively.sample, respectively.
Moreover, when the curing ageTheref
was 180 days, the results of compressive strength of T25, T50, T75, T100 were 102%, 107%,
ered that the compressive strength of ATCA concrete at all replacem
110%, and 116% of the controlled sample, respectively. Therefore, it can be considered that
rior to that of
the compressive the NCA
strength of ATCAconcrete atreplacement
concrete at all all curing ages.
levels was Furthermore,
superior to that of the c
the NCA concrete at all curing ages. Furthermore, the
of the concrete increases with the increasing replacement compressive strength of the concrete
level of AT
increases with the increasing replacement level of ATCA.

80
T0
70 T25
T50
Compressive strength (MPa)

60 T75
T100
50

40

30

20

10

0
3d 7d 28d 90d 180d
Figure 2. The test results of compressive strength of cubic sample.
Figure 2. The test results of compressive strength of cubic sample.
4.2.2. Splitting Tensile Strength of Cubic Sample
The tensile strength of concrete is a vital factor in evaluating the crack resistance of
4.2.2. Splitting Tensile Strength of Cubic Sample
structures [50]. The splitting tensile strength of the cubic sample was tested simultaneously
with theThe tensile strength.
compressive strength Theof concrete
results are shown isinaFigure
vital3.factor in evaluating
The measured values th
of splitting tensile strength of T25, T50, T75, T100 at 28 days are 3.92 MPa, 4.01 MPa,
structures [50].
4.11 MPa, and 4.17 The
MPa, splitting
which were 101%,tensile
103%, 106%,strength
and 107% of ofthethe cubicsample,
controlled sample w
ously with
respectively. At the compressive
180 days, strength.
the tested results of splittingThe results
tensile strength are shown
of T25, T50, T75,in Figu
T100 were 103%, 106% 108%, and 110% of the control. The development tendency of
values of splitting
splitting tensile strength wastensile strength
consistent of T25, strength
with the compressive T50, T75, T100
of ATCA at 28 day
concrete.
MPa, 4.11 MPa, and 4.17 MPa, which were 101%, 103%, 106%, and 10
sample, respectively. At 180 days, the tested results of splitting ten
T50, T75, T100 were 103%, 106% 108%, and 110% of the control. Th
dency of splitting tensile strength was consistent with the compressi
concrete.
 Materials 2021, 14, x FOR PEER REVIEW 6 of 14
aterials 2021, 14, x FOR PEER REVIEW
Materials 2021, 14, 5606 6 of 15

5 T0
T25
5 T50 T0

tensile strength (MPa)

4 T75
T100 T25
T50

(MPa)
3
4 T75
2
T100
strength
3
Spliting tensile Spliting

0 2
3d 7d 28d 90d 180d

Figure 3. The test result of splitting tensile strength.

1
4.2.3. Compressive Strength and Compressive Elastic Modulus of Prism Specimens
The test result of prism compressive strength and elastic modulus for NCA concrete
and ATCA concrete are shown in Figure 4. The values of prism compressive strength of
0
T25, T50, T75, T100 at 28 days were 44.6 MPa, 45.8 MPa, 47.4 MPa, and 48.5 MPa. The
3d 7d
percentage increase of prism compressive28d 90d with180d
strength, compared the control sample, for
T25,
FigureT50, T75,test
3. The and T100
result of was 2%, tensile
splitting 4%, 8%, and 10%, respectively. While for the age of 180
strength.
Figure
days, the 3. The testincrease
percentage resultfor ofT25,
splitting
T50, T75, tensile
and T100strength.
was 3%, 6%, 10%, and 13%, re-
4.2.3. Compressive Strength and Compressive Elastic Modulus of Prism Specimens
spectively.
Thecan
As testberesult
seen,of prism
from compressive
Figure strength
4b, the tested andofelastic
results modulus
compressive for NCA
elastic concrete
modulus of
4.2.3. Compressive Strength and Compressive Elastic Modulus of Pris
T25, T50, T75, and T100 at 28 days were 3.88 × 10 MPa, 3.94 × 10 MPa, 4.04 × 104 MPa,of
and ATCA concrete are shown in Figure 4. The values
4 of prism compressive
4 strength
T25,4.11
and T50, × T75,
The 104testT100
MPa, at 28 days
result were
of prism
respectively. 44.6
Compared MPa,
with 45.8
compressive MPa,
T0, the 47.4 MPa,
strength
percentage and
and
increase 48.5 MPa.
elastic
was The
3%, 4%,modulu
percentage increase of prism compressive strength, compared with the
7%, and 9%, respectively. While for the long-term elastic modulus, when the curing age control sample,
and
for
was
ATCA
T25, T50, T75,
180 days,
concrete
the percentage
are 2%,
and T100 increase
was shown
4%,3%,
was 8%,in Figure
and
6%, 10%,
9%,
4. The values
andrespectively.
of the
WhileSince
11%, respectively. for prism
age comp
com-
T25,
of
pressive T50,
180 days,
strengthT75,
the is anT100
percentage
adequate at index
28 days
increase for
forT25, were 44.6
T50, T75,
mechanical andMPa, 45.8
T100a was
properties, close3%, MPa,
6%, 10%,
relationship 47.4
and MPa,
ex-
13%,between
ists respectively.
compressive strength and elastic modulus of ATAC concrete.
percentage increase of prism compressive strength, compared with the
T25, T50,T0
T75, and T100 was 2%, 4%, 8%,
60
T0 and 10%, respectively. Whil 5

