Construction and Building Materials 123 (2016) 800–805

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Construction and Building Materials

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

Study on engineering properties of alkali-activated ladle furnace slag

geopolymer
Wei-Chien Wang a, Her-Yung Wang b,⇑, Hsin-Chieh Tsai b
a
Department of Civil Engineering, Chung Yuan Christian University, Chung Li, 32023, Taiwan, ROC
b
Department of Civil Engineering, National Kaohsiung University of Applied Sciences, 807, Taiwan, ROC

h i g h l i g h t s

 The increased L/S dilutes the concentration of the alkali agent, which effects the engineering properties.
 A higher amount of alkali agent yielded greater engineering properties.
 Curing in saturated limewater promotes the polymerization reaction.

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

Article history: Geopolymers, a new form of aluminosilicates, are environmentally friendly materials. These materials are
Received 11 May 2016 produced from industrial wastes. This study, based on the industrial waste, Ladle furnace slag (LFS),
Received in revised form 28 June 2016 employed an alkali-activated technology to activate LFS. The fixed alkali modulus ratio (SiO2/Na2O)
Accepted 15 July 2016
was 1. LFS Geopolymer was prepared at different liquid/solid ratios (L/S) of 0.35, 0.40 and 0.45 and with
different alkali agents of 4%, 6% and 8%. The LFS Geopolymer was cured under various conditions (air and
saturated limewater) to evaluate the mixture and engineering properties of LFS Geopolymer at different
Keywords:
ages. The results show that the workability of the LFS geopolymer increased with an increasing L/S and
Ladle furnace slag
Geopolymer
alkali agent. Moreover, the compressive strength and ultrasonic velocity increased with an increase in the
Curing condition alkali agent and a decrease in L/S, but the weight loss was reduced. Therefore, the appropriate use of
Alkali-activated paste alkali-activated technology can activate LFS, thereby enhancing its engineering properties. Curing in sat-
urated limewater can greatly improve the engineering properties of the geopolymer compared to air cur-
ing. Specifically, the compressive strength of LFS increases by 5.4–58.9%, and the ultrasonic velocity of LFS
increases by 0.84–22.9%. The thermal conductivity increases by 0.166–0.443 W/m
K, and the overall
shrinkage of LFS cured in the saturated limewater ranges between 0.0017% and 0.0342%, which is far
lower than samples cured in air, thus indicating that curing in saturated limewater can effectively pre-
vent LFS shrinkage.
Ó 2016 Published by Elsevier Ltd.

1. Introduction bon dioxide are emitted. The production of 1 ton of cement

With the increasing severity of natural disasters caused by glo-
bal warming and environmental problems, great importance is
attached to energy conservation, carbon reduction and environ-
mental protection. Civil engineering materials are turning to green
renewable resources and sustainable development [1]. Due to
rapid economic development and improvement in people’s living
standards, the use of cement is escalating, with the promotion of
public construction and high-rise buildings. In the cement produc-
tion process, tons of energy is consumed, and large amounts of car-
⇑ Corresponding author.
E-mail address: wangho@cc.kuas.edu.tw (H.-Y. Wang).
produces 0.85 ton of carbon dioxide, exerting an immense impact
on the environment [2]. The total CO2 emission from the cement
manufacturing industries worldwide accounts for 5–7% of all glo-
bal greenhouse gas emissions [3]. In an effort to tackle these envi-
ronmental problems, alternative materials must be found.
The iron and steel industry is thriving, and the product grades
are gradually improving. Steel slag is a waste material, or by-
product, of the steel-making process. An enormous amount of steel
slag is generated worldwide; for example, Europe alone generates
nearly 20 million tons of steel slag every year [4,5]. This ladle fur-
nace slag can effectively fill the voids of concrete because LFS has a
composition similar to that of water quenching blast furnace pow-
der (which consists mainly of CaO and SiO2), a pozzolanic and

http://dx.doi.org/10.1016/j.conbuildmat.2016.07.068
0950-0618/Ó 2016 Published by Elsevier Ltd.
 W.-C. Wang et al. / Construction and Building Materials 123 (2016) 800–805 801

