Construction and Building Materials 95 (2015) 312–328

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Construction and Building Materials

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

Mechanical properties, permeability and durability of accelerated

shotcrete
Jiabin Wang ⇑, Ditao Niu, Yongli Zhang
School of Civil Engineering, Xi’an University of Architecture and Technology, 710055 Xi’an, Shaanxi, China

h i g h l i g h t s

 Compressive and splitting tensile strength regression equation of shotcrete was established.
 Durability of ordinary concrete, shotcrete with and without steel fiber for the same mixture was tested.
 Compared with ordinary concrete, shotcrete had better durability except to chloride ions.
 Steel fiber can obviously improve the durability of shotcrete.
 Microstructure of specimens after erosion were characterized by using XRD, TG-DSC and SEM.

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

Article history: In this paper, the experiment is completed into two phases. In the first phase, the performance of setting
Received 14 March 2015 time of pastes, mechanical properties of shotcrete at different hydration age and permeability of shot-
Received in revised form 8 July 2015 crete at 90 day were tested. Meanwhile, in the second phase, the durability performance of shotcrete with
Accepted 15 July 2015
10% fly ash and 0.64 vt.% steel fiber was studied under environment corrosion which included freeze–
thaw cycle, accelerated carbonation test with and without bending load, sulfate attack, chloride ion dif-
fusion and acid corrosion respectively. The results showed that, in comparison to ordinary concrete (OC)
Keywords:
with the same mixture, ordinary shotcrete (OS) had better durability properties except to chloride ion.
Shotcrete
Permeability
Thus, steel fiber (steel fiber reinforced shotcrete, SFRS) not only led to much denser microstructure in
Durability shotcrete matrix but also could significantly improve the early-age compressive and splitting tensile
Mechanical properties strength, permeability and durability of shotcrete.
Microstructure Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction structure is subjected to lower temperature. Since positive and neg-

Sprayed concrete is concrete which is conveyed under pressure
through a pneumatic hose or pipe and projected into place at high
velocity, which simultaneous compaction, condensation and hard-
ening [1,2]. Compared with ordinary concrete without accelerator,
accelerated shotcrete has short final setting time and high
early-age mechanical properties [3,4]. Since shotcrete was used
as a part of lining structures on municipal tunnel of Frankfort
and Munich in 1970, shotcrete is widely used in different fields,
such as tunnel support, rapid repair, slope support, gas and oil
wells, and other underground structures [5–7].
On designing and construction of modern tunnel lining struc-
ture, shotcrete single layer lining structure become the trend of
future development [8,9]. First, in cold environment, especially in
North China and plateau region, shotcrete single layer lining
⇑ Corresponding author.
E-mail address: lty20020931@163.com (J. Wang).
ative temperature changed alternatively, shotcrete had been frozen
and melted repeatedly for almost 130 times on year. During the
cyclical process of freezing and thawing, free water and capillary
pore water in shotcrete undergoes alternating positive and negative
temperatures, lining structure would be damaged and the durability
of the structure would decrease [10]. Second, in mountain and saline
soil environment, shotcrete lining structure contacts with ground
water in a long time which is rich with sulfate minerals. At the same
time, due to the other side of lining structure contacts with air in
tunnel which have high temperature and humidity, shotcrete lining
structure is subjected to dry–wet cycles which lead to sulfate ions
diffused rapidly into shotcrete and undergoes with hydration prod-
ucts to form ettringite and gypsum. The erosion products can pro-
duce expansion stress which cause lining crack and spalling
[11,12]. Third, about subsea tunnel, shotcrete lining structure con-
tacts with high pressure water which is rich with chloride ion which
diffuses into shotcrete. Meanwhile, due to high concentration of CO2
and high humidity, carbonation is occurred on the inside surface of

http://dx.doi.org/10.1016/j.conbuildmat.2015.07.148
0950-0618/Ó 2015 Elsevier Ltd. All rights reserved.
 J. Wang et al. / Construction and Building Materials 95 (2015) 312–328
shotcrete single layer lining structure. Under the action of galvanic
cell and neutralization, pH value of shotcrete was decreased and steel
bar corrosion was occurred, then caused shotcrete lining cracks and
spalling which can decrease the durability and bearing capacity [13].
In a word, in the tunnel operation process, under the action of
surrounding rock deformation, high-pressure water and environ-
ment corrosion factors, lining structure disease in terms of cracking,
physical and chemical erosions, seepage and even shotcrete spalling
is appeared. Future more, the lining structure durability and service
life is seriously threatened [14]. Therefore, it has important signifi-
cance to research the durability of shotcrete single lining structure.
Nowadays, the durability of normal concrete have been investi-
gated widely and deeply [15,16]. However, be due to add accelera-
tor into concrete, the hydration process and products are different
from that of normal concrete. In addition, seeing that compressed
air was into shotcrete and not timely discharged, the isolating
micro pores was formed in shotcrete which air content was 2.5–
5.3% [17]. Therefore, the damage process and phenomenon of shot-
crete is also different from that of normal concrete. In recently
years, only a few investigations have been carried out on the shot-
crete durability. Park et al. [18] considered that shotcrete with sil-
ica fume and fly ash had better impermeability. Chen et al. [19]
analyzed the frost resistance of C25 shotcrete. After 400 freeze–
thaw cycles, the loss rate of weight, relative dynamic modulus of
elasticity, and compressive strength was 3.1%, 22.5% and 36.5,
respectively. In the meantime, Park et al. [20], Won et al. [21]
and Park et al. [22] reported the loss rate of relative dynamic mod-
ulus of elasticity was not more than 1% of shotcrete after 300
freeze–thaw cycles. Lee et al. [23] studied the accelerated carbon-
ation of shotcrete with alkali-free accelerator. The carbonation
depth was 7 mm after carbonation age 56 days. Ma et al. [24] dem-
onstrated shotcrete with silica fume had better carbonation resis-
tance for long term. Lee et al. [25] investigated the sulfate
erosion durability of shotcrete. After immersion 360 days, the loss
rate of compressive strength was more than 50%.
However, the research of shotcrete durability was confined and
not system. In order to analysis the durability of shotcrete single
layer lining structure, the permeability, carbonation resistance,
freezing and thawing cycles, sulfate erosion and chloride ion diffu-
sion of shotcrete with and without steel fiber were investigated.
And then, compressive and splitting tensile strength before and
after corrosion were tested.
Simultaneously, microstructure erosion products of shotcrete
after corrosion was characterized.
2. Materials and experiments
2.1. Materials
A PO.42.5 Ordinary Portland cement (OPC) and II class fly ash (FA) complying
with Chinese standard GB175-2007 [26] and GB/T1596-2005 [27] were used in this
experiment. Their characteristics were examined by using chemical analysis,
Fig. 1. Particle size distribution of cementitious materials. d10, d50, and d90 are the 10th, 50th, and 90th percentile by volume of the particle size distribution, respectively.
313
particle size analysis, and XRD. The chemical and physical properties of the cement
and fly ash were obtained by using X-ray fluorescence spectrometry. Fig. 1 shows
the particle size distribution of cement and fly ash. The fine aggregate used in this
study was natural river sand with a fineness modulus of 3.5. The coarse aggregate
used was gravel with continuous grading from 5 mm to 10 mm. The specific gravity
(kg/m3) and absorption (%) were 2650 and 0.61, respectively. Both aggregates com-
plied with the GB50086-2001 requirement [28]. The low-alkali accelerator (AC)
used contained NaAlO2 and Ca2SiO4 (C2S) as the major substances. The chemical
characteristics of the cement, fly ash, and accelerator are listed in Table 1.
Physical properties of cementitious materials are listed in Table 2.
2.2. Specimen preparation
Specimens of experiment were divided into three phases. In the first phase,
cement pastes for testing setting time were prepared. The addition of accelerator
and FA (FA to binder ratio, FA/b) was noted as the mass ratio between accelerator
and FA, and cementitious materials (include cement and fly ash). The mixtures of
all cement pastes are illustrated in Table 3. In the second phase, shotcrete speci-
mens for examining the permeability, compressive strength and splitting tensile
strength for hydration age were also prepared for nine mixtures. Finally, in the third
phase, shotcrete specimens for durability experiment was assign into three mix-
tures which included ordinary concrete (C43F10) with w/b 0.43 and 10% fly ash,
ordinary shotcrete (S43F10) with w/b 0.43 and 10% fly ash, and steel fiber rein-
forced shotcrete (S43F10SF50) with w/b 0.43, 10% fly ash and 50 kg/m3 steel fiber
(shown in Table 4). In each mixture, the sand to total aggregate ratio of 0.50 and
the mixing amount of water reducing and accelerator was 1% and 4% of the cemen-
titious material, respectively.
The concrete was first sprayed as large slabs with dimensions of
1 m  0.5 m  0.15 m using dry method. The slab molds were oriented 75° to the
ground, and the nozzle was oriented 90° relative to the bottom plate of the mold.
The distance between the nozzle and the bottom of the mold ranged from 0.85 m
to 1.2 m (Fig. 2a). After 3 h, slabs that had formed were removed and placed into
tunnel for 7 days of curing (Fig. 2b). The large slabs were subsequently cut into
standard cube specimens measuring 400 mm  100 mm  100 mm using an auto-
matic rock cutting machine (Fig. 2c). Afterwards, prism specimens were cut into
three cube specimens with lengths of 100 mm (Fig. 2d). Finally, specimens were
moisture-cured at 20 ± 2 °C and 95% relative humidity for 21 days and then
dry-cured until testing.
2.3. Spraying equipment
The dry mix shotcreting equipment featured a high capacity of 25 m3/h and was
produced by Changsha Keda Construction Mechanical Manufacturing Co., Ltd. The
pumping system allowed the maximum aggregate size to reach 16 mm. The shot-
creting equipment used is shown in Fig. 3. Cement, FA, aggregate and accelerator
were first mixed for 30 s and then forced into the pipe by a concrete pump with
compressed air at a pressure of 21 m3/min. Finally, high-pressure water was added
to the dry mixture and sprayed concrete from nozzle into molds.
2.4. Testing method
2.4.1. Setting time
Pastes of three w/b ratios and four FA amounts at different curing ages were
used for the setting time, which was measured according to ASTM C191-08 [29].
2.4.2. Permeability
Permeability is a method for characterizing the difficult degrees and abilities of
permeation, diffusion, and migration by gas, liquid, and ions under pressure, chem-
ical potential, and electric field. Permeability is an important part of concrete dura-
bility. The permeability study included air permeability, water absorption, and the
RCM method.
314 J. Wang et al. / Construction and Building Materials 95 (2015) 312–328

