Hindawi Publishing Corporation

Advances in Materials Science and Engineering

Volume 2015, Article ID 813052, 14 pages
http://dx.doi.org/10.1155/2015/813052

Research Article
Development of a New Type of Alkali-Free Liquid Accelerator
for Wet Shotcrete in Coal Mine and Its Engineering Application

Gang Zhou,1,2,3 Weimin Cheng,1,3 and Sen Cao1,3

1
State Key Laboratory of Mining Disaster Prevention and Control Co-founded by Shandong Province and the Ministry of
Science and Technology, Shandong University of Science and Technology, Qingdao 266590, China
2
Key Laboratory of Safety and High-efficiency Coal Mining, Ministry of Education, Anhui University of Science and Technology,
Huainan 232001, China
3
College of Mining and Safety Engineering, Shandong University of Science and Technology, Qingdao 266590, China

Correspondence should be addressed to Gang Zhou; zhougang@sdust.edu.cn

Received 21 June 2015; Revised 4 August 2015; Accepted 4 August 2015

Academic Editor: Santiago Garcia-Granda

Copyright © 2015 Gang Zhou et al. This is an open access article distributed under the Creative Commons Attribution License,
which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

In order to address issues such as large rebound rate, high dust concentration, and low compressive strength of shotcrete when
adding liquid accelerator during wet spraying, the factors influencing the efficiency of liquid accelerator were experimentally
analyzed. The single-admixture, combination, and orthogonal tests were conducted on the five fundamental raw materials required
to develop the new liquid accelerator. The WT-1 type liquid accelerator, which had better adaptability to different kinds of
cement, was developed with the mass concentration ratio of 55% aluminum sulfate octadecahydrate, 4% sodium fluoride, 2.5%
triethanolamine, 0.5% polyacrylamide, 5% bentonite, and 33% water. Experimental investigation showed that the initial setting
time of the reference cement with 6% mass content of this liquid accelerator was 2 minutes and 15 seconds, and the final setting
time was 7 minutes and 5 seconds. The compressive strength after 1 day of curing was 13.6 MPa and the strength ratio after 28
days of curing was 94.8%, which met the first grade product requirements of the China National Standard. Compared with the
conventional type liquid accelerator, the proposed type WT-1 accelerator is capable of effectively reducing the rebound rate and
dust concentration while significantly increasing the compressive strength of the shotcrete.

1. Introduction alkali-free product and from a powder product to a liquid

product [4, 5]. The research on the development of low
As one of the key techniques to ensure the safety of an alkaline liquid accelerator began in the early 1990s, when the
underground coal mine roof, anchor and spray support Nitto Chemical Industry Co. Ltd. synthetised an accelerator
is widely employed in sinking and drifting engineering. that contained alkali sulphate or carbonate and water-soluble
Accelerator is a common additive in anchorage shotcrete aluminium salt or traces of magnesium carbonate [6]. This
which significantly reduces the time frame for concrete accelerator was capable of reducing the strength loss of
grout to consolidate, accelerates the hardening process of concrete, but its adaptability to different types of cement and
the cement, ensures the achievement of sufficient concrete its workability were poor. In addition, the dust raised by its
strength in a short time frame, and reduces the rebound application and rebound rate was significant [7, 8]. Burge
rate and improves productivity [1–3]. Since wet shotcrete has synthetised a type of alkali-free liquid accelerator containing
become increasingly popular in China’s coal mines, the need an aluminium salt, corrosion inhibitor, and complexing agent
for a liquid accelerator for underground anchors and spray which produced concrete with compressive strengths at 1
support is of utmost importance. day, 3 days, and 28 days of 19 MPa, 32 MPa, and 48 MPa,
The earliest liquid accelerator was the Sika accelerator respectively, but the setting time of concrete was longer [9].
developed decades ago in Sweden which was developed from MBT of Sweden produced the MEYCOSA series of alkali-free
a strong alkaline product to a low alkaline and finally to an liquid accelerators which offered the advantages of high initial
2 Advances in Materials Science and Engineering