cementaceous material that has the cementing properties of
cement and a pozzolanic reaction, thus rendering the entire system
more compact [6]. Therefore, using LFS resources as a cementing
material can convert this industrial waste into a reusable resource
and attain the goal of carbon reduction.
Geopolymers are three-dimensional aluminum silicate inor-
ganic polymers composed of [AlO4] and [SiO4] tetrahedral that
are typically prepared from aluminum silicates or industrial wastes
and mixed with an alkali silicate solution under highly alkaline
conditions [7,8]. Unlike cement, which is bonded by hydration,
geopolymers utilize chemical bonding [9]. The production of
alkali-activated cements allows the use of a wide range of materi-
als (both minerals and byproducts) with compositions within the
systems of SiO2-Al2O3 or SiO2-Al2O3-CaO, such as blast furnace slag
[10].
The reaction mechanism and strength development of the
geopolymer are influenced by the type and concentration of the
First, NaOH, sodium silicate and water were mixed well prior to use. The LFS
was poured into a mixer for dry mixing and mixed again with the alkaline solution.
After completing the mixing, the paste was poured into a cubic specimens of
50 mm  50 mm  50 mm and a long specimens of 25 mm  25 mm  285 mm.
The molds were removed after 1 day. The samples were placed in air (25 ± 5 °C)
and saturated limewater curing grooves for curing. Mechanical properties tested
were at 3, 7 and 28 days. The shrinkage of the LFS was tested at 1, 3, 7, 14, 21
and 28 days, and anti-sulfate attacks were tested at 28 days.
2.3. Experimental methods
The slump flow was measured according to ASTM C230 [18]. The ultrasonic
velocity was tested in according to ASTM C597 [19]. The compressive strength
was tested in according to ASTM C109 [20]. The thermal conductivity was measured
with a portable heat transfer meter, and the thermal conductivity of the tested
alkali-activated cementing materials was measured using a probe. Shrinking was
carried out according to ASTM C157 [21]. Anti-sulfate attack was conducted accord-
ing to ASTM C1012 [22]. Drying and soaking cycles in sulfate were performed, and a
total of 5 cycles were conducted after 28 days to observe weight loss.

alkaline solution, curing temperature, curing conditions and speci-

fic surface area. The alkali activator is designed to activate multiple
calcium aluminum silicate minerals and is the most important fac-
tor in the hydration of these aluminum silicate minerals. Currently,
the commonly used alkali activators include sodium silicate,
sodium carbonate and NaOH. NaOH has a significant effect on
the structure and the compressive strength of geopolymers during
geopolymerization. Concentrated NaOH ensures the better cou-
pling of the solid particles both in the aqueous phase and in the
final structure of the geopolymeric system [11]. Additionally, the
concentration of the alkali activator is the second most important
factor for the hydration process and structural strength develop-
ment. The structural strength effect of the alkali activator increases
with the increase of its concentration. A low-concentration alkali
activator has a low structural strength and a low hydration rate.
Under highly alkaline conditions, polymerization occurs when
reactive alum inosilicates dissolve rapidly, releasing free [SiO4]
and [AlO4] tetrahedral units into the solution. The tetrahedral
units are alternatively linked into a polymeric precursor by sharing
an oxygen atom, thereby forming polymeric Si–O–Al–O bonds
[12,13], but these materials are easily weathered and fragile. These
problems can be addressed by adding different minerals and non-
shrinkage agents, curing in water or in other ways [14]. Because
water content and forming pressure has a significant effect on
the mechanical strength and sorptivity performance of geopoly-
mer, particularly in the fabrication of geopolymer pressed block
[15]. This is because both water content and forming pressure have
a direct influence on the total porosity of the geopolymer matrix
[16].
This study focused on LFS, which contains silicon and aluminum
oxide. Steel slag was processed in a polymerization reaction using
alkali-activation to prepare a ladle furnace slag geopolymer paste.
Then, the engineering properties of LFS were evaluated.
3. Results and discussion
3.1. Analysis of the physical and chemical properties of these materials
The physical and chemical properties of the materials used in
this study are detailed in Table 1. The LFS mainly composed of
CaO (48.6%) and SiO2 (23.7%). Its chemical composition is similar
to that of cement, and it has cementation and pozzolanic reactions.
Due to insufficient polymerization, sodium silicate was added to
supplement the Si ions and thereby enhance colloidal polymeriza-
tion. Additionally, 10 M NaOH (98% purity) was used to activate
the LFS in the geopolymer preparation. The TCLP poison dissolution
results are shown in Table 2. The TCLP result for LFS was mainly
composed of Ba (0.80421%), followed by Pb (0.024897%), whereas
the remaining compositions are low or not detected. This indicates
the raw materials leached less amounts of heavy metals.
3.2. Slump flow
Fig. 1 shows that when the L/S increased from 0.35 to 0.45, the
slump flow values increased by 9.3–86.1%, suggesting that increas-
ing the L/S can effectively enhance the workability of the geopoly-
mer. When the L/S was 0.45 and the alkali agent increased from 4%
to 8%, the slump flow increased from 155% to 183%. These results
show that the slump flow value increases with increasing
alkali agent, primarily because the alkali metal silicate solution is
relatively sticky, improving the workability.
Table 1
The physical chemistry properties of Materials.

