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Use of Water Reducers to Improve Grindability

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ACI MATERIALS JOURNAL

TECHNICAL PAPER

Title no. 108-M66

Use of Water Reducers to Improve Grindability and

Performance of Portland Cement Clinker
by Joseph J. Assaad and Salim E. Asseily
A comprehensive research project was undertaken to evaluate the
effect of liquid or powder water reducers (WRs) on the grindability
and clinker factor optimization during the production of portland
cement. Three WRs based on lignosulfonate (LS), polynaphthalene
sulfonate (PNS), and polycarboxylate (PC) were tested at various
concentrations. The efficiency of WRs to preserve their waterreduction properties following the grinding energy and rise of
temperature encountered in the grinding mill was quantified.
Regardless of the type of WR, test results have shown that the
incorporation of increased concentrations, whether in liquid or
powder forms, can improve grindability of clinker while at the
same time reduce water demand. All mortars prepared with the
high-range water-reducing admixture cement exhibited higher
compressive strengths compared to the ones made with the control
cement due to a decrease in the water-cement ratio (w/c) and
an improvement in cement fineness. For a given dosage, cement
ground with PC-based WR exhibited the highest levels of strength
increase. The clinker factor and grinding energy were found to
be simultaneously optimized by up to 32% and 5%, respectively,
through the substitution of clinker by pozzolan with a lower Mohs
hardness and incorporation of WR.
Keywords: cement; clinker; grinding aids; water reducers.

INTRODUCTION
In the cement industry, a great amount of electrical energy
(approximately 4 GJ of energy per tonne of cement) is
consumed during the grinding process of clinker and other
raw materials.1 Currently, it is quite common to reduce
such energy consumption by adding small quantities of
grinding aids (GAs), generally in the range of 0.02 to 0.14%
of the manufactured cement weight. The chemical basis
of GAs includes mainly ethanolamines, such as triethanolamine, monoethanolamine, and triisopropanolamine,
as well as glycols such as ethylene glycol and propylene
glycol.2-6 Because of their highly organic polar nature, such
additives can reduce the energy forces that cause attraction
and agglomeration of the newly produced cement particles.
Assaad et al.3 reported that the clinker factor and grinding
energy can be simultaneously optimized through the substitution of clinker by pozzolan and the incorporation of GA.
The use of 0.13% amine-based GA and 0.09% glycol-based
GAs are found to lead to 15.8% and 10.5% clinker reductions and energy savings of 4.5% and 2.3%, respectively.
It is widely accepted that water reducers (WRs) or highrange water-reducing admixtures are added in concrete
and mortar mixtures to improve workability for a given
water content and/or to improve strength for a given workability. Their chemical basis includes mainly lignosulfonate
(LS), polynaphthalene sulfonate (PNS), or polycarboxylate (PC), and are generally added at dosage rates varying
from 0.2 to 2% of the cement weight.7 Limited information
exists in the literature regarding the effect of intergrinding
such WRs (instead of conventional GAs) on the grindACI Materials Journal/November-December 2011

ability and physical properties of portland cement. In 1993,

Sultanov8 published a case study on the use of powder WRs
during the grinding process of clinker and gypsum without,
however, giving indications in regard to the chemical basis
or dosage rates of the WR used. The author found that intergrinding WRs with clinker can improve grindability and
decrease the pack set for a relatively long period of time.
Compared to the control cement, the incorporation of WR
during the grinding process was found to reduce water
demand by up to 25%. Sultanov8 noted that high-range
water-reducing admixture cement is characterized by high
strength, rapid strength gain, dense microstructure, and low
shrinkage. Despite such favorable technical characteristics, however, the intergrinding of the WR with clinker was
reported to not always be economically justified because of
its high cost, which therefore limits the use of high-range
water-reducing admixture cement to special applications,
such as the grouting of oil wells, abrasion-resistant airfields,
thin concrete shell construction, and so on.8
Bouzouba et al.9 evaluated the effect of intergrinding
different percentages of PNS with portland cement clinker
on the fineness, water demand, and compressive strength
of the final product. The PNS used was in powder form
and added at concentrations varying between 0.1 to 0.9%
by weight of the clinker and gypsum materials. No tests
were made to determine the effects of LS- or PC-based
WRs. A laboratory ceramic grinding mill with a capacity
of 1.5 kg (3.3 lb) and having different ball sizes was used
for grinding the clinker. Compared to the control cement,
the authors9 concluded that the addition of PNS can
reduce the grinding times by approximately 10 to 30%
for a given cement fineness. For a given grinding time
and Blaine fineness of approximately 4500 cm2/g (306
103 in.2/lb), mortars made with high-range water-reducing
admixture cement had higher compressive strengths by
approximately 15 to 25% than those made with the control
cement. On the other hand, water requirements of mortars
made with the high-range water-reducing adxmiture cement
were similar to those obtained from the control cement when
the same PNS dosage was added to the mixing water. Validation tests showed that slump loss, air content, bleeding,
setting times, and compressive strength of concrete made
using high-range water-reducing admixture cement are all
comparable to those of the concrete made with the control
cement when the PNS was added to the mixing water.9

ACI Materials Journal, V. 108, No. 6, November-December 2011.