Table 1
Chemical composition of cementitious materials and accelerator.

Raw materials SiO2 Al2O3 Fe2O3 CaO MgO SO3 TiO2 P2 O5 f-CaO Alkali Cl
OPC 19.50 6.45 3.08 57.57 1.21 2.01 0.34 0.43 0.81 1.14 0.007
FA 43.64 25.39 4.19 5.62 0.84 0.28 1.15 0.20 0.46 1.80 0.011
AC 14.74 18.83 4.17 32.72 0.64 0.29 1.48 0.30 – 10.47 0.30

Where alkali content is the sum of Na2O and 0.658K2O.

Table 2
Physical properties of cementitious materials.

Cementitious materials Density (g/cm3) Blaine fineness (cm2/g) Loss of ignition (%) Compressive Flexural strength
strength (MPa) (MPa)
3-day 28-day 3-day 28-day
OPC 3.08 3340 4.12 29.8 56.0 6.21 8.20
FA 2.09 4040 3.0 – – – –

pffiffi
Table 3 i¼AþS t ð2Þ
Mix proportions of pastes for setting time (g). 2
where Dw is the absorption water weight, g; Ar is the inflow surface area, m ; i is the
Pastes Cement Fly Water Water Accelerator w/b weight of absorbing water per unit area of the inflow surface, g/m2; A is a positive
ash reducing intercept; t is the immersion time, h; S is the water absorption index, g/m2 h0.5.
S43AC1.5 411 46 197 4.57 6.86 0.43
S43AC2 411 46 197 4.57 9.14 0.43 2.4.2.3. RCM test. The RCM test was conducted to examine the chloride migration
S43AC2.5 411 46 197 4.57 11.43 0.43 coefficient of shotcrete according to the NT Build 492-1999.11 standard [32].
S43AC3 411 46 197 4.57 13.71 0.43 The non-steady-state chloride ion coefficient was calculated by the following
S43AC4 411 46 197 4.57 18.28 0.43 equation:
S43AC5 411 46 197 4.57 22.85 0.43 rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi!
0:0239  ð273 þ TÞ  L ð273 þ T Þ  L  X d
S43AC6 411 46 197 4.57 27.42 0.43 DRCM ¼  X d  0:0238  ð3Þ
S38F10 468 52 197 6.20 20.80 0.38
ðU  2Þ  t U2
S43F10 411 46 197 4.57 18.28 0.43
where DRCM is the non-steady-state chloride ion coefficient, 1012 m2/s; U is the
S49F10 360 40 197 4.00 16.00 0.49
absolute voltage value, V; T is the average of the innate and final temperatures in
S43F0 457 0 197 4.57 18.28 0.43
the analyze solution, °C; L is the thickness of the specimens, mm; Xd is the average
S43F20 365 92 197 4.57 18.28 0.43
value of the penetration depth, mm; t is the test duration, h.
S43F30 319 138 197 4.57 18.28 0.43

2.4.3. Compressive and splitting tensile strength

2.4.2.1. Air permeability. Air permeability was tested by using an Auto Clam perme-
ability instrument with a 100 mm cubic shotcrete specimen [30]. Before testing, air
was implanted inside the instrument by syringe through the pipe until the air pres-
sure was more than 500 mbar (1 mbar = 500 Pa). After starting the test, the air pres-
sure was recorded per minute. Given the linear relationship between the natural
logarithm of air pressure and time, the slope (kA) of the liner could be used as an
index for evaluating air permeability.
2.4.2.2. Water absorption test. Water absorption test defines the ability of concrete
to absorb water according to the ASTM C1585 [31]. In order to ensure the consistent
performance of shotcrete, 54 cube casts with the size of 100 mm, were selected ran-
domly from the large slabs and divided into 6 groups which corresponded 6 immer-
sion age: 10 min, 20 min, 40 min, 1 h, 3 h and 7 h, respectively (Fig. 4). The
schematic of the water absorption test is listed in Fig. 5 and the water absorption
index (S) was calculated as the following equation.
Dw
i¼
Ar
Compressive strength and splitting tensile strength were used to evaluate the
compressive and splitting tensile strength of the specimens aged for 1, 3, 7, 28,
60, and 90 days. Compressive and splitting tensile strength tests were performed
in accordance with CS GB50081-2002 [33] by using a TENSON (Jinan, China)
600 kN servo-hydraulic testing machine.
2.4.4. Durability performance
2.4.4.1. Accelerated carbonation. Accelerated carbonation test was performed to
evaluate carbonation depth in accordance with Chinese standard GB/T
50082-2009 [34] (Part 11: The Method for Carbonation of Ordinary Concrete).
Accelerated carbonation test was conducted as follows:
(1) The test was performed using a prism specimen with a size of
100 mm  100 mm  400 mm, and three specimens were included in one
group.
(2) After 90 days of curing, the specimens were dried at 60 °C for 48 h. The surface
ð1Þ was then covered with epoxy resin except one side of 100 mm  400 mm used
in the experiment. The dried specimens were then placed in an automatic

Table 4
Mix proportions of shotcrete for permeability, mechanical performance, and durability (kg/m3).