T25
days, theT25
T50
percentage increase for T25,T50T50, T75, and T100 was 3%, 6%
50
4
Compressive strength (MPa)

Elastic modulas (×104MPa)

T75 T75
spectively.
T100 40 T100
3
As can be seen, from Figure 4b, the tested results of compressive
30

T25, T50, T75, and T100 at 28 days were 3.88 × 104 MPa, 3.94 × 104 M 2
20
and 4.11 × 104 MPa, respectively. Compared with T0, the percentage in
1
10
7%, and 9%, respectively. While for the long-term elastic modulus, w
was 1803d days,
7d the28dpercentage
90d 180d increase
3d
was7d3%, 6%,
0
28d
9%,
90d
and
180d
11%, resp 0

pressive strength is an adequate index for mechanical properties, a cl

(a) (b)
ists between compressive strength and elastic modulus of ATAC conc
Figure 4.
Figure The test
4. The test result
result of
of prism
prism compressive
compressive strength
strength and
and elastic
elastic modulus:
modulus: (a)
(a) compressive
compressive strength;
(b) compressive
strength; elastic modulus. 5
60 (b) compressive elastic modulus.

Asthis T0 from Figure 4b, the tested results of compressive elasticT0

cansection,
be seen, modulus
In T25the mechanical behaviors such as T25
cube compressive strength, splittingof
4 MPa, 3.94 × 104 MPa, 4.04 × 104 MPa,
T25, T50,
50 T75,
tensile strength,and T100 at 28 days were 3.88 × 10 T50 were
prism compressive strength, and elastic modulus of4all the samples
4 T50
Compressive strength (MPa)

and 4.11 × 10 MPa, respectively. Compared with T0, the percentage increase was 3%,
Elastic modulas (×104MPa)

tested simultaneously.
T75 The results show that the mechanical behavior of ATCA T75concrete
4%, 7%,
with and 9%,T100
respectively.
all replacement levels wereWhile for the
superior long-term
to NCA elastic
concrete. modulus, at
Furthermore, when the curing
a T100
certain cur-
40
age was 180 days, the percentage increase was 3%, 6%, 9%, and 11%, 3 respectively. Since
compressive strength is an adequate index for mechanical properties, a close relationship
30between compressive strength and elastic modulus of ATAC concrete.
exists
2
20

1
10
Materials 2021, 14, 5606 7 of 15

In this section, the mechanical behaviors such as cube compressive strength, splitting
tensile strength, prism compressive strength, and elastic modulus of all the samples were
tested simultaneously. The results show that the mechanical behavior of ATCA concrete
with all replacement levels were superior to NCA concrete. Furthermore, at a certain
curing age, the mechanical behavior of concrete containing ATCA is enhanced with the
increased replacement level. This might be due to the superior mechanical property of
ATCA, and better bond between cement and ATCA for the irregular surface. In related
research, Shettima et al. [25] reported a similar trend when IOT was reused as an aggregate.
They observed that the compressive strength and elastic modulus were superior to the
control sample (conventional concrete without IOT) at all levels of replacement. It was
demonstrated that the ATCA as a complete substitution for NCA possesses perfect physical
and mechanical properties. In order to further study the feasibility of ATCA for concrete,
the long-term performance was studied in the next section.