Chemical analysis (%)

2. Experimental
Ladle furnace slag SiO2 Al2O3 Fe2O3 CaO MgO Cr2O3

2.1. Experimental materials 23.7 4.2 1.21 48.6 8.1 0.01

This study used LFS provided by Walsin Lihwa. The NaOH used in this study was Silicate solution SiO2 Na2O Fe Water SiO2/Na2O
in the form of a white sheet and was used to prepare a 10 M activator solution with insoluble
laboratory deionized water. The solution was packaged and stored in acid and alkali matter
bucket. Sodium silicate was sticky, colorless and tasteless liquid.
28–30 9–10 0.02 0.2 2.8–3.3

2.2. Experimental mixture and variables NaOH NaOH NaCO3 NaCl Fe

98.2 0.165 0.0135 0.0004
This test included a total of 9 proportion groupings. The fixed alkali modulus
ratio (SiO2/Na2O) was 1. LFS Geopolymer was prepared using L/S of 0.35, 0.40 and Specific gravity Fineness(cm2/g) °Bé
0.45 and alkali agents of 4%, 6% and 8%. The test curing was carried out in air (D) Ladle furnace slag 2.85 5500 –
saturated limewater (W). The curing in saturated limewater was conducted accord- Silicate solution 1.38 – 37
ing to the ASTM C511 specification [17]. Ratios of material in mixture are shown in
Table 3. Note: Baume degrees (°Bé) was a method of solution concentration.
802 W.-C. Wang et al. / Construction and Building Materials 123 (2016) 800–805

Table 2
Toxicity characteristic leaching procedure of LFS.

Unit: mg/L
Metal extraction Cr Cu Cd Pb Ba As Hg Se
LSF 0.005114 N.D 0.000838 0.024897 0.80421 0.004524 0.0041 N.D
Regulatory limits 1.0 5.0 1.0 5.0 100.0 5.0 0.2 1.0

N.D (Not Detect): Below the detection value.

Table 3 W Alkali agent 4% 6% 8%

Compressive Strength (kgf/cm 2 )

Ratios of material in mixture. 160
L/S 0.35 L/S 0.40 L/S 0.45
Unit: kg/m3 140
SiO2/Na2O L/S Alkali agent LFS Silicate NaOH Water
(%) solution 120

1 0.35 4 1311 197 132 284 100

6 1260 284 190 189
8 1213 364 244 100 80
0.40 4 1224 184 123 331
6 1177 265 177 242 60
8 1133 340 228 160
40
0.45 4 1148 172 115 373
6 1103 248 166 290 20
8 1062 319 213 212
3 7 28 3 7 28 3 7 28
Age (days)

200 Fig. 2. Compressive strength of LFS geopolymer cured in saturated limewater.

L/S 0.35 L/S 0.40 L/S 0.45
180
160
140
Slump flow (%)

D Alkali agent 4% 6% 8%
Compressive Strength (kgf/cm 2)

160
120 L/S 0.35 L/S 0.40 L/S 0.45
100 140

80 120
60 100
40 80
20
60
0
4 6 8 4 6 8 4 6 8 40
Alkai agent (%) 20

Fig. 1. Slump flow of LFS geopolymer. 3 7 28 3 7 28 3 7 28

Age (days)

Fig. 3. Compressive strength of LFS geopolymer cured in air.