Shotcrete C43F10a S38F10 S43F10b S49F10 S43F0 S43F20 S43F30 S43F10SF40 S43F10SF50c S43F10SF60
Cement 411 468 411 360 457 365 319 411 411 411
Fly ash 46 52 46 40 0 92 138 46 46 46
FA/b 0.1 0.1 0.1 0.1 0 0.2 0.3 0.1 0.1 0.1
Fine aggregate 892 860 892 921 892 892 892 892 892 892
Coarse aggregate 892 860 892 921 892 892 892 892 892 892
Water 197 197 197 197 197 197 197 197 197 197
w/b 0.43 0.38 0.43 0.49 0.43 0.43 0.43 0.43 0.43 0.43
Water reducing 4.57 5.20 4.57 4.00 4.57 4.57 4.57 4.57 4.57 4.57
Steel fiber – – – – – – – 40 50 60
Accelerator – 20.80 18.28 16.00 18.28 18.28 18.28 18.28 18.28 18.28

Where S43F10SF50 means shotcrete with w/b 0.43, fly ash dosage of 10% and steel fiber content 50 kg/m3.
a
Mixture C43F10 is also called ordinary concrete (OC) in the article.
b
Mixture S43F10 is also called ordinary shotcrete (OS) in the article.
c
Mixture S43F10SF50 is also called steel fiber reinforced shotcrete (SFRS) in the article.
 J. Wang et al. / Construction and Building Materials 95 (2015) 312–328 315

Fig. 2. Production of test specimens. (a) Spraying concrete into molds; (b) demolding after 3 h; (c) cutting large slabs into prisms with sizes of 100 mm  100 mm  400 mm
and (d) cutting prisms into cubes with lengths of 100 mm.

Fig. 4. Water absorption index (S) of specimen with three water–binder ratio.

Fig. 3. Shotcreting setup used in this study. The loss rate of specimen after frost damage occurred was calculated as follows:

  "  2 #
accelerated carbonation chamber with carbon dioxide concentration of EdN f
20% ± 3%, relative humidity (RH) of 70% ± 5%, and temperature of 20 ± 2 °C. DP N ¼ 1   100 ¼ 1  N  100 ð4Þ
Ed0 f0
Carbonation ages were 7, 14, 28, 42, and 56 days, respectively.
(3) At the end of carbonation aging, the specimen was split from one end by
using a universal testing machine. After concrete specimens were split,  
W0  WN
the freshly split surface was cleaned and sprayed with 1% phenolphthalein DW N ¼ 1   100 ð5Þ
W0
ethanol solution. A purple-red color was obtained in the non-carbonation
part of the specimen with highly alkaline concrete. By contrast, no colora-
tion occurred in the carbonated part with weakly alkaline concrete. !
f cðtÞ0  f cðtÞN
(4) After 30 s, carbonation depth was measured using a Vernier caliper at an Df cðtÞN ¼ 1  100 ð6Þ
f cðtÞ0
interval of 10 mm; average carbonation depth was then calculated.

2.4.4.2. Freeze–thaw cycle. The freeze–thaw cycle of shotcrete was performed to
evaluate frost resistance in accordance with ASTM C666-03(2008) [35]. The exper-
iment was terminated when 300 freeze–thaw cycles were completed, 60% loss rate
of relative dynamic elasticity modulus was reached, or 5% weight loss ratio was
obtained.
where DPN is the relative dynamic elasticity modulus of specimen after N freeze–
thaw cycles, %; EdN is the transverse fundamental frequency of specimen after N
freeze–thaw cycles, Hz; Ed0 is the initial transverse fundamental frequency of spec-
imen, Hz; DWN is the weight loss rate of specimen after N freeze–thaw cycles, %; WN
is the weight of specimen after N freeze–thaw cycles, kg; W0 is the initial weight of
specimen, kg; Dfc(t)N is the loss ratio of compressive or splitting tensile strength of
316 J. Wang et al. / Construction and Building Materials 95 (2015) 312–328
Fig. 5. Schematic of the water absorption test.
specimen after N freeze–thaw cycles, %; fc(t)N is the compressive or splitting tensile
strength of specimen after N freeze–thaw cycles, MPa; and fc(t)0 is the initial strength
of specimen, MPa.
2.4.4.3. Sulfate erosion. An accelerated durability test was performed using a dry–
wet cycle method to analyze the sulfate attack of shotcrete. The experiment was
performed as follows:
 One dry–wet cycle included two steps. The specimens were initially dried at
60 °C for 8 h and then immersed in 10% Na2SO4 solution for 16 h.
 The experiment was subjected to five accelerated ages, including 15, 30, 60, 90,
120, and 150 cycles of drying and immersing.
 At the end of each accelerated aging, relative dynamic elasticity modulus,
weight loss rate, cubic compressive and splitting tensile strengths, and damage
layer thickness were examined.
Weight loss rate, relative dynamic elasticity modulus, and compressive and
splitting tensile strengths were used to characterize the internal compactness of
specimen after sulfate damage. Test procedures and calculation method were the
same as freeze–thaw cycle test.
The thickness of a damaged layer of specimens was calculated [36], and the test
method is illustrated in Fig. 6.
V 1 V 2 ti
hf ¼ qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi ð7Þ
2 V 22  V 21
where hf is the thickness of a damaged layer, mm; V1 is the surface wave of the dam-
aged phase, m/s; V2 is the surface wave of the undamaged phase, m/s; ti is the inter-
cept when range begins at 0 in a sonic-ranging liner of the undamaged phase.
2.4.4.4. Chloride ion diffusion. Immersion and salt spraying methods were used to
simulate shotcrete under seawater and in ocean–atmosphere zone to analyze chlo-
ride ion diffusion in shotcrete in a marine environment. The experiment was per-
formed as follows:
 A cubic specimen with 100 mm was dried at 60 °C for 24 h. Afterward, the spec-
imen was cooled at room temperature.
 The specimen was immersed in deionized water for 4 days and then transferred
to 3.5% NaCl solution for simulating shotcrete under seawater or in an auto-
matic salt spray chamber for simulating shotcrete in ocean–atmosphere zone.
In immersion, the experimental age was divided into six cycles: 30, 60, 90,
120, 150, and 180 days. In salt spray method, the experiment was subjected
to six ages: 30, 60, 90, 120, 150, and 180 cycles. Each cycle involved two stages:
spraying for 12 h and drying for 12 h (temperature at 35 °C).
Fig. 6. Test method for damage layer thickness. (a) Measuring mode schematic and (b) curves of distance and arrival time.
 At the end of each month, the specimen was dried at room temperature for
3 days and powdered in 15 layers by using a rotary impact drill with a depth
of 20 mm. Afterward, the powder in each layer was placed in a weighing bottle
and dried at 110 °C until constant weight was achieved. The chloride ion con-
centration of specimens was evaluated in accordance with ASTM C1218-99
[37] and ASTM C114-05 [38].
2.4.5. Microstructure
Microstructure characterization of specimen after corrosion included XRD anal-
ysis, thermal analysis, and corrosion products morphology.
XRD analysis was used to examine the mineral phase composition of the corro-
sion products at different curing ages. After being removed from the ethanol, the
mortar were first pulverized in ethanol by an agate mortar and passed to an
80 lm sieve as vacuum filtrating. The powder was dried at 60 °C for 8 h in a vacuum
drying oven. The XRD patterns of the mortar were tested by using XRD, with a Cu
Ka source, a scanning range of 7–60°, and a speed of 2° per minute.
Thermal analysis, particularly the thermogravimetric (TG)-differential scanning
calorimetry (DSC) hyphenated method, is an effectively method for quantifying and
identifying corrosion products, including ettringite, AFm, C2SH and portlandite. The
specimens for thermal analysis were prepared similar to the preparation for XRD
analysis. TG-DSC analysis was conducted by using a simultaneous thermal analyzer
with a uniform heating rate of 10 °C per minute from room temperature to 900 °C in
a gas flow atmosphere.
SEM was used to observe the microstructure and morphology of the corrosion
products. After compressive strength testing, few pieces of the specimens were
taken out from the specimen and immersed into ethanol to terminate hydration.
Before testing, the specimens were removed from the ethanol, air dried at room
temperature (RT) for 10 min, and then dried at 60 °C for 8 h. A platinum coating
was subsequently applied onto the surface of the specimens.
3. Results and discussion
3.1. Setting time
The setting times of cement pastes with different accelerator
dosages are presented in Fig. 7a. As the amount of added accelera-
tor increased, the setting time of the pastes obviously decreased. In
particular, the decrease amplitude of the final setting time was
fairly large. However, when the accelerator content exceeded 3%,
the decreasing tendency was not obvious. As the accelerator dos-
age exceeded 4%, the setting time of cement pastes became nearly
 J. Wang et al. / Construction and Building Materials 95 (2015) 312–328 317