5. Long-Term Behavior Experiments

5.1. Specimen Design
The shrinkage of concrete is one of the main causes of structural cracking [51]. The
CA can restrain the shrinkage of concrete [52,53]. Creep is one of the important indices
for the long-term performance of concrete. While there appears to be little research on the
creep behavior of tailing concrete. The creep performance of ATCA concrete will provide
some references for future research.
The drying shrinkage and creep were tested simultaneously in the laboratory with
constant temperature and humidity based on the Chinese Standard GB/T 50082-2009 [54].
The dimensions of the specimens used for the experimental study are listed in Table 5.

Table 5. Dimensions of the concrete specimens for shrinkage and creep.

No. Experiments Sample Shape Sample Size (mm)

1 Shrinkage Prism 100 × 100 × 515
2 Creep Prism 100 × 100 × 400

5.2. Results and Discussion

5.2.1. Drying Shrinkage
The test results of drying shrinkage are shown in Figure 5. Throughout the period of
the experiment, the shrinkage of concrete with all replacement levels of ATCA was less
than that of the controlled sample. At an early age, the shrinkage strains of all samples
were almost the same. However, at the curing age of 180 days, the shrinkage strains of T25,
T50, T75, and T100 were, respectively, 301 × 10−6 , 309 × 10−6 , 315 × 10−6 , 318 × 10−6 ,
and 329 × 10−6 , which were, respectively, 3%, 4%, 6%, and 9% less than those of the
controlled sample.

5.2.2. Creep
The creep tests of concrete specimens with loading ages of 7 days and 28 days were
conducted, and the creep coefficients were used to denote the creep performance. The test
results are shown in Figure 6. It can be observed from the figure that the creep of concrete
with all replacement levels of ATCA was less than the controlled sample. At an early age,
the creep coefficients of all samples were almost the same. However, at the curing age of
180 days, the creep coefficients of T25, T50, T75, and T100 loaded at the age of 7 days were
respectively 1.99, 1.93, 1.91, and 1.85, which were respectively 3%, 6%, 7%, 10% less than
the controlled sample. Furthermore, the creep coefficients decreased with the increase of
the loading age.
 than that of the controlled sample. At an early age, the shrinkage str
were almost the same. However, at the curing age of 180 days, the s
T25, T50, T75, and T100 were, respectively, 301 × 10−6, 309 × 10−6, 315 ×
Materials 2021, 14, 5606
329 × 10−6, which were, respectively, 3%, 4%, 6%, and 9% less8 ofthan
15
tho
sample.

350

300
aterials 2021, 14, x FOR PEER REVIEW 8 of
250
Shrinkage (×10-6 )
200
5.2.2. Creep
The150
creep tests of concrete specimens with loading ages of 7 days and 28 days we
conducted, and the creep coefficients were used to denote T0the creep performance. The te
results are
100shown in Figure 6. It can be observed from T25
the figure that the creep of concre
T50
with all replacement levels of ATCA was less than the controlled sample. At an early ag
the creep50 T75
coefficients of all samples were almost the same. However, at the curing age
T100
180 days, the creep coefficients of T25, T50, T75, and T100 loaded at the age of 7 days we
respectively
0 1.99, 1.93, 1.91, and 1.85, which were respectively 3%, 6%, 7%, 10% less tha
0 sample.
the controlled 30 Furthermore,
60 90 the creep
120 coefficients
150 180
decreased with the increase
the loading age. Ages (d)
Figure 5. Comparison of drying shrinkage.
Figure 5. Comparison of drying shrinkage.
2.2 1.8

2.0 1.6
1.8
1.4
1.6
1.2
Creep coefficient
Creep coefficient

1.4
1.0
1.2

1.0 0.8
T0
T0
0.8 0.6 T25
T25
T50
0.6 T50 0.4 T75
0.4
T75
T100
T100 0.2
0.2
0.0
0.0
0 30 60 90 120 150 180
0 30 60 90 120 150 180
Ages (d)
Ages (d)