strength, low chlorine content, and low dust concentration Table 1: Contents of main components of reference cement.
during construction [10–12]. The research and development
Free
on an alkali-free liquid accelerator in China began in late Tricalcium Tricalcium Alkali
calcium
1990s and was rapid because of the outstanding advantages aluminate silicate content
oxide
and requirement of shotcrete engineering in China. Pan
and Lv of Nanjing Technological University successfully 6–8% 55–60% ⩽1.2% ⩽1%
synthetised a type of NSA alkali-free liquid accelerator in
using an inorganic-organic composition which exhibited no
detrimental effects on the 28-day strength of the cement studies of accelerators, an initial selection experiment was
grout but adversely affected the initial strength [13, 14]. The conducted on a large range of materials [16, 18–21]. Finally
adaptability of the liquid accelerator to different types of five types of chemical raw materials apart from water have
cement was good. Ding et al. developed a type of DXQ been determined, which are represented as A, B, C, D, and E,
alkali-free liquid accelerator which minimized strength loss among which A is the major component of the accelerator.
at 28 days but did not appear to improve the initial strength Specifically, Material A is aluminum sulfate octadec-
[15]. In addition, the adaptability to various types of cement ahydrate which is the main coagulating constituent of the
and temperature was poor and the 28-day strength ratios of new type accelerator containing 51.4% anhydrous aluminum
different types of cement scattered significantly [16]. Han et al. sulfate. According to the related information, the aluminum
developed a type JL-1 low alkaline liquid accelerator using ion can accelerate the solidification process of cement when
sulphur aluminate and neutral sodium salt as coagulant and added into it. Moreover, the solidification time will reduce
optimised the product using polymer [17]. This accelerator greatly with the increasing in the amount of aluminum ion
effectively reduced the rebound rate and the strength loss at [22–26]. From the above it can be known that aluminum
28 days was minimal. It was beneficial to the durability of sulfate is an ideal component of accelerator, for it is alkali-free
concrete, but the performance was considerably affected by but has good coagulating effect.
different water-cement ratios and types of cement. Material B is sodium fluoride, a kind of metal fluoride
In summary, a variety of mixed results were obtained by in a solid powder state at room temperature with relatively
a number of researchers seeking developing a suitable liquid low solubility. The addition of single component B cannot
accelerator for shotcrete. However, due to the rigorous envi- reduce the solidification time for cement obviously. However,
ronmental conditions in underground coal mines, problems Material B is a kind of effective complexing agent. When A
with the development of shotcrete persist. These include low mixes with B, a relatively stable material, sodium hexafluo-
durability, low long-term strength, large rebound rates and roaluminate, is generated, which can increase the amount of
dust concentration, poor adaptability for various types of aluminum ion. The adding of mixture of A and B into cement
cement, and corrosive damage. These problems significantly can accelerate the formation speed of hydrate effectively, and
affect the health of the workers and the quality of the projects the cement can be coagulated quickly; then the strength and
and hinder the promotion of wet shotcreting in mines. Since stability of sprayed concrete can be improved in a short time.
the dry concrete spraying machine has been listed as outdated Material C is triethanolamine, an organic alkamine-typed
and prohibited by the State Administration of Work Safety, accelerator in a liquid state at room temperature which is
rapid development of the wet shotcreting technique in mines highly soluble in water, and it is nontoxic. As a kind of
of China is imminent. Therefore, it is of particular interest to catalytic agent, Material C can improve the solubility of
develop a liquid shotcrete accelerator that is highly efficient, aluminum sulfate and increase the amount of aluminum
economical, and environmentally friendly. ion in the accelerator solution, and the coagulating speed of
cement can be improved in this way.
2. Experimental Materials and Program Material D is polyacrylamide, a linear high molecular
weight polymer, and it is nontoxic. As a kind of good binder,
2.1. Experimental Materials a small amount of Material D can improve the cohesion of
cement paste. Besides, Material D can also lock moisture and
2.1.1. Cement. The reference cement is the special cement help coagulant components shorten solidification time, so it
for testing the performance of concrete admixture, which is a good synergist.
has a strength level exceeding 42.5. No composite material Material E is bentonite, a soil-state mineral with
is added. Moreover, the contents of main components of extremely small diameter of particle which is nontoxic
reference cement are shown in Table 1. and inexpensive. Material E plays an important role in
the new-type accelerator. Firstly, Material E shows good
2.1.2. Sand. The sand used in these experiments was standard cohesiveness after mixing with water because of its good
sand employed in strength tests of cement which complies hydrophilicity, which is useful in reducing the rebound rate
with the requirements of the ISO standard in national and dust concentration in the wet spraying field. Secondly,
standard GB/T17671-1999 Method of testing cements— Material E has great properties of suspension and dispersion,
Determination of strength. so it can work as a kind of thickening agent in the accelerator
solution to improve the stability of liquid. Thirdly, Material
2.1.3. Constituents of the New Type of Liquid Accelerator. E has large expansion coefficient and its volume can expand
Based on the literature review of domestic and international to 40 times as before after absorbing water, which can reduce
Advances in Materials Science and Engineering 3

the cracked phenomenon due to the volume shrinkage of 25

cement.
20
2.1.4. Existing Accelerator. In order to analyse the factors

Time (min)
affecting the coagulating performance of the accelerator, a 15
standard liquid accelerator produced by Jiangsu Bote New
Materials Co. Ltd. was used in the experiments. 10

5
2.2. Experimental Program
2.2.1. Standard of Evaluation of Accelerator. The industrial 0
5 10 15 20 25 30
standard of building materials in China JC477-2005 Flashing Material temperature (∘ C)
Setting Admixtures for Shotcrete specifies the requirements
of performance for an accelerator-added cement paste and Initial setting time
hardened mortar, as shown in Table 2. Final setting time

Figure 1: Effect of material temperature on the result of solidifica-

2.2.2. Measurement of Setting Time for Cement Paste. The tion at an environmental temperature of 20∘ C.
setting time of cement paste is the primary performance
indicator of an accelerator since a setting time that is too 25
short significantly undermines the normal hydration process
of concrete and affects the stability of the structure, while a
setting time that is too long leads to large rebound rate, which 20
reduced thickness of each layer of shotcrete and difficulty in
Time (min)

curing the concrete [27–29]. The Vicat apparatus was used to 15

measure the performance of accelerator.
10
2.2.3. Measurement of Strength of the Sand-Cement Grout.
The strength of sand-cement grout was measured using 5
a WDW3100 computer-controlled electric universal test
machine. Mould with a dimension of 40 mm × 40 mm ×
0
160 mm and standard curing box were used. 2 3 4 5 6 7 8
Accelerator content (%)
3. Experimental Analysis of Impact Factors of Initial setting time
the Coagulating Performance of Accelerator Final setting time

