Construction and Building Materials 24 (2010) 1700–1707

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Construction and Building Materials

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

Effect of superplasticizers on workability retention and initial setting time

of cement pastes
Min-Hong Zhang, Kritsada Sisomphon *, Tze Siong Ng, Dao Jun Sun
Department of Civil Engineering, National University of Singapore, 1 Engineering Drive 2, Singapore 117576, Singapore

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

Article history: This paper presents an experimental study on the effect of a newly developed modified lignosulphonate
Received 16 June 2008 (PLS) superplasticizer on the loss of workability and initial setting time of cement pastes in comparison to
Received in revised form 8 February 2010 those of polycarboxylate (PCE) and polynaphthalene (PNS) superplasticizers. The workability loss was
Accepted 8 February 2010
monitored by yield stress and effective viscosity of the pastes. The initial setting was monitored by heat
Available online 4 March 2010
development, change of rheological parameters with time, and penetration depth in cement pastes. The
relations among these methods were discussed. Different dosages of the superplasticizers were used to
Keywords:
obtain cement pastes with yield stress <6 Pa at 30 min at given water-to-cement ratios. The results
Heat development
Initial setting
showed that the pastes with PLS lost workability more slowly and had longer initial setting time com-
Lignosulphonate pared with those with PCE and PNS admixtures. Although the longer workable time is beneficial for
Polynaphthalene hot weather concreting, the longer initial setting time of such material has to be taken into consideration
Polycarboxylate where early strength development is essential.
Rheological parameters Ó 2010 Elsevier Ltd. All rights reserved.
Superplasticizer
Workability retention

1. Introduction
Properties of hardened cement paste and concrete are affected
by their flow behavior which is controlled primarily by the dispers-
ing of cement in mixing water and concrete mixture design.
Superplasticizers have been used extensively to disperse the ce-
ment particles and to improve the workability of concrete in prac-
tice. In hot weather conditions, superplasticizers with retarding
effects are commonly used to reduce the rate of cement hydration
and to extend workable time at jobsites to reduce pumping prob-
lems and to prevent cold joints. Thus, the selection of adequate
chemical admixtures and the evaluation of their effect on early
age properties such as workability retention and initial setting
time are of significant importance. These properties influence the
behavior of hardened cement pastes and concretes.
Lignosulphonates (LS) have been widely used in concrete as reg-
ular water reducing admixtures for many years due to their rela-
tively low prices. Significant advances have been made in the
production of LS based admixtures. With the development of
new modified LS superplasticizers, it has been reported that it is
possible to produce self-compacting concrete with such an admix-
ture [1]. However, there is not much information available on the
effect of the newly developed modified LS superplasticizer on
workability retention and initial setting time of cement pastes in
comparison to those of polycarboxylate and polynaphthalene
based superplasticizers. The research was therefore carried out.
This paper compares the results and discusses the effect of these
admixtures on workability retention and initial setting time of ce-
ment pastes. The workability retention was evaluated based on the
change of yield stress and effective viscosity with time. The initial
setting time was evaluated based on heat development, rheological
parameters change with time, and penetration depth in cement
pastes. The test methods for determining the initial setting time
was reviewed and discussed. The research on cement pastes will
provide information for designing concrete mixtures to achieve
workable concrete.
2. Background on determining the initial setting time and
workability retention
2.1. Initial setting determined by penetration depth

Setting is a term used to describe the stiffening of the cement

* Corresponding author. Present address: Faculty of Civil Engineering and
Geosciences, Delft University of Technology, Stevinweg 1, 2628 CN, Delft, The
Netherlands. Tel.: +31 1527 81325; fax: +31 1527 86383.
E-mail addresses: k.sisomphon@tudelft.nl, sisomphon@hotmail.com (K. Sisom-
phon).
paste, mortar, or concrete. In principle, the setting of cement is a
percolation process in which isolated or weakly bound particles
are connected by the formation of hydration products so that solid
paths are formed in the hardening pastes [2–5]. The setting of

