Advances in Cement Research Advances in Cement Research, 2016, 28(7), 475–484

Volume 28 Issue 7 http://dx.doi.org/10.1680/jadcr.16.00001

A grindability model for grinding aids
and their impact on cement properties
Sun and Liu
Paper 1600001
Received 01/01/2016; revised 13/04/2016; accepted 02/05/2016
Published online ahead of print 25/04/2016
Keywords: admixtures/cement paste/mortars

ICE Publishing: All rights reserved

A grindability model
for grinding aids and their
impact on cement properties
Zhenping Sun Yi Liu
Key Laboratory of Advanced Civil Engineering Materials of Ministry of Key Laboratory of Advanced Civil Engineering Materials of Ministry of
Education, Tongji University, Shanghai, China Education, Tongji University, Shanghai, China
(corresponding author: grtszhp@163.com)

This paper describes the grindability of four kinds of grinding aids – triethanolamine (TEA), propylene glycol (PG),
calcium lignosulfonate (CLS) and sodium tripolyphosphate (STPP) – and their impact on cement properties.
Experiments were carried out on cement samples to determine the specific surface area and sieve residue, on cement
paste to determine the normal consistency, setting time and heat release, and on cement mortar to assess the
compressive and flexural strength. The results showed that the increment of specific surface area (ΔS) at 30 min and
decrement of 30 μm sieve residue (Δη) for the four kinds of grinding aids showed an exponential function with an
increase in dosage. TEA, CLS and STPP showed good grindability to cement clinker, while PG even showed some
negative grindability. Through the chemical action of the grinding aids and their impact on particle size distribution
of the cement samples, TEA and PG were found to accelerate the heat release rate, while CLS and STPP delayed it.
TEA enhanced early mortar strength. CLS increased both the early and late mortar strength. STPP showed no
remarkable impact on mortar strength while PG was found to decrease the mortar strength.

Notation
D dosage of grinding aid
Rc ratio of compressive strength of mortar with grinding
aid compared with compressive strength of PC mortar
Rf ratio of flexural strength of mortar with grinding aid
compared with flexural strength of PC mortar
ΔS difference between the specific surface areas of
cement sample ground with grinding aid and
Portland cement
Δη difference in sieve residue
Introduction
The cement industry, which consumes great amounts of
resources and energy, is facing increasingly severe resource
and environmental challenges. Cement world production is
currently approximately 4 billion tons per year (Zhang et al.,
2015). The electrical energy consumed in cement production
is 110 kW/t, about 30% of which is used for the preparation
of raw materials and about 40% for final cement clinker grind-
ing (Atesok et al., 2005; Dundar et al., 2011). The industry
is also responsible for an average specific carbon dioxide
emissions intensity, due to electricity consumption, of 9·1 kg
carbon dioxide per ton (Katsioti et al., 2009). This results in
a significant cost increase of the final product, especially under
the current energy-scarce environment. A successful way to
help solve this problem is the extensive use of grinding aids
in the comminution process and a variety of grinding aids are
now widely applied in the cement industry. Grinding aids are
employed in almost all cement plants in Japan and over 50% of
cement plants in China use grinding aids. There is also a high
usage rate of grinding aids in European countries (Zhu et al.,
2010). With the application of grinding aids, the energy con-
sumption and carbon dioxide emissions of the cement industry
are much lower, and the cost involved in the grinding of cement
clinker is also reduced with the use of cement grinding aids.
Grinding aids are incorporated during the comminution of
clinker to reduce electrostatic forces and minimise the agglom-
eration of cement grains (Assaad and Issa, 2014; Assaad et al.,
2009; Engelsen, 2008). Currently, the most commonly used
grinding aids generally include highly purified chemicals such
as triethanolamine (TEA), triisopropanolamine (TIPA), pro-
pylene glycol (PG), inorganic salts such as polyphosphates,
as well as industry by-products such as molasses and calcium
lignosulfonate (CLS). During the grinding process, grinding
aid molecules can be adsorbed onto particle surfaces formed
by the fracture of electrovalent bonds (Ca–O and Si–O). This
causes a change in the physical and chemical properties of
the particle surface, with grinding aids thus playing both dis-
persion and grinding roles and hence reducing the energy
required for grinding.
Many researchers have studied the grinding effects of grinding
aids and their influence on cement properties. Katsioti et al.

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 Advances in Cement Research A grindability model for grinding aids
Volume 28 Issue 7 and their impact on cement properties
Sun and Liu