MS No. M-2010-282.R1 received March 10, 2011, and reviewed under Institute
publication policies. Copyright 2011, American Concrete Institute. All rights
reserved, including the making of copies unless permission is obtained from the
copyright proprietors. Pertinent discussion including authors closure, if any, will be
published in the September-October 2012 ACI Materials Journal if the discussion is
received by June 1, 2012.

Joseph Assaad is a Professor of Civil Engineering and R&D Manager at Holderchem

Building Chemicals S.A.L., Baabda, Lebanon. He received his PhD from the University
of Sherbrooke, Sherbrooke, Qubec, QC, Canada. His research interests include
grinding aids and strength enhancers for cement, rheology, formwork pressure,
underwater concrete, repair systems, concrete durability, and the use of geotechnical
equipment for testing cementitious-based materials modified with chemical and
mineral admixtures.
Salim Asseily is the Managing Director at Holderchem Building Chemicals S.A.L.
He received his BS in chemical engineering, his MS in operation research, and his
MBA from Columbia University, New York, NY. His research interests include the
development of cement additives, concrete admixtures, ready-to-use mortars, and
specialty chemicals.

SCOPE OF RESEARCH PROGRAM

Despite the limited data available in the literature, it is
clear that intergrinding WR with clinker reduces grinding
times for a given fineness and enhances cement properties.
However, several issues need further investigation to clearly
identify the advantages and limitations of such additions.
For example, for an admixture with a given solid content
added at a given dosage rate in concrete mixtures, it is well
established that the extent of water reduction increases when
the chemical basis of the WR changes from LS to PNS and
then to PC due to different WR characteristics and modes
of function.7 Furthermore, it is generally preferable to use
admixtures in liquid form (not powder) to facilitate accurate
dispensing and achieve better dispersion within the concrete
mixture.7,10 Based on this, the objective of the first phase
of this paper is to compare the efficiency of LS-, PNS-, or
PC-based WRs on the grindability of clinker and variations
of final cement properties, including Blaine fineness, sieve
residues, water demand, setting times, and compressive
strength. The WRs were added in liquid or powder forms.
Immediately after a grinding test in a laboratory grinding
mill, the temperature of the clinker and gypsum materials
generally increases from ambient to approximately 32 to
37C (90 to 99F).3,4 In real grinding mills, such a temperature rise may easily exceed 100C (212F), which thereby
increases the risks of dehydrating too much gypsum and
causes a false set situation.10 Cement manufacturers pay
special attention to limit the temperature rise to a maximum
of 95C (203F) by cooling down the exterior of the mill
with water or fresh air and sometimes by pulverizing water
inside the mill. Therefore, the second phase of this paper
seeks to quantify the capability of each type of tested WR
to preserve its efficiency when the clinker reaches higher
temperatures of 65 and 95 4C (149 and 203 39F) inside
the grinding mill. Liquid or powder WRs were interground
with the clinker, as their performances may be differently
affected by the temperature rise. This phase also seeks to

determine the effect of grinding energy on the performance

of LS-, PNS-, or PC-based WRs to reduce water demand.
As previously mentioned, the use of WR during the
grinding process of clinker is not always economically
justified, especially when added at dosage rates exceeding
1% of the cement weight. With todays constraints on the
necessity to reduce carbon dioxide (CO2) emissions and
optimize cement cost, however, a growing need has emerged
to develop and use new alternatives other than conventional
GAs that can substantially minimize the clinker factor while
maintaining adequate compressive strength. Therefore, the
objective of the third phase of this paper is to determine the
percent reduction of the clinker factor that can be achieved
while adding a given WR type and concentration. Other
characteristics dealing with the compatibility and stability of
cement performance as a function of time when ground with
different types of WR will be presented in a follow-up paper.
RESEARCH SIGNIFICANCE
The beneficial effects and limitations of intergrinding WR
with clinker are still not well understood and quantified.
This paper presents useful information regarding the effect
of incorporating various types of WR on the grindability
of clinker and final cement properties. Such data can be
of special interest to portland cement manufacturers and
grinding aid producers, as well as various environmental
organizations dealing with climate changes and the reduction
of usable energy.
EXPERIMENTAL INVESTIGATION
Materials and mixture proportions
Industrial clinker used for the production of ASTM
C150 Type I cement,11 natural pozzolan meeting the requirements of ASTM C618 Class N,12 and gypsum materials
were employed in this study. Their chemical compositions
are presented in Table 1. The relative hardness of the clinker,
pozzolan, and gypsum determined according to the Mohs
hardness scale were approximately 6, 4.5, and 2, respectively.
Three commercially available powder WRs were investigated in this study. The LS is derived from fractionated
spruce wood sulfite liquor with a bulk density of 0.53; pH
in a 10% solution of 8.2; and sulfur, sodium, and chloride
contents of 7.8%, 8.2%, and 0.12%, respectively. The PNS
had a bulk density of 0.62, pH in a 10% solution of 7.8, and
sodium sulfate and chloride contents less than 3% and 0.5%,
respectively. Finally, the PC had a bulk density of 0.55, pH
in a 10% solution of 5.9, and sulfur and sodium contents of
0.85% and 4.2%, respectively.
As previously mentioned, the three WRs were incorporated during the grinding process of clinker in either powder
or liquid forms. The liquid solutions were prepared by