The setting time of an accelerator and the strength of the Figure 2: Effect of accelerator mass content on setting time.
product at different ages are affected by a number of factors
including the method of operation, amount of accelerator
added, and temperature of the material. Therefore, it is the hydration reaction released a lot of heat in a short
necessary to analyse the primary impact factors in order time, which significantly reduced the final setting time of
to unify the test methods to acquire accurate results. The concrete. These results indicated that, during shotcreting,
reference cement and alkali-free liquid accelerator produced insulation should be implemented. During the experiment to
by Bote were used in the control experiments. develop a new type of liquid accelerator used in mines, the
environmental as well as material temperature was controlled
3.1. Effect of Material Temperature. Despite the fact that the at 20∘ C.
shotcreting temperature should be controlled at 20∘ C ± 2∘ C
as specified by JC477-2005 Flashing Setting Admixtures for 3.2. Effect of the Content of Accelerator on the Setting Time
Shotcrete, considering the actual conditions in coal mines, of Cement. At a fixed test temperature of 20∘ C of both
the effect of material temperature on the result of solidifica- environment and material, the effect of various accelerator
tion at an environmental temperature of 20∘ C was tested, as concentrations on the setting time of the reference cement is
shown in Figure 1. shown in Figure 2.
It could be seen from the test results that, with the increase According to Figure 2, during the process that content
in temperature of the material, the setting time decreased of accelerator increased from 2% to 6%, the initial setting
gradually, which was caused by the increase in reaction time reduced from 12 min to 3 min and the final setting time
speed of hydration between cement, accelerator, and water reduced from 23 min to 7 min. The final setting time did not
in condition that the temperature of the material increased. change generally when the content of accelerator was 4% and
After the temperature of the material increased to 15∘ C, 5%, while when the content of accelerator gradually increased
4 Advances in Materials Science and Engineering

Table 2: Performance requirements of cement paste and cement mortar mixing accelerator.

Test items
Product rating Cement paste Cement mortar
Compressive strength of Compressive strength ratio
Initial setting time/min Final setting time/min
one day/MPa of 28 days/%
First grade ≤3 ≤8 ≥7.0 ≥75
Qualified product ≤5 ≤12 ≥6.0 ≥70

Table 3: Effects of mixing time on setting time under the same test Table 4: Effect of vibration frequency on setting time under the
conditions. same test conditions.
Accelerator Accelerator Initial
Mixing Initial setting Final setting Test Vibration Final setting Test
mass mass setting
time/s time/min time/min error/s frequency time/min error/s
content/% content/% time/min
5 4.5 11.2 >15 0 4.8 7.0 >10
8 3.2 7.3 <10 3 3.4 7.3 <10
6 12 3.8 7.7 <10 6 5 3.3 7.7 <5
15 4.9 13.2 <5 10 3.5 8.3 <5
20 8.5 15.0 <5 20 4.0 10.0 <5
30 14.8 30.2 <5 30 4.4 12.5 <5

from 6% to 8%, setting time increased. The initial setting time stirring and the resulting shock destroyed these structures,
increased from 3 min when content was 6% to 7 min when leading to longer setting time. During field application, when
content was 8%, and the final setting time increased from concrete was pressed into the high pressure spray hose, the
7 min to 14 min. accelerator was added into the concrete with adding device at
It could be seen that there is an optimum value for the same time, and there is no mixing process.
the accelerator concentration and an ideal coagulating effect Therefore, in view of the influence of above mixing time
cannot be achieved when the content is too small or large. on the coagulating performance of the accelerator, taking the
Therefore, the optimum accelerator content should be used actual situation into consideration, the mixing time during
to minimize its waste and the long-term strength loss of the experiment was set to around 8 seconds just to ensure that
the concrete. Based on practical and empirical findings, the the accelerator is completely mixed with the cement grout.
mass content of accelerator was identified as 6% during the
experiment to develop a new type of liquid accelerator used 3.3.2. Effect of Frequency of Vibration. The setting speed
in mines. increased dramatically when the accelerator was added to
the cement grout and the liquidity of cement grout was lost
after mixing, so that hand or machine vibration was required
3.3. Effects of Experimental Operating Methods during moulding process. Therefore, in the condition that the
3.3.1. Effect of Mixing Time. The effect of different mixing mixing time was 8 seconds, the effect of the vibration fre-
time on the performance of the accelerator under the same quency on the performance of the accelerator was measured
experimental conditions was determined and the results are and the results are shown in Table 4.
shown in Table 3. It can be seen from the experimental results that when
It can be seen from Table 3 that the mixing time signif- compared with mixing time, the effect of vibration frequency
icantly affected the concrete setting time. When the mixing was smaller but not negligible. Delay in setting time would
time was less than 5 seconds, the liquid accelerator did not occur without vibration or with excessive vibration. There-
evenly disperse in the cement grout. The reproducibility of fore, the frequency of vibration was set at 5.
multiple trials was poor and error was significant. When
the mixing time was increased to 8–12 seconds, the initial 4. Results and Discussions
setting time, final setting time, and experimental errors were
significantly reduced and the effect of solidification was 4.1. Preparation of Mother Liquor for
outstanding. When the mixing time was increased to 15 the New Type of Liquid Accelerator
seconds, the setting time increased dramatically. This was due
to the fact that the hydration mesh structure in cement could 4.1.1. Single-Admixture of Material A. Because Material A is
be formed in an instant after the accelerator was added to the primary coagulating ingredient of the new accelerator,
the cement; at the same time, the effective components of it is necessary to experimentally determine its optimum
accelerator were also in constant consumption; continuous concentration range. An aqueous solution of Material A with
Advances in Materials Science and Engineering 5

Table 5: Aluminum sulfate octadecahydrate solubility.

∘
Temperature/ C 0 10 20 30 40 50 60 70 80 90 100
Solubility/(g/100 mL) 31.2 33.5 36.5 40.4 45.7 52.2 59.2 66.2 73.1 86.8 89.0

Table 6: Effects of aluminum sulfate mass content on the setting time and strength of cement.