0950-0618/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.conbuildmat.2010.02.021
 M.-H. Zhang et al. / Construction and Building Materials 24 (2010) 1700–1707 1701

cement pastes, therefore, will depend on factors that affect the
connectivity level between particles such as w/c [5,6].
In practice, the initial set indicates the loss of workability and
the beginning of the stiffening of the paste or concrete. Initial set-
ting of cement may be determined by ASTM methods C 191 based
on the principle of penetration resistance. In this test method, nor-
mal consistency of the paste is required. According to ASTM C 191,
the initial setting of a cement paste occurs when the Vicat needle
penetrates 25 mm into the cement paste.
2.2. Heat development due to cement hydration and initial setting
alternative to the penetration depth method determined by Vicat
needle. The yield stresses vs. time for the pastes are shown in
Fig. 2. The curves generally consist of two sections: (1) a slow steady
increase in the yield stress with time, and (2) a significant increase
in the yield stress indicating the change of cement paste from a li-
quid to a solid state. They define the time to reach the last point (‘‘B”
in Fig. 2) before the sharp increase in the curve as the initial setting
time. They investigated cement pastes with w/c of 0.30–0.45 with-
out admixtures, and found that the rheology method correlates well
with the Vicat setting time but the former provides more informa-
tion before the initial setting time than does the latter.

When in contact with water, cement hydrates which generates

heat. The workability retention and initial setting of cement paste
are related to the rate of cement hydration. Cement hydration at
early stage can be monitored from the heat generated using an iso-
thermal calorimeter as shown in Fig. 1. According to Mindess et al.
[7], Stage 1 in Fig. 1 corresponds to initial wetting Peak ‘‘A” fol-
lowed by induction or dormant period (Stage 2). At the end of
the dormant period and beginning of the accelerating period (Stage
3), C3S begins to hydrate rapidly and reaches a maximum rate
(Peak ‘‘B”) at the end of acceleration period. By this time, final
set has been passed and early hardening has begun. Initial setting
typically occurs at the beginning of the accelerating period.
Taylor et al. [8] investigated various combinations of cements,
mineral admixtures, and chemical admixtures using this method
and their results indicate fair correlation between the initial set
determined by this method and that by penetration resistance,
rheology, and ultrasonic p-wave.
2.3. Change of rheological parameters with time and workability
retention
3. Experimental details
3.1. Materials used
Portland cement of ASTM Type I (Table 1) was used in the study, and deionized
water was used for cement pastes. Modified lignosulphonate (PLS), polynaphtha-
lene (PNS), and polycarboxylate (PCE) based superplasticizers were included in this
study. Their characteristics are summarized in Table 2. The polycarboxylate based
admixture was obtained as solution with a concentration of 39.3%. The other two
admixtures were initially in powder form, and solutions were made in laboratory
with concentrations of 30% and 28% by mass for PNS and PLS admixtures, respec-
tively, recommended by manufacturer. Approximately 0.5% tributylphosphate by
mass of dry admixture was added to the solutions of all three admixtures to control
the air that may be entrained.
3.2. Proportion of cement paste mixtures
Proportion of mixtures with various superplasticizers was designed so that the
yield stress of the cement pastes was less than 6 Pa at 30 min. The mix proportions
of the cement pastes used in this research are shown in Table 3. The w/c of the ce-
ment pastes was 0.26 and 0.32.