3.3. Compressive strength

Fig. 2 shows that when the LFS geopolymer was cured in satu-
rated limewater, its compressive strength increased with increas-
ing age. The compressive strength dropped by 8.81–38.33% when
the L/S increased from 0.35 to 0.40. When the L/S increased from
0.40 to 0.45, the compressive strength decreased by 6.29–49.35%,
which is mainly because the increase in the L/S diluted the alkaline
agent and thereby reduced the compressive strength. When the
alkali agent increased by 4–6%, the compressive strength
decreased by 37.23–49.91%, and when the alkali agent increased
from 6% to 8%, the compressive strength increased by 24.11–
44.92%. The principal reason is that an increase in the alkali agent
causes an increase in the pH of the alkaline agent, more quickly
destroying the structure of LFS and generating more S–A–O col-
loids, thereby enhancing the compressive strength.
Figs. 3 and 4 shows the compressive strength of the LFS
geopolymer cured in air when the compressive strength of the
sample decreased at 28 days. This is mainly because the sample
suffers from shrinkage and weathering due to quick dehydration
in air curing that destroys the sample structure, causing cracks
and thus lowering the compressive strength. However, the com-
pressive strength of the sample increased by 5.4–58.9% in the sat-
urated limewater curing compared to that of air curing.
3.4. Ultrasonic velocity
Figs. 5 and 6 shows that a decrease in the L/S or an increase in
the alkali agent effectively enhanced the ultrasonic velocity.
Specifically, when the L/S increased from 0.35 to 0.45, the ultra-
sonic velocity declined by 2.66–10.38%. When the alkali agent
increased from 4% to 8%, the ultrasonic velocity increased by
5.22–17.21%. It is possible that the increase in alkaline solution
accelerated the polymerization reaction such that the sample
quickly removed excessive moisture and solidified more rapidly.
As a result, the more compact internal structure increases the
ultrasonic velocity. However, the ultrasonic velocity of the sample
increased by 0.84–22.9% in the saturated limewater curing com-
pared to that of air curing.
 W.-C. Wang et al. / Construction and Building Materials 123 (2016) 800–805 803

Fig. 4. Sample appearance of LFS geopolymer cured in air at 28 s.

W Alkali agent 4% 6% 8% W Alkali agent 4% 6% 8%

2500 2.0

Thermal Conductivity (W/m•K)

L/S 0.35 L/S 0.40 L/S 0.45 L/S 0.35 L/S 0.40 L/S 0.45
2400 1.9
Ultrasonic Velocity (m/s)

2300 1.8
2200
1.7
2100
2000 1.6
1900 1.5
1800 1.4
1700
1.3
1600
1500 1.2
1400 1.1
1300 1.0
3 7 28 3 7 28 3 7 28 3 7 28 3 7 28 3 7 28
Age (days) Age (days)

Fig. 5. Ultrasonic velocity of LFS geopolymer cured in saturated limewater. Fig. 7. Thermal conductivity of LFS geopolymer cured in saturated limewater.

D Alkali agent 4% 6% 8% D Alkali agent 4% 6% 8%

2500 2.0
L/S 0.35 L/S 0.40 L/S 0.45
Thermal Conductivity (W/m•K)

2400 L/S 0.35 L/S 0.40 L/S 0.45

1.9
Ultrasonic Velocity (m/s)

2300 1.8
2200 1.7
2100 1.6
2000 1.5
1900 1.4
1800 1.3
1700 1.2
1600 1.1
1500 1.0
1400 0.9
1300 0.8
3 7 28 3 7 28 3 7 28 3 7 28 3 7 28 3 7 28
Age (days) Age (days)
Fig. 6. Ultrasonic velocity of LFS geopolymer cured in air. Fig. 8. Thermal conductivity of LFS geopolymer cured in air.

3.5. Thermal conductivity 3.6. Shrinking

Figs. 7 and 8 shows that the thermal conductivity increased
with the increase in alkali agent. This is probably because the
increase in the alkali agent accelerated the polycondensation and
solidification of colloid, thus making the internal structure more
compact. Therefore, reducing the alkali agent can ensure a lower
thermal conductivity. With respect to the L/S, the changes in the
thermal conductivity were insignificant. The thermal conductivity
of the sample increased (0.166–0.443 W/m K) in the saturated
limewater curing compared to that of air curing. The reason was
that the samples were subject to quicker dehydration in air curing,
which caused internal holes in the samples. Cracks on the surface
of the samples affected the mechanical properties.
Fig. 9 shows that after curing in saturated limewater, the
shrinkage of LFS geopolymer increased slightly with age and that
the overall shrinkage ranged from 0.0017% to 0.0342%. The shrink-
age increased with increasing alkali agent, with the shrinkage
ranging from 0.0017% to 0.0141%. When the alkali agent was 8%,
the shrinkage had the maximum value (0.0083–0.0342%). It was
assumed that the increase in alkali agent helps dissolve more Si
and Al ions that participate in the inorganic polymerization reac-
tions, thus contributing to the sustained increase in shrinkage.
When the L/S increased, the shrinkage decreased (1.28–26.8%).
The reason was that the concentrated alkaline agent was diluted,
which led to the insufficient dissolution of the Si and Al ions and
804 W.-C. Wang et al. / Construction and Building Materials 123 (2016) 800–805