Content of Compressive
Content of Initial setting Final setting Compressive strength Compressive strength
aluminum strength ratio of 28
Material A/% time/min time/min of one day/MPa of 28 days/MPa
sulfate/% days/%
0 0 195 258 7.8 43.9 100
35 18 120 195 8.1 40.5 92
45 23 98 174 8.4 38.1 87
55 28 81 159 9.6 35.8 82
65 33 79 152 9.8 34.2 78
75 39 77 147 9.3 32.0 73

a concentration ranging from 0 to 75% was prepared and As can be seen from the test results in Table 7
used directly as an accelerator to measure the setting time and
strength with the addition content held at 6%. The solubility (1) the setting time was significantly reduced with the
and content of Material A on the setting time and strength of increase of the content of B; when the content of B was
cement are shown in Tables 5 and 6. around 4%, the effect of solidification was the opti-
As can be seen from the test results summarized in mum; however, the setting time appeared to increase
Tables 5 and 6 as the concentration of Material B kept increasing
which suggests that the addition of an appropriate
(1) with the increase in the content of A, the initial and amount of Material B improves the coagulating effect
final setting time decreased; however, the setting time of the accelerator;
did not change when the content of A exceeded 55%; (2) the addition of an appropriate amount of Material
at 20∘ C, the solubility of aluminium sulphate was B not only effectively increases the short-term speed
only 36.5 g; that is, the saturated concentration was of the hydration of cement leading to an increase
26.7%; however, when the content of A reached 55%, of compressive strength at 1 day, but also increases
the content of aluminium sulphate in the solution the compressive strength at 28 days; the increase of
was 28% which exceeded the saturated concentration; compressive strength at 28 days exceeded 100% when
therefore, the setting time will not decrease even when the content of Material B in the mixture was 4.5%.
the content of A increases;
(2) with the increase in the content of A, the compressive In conclusion, the content of Material B in the solution
strength after 1 day increased and the increasing was should be kept at 3.5% to 4.5% which takes 0.21% to 0.27% of
most significant when the content of A was below the mass of cement.
55%; however, the strength after 28 days decreased;
this result was caused by the addition of A which 4.1.3. Combination of Materials A and C. According to the
introduced bivalent sulphate ion which reacted with preparatory study, material C had a better effect of solidifica-
calcium hydroxide to produce dihydrate gypsum; tion with the mass content below 3%. Similarly, the content of
although the gypsum improves the initial strength, Material A in the mixture was set as 55% for combination with
expansive calcium sulphoaluminate is produced con- various amounts of Material C. The setting time and strength
tinuously which leads to a reduction of long-term with the addition of 6% of the accelerator were measured and
strength. results are shown in Table 8.
As can be seen from the test results in Table 8
Concluding from the test analysis of setting time and
strength, the optimum content of A in the solution is 55%, (1) the addition of Material C improved the coagulating
which is 3.3% of the mass of the cement. effect of aluminium sulphate; when the content of C
in the solution was 2% to 3%, the speed of hydration
4.1.2. Combination of Materials A and B. According to the of the cement significantly increased and the initial
preliminary test results, Material B had a better effect of setting time was reduced to below 50 minutes; how-
complexation with the mass content of 3% to 5%. Therefore, ever when the content of C exceeded 2.5%, the setting
the content of Material A was set as 55% for combination speed decreased, which suggests that the amount of
with various amounts of Material B. The content of the Material C in the accelerator should be limited;
accelerator was held at 6% and the setting time and strength (2) in a similar manner to Material B, the addition of
were measured and results are shown in Table 7. C increased the compressive strength of the concrete
6 Advances in Materials Science and Engineering

Table 7: Experimental results of combination of Materials A and B.

Compressive Compressive
Content of Content of Initial setting Final setting Compressive strength
strength of one strength of 28
Material A/% Material B/% time/min time/min ratio of 28 days/%
day/MPa days/MPa
0 0 195 258 7.8 43.9 100
0 90 162 9.1 37.8 86
3 51 101 10.3 40.5 92
55 3.5 29 79 10.7 41.1 94
4 22 52 11.2 42.8 97
4.5 24 59 10.3 44.0 100
5 25 60 9.5 45.2 103

Table 8: Experimental results of combination of Materials A and C.

Content of Content of Initial setting Final setting Compressive strength Compressive strength Compressive strength
Material A/% Material C/% time/min time/min of one day/MPa of 28 days/MPa ratio of 28 days/%
0 0 195 258 7.8 43.9 100
0 90 162 9.1 37.8 86
1 69 124 9.7 39.9 91
55 1.5 59 104 10.3 41.5 95
2 48 86 11.2 42.3 96
2.5 41 80 11.1 42.8 97
3 47 85 10.8 43.1 98

after 1 day of curing; when the content of C was Table 9: Orthogonal test proposal.
2%, the compressive strength after the 1-day cur-
ing reached the maximum value of 11.2 MPa, but it Content of
Test number Content of Content of
Material
decreased when the amount of C exceeded 2%; as the Material A/% Material B/%
C/%
amount of C was increased, the compressive strength
1 50 3.5 2
after 28-day curing increased, which suggests that
the addition of C helps to compensate for the loss 2 50 4 2.5
of strength incurred by the presence of aluminium 3 50 4.5 3
sulphate; when the content of C exceeded 1.5%, the 4 55 3.5 2.5
strength ratio at the 28-day cure was above 95%. 5 55 4 3
6 55 4.5 2
In summary, the optimum content of Material C in the 7 60 3.5 3
solution was 2% to 3%, which amounts to 0.12% to 0.18% of 8 60 4 2
the mass of cement. 9 60 4.5 2.5