Workability change with time is also of significance in practice

for transportation and casting of concrete before the initial set. The
workability retention may be evaluated by the change in rheolog-
ical parameters with time. With continued cement hydration, ce-
ment paste and concrete loss workability, and set. The flow of
cement pastes has been reported to fit several different mathemat-
ical forms [9], e.g. Bingham s ¼ so þ gc_ and Herschel–Bulkley
s ¼ so þ K c_ n models, where s is shear stress applied to material
in Pa, so is yield stress in Pa, and c_ is shear rate in s1. In Bingham
model, g is plastic viscosity in Pa.s and is assumed to be constant.
Fig. 2. Yield stress vs. time of cement pastes with different w/c ratios [11].
In Herschel–Bulkley model, K is the consistency index and n is the
power-law index. The Herschel–Bulkley model takes into account
changes in the effective viscosity with shear rate by assuming Table 1
the power-law expression, g ¼ K c_ n1 [10]. Depending on the value Chemical and mineral compositions and physical properties of cement used.
of ‘‘n”, the material flows as a shear thinning fluid (n < 1) or as a
Physical properties
shear thickening fluid (n > 1). The yield stress is the minimum Initial setting time, min 145
shear stress that must be exceeded in order for the material to Final setting time, min 210
flow. Once the flow has started, the effective viscosity determines Blaine fineness, m2/kg 391
flow rate of the cement pastes. Chemical composition, %
Amziane and Ferraris [11] examined the possibility of using rhe- Calcium oxide, CaO 65.0
ology method to determine initial setting of cement pastes as an Silica, SiO2 20.3
Aluminum oxide, Al2O3 4.7
Iron oxide, Fe2O3 3.2
Magnesia, MgO 0.9
Sodium oxide, Na2O 0.2
Potassium oxide, K2O 0.5
Total alkalinity as Na2O + 0.658K2O 0.53
Sulphuric anhydride as SO3 2.4
Loss on ignition (LOI) 1.9
Mineral composition according to Bogue calculation, %
Tricalcium silicate, C3S 67
Dicalcium silicate, C2S 8
Tricalcium aluminate, C3A 7
Tetracalcium alumninoferrite, C4AF 10
Fig. 1. Heat curve [7].
1702 M.-H. Zhang et al. / Construction and Building Materials 24 (2010) 1700–1707

Table 2
Characteristics of admixtures used.

Type Notation ASTM type Reducing substances, % Soluble SO4, % of dry admixture
a
Polycarboxylate PCE F n.m. n.m.a
Polynaphthalene PNS F n.m.a n.m.a
Purified lignosulphonate PLS G/F 0.5 0.2
a
n.m.: not measured.

Table 3
4. Results and discussion
Mix proportion of the cement pastes used for determining the heat development,
rheological parameters, and setting time of the cement pastes.
4.1. Effect of the admixtures on heat development due to cement
Mix Water/ Superplasticizer Superplasticizer dosage, %
hydration and initial set
cement type sbmca
1 0.26 No admixture –
The rates of cement hydration for the pastes with the superp-
2 PCE 0.13
3 PNS 0.39 lasticizers was monitored by a calorimeter and compared with
4 PLS 0.35 those of the corresponding control cement pastes (OPCs) as
5 0.32 No admixture – showed in Figs. 3 and 4. The time from the cement first in contact
6 PCE 0.10 with water and admixtures to the end of the dormant period and
7 PNS 0.30
8 PLS 0.28
the beginning of the acceleration period is summarized in Table 4.
Comparing the time of the control Portland cement pastes to those
a
sbmc: solid by mass of cement, %. with the admixtures, it seems that all the admixtures investigated
retarded the cement hydration. However, the degree of retardation
varied with the type and dosage of the admixtures. For the control
3.3. Test methods cement pastes, the acceleration period started at approximately
1 h, whereas the beginning of the acceleration period delayed
3.3.1. Determine the effect of admixtures on the rate of heat development of cement
about 2–3 h for the pastes with PNS and PCE admixtures, and about
pastes
The rate of cement hydration was monitored based on the heat development 16 h for the pastes with PLS admixtures.
from the cement pastes by an isothermal calorimeter at a temperature of 30 °C. This From the occurrence time and intensity of the Peak ‘‘B” after the
temperature was selected with the consideration of weather conditions in tropical acceleration period, it seems that PLS admixture had much stron-
countries such as Singapore. The calorimeter was calibrated and conditioned at
ger retarding effect compared with the PCE and PNS admixtures.
30 °C before experiments. All the ingredient materials, mixing utensils, and sample
ampoules were pre-conditioned to 30 °C as well. The cement was added into the
The time when the acceleration period started showed the same
solution of deionised water and admixture, and hand mixed for about 1 min. The trend (Table 4).
cement paste sample of 10 ± 2 g was then transferred into a sample ampoule with Experimental results showed that the w/c ratio also played a
the sample mass recorded. After capping the ampoule, the sample and reference role on the heat development of the cement pastes. For all the
ampoules were inserted into the calorimeter. The heat generated from the cement
admixtures, the pastes with higher w/c had lower Peak ‘‘B” com-
hydration was monitored continuously for about 48 h. The calorimeter started to
record heat 10 min after the cement was in contact with water. Because of this pro- pared with those with lower w/c. This may be attributed to the
cedure, the heat generated initially during mixing of the cement and water was not lower unit cement content in the pastes with higher w/c. However,
captured. the heat curves of the pastes with w/c of 0.32 showed slightly
broader peaks than those with w/c 0.26 which may be attributed
3.3.2. Determine the initial setting time of cement pastes by penetration depth method to the higher free water content in the formers which prolong
The initial setting time of the cement pastes was determined according to ASTM
the acceleration period of cement hydration. It was noted that
C 191 Method B with modification using an automatic Vicat apparatus. ASTM Meth-
od specifies that pastes used for the test should be proportioned and mixed to nor- the w/c had no significant effect on the occurrence time of Peak
mal consistency, and the initial setting time was the elapsed time required to ‘‘B” and the time when the acceleration period started which were
achieve a penetration of 25 mm. In this research, however, mix proportions shown controlled primarily by the properties of the cements and the
in Table 3 were used for the pastes. Therefore, the initial setting determined is af- retarding effect of the admixtures used. Based on the above re-
fected by the w/c and chemical admixtures used in the pastes.
marks, it can be concluded that this method cannot be used for
determining initial setting time of pastes since the setting is af-
3.3.3. Determine the rheological parameters of cement pastes
The rheological parameters were determined at various intervals from the time fected by the w/c. However, the method may provide useful infor-
water and admixture was in contact with the cement until the yield stress of the
cement pastes increased sharply compared with that at initial stage.
The admixture was added into mixing water and then mixed with the cement in
a Hobart mixer for about 4 min (1 min at speed 1, 2 min at speed 2, and another
Rate of Heat Evolution (mW/g)