Fig. 7. Setting times of cement pastes. (a) Setting time of cement pastes with seven dosage of accelerator and (b) setting time of cement pastes with three w/b and four
amount of fly ash.

invariant. Therefore, 4% accelerator was used in subsequent
experiments.
And then, the experiment data of setting times of pastes (4%
accelerator added) with three water–binder ratio and four dosage
of fly ash are presented in Fig. 7b. The initial and final setting times
of the paste increased significantly when the w/b ratio and FA
dosage increased. A large w/b ratio and FA amount could extend
the final setting time and reduce the early performance of
shotcrete.
3.2. Compressive and splitting tensile strength
The compressive and splitting tensile strength of shotcrete by
different w/b ratios, inclusion of FA and amount of steel fiber are
listed in Table 5. With increasing age and content of steel fiber,
and decreasing w/b ratio, the compressive and splitting tensile
strength of the specimens showed a tendency to increase.
However, compared with S43F0, the compressive strength of the
specimens with FA content significantly decreased at an early cur-
ing age. After 28 days of curing, the compressive and splitting ten-
sile strength of shotcrete with FA increased. A 20% FA mixture
provides the highest comprehensive strength. With the weight of
steel fiber increased, compressive and splitting tensile strength
was high. Moreover, the growth rate of splitting tensile strength
was bigger than that of compressive strength.
In compared with C43F10, the compressive and splitting tensile
strength of S43F10 was lower. With accelerator in shotcrete, set-
ting time was faster than ordinary concrete. Because lots of thick
rod-like ettringite and albite crystal, and calculate silicate hydrate
(CSH gel) formatted, young shotcrete had high strength [39].
Nevertheless, with curing age increased, the density of shotcrete
was lower than that of ordinary concrete. Thus, the strength of
hardening shotcrete was only about 70% of ordinary concrete.
In order to estimate the relationship between strength and w/b
ratio, dosage of fly ash, and curing age, the regression analysis
(curve fitting technique) was used. From the large number of tests,
Eqs. (8) and (9) are the suitable regression model for describing the
relationship.
 
W FA
f ðt Þ ¼ k s a þ b þ N 1 ½N2 þ d ln ðt þ N3 Þ ð8Þ
C C
 s 2 s
ks ¼ e þf þ1 ð9Þ
c c
where ks is the parameters of steel fiber, w is the usage amount of
water per cubic meter (m3) of shotcrete, kg, c is the content of

Table 5
Compressive and splitting tensile strength of ordinary concrete and shotcrete for curing age.

Mix Curing age (days)

1 3 7 28 60 90 180 360
Compressive strength (MPa)
S38F10 14.07 20.73 25.89 35.33 40.50 46.97 48.55 50.01
S43F10 10.21 17.37 23.49 28.78 35.75 41.63 44.61 46.90
S49F10 8.04 14.53 19.70 26.38 32.92 38.64 45.62 46.72
S43F0 14.79 21.50 25.94 30.72 37.13 37.79 41.65 50.53
S43F20 8.75 16.92 21.56 34.28 43.27 48.81 51.23 54.36
S43F30 6.30 15.90 20.44 33.80 41.02 47.23 51.34 53.01
S43F10SF40 11.76 18.13 25.42 31.76 38.27 43.24 51.61 55.33
S43F10SF50 13.71 19.46 28.13 36.08 42.39 46.49 52.42 55.98
S43F10SF60 14.11 23.35 32.04 38.67 44.29 49.47 55.43 57.80
Splitting tensile strength (MPa)
S38F10 1.87 2.35 3.12 3.99 4.53 4.70 5.54 5.61
S43F10 1.43 2.25 2.54 3.27 3.85 4.29 4.68 4.77
S49F10 1.24 1.54 2.34 3.10 3.79 4.27 4.39 4.46
S43F0 1.8 2 2.43 2.94 3.66 4.01 4.07 4.23 4.37
S43F20 1.29 2.04 2.33 3.38 4.07 4.41 4.91 5.24
S43F30 0.83 1.55 2.25 3.84 4.06 4.48 5.03 5.42
S43F10SF40 1.57 2.48 2.71 3.53 4.15 4.46 5.05 5.45
S43F10SF50 1.72 2.73 3.01 3.81 4.38 4.68 5.26 5.61
S43F10SF60 2.04 3.14 3.51 4.34 4.82 5.08 5.65 5.98
318 J. Wang et al. / Construction and Building Materials 95 (2015) 312–328

OPC per m3, kg, FA is the dosage of fly ash in shotcrete per m3, kg, t Table 7
is the curing age, d and a, b, d, e, f, N1, N2, and N3 is the parameters. Carbonation depth (XC) of specimen after accelerated carbonation.

The effects of w/b ratio, FA amount and curing age on compres- Mix 7-day 14-day 21-day 28-day 42-day
sive and splitting tensile strengths were established according to (mm) (mm) (mm) (mm) (mm)
the following equations: C43F10 5.22 7.45 8.19 9.05 9.72
  S49F10 5.46 6.69 7.53 8.45 9.56
0ðt Þ w FA S43F10 5.12 6.34 7.21 8.38 9.16
f cc ¼ ks 3:485 þ 2:287 þ 4:209 ½3:314 þ 2:508ln ðt þ 0:250Þ
c c S38F10 4.25 6.28 7.04 7.82 8.79
S43F0 5.50 6.85 7.44 8.58 9.35
R2 ¼ 0:972 ð10Þ S43F20 4.02 5.52 6.59 8.04 9.21
S43F30 4.56 5.72 7.38 8.61 9.70
s 2 s S43F10SF40 3.45 4.71 5.28 6.17 7.39
ks ¼ 13:375  0:580 þ 1 ð11Þ S43F10SF50 3.23 4.56 5.00 5.76 6.21
c c
S43F10SF60 2.76 3.79 4.14 4.84 5.16
 