4.1.4. Orthogonal Matching Tests. The optimum range for

the concentration of the three additive materials was deter- The setting time and strength for each group were
mined from single-admixture of aluminium sulphate and the measured according to orthogonal matching and the results
combination of aluminium sulphate with Materials B and are shown in Figures 3 and 4.
C. However, the mechanism of the effect on the hydration To better demonstrate the effects of A, B, and C in the
process of cement is different and the effect of the combined mother liquor, range analysis was conducted on the results of
action of the three materials is unknown. In order to evaluate orthogonal matching tests as shown in Table 10.
the optimum admixture of the combination of the three mate- It can be seen from the results of orthogonal matching
rials, it was necessary to determine the concrete materials’ tests in Table 10 that
properties when adding all of the materials simultaneously.
In order to simplify the experiment, A, B, and C were (1) the effect of combining A, B, and C was evi-
selected as the three primary factors and orthogonal tests dent; not only did the setting time in most cases
were conducted on three levels in which A was tested at 50%, meet the requirement of a qualified accelerator dic-
55%, and 60% and B at 3.5%, 4%, and 4.5%, while C was tated by JC477-2005 Flashing Setting Admixtures
presented at 2%, 2.5%, and 3%, as shown in Table 9. for Shotcrete, but the compressive strength ratio at
Advances in Materials Science and Engineering 7

Table 10: Range analysis of the main components in mother liquor.

Determination items A B C Factors sorting and

optimal group
Setting time
Initial setting time/s
Mean value 1 241.7 243.3 230.0
Mean value 2 220.0 213.3 240.0 Factors sorting: BAC
Mean value 3 235.0 240.0 226.7 Optimal group: A2 B2 C3
Range 21.7 30 13.3
Final setting time/s
Mean value 1 566.7 570.0 558.3
Mean value 2 530.0 516.7 550.0 Factors sorting: BAC
Mean value 3 555.0 565.0 543.3 Optimal group: A2 B2 C3
Range 36.7 53.3 15.0
Compressive strength
Compressive strength of one day/MPa
Mean value 1 12.5 11.0 11.1
Mean value 2 11.6 11.6 11.2 Factors sorting: ABC
Mean value 3 9.5 11.1 11.3 Optimal group: A1 B2 C3
Range 3.0 0.6 0.2
Compressive strength of 28 days/MPa
Mean value 1 44.8 42.1 42.6
Mean value 2 42.6 42.8 43.1 Factors sorting: ABC
Mean value 3 41.5 44.1 43.2 Optimal group: A1 B3 C3
Range 3.3 2.0 0.6

14 50 120

45
12

Compressive strength ratio of 28 days (%)

100
40
Compressive strength (MPa)

10 35
80
30
Time (min)

8
25 60
6
20
40
4 15

10
20
2
5

0 0 0
1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 7 8 9
Test number Test number
Initial setting time Compressive strength of 1 day
Final setting time Compressive strength of 28 days
Initial setting time standard of qualified Compressive strength standard of 1 day for
product in JC477-2005 qualified product in JC477-2005
Final setting time standard of qualified Compressive strength ratio of 28 days
product in JC477-2005 Compressive strength ratio standard of 28 days for
qualified product in JC477-2005
Figure 3: Setting time of orthogonal test.
Figure 4: Compressive strength of orthogonal test.
8 Advances in Materials Science and Engineering

28 days was also above 93%, which exceeds the 10

requirement for a first grade accelerator which is 75%;
9
(2) it is evident from the results of range analysis that
the sequence of significance for the three materials 8
in terms of initial and final setting time was B >
A > C; in terms of compressive strength at 1 day 7
and compressive strength at 28 days, the sequence
was A > B > C; an improvement effect in setting 6

Time (min)
time can be achieved by adjusting Material B, while
an improvement in strength can be achieved by 5
adjusting Material A; Material C appears to play a
supplementary role; 4

(3) the mother liquor of the new accelerator is good in 3

terms of developed compressive strength, but it did
not meet the requirement of a first grade accelerator in 2
terms of setting time; therefore, further optimization
of the mother liquor is required to reduce the setting 1
time.
0
0.2 0.3 0.4 0.5 0.6
In conclusion, the formula of the mass content for each
Content of D (%)
material in mother liquor is Material A: 55%; Material B: 4%;
Material C: 2.5%, and the remainder is water. According to Initial setting time
the content of accelerator in cement, Materials A, B, and C Final setting time
constitute 3.3%, 0.24%, and 0.15% of the final mass of cement, Initial setting time standard of first grade in JC477-2005
respectively. Final setting time standard of first grade in JC477-2005

Figure 5: Setting time of cement grout mixing with mother liquid

4.2. Optimum Combination for the Mother Liquor of the Accel- and Material D.
erator. To further reduce the concrete setting time, improve
the viscosity of the new accelerator, and reduce the rebound
rate, testing was conducted to optimize the mother liquor by (1) the addition of D further improved the coagulating
combining with Materials D and E. Initial tests determined effect of the accelerator; in addition to the case when
that, with Material D at 0.2% to 0.6% and Material E at 3% the content of D was 0.2%, the requirement of a first
to 7% in the accelerator, the modified accelerator exhibited grade accelerator was met in terms of setting time;
outstanding viscosity and the performance of the accelerator in particular, the coagulating effect was the optimum
was excellent. when the content of D was 0.4% to 0.5% in which the
Because Materials D and E play the roles of solidification initial setting time was the shortest when the content
and viscosity enhancement in the new accelerator mainly and was 0.4% and the final setting time was the shortest
their impacts on the strength of cement mortar are small, when the content was 0.5%;
optimizing tests of the mother liquid with Materials D and (2) it was observed from the tests that the addition
E were conducted without strength tests and the strength was of D to the mother liquid improved the viscosity;
measured after the optimized formula was determined. when added to the cement grout, the viscosity of the
In addition, since the cement grout hardens rapidly grout was improved dramatically and the viscosity
after the addition of accelerator, the viscosity is difficult enhancement was the optimum when the content of
to measure. The viscosity of the accelerator itself cannot D was 0.5%; further increases in the content of D
accurately reflect the viscosity of concrete after the addition led to overwhelmed viscosity of the accelerator and
of the accelerator. Therefore, the viscosity was estimated by resistance of the mixture during transport increased;
observation. therefore, the optimum content of D was set at 0.5%.