1 min at speed 2 after scrapping the bottom of the bowl). Before each test, the paste
6.0
was remixed in the mixer for about 10 s.
OPC
A Hakka RV1 rheometer with coaxial cylinder configuration was used to deter- 5.0 PCE
mine the rheological parameters of the cement pastes. The torque resulting from
4.0 PNS
the material resistance was measured at the inner rotating cylinder, which had a
length of 55 mm and a diameter of 38 mm. Gap between the inner and the outer PLS
3.0
cylinders was 2.7 mm. The surfaces of the inner and outer cylinders were serrated
so that the slippage between the cement paste samples and the surfaces of the cyl- 2.0
inders was minimized. The shear rate first increased from 0.5 to 50 s1in 50 s and
then decreased to 0.5 s1 also in 50 s. A total of 100 data points were collected at 1.0
various shear rates from 50 to 0.5 s1. The down curve (from 50 to 5 s1) was used
to calculate the yield stress of the cement paste based on Herschel–Bulkley model. 0.0
0 500 1000 1500 2000 2500 3000
Due to the shape of the curves, using Bingham model fitting resulted in negative
yield stresses as observed by De Larrard et al. [12] as well. The data, therefore, were Time (minutes)
fitted by Herschel–Bulkley model to determine the yield stress and effective
viscosity. Fig. 3. Rate of heat evolution of cement pastes with w/c of 0.26.
 M.-H. Zhang et al. / Construction and Building Materials 24 (2010) 1700–1707 1703

Rate of Heat Evolution (mW/g)

200
6.0 180
160 PLS

Shear stress (Pa)

5.0 OPC PNS
140
4.0 120 PNS

3.0 PCE PLS

100
80
2.0 60 PCE
1.0 40
20
0.0 0
0 500 1000 1500 2000 2500 3000 0 20 40 60
Time (min) Shear rate (1/s)

Fig. 4. Rate of heat evolution of cement pastes with w/c of 0.32. Fig. 5. Shear stress vs. shear rate for cement pastes with w/c = 0.26 at 30 min
(descending curves).
mation for estimating initial setting time of cement pastes at given
w/c due to the effect of admixtures.
The mechanism of retardation in cement paste depends on the
type of admixtures. For lignosulphonate based admixtures, it has
80
long been recognized that residual matters such as sugars and re-
lated salts are only partly responsible for their retarding effect 70 PLS

Shear stress (Pa)