(a) (b)
Figure 6. ComparisonFigure
of creep:6.(a)Comparison
creep for concrete loaded(a)
of creep: at the age for
creep of 7 concrete
days; (b) creep for concrete
loaded loaded
at the age of 7atdays;
the age(b)
of creep for con
28 days. crete loaded at the age of 28 days.
In this section, the drying shrinkage and creep of all the samples were tested at the
In this
same section,
time. the drying
The results showedshrinkage and creep
the drying shrinkage ofcreep
and all the samples
of ATCA werewith
concrete tested at t
samealltime.
replacement levelsshowed
The results were superior to thoseshrinkage
the drying of the controlled sample.
and creep of Furthermore,
ATCA concretethe with a
drying shrinkage and creep of ATCA concrete decreased with the increased
replacement levels were superior to those of the controlled sample. Furthermore, the dr replacement
level of ATCA. The factor for lower drying shrinkage and creep of ATCA concrete could be
ing shrinkage and creep of ATCA concrete decreased with the increased replacement lev
attributed to the higher compressive strength of ATCA, and better bond between cement
of ATCA. The
and ATCA. To factor
furtherfor lower
study drying shrinkage
the feasibility of ATCA forand creep
concrete, theof ATCA behavior
durability concreteis could
attributed
discussedto the higher
in the compressive strength of ATCA, and better bond between ceme
next section.
and ATCA. To further study the feasibility of ATCA for concrete, the durability behavi
is discussed in the next section.

6. Durability Performance Experiments

6.1. Specimen Design
Durability is the most critical factor affecting the life cycle of concrete structure
Some indices such as freezing and thawing, carbonation, and chloride ion penetratio
have been investigated in the related studies. Since there may be some impurities in th
 Materials 2021, 14, 5606 9 of 15

aterials 2021, 14, x FOR PEER REVIEW

6. Durability Performance Experiments 9 of
6.1. Specimen Design
Durability is the most critical factor affecting the life cycle of concrete structures. Some
indices such as freezing and thawing, carbonation, and chloride ion penetration have
Table 6. Dimensions of the concrete
been investigated specimens
in the for durability
related studies. performance
Since there may be some experiments.
impurities in the tailing
aggregates, the cracking sensitivity and alkali activity should be paid attention to as well.
No. ExperimentsIn this section, the durabilitySample Shapesuch as freezing and thawing,
performance Sample Sizeactivity,
alkali (mm)
1 chloride ion penetration, cracking
Frost-resistant performance sensitivity, and carbonation was studied
Prism 100 ×systematically.
100 × 400
The dimensions of the specimens used for the experimental study are listed in Table 6.
2 Alkali activity Prism 25 × 25 × 280
3 Chloride permeability Cylinder
Table 6. Dimensions of the concrete Ø100 × 50
specimens for durability performance experiments.
4 Cracking sensitivity Plate 800 × 600 × 100
No. Experiments Sample Shape Sample Size (mm)
5 Carbonation Cube 100 × 100 × 100
1 Frost-resistant performance Prism 100 × 100 × 400
2 Alkali activity Prism 25 × 25 × 280
6.2. Results3 and Discussion
Chloride permeability Cylinder Ø100 × 50
4 Cracking sensitivity Plate 800 × 600 × 100
6.2.1. Frost-Resistant
5 Performance
Carbonation Cube 100 × 100 × 100
The frost resistance ability of concrete is expressed by surface peeling and relativ
6.2. Results
dynamic and Discussion
modulus of elasticity, which is measured by the ultrasonic method [55]. The te
6.2.1. Frost-Resistant
result can help to determinePerformance
the durability of concrete under extreme low-temperatu
conditions.TheThe
frostresults
resistance
of ability of concrete
freeze-thaw testisare
expressed
shownby insurface
Figurepeeling
7. Theand relative
frost-resistant pe
dynamic modulus of elasticity, which is measured by the ultrasonic method [55]. The test
formance of all samples meets the index of F300. After 300 cycles
result can help to determine the durability of concrete under extreme low-temperature
of freeze-thaw, the r
sultsconditions.
of mass loss Theofresults
T0, T25, T50, T75, and
of freeze-thaw T100
test are were,
shown respectively,
in Figure 2.07%, 2.02%, 1.99%
7. The frost-resistant
1.92%, and 1.90%,
performance of which were
all samples far lower
meets the indexthan 5% required
of F300. After 300 by theofcode.
cycles The values
freeze-thaw, the of rel
results of mass loss of T0, T25, T50, T75, and T100 were, respectively,
tive dynamic elastic modulus of T0, T25, T50, T75, and T100 were, respectively, 80.1% 2.07%, 2.02%, 1.99%,
1.92%,
81.9%, 83.7,and 1.90%,
84.9%, andwhich were
85.8%, far lower
which were than
far5% required
higher thanby60%
the required
code. Theby values of
the code. It ca
relative dynamic elastic modulus of T0, T25, T50, T75, and T100 were, respectively, 80.1%,
be seen from the test results that the frost-resistant performance of concrete
81.9%, 83.7, 84.9%, and 85.8%, which were far higher than 60% required by the code. It can
with ATC
was slightly better.
be seen from The
the test factor
results thatfor
thebetter frost-resistant
frost-resistant performanceperformance of ATCA
of concrete with concrete r
ATCA was
sulted frombetter.
slightly the superior
The factorwater absorption
for better andperformance
frost-resistant firmness ofofATCA [35]. resulted
ATCA concrete
from the superior water absorption and firmness of ATCA [35].
Percentage of rative dynamic elastic modulus (%)