4.2.1. Modification of Mother Liquid by Combination with 4.2.2. Combination of the Modified Mother Liquor with Mate-
Material D. When D was added to the mother liquid with rial E. A solution of 61.5% content with the mother liquid and
a specified content ratio of 0.2% to 0.6% in the combination 0.5% with Material D was used for the optimum combination
solution, the setting time was measured at an accelerator experiments with Material E. The characteristics of E were
concentration of 6%. The setting time of cement grout when fully utilized to further improve the stability of the solution
the mother liquid was combined with Material D is shown in and viscosity and durability of the concrete. The content of E
Figure 5. during combination tests was 3% to 7%. The setting time was
It can be seen from the experimental results and observa- measured and the viscosity of cement grout was estimated
tions that by observation. The setting time of the cement grout when
Advances in Materials Science and Engineering 9

6 (a) Sample 1
Time (min)

3
(b) Sample 2
2

0
3 4 5 6 7
Content of E (%)
(c) Sample 3
Initial setting time
Final setting time Figure 7: New cement grout just added accelerator.
Initial setting time standard of first grade in JC477-2005
Final setting time standard of first grade in JC477-2005
Table 11: Mass content of each component of WT-1 alkali-free liquid
Figure 6: Setting time of cement grout mixing with modified
accelerator.
mother liquor and Material E.
Component A/% B/% C/% D/% E/% Water/%
Mass content in 55 4 2.5 0.5 5 33
the modified mother liquor was combined with Material E is accelerator
shown in Figure 6 and the freshly mixed cement grout after Mass content in 3.30 0.24 0.15 0.03 0.30 1.98
the accelerator liquid was added is shown in Figure 7. cement grout
It can be seen from the combination tests of the modified
mother liquor with Material E that
(1) when the solution with E was added, the initial setting 4.4. Measurement of the Performance of
time of the cement grout did not vary significantly; the New Liquid Accelerator
with the increase of the content of E, the initial setting
time decreased and the minimum time was observed 4.4.1. Solid Content. Since the solid content of the accelerator
when the content of E was 5%; when the content affects the usage and performance, the solid content of
exceeded 5%, the setting time increased; with the the new accelerator was measured according to industrial
increase of the content of E, the final setting time standard of building material JC477-2005 Flashing Setting
increased; Admixtures for Shotcrete.
(2) during observation of these tests, Material E exhibited (1) Test Method. Place 10 g ± 0.2 g of the sample into a clean
the effect of improving the viscosity of the solution; and previous weighed flat weighting bottle, dry in vacuum
when added to the cement grout, the viscosity of until a constant weight is achieved, and then cool in a
the grout was further improved which was beneficial desiccator with silica gel to room temperature and weight the
in reducing the material rebound of concrete during sample to 0.1 g.
spraying process; in consideration of the effect of E on
the setting time, the density of addition was set as 5% (2) Analysis of Test Results. The measured results of the solid
where the viscosity was the optimum and the setting content of the accelerator are shown in Table 12.
time met the requirement of a first grade product. Industrial standard of building material JC477-2005
Flashing Setting Admixtures for Shotcrete provides that the
4.3. Determination of the Formula for the New Liquid Acceler- solid content of accelerator should be less than the minimum
ator. According to the reported experimental data, the final control values of production plant. It can be seen from the
formula of the new liquid accelerator can be determined as measured results that the solid content of the new liquid
shown in Table 11. The new liquid accelerator used in mines accelerator was 60.5%, less than the limit of 70% solid content
is named as WT-1 alkali-free liquid accelerator, referred to as of the vast majority of the production plant, meeting the
WT-1 accelerator hereafter. requirement of the relevant China industry standard.
10 Advances in Materials Science and Engineering