Table 1Chemical compositions of clinker, pozzolan, and gypsum

SiO2, %
Clinker

Pozzolan

Gypsum

22.5

Al2O3, %

Fe2O3, %

CaO, %

MgO, %

SO3, %

5.1

4.86

61.35

1.6

0.65

Loss on ignition is 1.18%; Na2Oeq is 0.45%; free lime is 0.7%; specific gravity is 3.12
68.55

16.7

4.6

2.8

2.24

0.15

Loss on ignition is 3.25%; moisture content is 0.05%; Na2Oeq is 1.05%; pozzolanic activity index with portland cement at 28 days is 80.1%
2.7

0.55

0.4

31.5

1.5

43.2

Free water (T < 45C) is 0.03%; combined water (T < 230C) is 15.6%; carbon dioxide is 3.7%

Note: C = (F 32)/1.8.

2

ACI Materials Journal/November-December 2011

dissolving 40% dry component with 60% water and were

added during the grinding process at dosage rates of 0.25%,
0.6%, and 0.9% of the total cement weight. The minimum
dosage of 0.25% was selected following several grinding
trial tests, which indicated that dosages below such a value
will not lead to noticeable differences in terms of grindability and final cement properties. On the other hand, no
tests were made at dosages higher than 0.9% of the cement
weight, given the significant increase in cost that may result
compared to conventional GAs generally added at concentrations not exceeding 0.14% of the cement weight.
The powder WRs were incorporated, as commercially
available, at concentrations equivalent in terms of solid
content to those used when the admixture was added in a
liquid form. For example, the equivalent dosage for 0.6% of
liquid additive is 0.6% 40% = 0.24% of dry component.
Dosages of 0.25% and 0.9% in liquid forms correspond to
0.1% and 0.36%, respectively, when added in powder forms.
One mixture design composed of 95% clinker and 5%
gypsum was used in Phases 1 and 2 to evaluate the effect of
liquid or powder WRs on the grindability of clinker at various
temperatures. On the other hand, the clinker was substituted
by various percentages of the pozzolan in Phase 3 to determine
the effect of WR on the clinker factor, whereas the gypsum
material remained constant at 5% of the total mixture.
Testing equipment and procedures
A 50 L (13.25 gal.) laboratory grinding mill with a drum
diameter, drum length, and rotational speed of 400 mm
(15.7 in.), 400 mm (15.7 in.), and 50 rpm, respectively, was
used (Fig. 1).2 A total of 80 kg (176 lb) steel balls (36 kg
[79.2 lb] of 20 mm [0.78 in.] diameter and 44 kg [96.8 lb]
of 30 mm [1.18 in.] diameter) were used for grinding a quantity of approximately 12 kg (26.4 lb) of clinker, gypsum, and
pozzolan. Prior to grinding, these latter raw materials were
crushed and sieved so that all particles were less than 10 mm
(0.4 in.). The gypsum and pozzolan were dried to a constant
weight at 45 and 105C (113 and 221F), respectively, prior
to use. It should be noted that periodic calibration tests were
done using standard limestone material.2
The grinding mill operated in a room where the ambient
temperature and relative humidity were 23 2C (73 36F)
and 55 5%, respectively. The mill was connected to an
electric counter for monitoring the specific energy consumption Ec used for testing. In Phases 1 and 2, the Ec was set
to 38 kWh/tonne. Given that the clinker was substituted by
the pozzolanic material with a lower relative Mohs hardness,
the Ec was adjusted in Phase 3 so that the Blaine fineness
of all cement mixtures would be 3250 100 cm2/g (221
7 103 in.2/lb) determined using the Blaine apparatus
according to ASTM C204.13
Following the end of grinding, the temperature of
the 12 kg (26.4 lb) cement sample obtained was found to be
approximately 32 to 37C (90 to 99F). Therefore, to simulate the effect of increased temperatures on the variations of
cement properties ground with or without WRs, the 12 kg
(26.4 lb) sample was divided into three parts (A, B, and C)
of 4 kg (8.8 lb) each. Part A was considered without modification for testing (Phase 1), whereas Parts B and C were
heated in an oven to attain temperatures of 65 and 95 4C
(149 and 203 39F), respectively (Phase 2). The procedure used for heating Parts B and C consisted of placing the
samples in a preheated oven at the desired temperature for
2.5 hours. Such time generally corresponds to that normally
ACI Materials Journal/November-December 2011

Fig. 1Photo of grinding mill.