100
2.1
98

1.8 96
Percentage of mass loss (%)

94
1.5 92
90
1.2 88
86
0.9 T0 T0
T25 84 T25
0.6 T50 82 T50
T75 80 T75
0.3 T100 78 T100
76
0.0
0 50 100 150 200 250 300
0 50 100 150 200 250 300
Cycle of freezing and thawing Cycle of freezing and thawing

(a) (b)
Figure 7. ComparisonFigure
of frost-resistant performance:
7. Comparison (a) the test result
of frost-resistant of mass loss; (b)
performance: (a)the
thetest result
test of relative
result of mass dynamic
loss; (b) the test
elastic modulus. result of relative dynamic elastic modulus.

6.2.2. Alkali Activity

Under complex conditions, certain minerals in the aggregate could react chemical
with the alkali (K2O, Na2O) in the concrete, causing expansion, crack, or even damage
concrete. In order to evaluate the alkali-silicic acid reaction of ATCA aggregates, the alka
 Materials 2021, 14, 5606 10 of 15

6.2.2. Alkali Activity

Under complex conditions, certain minerals in the aggregate could react chemically
with the alkali (K2 O, Na2 O) in the concrete, causing expansion, crack, or even damage in
concrete. In order to evaluate the alkali-silicic acid reaction of ATCA aggregates, the alkali
activity experiment was conducted. For 14 days, all samples were placed in the NaOH
solution, of which the concentration was 1 mol/L, and the temperature was (80 ± 2) ◦ C.
aterials 2021, 14, x FOR PEER REVIEW
The length of the sample was measured, by which the expansion rate of length was
calculated, and the alkali activity of aggregate was evaluated.
The experimental results are shown in Figure 8. After the 14-day immersion in alkali
solution, there was no crack, swell, colloid overflow, or other undesirable phenomena. It
was explicitly found that the expansion rate was stable at 10 days. The expansion rates of
which were all less than 1‰ of the standard required. The alkali
T0, T25, T50, T75, and T100 were 0.71‰, 0.73‰, 0.77‰, 0.79‰, and 0.80‰, respectively,
seemed
which weretoall increase
less than 1‰with the
of the substitution
standard amount
required. The of ATCA.
alkali activity However
of samples
seemed to increase with the substitution
not significant and can be neglected. amount of ATCA. However, the difference was
not significant and can be neglected.

0.9
T0
0.8 T25
0.7
T50
T75
T100
Expansion rate (‰)

0.6

0.5

0.4

0.3

0.2

0.1

0.0
3d 7d 10d 14d
Figure 8. Comparison of alkali activity.
Figure 8. Comparison of alkali activity.
6.2.3. Chloride Permeability
It isChloride
6.2.3. well knownPermeability
that chloride migrates with moisture in concrete [56,57], and it
is important to monitor chloride permeability and moisture level in a concrete struc-
It is In
ture [58,59]. well knownthe
this research, that chloride
chloride migrates
permeability with
of concrete was moisture
determinedin by concre
the electric flux method illustrated as Figure 9. The results of the measured electric
important to monitor chloride permeability and moisture level in a
flux of T0, T25, T50, T75, and T100 were 869 coulombs, 862 coulombs, 853 coulombs,
[58,59].
843 coulombs,In and
this832research, the28chloride
coulombs after permeability
days of curing, ofdifference
respectively. The concrete was dete
in chlo-
ride
tricpermeability
flux method of concrete was not significant.
illustrated as FigureBased on the
9. The code, if of
results the the
passed charge
measured ele
was above 4000 coulombs, chloride ion penetrability was high penetrability (grade I),
T50, T75,
2000–4000 and T100
coulombs were penetrability
was moderate 869 coulombs, 862
(grade II), coulombs,
1000–2000 coulombs 853
werecoulombs
low
832 coulombs after 28 days of curing, respectively. The difference
penetrability (grade III), and 100–1000 coulombs was very low penetrability (grade IV). in ch
According to the evaluation index, the chloride permeability of all samples was very low
of concrete
(grade IV). was not significant. Based on the code, if the passed cha
coulombs, chloride ion penetrability was high penetrability (grade I), 2
was moderate penetrability (grade II), 1000–2000 coulombs were low
III), and 100–1000 coulombs was very low penetrability (grade IV). Ac
uation index, the chloride permeability of all samples was very low (g