Table 12: Measured results of the solid content of the accelerator. 28 days of cure was higher than that of the P.O42.5 normal
Average
Portland cement, but the difference was not significant.
Sample Mass after Solid
solid
mass/g drying/g content/%
content/% 5. Field Application
10.1 6.2 61.4
60.9 The established WT-1 accelerator was applied at an anchoring
9.9 6.1 61.6
and shotcreting site in the belt roadway of the south wing
10.2 6.1 59.8 of the Yankuang Group’s Dongtan coal mine in Shandong
province. A comparative analysis was conducted using a con-
ventional GOR-I liquid accelerator in terms of rebound rate,
4.4.2. Adaptability Tests on the New Accelerator. In the exper- dust concentration, and compressive strength of shotcrete.
iment conditions outlined by JC477-2005 Flashing Setting The site of wet spraying is shown in Figure 8.
Admixtures for Shotcrete, the adaptability of WT-1 acceler-
ator with different types of cement was measured as shown 5.1. Comparative Analysis of Rebound Rate. This process
in Table 13. Selected cements included the reference cement began with laying a plastic film on the bottom slab of
and wet spraying cement used in Xinjulong coal mine in
the tunnel. Next, 0.5 m3 of concrete was sprayed onto the
Shandong province, Xin’an coal mine of Zaozhuang Mining
arch and the rebound material was collected, weighted, and
Group, and Dongtan coal mine of Yankuang Group.
calculated after spraying. The two sides of the tunnel were
It could be concluded by comparative analysis about the
then sprayed with the same approach. The calculated results
measurement results of Table 13 and the industry standard
for rebound rate are shown in Table 15.
that
The data in Table 15 showed that
(1) under the fixed conditions of 6% mixing content the (1) the rebound rate of the material employing differ-
initial setting time of WT-1 accelerator for different ent accelerators was nonadded accelerator > GOR-I
cements was less than 5 min and the final setting accelerator > WT-1 accelerator, which suggested that
time was less than 12 min, meeting the qualified the two types of accelerators reduced the rebound
requirement outlined in the national standard JC477- rate of wet spraying concrete to different extents;
2005 Flashing Setting Admixtures for Shotcrete; dur- in particular, the performance of the wet spraying
ing reference cement tests, the initial setting time concrete that lacked an accelerator did not meet the
of WT-1 accelerator was less than 3 min, and the requirement outlined in national standard GB50086-
final setting time was less than 8 min, meeting the 2001 Specifications for Bolt-Shotcrete Support that
requirement of first grade product, which showed the rebound rate at the sides should be less than 15%
that the WT-1 accelerator had better adaptability to and for the arch less than 25%;
different cements;
(2) the average rebound rate of concrete with the addition
(2) the order of the setting times from short to long of WT-1 accelerator was 9.5% and 5.4% less than
is reference cement 42.5 < normal Portland cement that without and with the addition of GOR-I liquid
P.O42.5 < composite Portland cement P.C42.5 < com- accelerator, and WT-1 accelerator effectively reduced
posite Portland cement P.C32.5, which suggested that the amount of concrete rebound when shotcreting
the setting time of higher grade cement is shorter than the arch and two sides; therefore, it appeared that
that of lower grade and the setting time of normal the viscosity enhancement ingredients in the WT-1
Portland cement is shorter than composite Portland accelerator improved the adhesion of the concrete and
cement. Therefore, it is recommended that the normal to the tunnel surface;
Portland cement with strength grade above 42.5 be (3) the composition of WT-1 accelerator is noncorrosive
used in wet spraying process in the mines. and there were no reports of worker health or safety
complaints; however, when using the GOR-I accelera-
4.4.3. Effect of the New Accelerator on the Cement Strength. tor during shotcreting, particulates of the accelerator
In order to evaluate the effect of the WT-1 accelerator on the could be observed in the air and the accelerator mixed
strength of cement, strength measurements were conducted with the rebounded concrete was irritating, which
on the reference cement and normal Portland cement P.O42.5 caused skin burns of the workers.
used for wet spraying in Xinjulong coal mines in Shandong.
The reference cement was denoted as “JZ” and P.O42.5 5.2. Comparative Analysis of Dust Concentration. The filter
normal Portland cement was denoted as “PT.” The test results weighing method was used to measure the accumulated dust.
are shown in Table 14. The sampling points for measuring the dust are shown in
The test results revealed that the average compressive Figure 9 and the measured results are listed in Figures 10 and
strength and compressive strength ratio of 28 days all satisfied 11.
the requirement detailed in the national standard when the The data in Figures 10 and 11 showed that the WT-1
content of addition was 6% whether “JZ” or “PT” cement. accelerator was superior to the GOR-I accelerator in pre-
The compressive strength of the reference cement at 1 day and venting the generation of dust in the Dongtan coal mine.
Advances in Materials Science and Engineering 11

Table 13: Adaptability test of WT-1 type accelerator.

Cement kinds Cement sources Content of Initial setting Final setting

accelerator/% time/min time/min
Reference cement 42.5 Reference cement 6 2.3 7.1
Normal Portland cement P.O42.5 Shandong Xinjulong coal mine 6 3.1 7.7
Composite Portland cement P.C32.5 Xin’an coal mine of Zaokuang Group 6 4.6 11.8
Composite Portland cement P.C42.5 Dongtan coal mine of Yankuang Group 6 3.5 10.3

Table 14: Effects of WT-1 type accelerator on the strength of cement paste.

Test Average compressive strength/MPa Compressive strength

Cement Content of accelerator/%
number 1d 28 d ratio of 28 days/%
1 JZ 0 7.8 43.9 100
2 PT 7.2 43.1 100
3 JZ 6 13.6 41.4 94.3
4 PT 12.5 40.2 93.3