needed for grinding clinker in a real ball mill to a Blaine
fineness of approximately 3500 cm2/g (238 103 in.2/lb).
Regular temperature checks were conducted to ensure that
the powdered cement samples reached the specified temperatures. Prior to testing, all A, B, and C parts were allowed to
cool down for 24 hours to an ambient temperature of 23
2C (73 36F).
Chemical and physical tests were performed using the
cement sample ground with or without WR. The chemical
tests such as the loss on ignition, silicon dioxide (SiO2),
magnesium oxide (MgO), sulfur trioxide (SiO3), and so
on were determined according to the ASTM C114 Test
Method,14 and were found to be relatively close to those of an
ASTM C150 Type I control cement prepared without WRs.
The water demand needed to achieve normal consistency
and Vicat initial and final setting times were determined
according to ASTM C18715 and ASTM C191,16 respectively. The compressive strength was taken as the average
of three 50 mm (2 in.) cube specimens according to
ASTM C109.17 In this latter test method, the mortar mixtures
were prepared using 740 g (1.63 lb) of ground cement,
2035 g (4.47 lb) of sand, and an adjustable amount of water
to produce a flow of 110 5% as per ASTM C109. The
mortar cubes were stored side by side in saturated lime water
until the time of testing.
EXPERIMENTAL RESULTS AND DISCUSSION
Phase 1: Effect of WR type and concentration on
cement properties
The Blaine fineness, water demand, final setting time,
and compressive strength after 7 and 28 days obtained for
cement ground with various types and concentrations of
WRs are summarized in Table 2, along with the properties
of the control cement ground without WRs. The discussion
and analysis provided in the following regarding the effect
of WR on the variations of cement properties with respect
to the control mixture are based on the following equation:
D(property) = (property measured on cement ground with
given WR concentration property of control cement)/
property of control cement 100.
3

Table 2Test results obtained following grinding of clinker with either LS, PNS, or PC-based WR in liquid
or powder form
Reference
*

Dosage rate, %

Liquid LS

Liquid PNS

Liquid PC

0.25

0.6

0.9

0.25

0.6

0.9

0.25

0.6

0.9

Blaine, cm2/g

3245

3315

3380

3430

3300

3345

3450

3360

3390

3585

Water demand, %

23.5

22.8

22.2

22

22.9

22

20.8

22.5

21.2

19.6

Final set, minutes

180

175

185

160

185

170

160

175

165

150

7-day compression, MPa

22.6

22.9

23.8

24.5

23.2

25

26.8

24.2

26

28.3

28-day compression, MPa

31.7

32.9

34

35.2

33.4

35

37.4

34

36.6

39.5

Reference
*

Dosage rate, %

Powder LS

Powder PNS

Powder PC

0.1

0.24

0.36

0.1

0.24

0.36

0.1

0.24

0.36

Blaine, cm /g

3245

3290

3280

3390

3275

3300

3380

3315

3410

3520

Water demand, %

23.5

232

22.6

22.2

23

22.1

21.4

22.2

21.5

20.4

Final set, minutes

180

190

170

160

175

165

165

180

160

155

7-day compression, MPa

22.6

23.5

23

24.1

23.1

24.2

25.9

23.4

24.7

26.8

28-day compression, MPa

31.7

32.6

33.5

34.8

32.3

34.1

36.1

33

35.6

38.4

Indicates that dosage rates are given in percent of total mixture.

Notes: Mixture is 95% clinker and 5% gypsum; Ec is 38 kWh/tonne; cement temperature after grinding is 32 to 37C; 1 cm2/g = 6.8 105 in.2/lb; 1 MPa = 145 psi; C = (F 32)/1.8.

Fig. 2Variations of D(Blaine) values after addition of WR

in liquid or powder forms.

Fig. 3Variations of D(water demand) values after addition

of WR in liquid or powder forms.
Variations in cement finenessThe variations in D(Blaine)
values for mixtures made with various concentrations of LS-,
PNS-, or PC-based WRs are plotted in Fig. 2. Regardless of
the type of WR, the incorporation of increased concentra4