Materials 2021, 14, 5606
T50, T75, and T100 were 869 coulombs, 862 coulombs, 853 coulombs, 843 coulombs, and
832 coulombs after 28 days of curing, respectively. The difference in chloride permeability
of concrete was not significant. Based on the code, if the passed charge was above 4000
coulombs, chloride ion penetrability was high penetrability (grade I), 2000–4000 coulombs
was moderate penetrability (grade II), 1000–2000 coulombs were low penetrability (grade
11 of 15
III), and 100–1000 coulombs was very low penetrability (grade IV). According to the eval-
uation index, the chloride permeability of all samples was very low (grade IV).

Figure 9.
Figure 9. Chloride
Chloride permeability
permeability experiment.
experiment.

6.2.4.
6.2.4. Cracking Sensitivity
Sensitivity
High-strength concrete structures
High-strength concrete structuresare aremore
moreprone
pronetotocracking
cracking[60],[60], and
and cracks
cracks in in
con-con-
crete
crete enable
enable water migration
migration [61]. [61].Therefore,
Therefore,crackcracksensitivity
sensitivityand anddetection
detection have
have received
received
much attention
much attention [62,63].
[62,63].InInthis thisresearch,
research, thethecracking
cracking sensitivity
sensitivity of concrete
of concretespecimens
specimens at
anan
at early ageage
early waswas
tested
testedwithwith
the plate method
the plate (Figure
method 10). The
(Figure values
10). The of measured
values crack-
of measured
ing area area
cracking per unit area area
per unit of T0,ofT25, T50, T50,
T0, T25, T75, T75,
and T100
and T100concrete were were
concrete 239 mm2392/m
mm2, 2243
/m2 ,
mmmm
243 2 2
/m ,/m
2 2
248 ,mm
248 /m
2 2 2
mm, 250 2
/mmm , 250/m
2 mm2 2
, and 2
/m256 mm256
, and 2/mmm
2 2 2
, respectively. As per the
/m , respectively. Ascode,
per11 ifofthe
the code,
Materials 2021, 14, x FOR PEER REVIEW 14
ifmeasured
the measuredcracking area per
cracking areaunitperarea
unitwasareaabove 1000 mm
was above 10002/mmm 2 /m
2, the 2 , the cracking
cracking sensitivity of
sensitiv-
concrete
ity was classified
of concrete as grade
was classified L-I, 700–1000
as grade mm2/m
L-I, 700–1000 mm 2 /m
2 was 2 was classified
classified as gradeasL-II,
grade400– L-II,
400–700 2 /m2 was classified as grade L-III, 100–400 mm2 /m2 was classified as grade
700 mm2mm /m2 was classified 2as grade L-III, 100–400 mm2/m2 was classified as grade L-IV
2 was classified as grade L-V. According to the evaluation
L-IV and less than 100 mm /m
and less than 100 mm /m was classified as grade L-V. According to the evaluation index,
2 2
index, the cracking
the cracking sensitivities
sensitivities of all samples
of all samples were very were very(grade
good good L-IV).
(grade L-IV).

(a) (b)
Figure 10.
Figure 10. Cracking
Cracking sensitivity
sensitivityexperiment:
experiment:(a)
(a)blade
blademold;
mold;(b)
(b)crack observation.
crack observation.