Table 15: Rebound rate of shotcrete. product; however, the WT-1 accelerator had a com-
Average
pressive strength ratio at 28 days that was 90.1%
Rebound which far exceeded the requirement of first grade
Accelerator Position rebound
rate/% product which was 75%; moreover, regardless of the
rate/%
Without adding Arch 26.2 type of accelerator added, the 28-day strength of the
20.9 concrete met the requirements of 20 MPa outlined
accelerator Two sides 15.5
in GB50086-2001 Specifications for Bolt-Shotcrete
Arch 13.3
WT-1 type accelerator 11.4 Support; there were no failed cases and the effect of
Two sides 9.4
wet spraying support was outstanding;
Arch 21.3
GOR-I type accelerator 16.8
Two sides 12.2 (2) the strength of concrete mixed in the lab was normally
much higher than that of shotcrete large slabs for two
reasons; first, the methods of fabrication are different;
The WT-1 accelerator achieved better dust prevention effects, the lab specimens were hand spaded, while, in the
validating the contribution of viscosity enhancement by the mine, the concrete was blown into precast moulds
select ingredients in the accelerator. The improved viscosity using compressed air; as a result, the onsite samples
captures the particulates of concrete and agglomerates them were less compact than the lab samples, and the onsite
which further reduces dust concentration at the site of wet concrete is not as evenly blended as the lab concrete.
spraying. The average total dust density in the entire anchor-
ing and shotcreting site was reduced from 13.08 mg/m3 in 6. Conclusions
the case of nonadded accelerator and 7.95 mg/m3 in the
case of GOR-I accelerator to 2.47 mg/m3 using the WT-1 (1) Experimental analysis of the primary factors affecting
accelerator. The average inhalable dust concentration reduced the performance of liquid accelerators yielded the
from 6.28 mg/m3 and 3.93 mg/m3 to 1.10 mg/m3 . following conclusions. Different mixing time signif-
icantly affects the setting time. When the mixing
time was about 8 seconds, the setting time was the
5.3. Comparative Analysis of Compressive Strength of Shotcrete.
shortest, so it was the optimum mixing time selected
The compressive strength of the shotcrete was measured
in this experimental study. When compared with
according to national standard GB50086-2001 Specifications
mixing time, concrete vibration frequency has less of
for Bolt-Shotcrete Support. The compressive strength after 28
an effect on the setting time and the coagulating effect
days of curing was tested and listed in Table 16.
was the best when the vibration frequency was 5. A
As can be seen from the data in Table 16
better coagulating effect could be achieved when the
content of the accelerator was about 6%. The setting
(1) when the accelerator was included in the shotcrete, time of the concrete decreases with the increase of
the compressive strength at the 28-day cure gener- temperature of material.
ally decreased; the 28-day cure strength loss of the
high alkalinity GOR-1 accelerator exceeded 25% and (2) Extensive preliminary experimental testing resulted
the requirements of first grade product outlined in the selection of five materials to develop a new
in JC477-2005 Flashing Setting Admixtures for type of liquid accelerator for shotcreting in mines.
Shotcrete were not met but it was still a qualified These are as follows. Material A is aluminum sulfate
12 Advances in Materials Science and Engineering

Table 16: Testing results of compressive strength about sprayed concrete.

Accelerator Compressive strength of 28 days/MPa Average strength/MPa Compressive strength

ratio of 28 days/%
Without adding accelerator 38.2 37.7 35.8 37.9 100
39.9 38.0 37.7
WT-1 type accelerator 35.8 31.2 36.1 33.8 89.2
32.0 34.9 32.9
GOR-I type accelerator 26.7 27.4 26.5 27.8 73.5
30.1 28.8 27.5

Figure 8: The site of wet spraying.

octadecahydrate which is the main coagulating con- ratio after 28 days of curing is 94.8%, which meet
stituent of the new accelerator and it contains 51.4% the requirement of a first grade product. The field
of anhydrous aluminum sulfate. Material B is sodium application in an anchoring and shotcreting site at
fluoride, C is triethanolamine, D is polyacrylamide, the Dongtan coal mine showed that WT-1 accelerator
and E is bentonite. According to the single-admixture outperformed conventional accelerators in terms of
experiment of A, combination tests of A with B and rebound rate, dust concentration, and compressive
C were conducted, respectively, orthogonal matching strength of shotcrete.
tests for A, B, and C were carried out, and the formula
of the mother liquor for the accelerator was deter-
mined. By the combination tests of mother liquor
Conflict of Interests
with the accelerator with D and E, WT-1 alkali-free The authors declare that there is no conflict of interests
liquid accelerator was developed; the quality content regarding the publication of this paper.
of each component was Material A: 55%; Material B:
4%; Material C: 2.5%; Material D: 0.5%; Material E:
5%, and the water is 33%. According to the fact that Acknowledgments
the content of accelerator in the cement is 6%, the
This work was financially supported by State Key Program
content ratios relative to the cement of A, B, C, D, and
of National Natural Science of China (Grant no. U1261205);
E and the water are 3.3%, 0.24%, 0.15%, 0.03%, 0.3%,
National Natural Science Foundation of China (Grant nos.
and 1.98%.
51474139, 51204103, and 51404147); SDUST Research Fund
(3) The performance of WT-1 accelerator was measured (Grant no. 2014JQJH106); China Postdoctoral Science Foun-
according to JC477-2005 Flashing Setting Admix- dation (2015M570602); Open Fund of the State Key Lab-
tures for Shotcrete and GB50086-2001 Specifications oratory of Mining Disaster Prevention and Control Co-
for Bolt-Shotcrete Support. Test results showed that Founded by Shandong Province and the Ministry of Science
the adaptability of WT-1 accelerator with different and Technology (Grant no. MDPC2013KF13); Open Fund
types of cement that were described in this paper of the Key Laboratory of Safety and High-Efficiency Coal
is outstanding. When the content of the accelerator Mining, Ministry of Education (Anhui University of Science
is 6%, measured by the reference cement which and Technology, Grant no. JYBSYS2014105); Science and
was described in this paper, the initial setting time Technology Project of Huangdao District, Qingdao (Grant
is 2 minutes and 15 seconds and the final setting no. 2014-1-30); Joint Innovative Center for Safe and Effective
time is 7 minutes and 5 seconds. The compressive Mining Technology and Equipment of Coal Resources of
strength after 1 day of curing is 13.6 MPa and strength Shandong Province; Shandong Province “Taishan Scholar”
Advances in Materials Science and Engineering 13

Spray gun

Wet spraying Mixer

machine
1 2 3 4
Central part of 2m
5m 1m
wet shotcrete zone

Figure 9: The sampling points for measuring the dust.

18 Project Fund; The Key Technology Projects of Chinese State

16 Administration of Work Safety for Preventing Major Safety
Whole dust concentration (mg·m−3 )

Production Accidents (Shandong-0083-2015AQ).

14
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