w FA
f st ðtÞ ¼ 4:858 þ 2:354 þ 4:908 ½0:531 þ 0:214ln ðt  0:050Þ
c c carbonation age was prolonged. Along the whole accelerated car-
R2 ¼ 0:965 ð12Þ bonation test, the carbonation depth of S43F10SF50 was less than
that of S43F10 and C43F10. At test age of 42 days, the carbonation
s 2 s depths of S43F10SF50 were 67.79% and 63.89% of those of speci-
ks ¼ 20:037  1:427 þ 1 ð13Þ mens S43F10 and C43F10, respectively.
c c
The test results on the carbonation depth of specimen measured
where fcc(t) is the compressive strength of shotcrete as a function of are represented by the values of corresponding carbonation coeffi-
curing age, MPa, fst(t) is the splitting tensile strength of shotcrete cient (KCC). KCC is inversely proportional to the carbonation resis-
with curing age, MPa. tance of concrete and was estimated using the empirical
relationship:
3.3. Durability pffiffiffi
X ¼ K CC T ð14Þ
3.3.1. Permeability where X is the tested carbonation depth (mm), T the period of accel-
Permeability is one of the most important indexes of shotcrete erated carbonation age, day; KCC is the corresponding carbonation
durability. In addition, permeability directly influence the durabil- coefficient, mm/day0.5.
ity of shotcrete: (1) Air permeability index kA can characterize the The carbonation coefficient KCC and correlation coefficient R2
accelerated carbonation resistance; (2) water absorption index S are listed in Table 8. With water–binder ratio increased and
can represent the frost resistance; and (3) non-steady-state chlo- amount of steel fiber decreased, the carbonation depth was
ride ion coefficient index DRCM can characterize the harmful ions increased. However, with dosage of fly ash enlarged, the carbon-
erosion resistance, such as chloride ion and sulfate ion. ation depth of specimen was first increased and then decreased.
The air permeability (kA), water absorption index (S) and When fly ash content was 20%, fly ash shotcrete had the minimum
non-steady-state chloride ion coefficient (DRCM) of the shotcrete carbonation depth. By using regression method, it was found that
specimen is listed in Table 6. The permeability of shotcrete there was exponential relationship between KCC and water–binder
decreased with increasing w/b ratio and amount of steel fiber. ratio, quadratic relationship between KCC and dosage of fly ash, and
However, the permeability of shotcrete first decreased and then logarithmic relationship between KCC and steel fiber content. The
increased with increasing FA content. regression Eqs. (15)–(17) were fitted as follows:
 
3.3.2. Accelerated carbonation ðw=bÞ
Water—binder ratio : K CCðwÞ ¼ EXP 0:1047 þ 0:3276
The carbonation depths of shotcrete are listed in Table 7. As car- b 0:43
bonation age was prolonged, shotcrete depth increased. When car- R2 ¼ 0:952 ð15Þ
bonation age was 42 days, the carbonation depths of specimens
C43F10, S43F10 and S43F10SF50 were 1.862 times, 1.788 times  2
FA FA
and 1.924 times than that of 7 days, respectively. In comparison Dosage of fly ash : K CCðFAÞ ¼ 1:61  0:2632 þ 0:1518
0:1 0:1
to C43F10, the carbonation depth of shotcrete was lower. The car-
bonation depth of S43F10 was 98.08% of that of ordinary concrete R2 ¼ 0:637 ð16Þ
at carbonation age of 7 days. When accelerated age increased to  
42 days, the carbonation depth of S43F10 was 94.23% of that of SF
Amount of steel fiber : K CCðSFÞ ¼ LN 4:726  1:88
specimen C43F10. Meanwhile, the absolute value was larger as 50
R2 ¼ 0:997 ð17Þ
Table 6 Reported from Tables 6 and 8, the carbonation coefficient KCC
Air permeability, water absorption index and non-steady-state chloride ion coeffi-
cient of the shotcrete specimen.
and air permeability index kA had the same changing trend. With
increasing of air permeability index, carbonation coefficient also
Mix kA S (g/m2 h0.5) DRCM (1012 m2/s) increased. By using regression analysis, the Eq. (18) was estab-
S38F10 0.013 220.89 18.93 lished for describing the relationship between carbonation coeffi-
S43F10 0.020 172.24 20.98 cient KCC and air permeability index kA (Fig. 8).
S49F10 0.038 150.99 27.34
 
S43F0 0.031 229.74 26.05 0:0012
S43F20 0.011 146.81 18.24 K CC ¼ EXP 0:5064  R2 ¼ 0:53 ð18Þ
kA  0:0071
S43F30 0.016 158.44 18.66
S43F10SF40 0.016 164.89 15.64 The compressive and splitting tensile strength of specimens
S43F10SF50 0.012 152.18 14.69
after accelerated carbonation are presented in Table 9. With the
S43F10SF60 0.009 139.01 13.28
carbonation depth deeper, the compressive strength and splitting
 J. Wang et al. / Construction and Building Materials 95 (2015) 312–328 319

Table 8
KCC and R2 of accelerated carbonation specimen.

Mix Formworking concrete Shotcrete

Water binder ratio Dosage of fly ash (%) Amount of steel fiber (kg/m3)
0.49 0.43 0.38 0 10 20 30 40 50 50
KCC 1.697 1.613 1.553 1.476 1.610 1.553 1.462 1.569 1.174 1.065 0.888
R2 0.945 0.953 0.960 0.973 0.940 0.960 0.996 0.991 0.992 0.961 0.957

Relative splitting tensile strength:

0
f stN;C43F10  
0 ¼ EXP 0:0019X C;C43F10 þ 0:0005X 2C;C43F10 R2 ¼ 0:984
f st0;C43F10
ð22Þ

0
f stN;S43F10  
0 ¼ EXP 0:0003X C;S43F10 þ 0:0022X 2C;S43F10 R2 ¼ 0:943
f st0;S43F10
ð23Þ

Fig. 8. Relationship between carbonation coefficient KCC and air permeability index
kA.
tensile strength was stronger. In comparison to ordinary concrete,
the growth rate of compressive and splitting tensile strength of
specimen S43F10 and S43F10SF50 were greater. As examination
age 56 days, the increase rate were 2.89 times and 1.25 times of
compressive strength and splitting tensile strength than those of
ordinary concrete. For that of S43F10SF50, the growth rate of split-
ting tensile strength was more obvious.
In order to analysis the strength after carbonation, the relation-
ship between carbonation depth and relative strength was estab-
lished as Eqs. (19)–(24).
Relative compressive strength:
0
f cN;C43F10
0 ¼ 0:0127X c;C43F10 þ 1 R2 ¼ 0:817
f c0;C43F10
0
f cN;S43F10
0 ¼ 0:0435X c;S43F10 þ 1 R2 ¼ 0:977
f c0;S43F10
0 un-corrosion shotcrete and rod-like ettringite, providing a favor-
f cN;S43F10SF50
0 ¼ 0:0213X c;S43F10SF50 þ 1 R2 ¼ 0:925
f c0;S43F10SF50
0
f stN;S43F10SF50  
0 ¼ EXP 0:0003X C;S43F10SF50 þ 0:004X 2C;S43F10SF50
f st0;S43F10SF50
R2 ¼ 0:993 ð24Þ
In the forming process of shotcrete, cementitious materials and
aggregate are sprayed at high velocity under air pressure and com-
pacted under continuous impacted. Therefore, the density of shot-
crete was lower than ordinary concrete and diffusion velocity of
CO2 was slow in shotcrete. For the above reason, the carbonation
resistance of shotcrete was better than ordinary concrete. Steel
fiber could improve the pore structure and inhibit the emergence
and development of drying shrinkage cracks at early age. In the
meantime, steel fiber also hinder the carbonation shrinkage cracks
in shotcrete. Thus the carbonation resistance was enhanced.
Carbonation is a complicated physicochemical process. The
reaction products can fill in pores and interfacial transition zone
(ITZ) of concrete and increase the density of concrete. So the com-
pressive and splitting tensile strength was larger with the carbon-
ation depth deeper. Compared with ordinary concrete, the initial
density of shotcrete was high. There was high increasing rate of
strength after filling few amount of carbonation products in pores.
ð19Þ While the carbonation products was filled into the boundary of
fiber and matrix, the interface bonding stress and fracture energy
was increased. Therefore, the splitting tensile strength of SFRS
was obviously enhanced.
ð20Þ
SEM(s) and EDS of specimen S43F10 after carbonation are listed
in Fig. 9. There was micro-crack with length of 50 lm in
ð21Þ able place for growing of CaCO3 crystal, was uniform distributed
in microcrack (Fig. 9a). As accelerated age 7 days, there was

Table 9
Compressive strength (fc0 ), splitting tensile strength (f0st ) of specimen after accelerated carbonation.