tions, whether in liquid or powder form, is shown to improve

the grindability of cement. For example, at 38 kWh/tonne,
the addition of 0.25%, 0.6%, or 0.9% of liquid PNS led to an
improvement in D(Blaine) by 1.7%, 3.1%, and 6.3%, respectively. Such rates of fineness improvement are in complete
agreement with the findings of Bouzouba et al.9 It should be
noted that better grindability of clinker was obtained when
using liquid WR rather than powder WR.
For fixed concentration, the improvement in cement fineness compared to the control mixture was found to be quite
similar when using either LS- or PNS-based WRs (Fig. 2).
Nevertheless, the use of PC-based WR was more efficient,
particularly at high dosage rates. For example, at a dosage of
0.9% of cement weight, the D(Blaine) increased from 5.7%
and 6.3% for the liquid LS- and PNS-based WRs, respectively, to 10.5% in the case where the liquid PC-based WR
was used.
In addition to the Blaine fineness, it is important to note that
the fineness of all cement mixtures ground with or without
WRs was evaluated by determining the residues obtained by
sieving on 100, 80, 63, and 38 m meshes (values are not
reported in Table 2 for clarity reasons). Generally, higher
Blaine values reflecting increased cement fineness were
found to be well correlated to lower residues with coefficients of correlation (R2) greater than 0.85.
Variations in water demandCompared to the control
cement, which required 23.5% water to reach a normal
consistency (as per ASTM C187), the addition of various
concentrations of either liquid or powder WRs during the
grinding process resulted in reduced water demand (Fig. 3).
For example, D(water demand) decreased by 5.5%, 7.2%,
and 11.9% when intergrinding powder PC-based WRs
at dosage rates of 0.1%, 0.24%, and 0.36% of the cement
weight, respectively. This indicates that the WR molecules,
whether based on LS, PNS, or PC, remained sufficiently
active following the end of the grinding process to reduce
cement flocks, liberate mixing water, and improve workability. Furthermore, for a given WR type and solid content,
it can be observed that WRs incorporated in liquid form
exhibited better water reductions compared to those added in
ACI Materials Journal/November-December 2011

powder form, most likely due to improved dispersion within

the mixture.
At relatively low dosage rates, the extent of water reduction resulting from cement ground with either LS- or PNSbased WRs was quite similar (Fig. 3). On the other hand,
cement ground with PC-based WRs exhibited the highest
levels of water reduction compared to the control mixture.
For example, D(water demand) decreased by 16.6%, 11.5%,
and 6.4% when using liquid PC, PNS, or LS molecules,
respectively, at a rate of 0.9% of cement weight.
Variations in setting timesThe incorporation of LS-,
PNS-, or PC-based WRs in liquid or powder forms during
the grinding of clinker accelerated the setting times of
cement compared to those obtained from the control mixture
(Table 2). For example, a decrease in the final setting time
from 180 to 165 and 150 minutes was measured for the
control cement and that incorporating 0.6% and 0.9% of
liquid PC-based WRs, respectively. This can normally be
attributed to the improved fineness that leads to increased
rates of cement hydration following mixing with water.
Additionally, setting times determined as per ASTM C191
may be shortened due to the reduction in water content
necessary to achieve normal consistency.
Variations in compressive strength of mortarsThe variations in D(compressive strength) after 28 days for mortars
made with cement ground with various concentrations of
either liquid or powder LS-, PNS-, or PC-based WRs are
plotted in Fig. 4. As can be seen, all mortars prepared with

the high-range water-reducing admixture cement exhibited

higher strength values compared to the ones made with the
control cement. Such a strength increase can be directly
related to the reduction in water demand of tested mortars
necessary to yield a flow of 110 5% (as per ASTM C109),
thus decreasing the water-cement ratio (w/c) and increasing
compressive strength. Furthermore, it should be noted that
the improvement in cement fineness with the addition of
WR may greatly contribute to increasing the development of
strength at all ages.3,4
Mortars made with cement ground with PC-based WR
exhibited significantly higher compressive strengths as
compared to those made with cement ground with PNSor LS-based WRs (Fig. 4). For example, an increase in
D(compressive strength) from 7.3% to 10.4% and 15.5%
was obtained for mortars prepared with cement ground with
0.6% of liquid LS-, PNS-, or PC-based WRs, respectively.
As previously mentioned, this is directly related to the extent
of water reduction achieved following the addition of WRs.
Phase 2: Effect of grinding energy and
temperature increase on WR performance
Effect of grinding energyTo determine whether the
performance of WRs to reduce water demand is affected
by the grinding process of the clinker and gypsum materials, a series of tests was conducted by adding the liquid or
powder WRs to the mixing water of the control cement, then
comparing the results with those obtained from the cement
interground with WRs. The water demand (ASTM C187)
and compressive strength (ASTM C109) values obtained
when the WR is added to the mixing water in the control
cement are summarized in Table 3.
Generally speaking, the variations in D(water demand)
plotted in Fig. 5 for all tested mixtures showed that the efficiency of WR to reduce water demand tends to decrease
if such admixtures are added during the grinding process.
Although it is quite difficult to establish clear and definite
explanations, it is believed that such variations may be
attributed to changes in the polymer structure and shape
(including molecular weight, chain length, ionic charges,
apparent surface potential, and so on)7 that resulted during the
grinding process. On the other hand, it should be noted that
the D(water demand) variations were significantly affected
by the WR type used. For example, D(water demand) did not
vary by more than 2.5% in the case where the LS- or PNSbased WRs are used. On the contrary, such variations ranged

Fig. 4Variations of mortars D(compressive strength) after

28 days after addition of WR in liquid or powder forms.