[13,14]. Various other mechanisms of retardation such as adsorp- 60
tion, complexation, precipitation, and nucleation also contribute 50
to retardation effects on cement hydration [15–17]. The retarda- 40 PNS
tion of lignosulphonates has been believed to be caused partly by
30
adsorption of their molecules onto the surface of anhydrous ce-
20 PCE
ment compounds, which creates a barrier to the cement hydration
[18,19]. The inhibition of nucleation and growth of crystalline 10
hydroxide due to the adsorption of organic compounds was also 0
suggested as a retarding feature of C3S hydration [18]. The nucle- 0 20 40 60
ation model considers the adsorption of admixtures on hydration Shear rate (1/s)
products and not on anhydrous cement compounds [17]. The cre-
Fig. 6. Shear stress vs. shear rate for cement pastes with w/c = 0.32 at 30 min
ation of a layer of precipitated calcium salts on anhydrous alkaline (descending curves).
cement compounds was also proposed to be partly responsible for
hydration retardation [20].
For polynaphthalene based superplasticizers, Jolicoeur and Sim- shown in Figs. 5 and 6, respectively. Based on Herschel–Bulkley
ard [21] suggested that the retardation was mainly due to the model (s ¼ so þ K c_ n ), yield stress so and parameters K and n of
adsorption of admixtures on nucleating hydrate particles and the cement pastes are summarized in Table 5. The R2 of data fitting
intercalation into hydrate phases already formed such as ettringite to the model was P0.95. The yield stress of the cement pastes at
which inhibit the development of hydration products. 30 min was <6 Pa. For all the pastes samples, the power-law index
For polycarboxylate based superplasticizers, Uchikawa et al. ‘‘n” was >1 which indicates that these cement pastes behave as
[22] showed that a chelate formed in pastes as a result of interac- shear thickening materials, consistent with the observations for ce-
tion between Ca2+ ions and the admixture molecules would lower ment pastes with superplasticizers by Martin et al. [23].
the Ca2+ concentration in the system, thus hinder solid phase The yield stress of the cement pastes increased with time due to
nucleation and hydration products growth, and retard cement cement hydration (Figs. 7 and 8). The time when the yield stress of
hydration. the cement pastes increased sharply is summarized in Table 4 to be
compared with other data. Although the yield stresses of the ce-
4.2. Effect of the admixtures on the change of rheological parameters ment pastes with PCE and PNS admixtures were lower than that
with time with PLS admixture at 30 min (Table 5), the yield stress of the
formers increased with time in faster rates compared with that
Shear stress vs. shear rate graphs of the cement pastes with dif- of the latter (Figs. 7 and 8). The yield stress of the pastes with
ferent admixtures at w/c ratios of 0.26 and 0.32 at 30 min are PCE and PNS increased significantly with time after about 1.3–

Table 4
Initial setting time determined by various methods.

Type of admixture w/c Time to the beginning of acceleration Time when yield stress Initial setting time by
period from heat curve, min increase significantly, min Vicat test, min
No admixture 0.26 60 n.m.a 90
PCE 260 110 300
PNS 175 75 230
PLS 1025 475 990
No admixture 0.32 60 n.m.a 140
PCE 220 150 415
PNS 170 120 290
PLS 1030 680 1105
a
n.m. – not measured due to high yield stress.
1704 M.-H. Zhang et al. / Construction and Building Materials 24 (2010) 1700–1707

Table 5
Yield stress and parameters ‘‘K” and ‘‘n” based on Herschel–Bulkley model for various cement pastes at 30 min.

Type of admixture w/c Yield stress, Pa Consistency index, ‘‘K” Power-law index, ‘‘n”
PCE 0.26 1.83 0.14 1.59
PNS 5.27 0.34 1.46
PLS 5.71 1.88 1.15
PCE 0.32 1.00 0.04 1.62
PNS 1.01 0.17 1.38
PLS 2.72 0.52 1.23