6.2.5. Carbonation Depth

6.2.5. Carbonation Depth
The test result
result of of carbonation
carbonationdepth depthisisshown
shownininFigure
Figure11.11.The
Themeasured
measured values
values of of
carbonation depth of T25, T50, T75, and T100 were 5.30 mm, 5.61 mm,
carbonation depth of T25, T50, T75, and T100 were 5.30 mm, 5.61 mm, 5.82 mm, 6.03 mm, 5.82 mm, 6.03 mm,
and
and 6.15 mm, whichwhich werewere 6%,6%, 10%,
10%,14%,
14%,16%
16%less
lessthan
thanthat
thatofofthe
thecontrolled
controlledsample.
sample. AsAs
per
per the
the code,
code, ifif the
thecarbonation
carbonationdepth depthwas
wasabove
above30 30mm,
mm,concrete
concreteresistance
resistancetotocarbonation
carbona-
was classified
tion was as grade
classified as gradeI, 20–30
I, 20–30mmmm was
wasclassified
classifiedas
as grade II, 10–20
grade II, 10–20mm mmwaswas classified
classified
as
as grade III, 0.1–10
0.1–10 mm mm was wasclassified
classifiedas
asgrade
gradeIV IVand
andless
lessthan
than0.10.1mm
mm was
was classified
classified as as
grade
grade V.V. According
According to the the evaluation
evaluationindex,
index,thetheresistance
resistanceabilities
abilitiestotocarbonation
carbonation of of
allall
samples
samples were very very good
good (grade
(gradeIV).IV).Furthermore,
Furthermore,withwiththe
theincrease
increase ofof substitution
substitution level,
level,
the
the ability of resistance
resistance to to carbonation
carbonationwas wasenhanced.
enhanced.

7 T0
T25
6 T50
T75
tion depth (mm)

5 T100

3
 tion was classified as grade I, 20–30 mm was classified as grade II, 10–20
as grade III, 0.1–10 mm was classified as grade IV and less than 0.1 mm
grade V. According to the evaluation index, the resistance abilities to
Materials 2021, 14, 5606 samples were very good (grade IV). Furthermore, with the increase
12 of 15 of
the ability of resistance to carbonation was enhanced.

7 T0
T25
6 T50
T75
Carbonation depth (mm)
5 T100

0
3d 7d 14d 21d 28d
Figure 11. Comparison of carbonation depth.
Figure 11. Comparison of carbonation depth.
7. Conclusions
Based on the systematical studying of the performance of antimony tailing coarse
7. Conclusions
aggregate (ATCA) concrete and the comparison with natural coarse aggregate (NCA)
Based
concrete, on the have
the researchers systematical
the following studying of the performance of antim
main conclusions:
(1) ATCA as(ATCA)
aggregate a completeconcrete
substitutionand
for NCA in concrete possesses
the comparison withgood workability,
natural coarse agg
which is nearly the same as NCA concrete.
crete, theasresearchers
(2) ATCA have theforfollowing
a complete substitution mainpossesses
NCA in concrete conclusions:
perfect physical
(1) and
ATCAmechanical properties. The cubic compressive strength, cubic splitting tensile
as a complete substitution for NCA in concrete possesses
strength, prism compressive strength, and elastic modulus of ATCA concrete with all
which islevels
replacement nearly the same
is superior to thatas
of NCA concrete.
NCA concrete.
(2) ATCA as a complete substitution for NCA
(3) The drying shrinkage and creep of ATCA concrete decreaseinwith
concrete possesses
the increased re- pe
placement level of ATCA. Furthermore, the drying shrinkage and creep of ATCA
mechanical
concrete properties.
with all replacement levels The cubicto the
are superior compressive strength, cubic
controlled sample.
(4) The ability of resistance to carbonation, the frost-resistant, and the chloride permeabil-
ity performance of ATCA concrete are enhanced. While the alkali activity and cracking
sensitivity behavior of the samples with ATCA seem to be decreased. Nevertheless,
the difference is not significant and can be neglected.
(5) It is found that all of the control indices meet the requirements of the current industry
standards of China. The utilization of ATCA as a complete substitute for NCA in
high-strength concrete has very important environmental and economic benefits.

Author Contributions: Conceptualization, L.L. and J.W.; methodology, L.L. and J.W.; validation, L.L.,
L.Z. and R.D.; formal analysis, R.D., S.Z. and G.W.; writing—original draft preparation, L.L., J.W. and
L.Z.; writing—review and editing, L.L. and L.Z.; project administration, R.D., S.Z. and G.W.; funding
acquisition, J.W. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by the National Nature Science Foundation of China (Grant
No. 51408218), the Hunan Nature Science Foundation of China (grant No. 2020JJ4310), and Hunan
Education Department (Grant No. 18A202).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Materials 2021, 14, 5606 13 of 15

Conflicts of Interest: The authors declare no conflict of interest.

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