Table 3Test results obtained when LS, PNS, and PC-based WR are added to mixing water
Reference
Dosage rate,* %

Liquid LS

Liquid PNS

Liquid PC

0.6

0.9

0.6

0.9

0.6

0.9

Water demand, %

23.5

22

21.4

21.5

20.2

19.5

17.8

7-day compression, MPa

22.6

24.4

25.2

24.6

26.6

27.1

30.3

28-day compression, MPa

31.7

33.5

36.3

35.6

38.7

39.3

41.5

Reference
Dosage rate,* %

Powder LS

Powder PNS

Powder PC

0.24

0.36

0.24

0.36

0.24

0.36

Water demand, %

23.5

22.4

22.2

21.8

21

20.6

18.8

7-day compression, MPa

22.6

23.5

25.1

24.7

26.2

25.4

28.6

28-day compression, MPa

31.7

32.8

35.2

33.7

36.1

36

39.9

Indicates that dosage rates are given in percent of total mixture.

Notes: Mixture is 95% clinker + 5% gypsum; Ec is 38 kWh/tonne; cement temperature after grinding is 32 to 37C; 1 MPa = 145 psi; C = (F 32)/1.8.

ACI Materials Journal/November-December 2011

Fig. 5Comparison of D(water demand) variations in case

WR is added during grinding process or to mixing water of
control cement.

Fig. 6Comparison of D(compressive strength) variations

in case WR is added during grinding process or to mixing
water of control cement.

from 3% up to 7.5% for the cement mixtures prepared with

the liquid or powder PC-based WRs.
The variations of D(compressive strength) after 7 days
for mortars made with high-range water-reducing adxmiture cement and those prepared with the control cement
where the WR is added to the mixing water are illustrated in
Fig. 6. Following similar trends as those shown in Fig. 5, the
changes in D(compressive strength) values remained limited
to 4% with the use of either liquid or powder LS- or PNSbased WRs, whereas they varied from 3 to 9% with the use
of PC-based WRs.
Effect of temperature increaseThe water demand and
compressive strength values determined on cement mixtures
ground with or without WRs after being stored for 2.5 hours
at temperatures of 65 and 95 4C (149 and 203 39F)
are summarized in Table 4. It is important to note that the
tests were conducted following 24 hours after the heating
process, whereby the cement sample was allowed to cool
down to ambient temperature. The cement fineness evaluated
using the Blaine fineness and sieve residue methods was also
measured; however, it was found to be nearly unaffected by
the temperature rise.
The variations in D(water demand) values for cement
mixtures ground with powder WRs are illustrated in Fig. 7.
Generally speaking, the increase of temperature under which
the cement sample was stored appeared to limit the water
reduction capability of the WR. For example, D(water
demand) decreased from 8.9% to 8.1% and 7.2% at temperatures
of 35, 65, or 95 4C (95, 149, or 203 39F), respectively,
for cement ground with 0.36% powder PNS-based WRs.
Similar trends were obtained in the case where the liquid
WR was used during grinding (Table 4). Nevertheless, the
spread of D(water demand) decrease was found to be higher
with the use of the liquid WR compared to that resulting
from the powder WR. For example, as can be seen in
Fig. 8, the difference in D(water demand) values determined
between 35 and 95 4C (95 and 203 39F) was limited to
approximately 2% in the case where powder WRs are inter-

Table 4Effect of temperature increase on performance of LS, PNS, and PC-based WR

Liquid LS
*

Dosage rate, %
Water demand, %
Cement temperature = 65C 7-day compression, MPa
28-day compression, MPa
Water demand, %
Cement temperature = 95C 7-day compression, MPa
28-day compression, MPa

Liquid PNS

0.25

0.6

0.9

0.25

0.6

0.9

0.25

0.6

0.9

22.9

22.4

22.4

23.2

22.3

21.2

22.6

21.1

20

22.7

23.5

24.6

23.4

24.5

26.6

24

25.4

28

33

33.7

34.9

33.4

35.1

37

33.8

36.2

39

23.2

22.5

22.8

23.3

22.5

21.5

22.8

21.4

20.2

22.3

23.3

24.4

23.6

24.3

26.3

23.5

25.1

27.4

32.7

33.7

34.6

33.1

35.2

36.5

33.5

35.7

38.2

Powder LS
*

Dosage rate, %

Powder PNS

0.1

0.24

0.36

23.3

22.6

23.7

22.8

28-day compression, MPa

32.8

Water demand, %

Water demand, %
Cement temperature = 65C 7-day compression, MPa

Cement temperature = 95C 7-day compression, MPa

28-day compression, MPa

Liquid PC

Powder PC

0.1

0.24

0.36

0.1

0.24

0.36

22.4

23

22.2

21.6

24.3

23.4

23.9

25.8

22.4

22

20.6

23.2

24.7

26.5

33.6

34.5

32.5

33.9

35.7

32.8

35

37.9

23.2

22.6

22.5

23.1

22.4

21.8

22.4

22

20.8

23.5

22.5

24.5

32.6

33.8

34.2

23.1

23.6

25.5

22.8

24.5

25.9

32.5

33.6

35.6

32.5

34.6

37.2

Indicates that dosage rates are given in percent of total mixture.