Mix Non- 7-day 14-day 21-day 28-day 42-day

carbonation
fc00 f0st0 fcN0 fstN0 fcN0 fstN0 fcN0 fstN0 fcN0 fstN0 fcN0 fstN0

Absolute value (MPa)

C43F10 50.57 4.52 53.22 4.64 55.41 4.73 54.40 4.79 56.56 4.81 59.87 4.95
S43F10 35.75 3.85 44.31 3.93 46.03 4.32 47.26 4.57 51.07 4.67 52.02 4.90
S43F10SF50 42.63 4.07 44.45 4.21 47.70 4.35 48.01 4.59 48.41 4.63 49.52 5.14
Relative value (%)
C43F10 1 1 1.052 1.027 1.096 1.046 1.076 1.060 1.118 1.064 1.184 1.095
S43F10 1 1 1.239 1.021 1.288 1.122 1.322 1.187 1.429 1.213 1.455 1.273
S43F10SF50 1 1 1.043 1.034 1.119 1.069 1.126 1.128 1.136 1.138 1.162 1.263
320 J. Wang et al. / Construction and Building Materials 95 (2015) 312–328

loose-pellet-like CaCO3 crystal nucleus which analyzed by EDS
(Fig. 9b and i) at the end portion of ettringite. Increased to 14 days,
ettringite crystal was lost in micro-pores, and the capillary wall
changed from rough to smooth and from irregular to rule (Fig. 9c
and j). With carbonate reaction going on, CaCO3 whisker grew up
to intersect each other, and filled in pores and micro-cracks
(Fig. 9d and k). Simultaneously, CSH gel reacted with CO2 gas to
form calcium carbonate which deposited on the surface of
micro-pores (Fig. 9e–g, l and m). When accelerated carbonate
was 56 days, there was none large diameter pores and a great
many of micro-pores in specimen (Fig. 9h). Consequently, the den-
sity of specimen and compressive and splitting tensile strength
were increased.
3.3.3. Freezing and thawing cycle
Relative dynamic elasticity modulus and weight loss rate are
shown in Table 10. As freeze–thaw cycle increased, the relative
dynamic elasticity modulus and weight loss rate were great.
After 100 freeze–thaw cycles were completed, the relative dynamic
elasticity modulus and weight loss rate of C43F10 were 63% and
3.51%, respectively. The relative dynamic elasticity modulus and
weight loss rate of S43F10 were 15.87% and 32.48% of C43F10,
respectively; the relative dynamic elasticity modulus and weight
loss rate of S43F10SF50 were 17.46% and 21.37% of C43F10, respec-
tively. In this period, C43F10 was frost damaged. After 200 freeze–
thaw cycles were completed, the relative dynamic elasticity mod-
ulus and mass loss rate of S43F10SF50 were 43.75% and 75.38% of

Fig. 9. SEMs and EDS spectra images of shotcrete after carbonation.

 J. Wang et al. / Construction and Building Materials 95 (2015) 312–328 321

Table 10
Relative dynamic elasticity modulus and weight loss rate of specimen after freeze–thaw cycles.

Specimen Freeze and thaw cycles

0 25 50 75 100 125 150 175 200 225 250
Relative dynamic elasticity modulus (%)
C43F10 1 0.89 0.87 0.73 0.37
S43F10 1 0.97 0.93 0.91 0.90 0.89 0.82 0.75 0.52 0.49
S43F10SF50 1 0.98 0.96 0.93 0.90 0.89 0.87 0.86 0.79 0.73 0.57
Weight loss rate (%)
C43F10 0 0.48 1.09 1.97 3.51
S43F10 0 0.13 0.31 0.79 1.14 1.33 1.99 2.5 3.33 5.40
S43F10SF50 0 0.07 0.23 0.45 0.75 0.96 1.21 1.37 2.51 2.92 3.80

those of S43F10. Thus, the frost resistance of S43F10 was higher
than that of C43F10, and steel fiber could significantly improve
frost resistance of shotcrete.
The compressive and splitting tensile strengths of specimen are
listed in Fig. 10. With increasing freeze–thaw cycle, the compres-
sive and splitting tensile strengths reduced. The frost resistance
values of S43F10 and S43F10SF50 were higher than those of
C43F10. Compressed air was present in shotcrete and not timely
discharged; as such, enclosed micropores (Fig. 11) were formed
in shotcrete with air contents of 2.5–5.3% [17]. During freeze–thaw
cycle, the micropores helped relieved the frost-heave pressure on
capillary pore water and osmotic pressure of super cooled water
migration. These pores could also reduce freeze–thaw damage.
S43F10SF50 showed excellent frost resistance mainly because steel
fiber weakened damage caused by frost resistance-induced tensile
stress on the matrix and improved the fracture energy of specimen.
As a result, S43F10SF50 yielded a higher compressive and splitting
tensile strengths at the same freeze–thaw cycle times.
The SEMs of specimens after freezing and thawing cycle are
listed in Fig. 12. Reported from figures, the inside of specimen
was dense expect mixture C43F10 because of there were
micro-pore with diameter of 2–5 lm and micro-cracks with width
of more than 5 lm (Fig. 12a). These cracks provided channels for
migrating of super-cooled water and produced stress concentra-
tion which accelerated the frost damage. After 100 cycles, the
amount of pores inside of C43F10 was raised and diameter of pores
was the increasing trend (Fig. 12b). In mixture S43F10, CSH gel lost
slowly and Ca(OH)2 appeared. Meanwhile, the penetrating crack
was emerged in specimen (Fig. 12c). Correspondingly, there was
no significantly change in mixture S43F10SF50 (Fig. 12d). When
freezing and thawing cycle was 200, in mixture S43F10, the net
structure (Fig. 12e) appeared in specimen which made of ettringite
and albite crystal and there was less CSH gel in (Fig. 12f). By con-
trast, the frost damage of mixture S43F10SF50 was slight and there
was only few interconnected micro-pores in shotcrete matrix
under the tensile stress was generated by steel fiber (Fig. 12g).
Alternatively, steel fiber can improve the microstructure and frost
resistance of shotcrete.
3.3.4. Sulfate attack
The relative dynamic elasticity modulus of ordinary concrete
decreased as accelerated aging was prolonged (Fig. 13). However,
the change in relative dynamic elasticity modulus of shotcrete
was observed in three stages as follows: initial downward stage
(less than 15 cycles), stable stage (more than 15 cycles but less
than 30 cycles), and rapidly declining stage (more than 60 cycles).
With 150 dry–wet cycles, the loss ratios of the relative dynamic
elasticity modulus of undamaged specimens were 78.7%, 83.1%,
and 87.7%.
Fig. 14 shows the weight loss ratios of damaged specimens. In
ordinary concrete, the mass loss ratio of shotcrete was observed
in three steps: increasing step, stable step, and decreasing step.
The weight of SFRS initially increased by 0.55% and then became
stable. Steel fiber can inhibit internal expansion and crack propaga-
tion in a specimen. Thus, cracking spalling degree on a specimen
surface was reduced.
Reported from Figs. 13 and 14, the sulfate resistance of ordinary
concrete was better than the other two mixture when dry–wet
cycles was less than 60. This is because ordinary concrete had bet-
ter mechanical properties, better pore structure and worse

Fig. 10. Relative compressive and splitting tensile strength of specimen after
freeze–thaw cycles. Fig. 11. Enclosed pores in shotcrete.
322 J. Wang et al. / Construction and Building Materials 95 (2015) 312–328

Fig. 12. SEMs of specimen after freezing and thawing damage. (a) Undamaged specimen C43F10; (b) specimen C43F10 after 100 freeze–thaw cycles; (c) specimen S43F10
after 100 freeze–thaw cycles; (d) specimen S43F10SF50 after 100 freeze–thaw cycles; (e) net structure of speciem S43F10 after 200 freeze–thaw cycles; (f) ettringite and
ablite in specimen S43F10 after 200 freeze–thaw cycles and (g) interconnected micro-pores and micro-cracks in specimen S43F10SF50 after 200 freeze–thaw cycles.