2.5 h, whereas that with PLS admixture increased significantly 50

with time after about 7.9–11.3 h depending on the w/c. PCE
40 PNS

Yield Stress, Pa
From Table 5, it was observed that the pastes with PLS admix- PLS
ture had higher ‘‘K” value, but lower ‘‘n” value compared with 30
those of the corresponding ones with PCE and PNS admixtures.
The ‘‘K” and ‘‘n” values did not remain constant. The former gener- 20
ally trended up with time, whereas the latter generally trended
slightly lower with time. Among the three admixtures, PLS had 10
the lowest index ‘‘n” values ranged between 1.0 and 1.3. Values
0
of ‘‘n” higher than 1.5 were observed for the pastes with PCE and 0 200 400 600 800 1000
PNS admixtures at the first 15 min, which indicate higher shear Time (min)
thickening behavior for these pastes at early age.
From the parameters of ‘‘K” and ‘‘n” in Herschel–Bulkley model, Fig. 8. Yield stress change with time, w/c = 0.32.
effective viscosity of the cement pastes was calculated at
c_ = 25 s1, and plotted against time (Figs. 9 and 10). The effective
viscosity of the pastes with the PLS admixture was higher than
the corresponding ones with PCE and PNS admixtures at 30 min.
6
At w/c of 0.32, the effective viscosity of the cement pastes with
PCE and PNS admixtures increased more quickly with time than
Effective viscosity

that of the paste with PLS admixture. At w/c of 0.26, no data on

4
effective viscosity for pastes with PNS and PCE admixtures were
obtained after about 2 and 3 h, respectively, due to the increase
in the yield stress so that the measurement became difficult. How-
2
ever, the effective viscosity of the paste with PLS admixture re-
mained relatively low until about 8 h. Comparing the cement
PCE PNS PLS
pastes with w/c of 0.26 and 0.32, it seems that the former has high-
0
er effective viscosity than the latter. 0 200 400 600 800
The viscosity of the cement pastes without admixtures gener- Time (min)
ally increases with time due to cement hydration. However, it
was observed from Figs. 9 and 10 that the viscosity of the pastes Fig. 9. Effective viscosity change with time, w/c = 0.26 (shear rate = 25 s1).
with PLS decreased slightly during the first hour, whereas the vis-
cosity of the pastes with PCE and PNS increased with time. This
may be explained by the effect of admixture adsorption and mech- dispersion is dominated by electrostatic repulsion [28,29]. For
anism of dispersion. modified lignosulphonate based superplasticizers, the dispersion
Published research indicates that different admixtures have dif- may be attributed to a combination of electrostatic repulsion and
ferent mechanisms for dispersing cement particles in water. For steric hindrance effect [30]. According to Ramachandran et al.
polycarboxylate based superplasticizers, the main mechanism of [31], although lignosulphonate based admixtures have linear
the dispersion is due to steric hindrance effect that results from molecular structures, the steric effect is caused by the cross-linked
the extension of their graft chains away from the surface of cement molecules taking up a relatively large volume on the surface of ce-
particles [24–27]. For polynaphthalene based superplasticizers, the ment particles.
Fig. 11 [32] shows the adsorption of the three admixtures on ce-
ment particles and hydration products in fresh cement pastes with
50 w/c ratio of 0.34 within the first 60 min. The adsorption of superp-
PCE lasticizers was measured by solution depletion method by compar-
PNS
40
Yield Stress, Pa

PLS ing the amount of superplasticizers remained in the solutions

30
extracted from fresh cement pastes and the amount originally
added. The results were expressed as percentages of the superp-
20 lasticizers adsorbed relative to the total amounts of the superplast-
icizers added. The concentrations of PNS and PLS superplasticizers
10 in the solutions were measured by a UV–visible spectrometer. The
concentrations of the PCE superplasticizer in the solutions were
0
0 200 400 600 800 determined by a total organic carbon content (TOC) analyzer. De-
tails of the adsorption test procedure can be found in [32].
Time (min)
In the pastes with PCE admixture, almost all the admixture
Fig. 7. Yield stress change with time, w/c = 0.26. was immediately adsorbed on cement particles, and remained
 M.-H. Zhang et al. / Construction and Building Materials 24 (2010) 1700–1707 1705

2.0 4.3. Effect of the admixtures on initial setting determined by

Effective viscosity penetration depth
1.5
Penetration depth of the cement pastes with various admix-
tures determined by the Vicat needle test is shown in Figs. 12
1.0
and 13 in comparison to that of the corresponding control pastes.