Notes: Mixture design is 95% clinker + 5% gypsum; Ec is 38 kWh/tonne; 1 MPa = 145 psi; C = (5/9)(F 32).

6

ACI Materials Journal/November-December 2011

ground with the cement, whereas such a difference increased

to 3.5% with the use of liquid WRs.
The relationships between D(water demand) and
D(compressive strength) measured at 28 days for cement
mixtures stored at various temperatures are shown in Fig. 9.
As typically expected, the decrease in D(water demand) led
to reduced variations in the mortars compressive strengths
determined at temperatures of 35, 65, or 95 4C (95, 149,
or 203 39F).
Phase 3: Optimization of clinker factor through
use of WR
ASTM C465 specification for GAsThe a commonly
used standard specications for GAs is ASTM C465,18 which
defines acceptance criteria and tests to be used for determining
whether a processing addition dramatically affects portland
cement properties described in ASTM C150. Among the
relevant physical requirements stipulated by ASTM C465
include the setting times of cement ground with GAs, which
should not vary by more than 1 hour or 50%, whichever is
less, from those obtained by the control cement. On the other
hand, the mortar compressive strength should not be less
than 95% of the value resulting from a similar mortar made
with the corresponding control cement. ASTM C465 specifies that the water demand to achieve normal consistency
(ASTM C187) for the cement containing GAs should not
increase by more than 1.0% from that required by the control
cement. Such a requirement, however, is of limited use in
this study, given that all WRs resulted in a decrease in water
demand, and no limitations are given by the standard in case
a decrease in water demand takes place.
Effect of WR type and concentration on decrease in clinker
factorA series of tests was conducted by decreasing the
clinker factor and adjusting the concentrations of the liquid
LS-, PNS-, or PC-based WRs to maintain setting times and
compressive strengths within ASTM C465 limitations.
Typical results showing the effect of three concentrations of
WRs on the variations of cement properties are summarized
in Table 5. As indicated in the testing program, lower Ec
values were needed to maintain a Blaine fineness of 3250
100 cm2/g (221 7 103 in.2/lb) when increased clinker
substitutions by the pozzolan were made. For example, Ec
decreased by 2.6%, 3.9%, and 5% when the factor of clinker
substitution by pozzolan was set to 16%, 24%, and 32%,
respectively, and PC-based WR at 0.4%, 0.7%, and 0.9% of
the cement weight, respectively, was added (Table 5). This
can be attributed to the reduced level of cement agglomeration resulting from increased WR concentrations, and the
lower pozzolan Mohs hardness value compared to that of
clinker (approximately 4.5 and 6, respectively).
As can be seen from Table 5, the effect of increasing the
substitution of clinker by pozzolan resulted in delayed setting
times, but without exceeding the ASTM C465 limitation. For
example, the final setting increased from 180 to 195 minutes
and 210 minutes when the clinker factor decreased from 95%
to 76% and 70%, respectively, for cement mixtures interground with 0%, 0.8%, and 0.9% PNS-based WRs, respectively. This could be due to the decreased clinker concentration, which results in fewer hydration reactions and lower
heat development that take place upon mixing with water.3
The variations in D(compressive strength) values with respect
to the clinker factor decrease for cement ground with different
concentrations of LS-, PNS-, or PC-based WRs are plotted in
Fig. 10. The line showing the 5% limitation required by ASTM
ACI Materials Journal/November-December 2011

Fig. 7Effect of temperature increase on variations of

D(water demand) values after addition of powder WR.
(Note: 1C = (F 32)/1.8.)

Fig. 8Difference of D(water demand) values determined

at 35 and 95 4C after addition of liquid or powder WR.
(Note: 1C = (F 32)/1.8.)

Fig. 9Relationships between D(water demand) and

D(compressive strength) determined at various temperatures. (Note: 1C = (F 32)/1.8.)
C465 is shown. The decrease in the clinker factor, coupled
with increased WR concentration, is shown to maintain
D(compressive strength) values toward the positive region
until reaching a certain threshold clinker factor beyond
which the D(compressive strength) exceeds the permissible
7

Table 5Effect of liquid WR on reduction of clinker factor

Control

Liquid LS

Liquid PNS

Liquid PC

Clinker, %

95

90

85

81

84

76

70

80

72

65

Clinker decrease, %

0.05

0.11

0.15

0.12

0.20

0.26

0.16

0.24

0.32

Gypsum, %

Pozzolan, %

10

14

11

19

25

15

23

30

Ec, kWh/tonne

38

38

37.6

37.2

37.5

37

36.6

37

36.5

36.1

Ec decrease, %

1.05

2.11

1.32

2.63

3.68

2.63

3.95

5.00

Dosage rate of WR,* %

0.3

0.5

0.9

0.4

0.8

0.9

0.4

0.7

0.9

Blaine, cm /g

3245

3330

3225

3190

3305

3290

3250

3320

3270

3300

Water demand, %

23.5

23.2

22.7

21.8

22.2

21

20.5

22

21.1

19.4

Final set, minutes

180

185

195

200

190

195

210

190

200

225

7-day compression, MPa

22.6

22.4

23.4

22.3

22.9

22.5

21.8

22.8

23.7

22

28-day compression, MPa

31.7

32.6

33.5

29.6

32.4

32.9

30.4

31.6

33.4

30.3

Indicates that dosage rates are given in percent of total mixture.