W Alkali agent 4% 6% 8% Alkali agent 4% 6% 8%

0.000 24 L/S 0.35 L/S 0.40 L/S 0.45
22
-0.004 20
-0.008 18
16

Weight loss (%)

Shrinkage (%)

-0.012 14
12
-0.016 10
8
-0.020 6
-0.024 4
2
-0.028 0
-2
-0.032 -4
L/S 0.35 L/S 0.40 L/S 0.45 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5
-0.036
1 3 7 14 21 28 1 3 7 14 21 28 1 3 7 14 21 28 Cycles of test
Age (days) Fig. 11. Weight loss of LFS geopolymer.

Fig. 9. Changes in shrinkage of LFS geopolymer cured in saturated limewater.

increases, the presence of holes diminishes, which contributes to

D Alkali agent 4% 6% 8%
the increased relative durability.
0.0

-0.2
4. Conclusions
Shrinkage (%)

-0.4

-0.6
-0.8
-1.0
-1.2
-1.4 L/S 0.35 L/S 0.40
1 3 7 14 21 28 1 3 7 14 21 28 1 3
Age (days)
Fig. 10. Changes in shrinkage of LFS geopolymer cured in air.
the failure of the continuous polymerization reactions. Therefore,
the shrinkage was relatively minor.
Fig. 10 shows the shrinkage behavior of air-cured LFS geopoly-
mer. The increase in the alkali agent caused a significant increase
in shrinkage. Different L/S also affected the drying shrinkage of
the samples. The overall shrinkage was approximately 0.0085–
1.42%. When the alkali agent was 6% and 8%, excessive shrinkage
or cracks in the samples caused the samples to break, exceeding
the measurement range.
The shrinkage of the samples cured in saturated limewater was
far less than that of the samples cured in air. This is because water
loss results in greater shrinkage. Curing in saturated limewater
provides a continuous water supply and supports the polymeriza-
tion reaction, effectively preventing the shrinkage of the LFS
geopolymer.
3.7. Anti-sulfate attack
Fig. 11 shows the weight loss following anti-sulfate attack at
different L/S and with different amounts of alkali agent. When
the alkali agent was 8%, the L/S increased from 0.35 to 0.45, and
the weight loss ranged from 2.64% to 2.92%. This indicates that
the weight loss of the sample increases with an increase in L/S.
When the L/S was 0.35 and the alkali agent increased from 4% to
8%, the weight loss declined. This is because insufficient alkalinity
reduced the dissolution of Si and Al ions, which resulted in an
incomplete inorganic polymerization reaction and a loose struc-
ture. Therefore, when the L/S decreases and the alkali agent
1. When the L/S and alkali agent increase, the LFS geopolymer has
excellent workability.
2. The increased L/S dilutes the concentration of the alkali agent,
which affects the colloidal structure of aluminum and generat-
ing tiny holes and thereby reducing the compressive strength
and ultrasonic velocity while increasing the weight loss. How-
L/S 0.45
ever, because the changes in the shrinkage of the sample are
7 14 21 28 slight, the changes in the thermal conductivity are insignificant.
3. Increasing the alkali agent increases the pH of the alkaline
agent, destroying the LFS structure more quickly and making
the colloidal structure more compact, thus increasing the com-
pressive strength and ultrasonic velocity. Weight loss decreases
with increasing alkali agent. However, as the alkali agent
increases, the shrinkage and thermal conductivity of the sample
increase accordingly.
4. Curing in saturated limewater promotes the polymerization
reaction due to the incorporation of additional alkali; thus,
the engineering properties of LFS cured in saturated limewater
outperform those of LFS cured in air and shrinkage was effec-
tively prevented.
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