0.5
PCE PNS PLS
40
0.0
0 200 400 600 800 1000

Penetration (mm)
30
Time (min)

Fig. 10. Effective viscosity change with time, w/c = 0.32 (shear rate = 25 s1). 20

10 PCE
PNS
100% PLS
Control
0
80% 0 300 600 900 1200 1500
Time (min)
Adsorption (%)

60%
Fig. 13. Penetration depth from Vicat needle test, w/c = 0.32.
40% PCE
PNS
20% 40 40
PLS Yield stress
PCE
0% Penetration

Penetration (mm)
Yield stress (Pa)
0 10 20 30 40 50 60 30 30
Time (minutes)

Fig. 11. Adsorption of superplasticizers in cement pastes with a w/c of 0.34 [32]. 20 20

10 10

40
0 0
0 200 400 600
Penetration (mm)

30
Time (min)

40 40
20
Yield stress

PCE PNS Penetration

Penetration (mm)
Yield stress (Pa)

30 30
10 PNS
PLS
Control
20 20
0
0 300 600 900 1200 1500
Time (min) 10 10

Fig. 12. Penetration depth from Vicat needle test, w/c = 0.26.
0 0
0 200 400 600
adsorbed during the 60 min. For the PNS and PLS admixtures, the Time (min)
adsorption increased slightly with time. As the cement in the
40 40
pastes with PNS is dispersed mainly by electrostatic repulsion,
PLS
the more adsorption would reduce the admixture in solution and Yield stress
thus increase the paste viscosity which would reduce the workabil-
Penetration (mm)

Penetration
Yield stress (Pa)

30 30
ity. In the pastes with PLS, however, the cement is dispersed
through a combination of electrostatic repulsion and steric hin-
20 20
drance effects. Although the increase in the adsorption of PLS with
time at early age reduced the admixture in solution, it increased
the amount adsorbed. This suggests that the steric hindrance effect 10 10
will increase with time, whereas the electrostatic repulsion effect
will decrease with time for the PLS admixture. This may explain
0 0
the reduction of effective viscosity at early age observed. 0 300 600 900 1200 1500
The data on the yield stress and effective viscosity indicate that
Time (min)
the paste with PLS admixture had longer workable time than that
with PCE and PNS admixtures. This is particularly beneficial for Fig. 14. Comparison of changes on yield stress and penetration depth with time for
concrete cast in hot weather conditions. pastes with w/c of 0.26.
1706 M.-H. Zhang et al. / Construction and Building Materials 24 (2010) 1700–1707

The initial setting time of the pastes with the penetration depth of
25 mm was summarized in Table 4. The results show that the ini-
tial setting times of the pastes with superplasticizers were longer
than those of the control pastes. This indicates retardation of the
superplasticizers, consistent with the results on heat development
discussed before. The results show that the initial setting of the
pastes with w/c of 0.26 was slightly shorter than that with w/c of
0.32. In both cases, the setting was affected not only by w/c, but
also by the type and dosage of the superplasticizers used. The ini-
tial setting times of the pastes with PCE and PNS admixtures were
more than 10 h shorter than that with PLS admixture. Although the
pastes with PLS admixture had longer workable time, the longer
setting time has to be taken into consideration in practice when
early strength development is essential.
4.4. Discussion
Table 4 summarizes the initial setting time determined by var-
ious methods. From the data shown in Table 4, it seems that the
initial setting time determined by the penetration depth from Vicat
needle test is much longer than that defined by the yield stress
40
measurement suggested by Amziane and Ferraris [11]. As afore-
mentioned, the setting time determined by the penetration depth
is used to describe an arbitrarily chosen stage of setting. To find
out the changes in workability before the setting defined by the
penetration depth, the yield stress and penetration depth of each
paste is plotted on the same graph as shown in Figs. 14 and 15.
The figures show that the yield stress of the pastes increased shar-
ply and the pastes were changing from liquids to solids long before
the initial setting times by the Vicat needle test were reached.
Since the initial setting time, per definition, indicates a significant
loss of workability and the beginning of the stiffening of the paste,
the initial setting time determined by the change of yield stress
provides more precise information than the penetration depth test
of the pastes. This is consistent with the results by Amziane and
Ferraris [11].
Although the data obtained with the three different tests in Ta-
ble 4 show similar trends when comparing cement pastes with dif-
ferent admixtures, it seems that the actual time related to the
initial setting varied according to the tests. It is recognized that
the heat curves assesses the extent of cement hydration whereas
the initial setting is a physical phenomenon; different extents of
hydration are required to achieve setting depending on mixture
proportions and w/c of mixtures [6]. Nevertheless, the calorimetry
and heat curves may provide useful information for estimating ini-
40
tial setting time of cement pastes incorporating superplasticizers
Penetration depth (mm)