Notes: 1 cm2/g = 6.8 105 in.2/lb; 1 MPa = 145 psi.

Fig. 10Effect of clinker factor reduction on variations of

D(compressive strength) after addition of various concentrations of liquid WR.

Fig. 11Effect of liquid WR on optimization of clinker factor

and energy consumption.
strength loss limit of 5% set by the standard. For example, for
a clinker reduction of 11% compared to the control cement,
the LS-based WR had to be added at a dosage of 0.5% of
the cement weight to maintain adequate D(compressive
strength). With a further decrease of the clinker to 15%, it
8

can be seen that the D(compressive strength) after 28 days

exceeded the 5% limitation despite the use of an an LS-based
WR at a higher dosage of 0.9% (Fig. 10). The compensation
of compressive strength while reducing the clinker factor is
mainly attributed to reduced water demand (Table 5), thus
decreasing w/c and increasing strength.
Comparison between WRs and conventional GAs to
optimize clinker factorIn a previous study, Assaad
et al.3 evaluated the effect of various concentrations of
conventional amine- and glycol-based GAs on Ec reductions
and variations of cement properties when decreasing the
clinker factor. The maximum concentrations of GA were
determined based on the percent increase in water demand
(limitation set to 1.0% by ASTM C465) and were found
to correspond to 0.13% and 0.09% of the cement weight
when using the amine- or glycol-based GA, respectively. At
those dosage rates, Assaad et al.3 reported that the clinker
reductions are 15.8% and 10.5%, respectively, whereas the
energy savings are 4.5% and 2.3%, respectively.
The plots showing the effect of WR type and concentration
on the percent reductions of the clinker factor and Ec value
are given in Fig. 11. As can be seen, the addition of a higher
concentration of liquid WR is shown to increase the percent
decrease of the clinker factor and Ec. At the maximum tested
dosage rate of 0.9% of the cement weight, the reduction of
clinker factor corresponds to 15%, 26%, and 32% with the
use of LS-, PNS-, or PC-based WRs, respectively, whereas
the Ec value decreased by 2.1%, 3.7%, and 5%, respectively.
Such results clearly illustrate the benefits of incorporating
WRs compared to conventional GAs to substantially optimize the clinker factor and reduce energy consumption.
CONCLUSIONS
Based on the aforementioned results, the following conclusions can be warranted:
Regardless of the WR type, the incorporation of increased
concentrations in liquid or powder forms during the
clinker grinding process can improve grindability. For a
fixed dosage, the improvement in cement fineness was
quite similar when using LS- or PNS-based WRs. The
use of PC-based WRs was more efficient, particularly at
high dosage rates.
ACI Materials Journal/November-December 2011

Compared to the control cement, the addition of various

concentrations of either liquid or powder WRs resulted
in reduced water demand. At relatively low dosage rates,
the extent of water reduction resulting from cement
ground with either LS- or PNS-based WRs was quite
similar. Cement ground with PC-based WRs exhibited
higher levels of water reduction.
The incorporation of WRs during the grinding of clinker
accelerated the setting times of cement compared to those
obtained from a control mixture. This was attributed to
improved fineness and reduction in water demand.
All mortars prepared with the high-range water-reducing
admixture cement exhibited higher strength values
compared to the ones made using the control cement.
Such a strength increase was related to a decrease in the
w/c and the improved cement fineness. Mortars made
with cement ground with PC-based WRs exhibited
significantly higher strengths compared to those made
with cement ground with PNS- or LS-based WRs.
The efficiency of WRs to reduce water demand decreases
when such admixtures are added during the grinding
process compared to that resulting if the same dosage of
WR is added to the mixing water of the control cement.
Such a decrease was limited to 2.5% in the case where LSor PNS-based WRs were used, whereas it varied from 3 to
7.5% for the cement prepared with PC-based WRs.
The increase of temperature under which the cement
samples were stored limited the water reduction properties of the WRs. The spread of water demand decrease,
however, was higher when using liquid WRs compared
to that resulting from powder WRs.
The clinker factor and grinding energy can be substantially optimized through the substitution of clinker by
pozzolan with a lower Mohs hardness and incorporation
of WR. For cement interground with liquid LS-, PNS-,
or PC-based WRs at a dosage of 0.9%, the reduction of
the clinker factor was found to correspond to 15%, 26%,
and 32%, respectively, whereas the Ec value decreased
by 2.1%, 3.7%, and 5%, respectively.
ACKNOWLEDGMENTS

The authors wish to acknowledge the personnel in the R&D Department

at Holderchem Building Chemicals S.A.L. Laboratories for conducting the
experimental testing program.

ACI Materials Journal/November-December 2011

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