Fig. 13. Relative dynamic elasticity modulus of specimens by different accelerated Fig. 14. Weight loss ratio of specimens by different accelerated aging.
aging.

steel fiber reinforced shotcrete, became better. Due to lots of

permeability than ordinary shotcrete and steel fiber reinforced
shotcrete. At the beginning of erosion, sulfate was difficult to dif-
fuse the inside of ordinary concrete. The relative amount of corro-
sion products in mixture C43F10 was less than shotcrete.
Therefore, the original performance of ordinary concrete was bet-
ter than shotcrete.
With the increasing number of dry–wet cycle, sulfate resistance
of ordinary concrete get worse and that of shotcrete, especially
micro-pores and high porosity of shotcrete, there were more space
to hold corrosion products such as ettringite and gypsum. Also the
performance of shotcrete was stable. When dry–wet cycle was
more than 60, the relative dynamic elasticity modulus and weight
loss of ordinary shotcrete was obviously decreased. However, com-
pared with mixture S43F10, the weight loss of steel fiber reinforced
shotcrete stabled during the whole experiment. This is due to steel
fiber eliminated the swelling stress of ettringite and gypsum.
 J. Wang et al. / Construction and Building Materials 95 (2015) 312–328
Fig. 15. Compressive and splitting tensile strength of specimens under accelerated
aging.
Fig. 16. Damage layer thickness of specimen.
Fig. 17. XRD patterns of specimen under different accelerated aging.
The mechanical properties of damaged specimens are presented
in Fig. 15. The compressive and splitting tensile strengths initially
increased and then decreased. The mechanical properties of
C43F10, S43F10, and S43F10SF50 reached the maximum values
during dry–wet cycles of 15, 30, and 60, respectively. Afterward,
strength quickly decreased.
The thickness of the damaged layer of the specimen after sulfate
attack was tested (Fig. 16). As accelerated aging was prolonged, the
thickness of the damaged layer increased, but growth varied. The
323
Fig. 18. Thermal analysis of corrosion shotcrete by different accelerated aging.
Fig. 19. Thermal analysis curves of specimen S43F10 (depth of 2 mm according to
the surface) [40].
initial thickness of ordinary concrete was 74.55% than that of shot-
crete. Finally, damage layer thickness of ordinary concrete reduced
rapidly and was 105% than that of shotcrete. Erosion rate was slow
because of high strength and density of ordinary concrete. As the
amount of corrosion products increased, specimen performance
rapidly deteriorated. The enclosed pores in shotcrete can accom-
modate a large number of corrosion products and improve sulfate
resistance. Steel fiber can significantly improve the internal
324 J. Wang et al. / Construction and Building Materials 95 (2015) 312–328

microscopic pore structure of sprayed concrete and enhance sul- erosion reaction rate was quickly. Therefore, gypsum and mirabi-
fate corrosion resistance. lite were appeared in the corrosion products at the specimen sur-
At the beginning corrosion, the SO2 4 ion in solution was face part. Although the compressive and splitting tensile strength
absorbed to the surface of specimens, and then diffusion into spec- of specimen increased, the surface damage layer was formed.
imen. Sulfate ion reacted with portlandite and [AlðOHÞ ] to form Consequently, the main damage mode of specimen under sulfate
ettringite (as seen in Figs. 17–19 and 20b). erosion was ettringite erosion.
With dry–wet cycles increased, ettringite crystal was abnormal
 growth. Swelling stress appeared in micro-pores and -cracks and
2½AlðOHÞ4  þ 6Ca2þ þ 4OH þ 3SO2
4 þ 26H2 O
took them propagation. This can provide the channel for sulfate
! 3CaO  Al2 O3  3CaSO4  32H2 O ions diffusion and increase the sulfate damage.
With the concentration of sulfate ions increased, the concentra-
In this stage, the micro-pores and -cracks was hold with ettring-
ite which can increased the density of specimen. However, due to tion product of Ca2+ and SO2
4 in pore solution was reached to that

high sulfate ions concentration at the specimen surface, the of gypsum and the gypsum crystal was precipitated (Fig. 20d). At

Fig. 20. SEMs of specimen S43F10 after dry–wet cycles.

 J. Wang et al. / Construction and Building Materials 95 (2015) 312–328 325

the same time, in the drying state, sodium sulfate solution crystal-
lized to form mirabilite (also seen in Fig. 20b). With the erosion
reaction going on, the reduced content of portlandite accelerated
the CSH decomposition (Figs. 17 and 18).

Ca2 þ þSO2
4 ! CaSO4

Naþ þ SO2
4 þ 10H2 O ! Na2 SO4  10H2 O

xCaO  ySiO2  zH2 O ! xCaðOHÞ2 þ ySiO2  zH2 O

Due to the volume expansion inside specimen with the forming
process of ettringite and gypsum crystal (Fig. 20e), the
micro-cracks was generated on the surface of specimens. Thus,
the solution filled into micro-cracks and crystallized which can
take cracks extended. Finally, sulfate resistance of specimen was Fig. 22. Thermal analysis of corrosion shotcrete by different depth according to the
rapid deteriorated. Therefore, in this stage, the main damage mode surface.
of specimen under sulfate erosion was chemistry erosion of
ettringite and gypsum, and physical erosion of sodium sulfate crys-
tallization (Fig. 20f and g).
Compared with specimen S43F10 (Figs. 21 and 22), mixture
S43F10SF50 had better sulfate resistance. This is because steel fiber
can improve the pore structure and reduce the micro-pores and
-cracks and dry shrinkage cracks of shotcrete. With the dry–wet
cycle prolonged, erosion products, such as ettringite, gypsum and
mirabilite, were formed and filled into micro-pores (Figs. 23 and
24). Under the effect of dry–wet cycle, steel fiber can effectively
inhibited the micro-cracks propagation due to expansion on heat-
ing and contraction on cooling and expansion stress. At the same
corrosion age, the density and erosion products of specimen
S43F10SF50 were different with those of specimen S43F10. As
dry–wet cycle of 60 times, micro-cracks of specimen S43F10SF50
were filled with ettringite (Fig. 25a and c). When dry–wet cycle
of 150 times, ettringite crystal which in micro-pores presented
abnormal growth. (Fig. 25b and d) Meanwhile, with the depth
according to specimen surface deep, the amount of ettringite was
Fig. 23. XRD patterns of specimen S43F10SF50 by different depth according to
first increased and then decreased, and finally became stability. surface on 150 cycles.
Similarly, the content of gypsum continued to decrease. There
was none gypsum in specimen when the depth according to sur-
face was more than 6 mm. however, C2SH and portlandite was first
increased and then stabile (as shown in Fig. 24). The number of
micro-cracks and micro-pores of specimen S43F10SF50 was obvi-
ously less than that of specimen S43F10.

3.3.5. Chloride ion diffusion

Chloride ions migrated into shotcrete through diffusion, capil-
lary absorption, and penetration when shotcrete comes in contact

Fig. 24. Thermal analysis of specimen S43F10SF50 by different depth according to

the surface.

with seawater. Chloride ion migrated to the inner layer of shotcrete

Fig. 21. XRD patterns of specimen by different depth according to surface on 150
cycles.
through capillary absorption as the main mode because of unsatu-
ration on specimen surface; the migration depth usually reaches
5–15 mm. Based on concentration gradient, chloride ion migrated
through diffusion as the main mechanism. However, migration
velocity decreased because of surface tension and diffusion resis-
tance. Compared with capillary absorption and diffusion, the pen-
etration of chloride ion in shotcrete was negligible.
326 J. Wang et al. / Construction and Building Materials 95 (2015) 312–328

Fig. 25. SEM images and EDS patterns of specimen S43F10SF50 after dry–wet cycle. (a) 60 dry–wet cycles; (b) 150 dry–wet cycles; (c) EDS pattern of point 6 in (a) and (d) EDS
pattern of point 7 in (b).