PCE with retarding effects at a given w/c, particularly for relative

Yield stress (Pa)

30 30 comparison.
It is recognized that the hydration reactions starts in the first
few minutes after the cement is in contact with water and that it
20 20
consumes part of the admixture added. The admixture consumed
may no longer be available for the dispersion of cement particles.
10 10 Because significant part of the consumption takes place during
Yield stress
the first few minutes, adding the admixtures later will result in
Penetration
better dispersion if the same amount of the admixtures is used.
0 0
0 200 400 600 However, due to the different compositions of admixtures and
mechanisms on dispersion of these admixtures, delayed addition
Time (min)
of the admixtures may not lead to the same extent of the improve-
40
ment for the dispersion. Composition and specific surface of ce-
40
ment also affect the rate of hydration reactions during the first
Penetration depth (mm)

PNS few minutes and thus consumption of the admixtures. Therefore,

Yield stress (Pa)

30 30 the relative amount of the admixtures required to achieve similar

workability may vary depending on the type of admixture and
20 20 on the time of addition of the admixtures.

10 10
5. Summary and conclusions
Yield stress
Penetration
0 0 In this research cement pastes were prepared with given water-
0 200 400 600 to-cement ratios of 0.26 and 0.32 using different types and dosages
Time (min) of the superplasticizers. The cement pastes had yield stress of <6 Pa
at 30 min. Based on the experimental results, the following conclu-
40 40
sions may be drawn:
Yield stress PLS
Penetration depth (mm)

Penetration
1. The modified lignosulphonate (PLS), polycarboxylate (PCE), and
Yield stress (Pa)

30 30
polynaphthalene (PNS) based superplasticizers investigated
retarded cement hydration. However, the degree of retardation
20 20
varied with the type and dosage of the admixtures. The PLS
admixture had much stronger retarding effect compared with
10 10 the PCE and PNS admixtures.
2. The shapes of the shear stress – shear rate curves indicated that
the cement pastes were shear thickening materials. The pastes
0 0
0 300 600 900 1200 1500 with PCE and PNS admixtures showed higher shear thickening
behavior than that with PLS admixture. Although the yield
Time (min)
stresses and effective viscosity of the cement pastes with the
Fig. 15. Comparison of changes on yield stress and penetration depth with time for PCE and PNS admixtures were lower than those with the PLS
pastes with w/c of 0.32. admixture at 30 min, the yield stress and effective viscosity of
 M.-H. Zhang et al. / Construction and Building Materials 24 (2010) 1700–1707
the formers increased more rapidly with time compared with
the latter. This indicated that the paste with the PLS admixture
had longer workable time than that with the PCE and PNS
admixtures.
3. The initial setting times of the pastes with the PCE and PNS
admixtures determined by the penetration depth method were
much shorter than that with the PLS admixture. Although the
pastes with PLS admixture had longer workable time, the longer
setting time has to be taken into consideration in practice
whenever early strength development is essential.
4. Since the initial setting time indicates the loss of workability to
such an extent that the paste is no longer workable, the initial
setting time determined by the change of yield stress provides
more precise information than the penetration depth test of
the cement pastes. The heat development curves may provide
useful information for estimating initial setting time of cement
pastes incorporating superplasticizers with retarding effects at
a given w/c.
Acknowledgements
The authors greatly appreciate Borregaard Industry Ltd. for
funding this research project, and Dr. Kare Reknes and Mr. Philip
Chuah for constructive comments and discussion. The authors
would like to thank Ang Beng Oon of Structure laboratory, National
University of Singapore (NUS) for his assistance in the various
experiments. Dr. Tam Chat Tim’s review was appreciated.
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