The chloride ion concentrations of shotcrete at different exper- the specimen was cut from large slags, and great amounts of ITZ
imental ages and environments are listed in Fig. 26. As depth and pores were found around aggregate and steel fiber, which pro-
increased on the basis of specimen surface, chloride ion concentra- vided the passage of chloride ion migration.
tion initially increased until peak concentration was reached; chlo- Because shotcrete single layer lining structure is immersed in
ride ion concentration decreased and became stable. At the same sea water or exposed in marine environment, chloride ion was dif-
depth of the specimen, the chloride ion concentration increased fused in shotcrete under the effect of osmotic pressure. Therefore,
as experimental age was prolonged. At corrosion age of more than the transport of chloride ion in specimens was in accordance with
120 days, the peak concentration of the specimen immersed in a Fick’s second low which listed as follows [41]:
salt solution reached a concentration similar to that of the speci-  
men on the surface, and the range of chloride ion convection zone @C @ @C
¼ D ð25Þ
reduced. By contrast, the peak concentration of the specimen in the @t @x @x
salt-sprayed environment was different from that of the specimen
where x is the depth according to specimen surface, mm; C is the
in the surface; convection zone increased.
chloride ion mass percentage of specimen in the depth x, %; t is
Chloride ion concentration on a specimen surface varied from
the time of immersion or sprayed, s; D is the chloride ion diffusion
high to low in the following order: S43F10, S43F10SF50, and
coefficient, m2/s.
C43F10. This result is attributed to the rate of chloride ion diffusion
When the chloride ion is in the one-dimensional diffusion state,
that depends on the density and permeability of a specimen. In the
the boundary condition and initial condition of Fick’s second law
spray process, a large number of pores were evenly distributed in
are assumed as follows:
shotcrete; the density of specimen was lower than that of ordinary
concrete. With an accelerator in concrete, hydration rate was abso- Cjx¼0 ¼ C s ; Cjt¼0;x>0 ¼ C 0 ; Cjx¼1 ¼ C 0 ; ð26Þ
lutely fast, and high amount of hydration heat was released in a
short time. Ettringite and CSH gel quickly formed and specimen The analytical solution is as follows:
microstructure loosened.   
With steel fiber in shotcrete, the distribution of chloride ion was x
Cðx; tÞ ¼ C 0 þ ðC s  C 0 Þ 1  erf pffiffiffiffiffiffi ð27Þ
the same as that in ordinary shotcrete. As experimental age was 2 Dt
prolonged, the convection zone range became smaller for specimen
where C(x, t) is the chloride concentration in depth x at immersion
at under seawater but larger for specimen at salt-sprayed environ-
or sprayed time t, %; C0 is the initial chloride concentration, %; Cs is
ment. The chloride ion concentration on the surface layer of
the surface chloride concentration, %; erf(x) is error function:
S43F10SF50 was lower than that of S43F10 under seawater. The
chloride ion concentration was higher in a salt-sprayed environ- Z z
2

ment than under seawater. On the one hand, steel fiber could inhi- erf ðzÞ ¼ pffiffiffiffi EXP u2 du ð28Þ
p 0
bit the generation and expansion of microcracks when shotcrete
was young. On the other hand, steel fiber could improve the micro- By using regression analysis method, the chloride diffusion coeffi-
structure, density, and pore tortuosity of shotcrete. Nevertheless, cient D of specimens was obtained and listed in Fig. 27.
 J. Wang et al. / Construction and Building Materials 95 (2015) 312–328 327

Fig. 26. Chloride ion concentration of specimen at different age and environment.

Fig. 27. Chloride ion diffusion coefficient and surface chloride concentration of specimen C43F10, S43F10 and S43F10SF50 at four immersion or sprayed salt testing age. (a)
Chloride ion diffusion coefficient of specimens at immersion environment and (b) chloride ion diffusion coefficient of specimen at salt sprayed environment.

Reported in Fig. 27, it was found that there were several laws
about chloride ion diffusion coefficient and surface chloride con-
centration. First, with test age prolonged, chloride ion diffusion
coefficient of specimens was decreased. More precisely, there
was exponential relationship between chloride ion diffusion coef-
ficient and immersion or salt sprayed time. Second, it also shown
that the chloride ion diffusion coefficient of specimen S43F10
was more than that of mixture C43F10 and S43F10SF50. Third, dif-
fusion coefficient of specimen at salt sprayed environment was
greater than that at immersion environment. This is because that
there is a lot of capillary pores in specimen S43F10 which provide
channels for chloride ion diffusion. At immersion environment,
chloride ion quickly migrated into specimen. However, at salt
sprayed environment, under the action of capillary absorption,
the migration speed of chloride ion was more rapid due to speci-
men was in the non-saturation state for a long time.
4. Conclusions
Shotcrete is widely applied in tunneling and underground
structure; thus, understanding its mechanical properties and dura-
bility is important. In this study, the mechanical properties of shot-
crete was tested. Meanwhile, the durability of ordinary concrete
(mixture C43F10), ordinary shotcrete (mixture S43F10) and steel
fiber reinforced shotcrete (mixture S43F10SF50) was also
researched. On the basis of the test and theory analysis, the follow-
ing conclusions can be obtained.
The initial and final setting times of the pastes increased signif-
icantly when w/b ratio and FA dosage increased. Meanwhile, com-
pressive and splitting tensile strengths had a better relationship
with curing age, water–binder ratio, fly ash amount and dosage
of steel fiber. With the increase in fly ash dosage and decrease in
w/b, the strength of the specimen increased exponentially.
328 J. Wang et al. / Construction and Building Materials 95 (2015) 312–328
With hydration age, w/b, and amount of steel fiber increased,
the permeability of shotcrete was worse than ordinary concrete.
With increasing of fly ash and steel fiber content, the permeability
of shotcrete was decreased. However, with dosage of fly ash
increased, the permeability of shotcrete first fell and then rose.
The carbonation depth of ordinary concrete was more than that
of ordinary shotcrete and steel fiber reinforced shotcrete. That is,
shotcrete had batter carbonation resistance and there was to have
relationship between carbonation coefficient KCC and air perme-
ability kA. Similarly, the frost and sulfate resistance of ordinary
shotcrete was much better than that of ordinary concrete. This is
because large amount of micro-pores can decrease the
frost-heaving force from super-cooled water migration and swell-
ing stress from corrosion products. In addition, chloride ions con-
centration of ordinary shotcrete was higher than that of ordinary
concrete. Reported in experiment data, chloride ions diffusion per-
formance had obviously relationship with attack environment and
immersion and salt sprayed time. Meanwhile, chloride ion concen-
tration and diffusion coefficient of concrete in salt sprayed envi-
ronment was much more than that in salt immersion. More
importantly, because steel fiber can improved the micro-pore
structure and relieved the damage tensile stress, the durability of
steel fiber reinforced shotcrete was significantly improved than
ordinary shotcrete.
Further research is needed to investigate the frost and sulfate
resistance, and chloride ion diffusion of shotcrete with different
water–binder ratio, fly ash content and amount of steel fiber.
And then, the durability of shotcrete under multi-factor coupling
participation was also need to analyze.
Acknowledgements
Thanks are due to former master students at the Xi’an
University of Architecture and Technology for their help in exper-
iment and calculations, in particular, Ding Sha, Liu Yaping, Zhou Yu,
Tong Zhenyu and Ma Rui. And this project is financially supported
by the National Natural Science Foundation of China (No.
51278403), the Program for Innovative Research Team in
University of China’s Ministry of Education (IRT 13089) and the
Doctor Innovation Foundation of Xi’an University of Architecture
and Technology (DIF-XAUAT).
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