(2009) indicated that TEA and TIPA used as grinding Preparation of cement samples
aids increased the grindability index up to 14% and 26%, Portland cement samples were produced by intergrinding 96%
respectively. Heren and Ölmez (1996) found that the hydration clinker and 4% gypsum in a ball mill. All the cement samples
of tricalcium aluminate (C3A) was accelerated in the presence were ground to a fixed Blaine fineness of 370 ± 10 m2/kg. Prior
of TEA due to the accelerated formation of hexagonal alumi- to grinding, the pre-selected grinding aid concentrations were
nate hydrate and its transformation to a cubic form. Sandberg added to the mix. Every 5 kg cement sample was produced
and Doncaster (2004) proposed that TIPA, used as a grinding after one grinding cycle. Table 3 lists the proportions of the
aid, enhanced the strength of cement: the average strength grinding materials used and the sample notation.
improvement was found to be 10% in hydrated Portland
cement paste and 9% in mortar. However, there is a lack of Testing procedure and specimen preparation
research regarding mathematical laws for the grindability of The cement sample particle size distribution (PSD) was meas-
grinding aids and the influence of grinding aids on cement ured using a Beckman Coulter LS230 laser particle analyser,
properties also needs to be studied further. which had a test scope of 0·04 μm to 2000 μm. The specific
surface area of the cement samples was measured according to
The first objective of the work reported in this paper was to GB/T 8074 (CNS, 2008b) with an FBT-9 automatic tester.
assess the grinding effect of four kinds of grinding aids, includ-
ing the increase in specific surface area after the same grinding All pastes were mixed in a laboratory mixer using water cooled
time and the sieve residue, in order to develop mathematical to a constant temperature of 20 ± 2°C. The ambient tempera-
laws for the grindability of grinding aids. The second objective ture and relative humidity during testing were maintained at
was to study the impact of the four kinds of grinding aids on 20 ± 2°C and 55 ± 5%, respectively. The water demand required
cement properties, including water demand for normal consist-
ency, setting time, heat release and mortar strength. Such data
could be of great significance to the development of the Constituent Content: mass %
cement industry.
Calcium oxide (CaO) 63·1
Silicon dioxide (SiO2) 24·1
Experiments Iron oxide (Fe2O3) 3·3
Aluminium oxide (Al2O3) 4·3
Materials Magnesium oxide (MgO) 1·2
Industrial clinker was used for the production of cement Sulfur trioxide (SO3) 0·8
samples. The chemical and mineral composition of the clinker R2O (K2O + Na2O) 0·9
is shown in Table 1 and Figure 1. The mineral composition of Phosphorus pentoxide (P2O5) 0·2
the clinker calculated from Bogue’s equations and the results Other 2·1
obtained by the X-ray diffraction (XRD) technique showed Tricalcium silicate (C3S) 39·8
consistency. Gypsum was used as a cement-coagulation agent. Dicalcium silicate (C2S) 39·2
Tricalcium aluminate (C3A) 6·0
The grinding aids used in this study – triethanolamine (TEA), Tetracalcium aluminoferrite (C4AF) 10·0
propylene glycol (PG), calcium lignosulfonate (CLS) and
sodium tripolyphosphate (STPP) – were all chemical grade. Table 1. Chemical and mineral composition of clinker
The chemical and structural formulae of the grinding aids (by mass)(%)
used are shown in Table 2.

5000 C3S C4AF

Intensity: arbitrary units

C2S Silicon dioxide

4000
C3A
3000
2000
1000
0
5 10 15 20 25 30 35 40 45 50 55 60 65 70
2θ : degrees

Figure 1. XRD pattern of cement clinker

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 Advances in Cement Research A grindability model for grinding aids
Volume 28 Issue 7 and their impact on cement properties
Sun and Liu

to achieve normal consistency was determined following the
test method detailed in GB/T 1346 (CNS, 2011). Using the
same cement paste, the initial and final setting times were then
determined as per GB/T 1346 (CNS, 2011).
The heat release of the cement pastes was tested by means
of a Thermometrics TAMair, with a minimum resolution of
0·1°C. The temperature was recorded every minute and the
heat release was evaluated using cement pastes prepared with a
water/cement (w/c) ratio of 0·3.

Grinding Molecular Structural formula Following GB/T 17671 (CNS, 1999) to evaluate mortar
aid formula strengths, the cement samples were mixed with standard sand
and water to obtain a water:cement:sand weight proportion
TEA C6H15NO3 OH
of 0·5:1:3, such that the cementitious material content was
HO
N 450 g. After mixing, the specimens were cast in moulds meas-
uring 40  40  160 mm3. After curing the specimens for 24 h
at 20 ± 1°C, they were demoulded and immersed in water
OH at 20 ± 1°C until the mortar strength was tested. The mortar
PG C 3 H 8 O3 strength of each sample was measured 3 d and 28 d after cast-
HO OH ing. Each sample’s flexural strength was based on the average
OH of three specimens and each sample’s compressive strength was
CLS C20H24CaO10S2 based on the average of six specimens.
O CH CH2 CH2

OCH3 SO3M n Results and discussion

STPP Na5P3O10 O– Na+ Grindability model for grinding aids
O
O O Sieve residue, specific surface area and average particle size
P Na+
O– P are usually used to reflect cement fineness (Lan et al., 2006).
P O–
Na+ – The specific surface area and sieve residue are very important
O O– O O
indexes in cement production (Bonen and Sarkar, 1995). In
Na+ Na+
this research, the increments of specific surface area and sieve
Table 2. Chemical and structural formulae of the grinding aids residue were used as indicators to evaluate the grindability of
used in this study the four kinds of grinding aids.

Specific surface area

Sample Clinker: Gypsum: TEA: PG: CLS: STPP: In this paper, ΔS is defined as the difference between the
g g g g g g specific surface areas of cement samples ground with grinding
aids and Portland cement (PC) after 30 min grinding. Figure 2
PC 4800 200 — — — —
PT1 4800 200 0·5 — — —
PT2 4800 200 1·0 — — — 40 PT1–PT4
PT3 4800 200 1·5 — — — PP1–PP4
PT4 4800 200 2·0 — — — PCL1–PCL4
30
PP1 4800 200 — 0·5 — —
PS1–PS4
∆S: m2/kg1

PP2 4800 200 — 1·0 — —

PP3 4800 200 — 1·5 — — 20
PP4 4800 200 — 2·0 — —
PCL1 4800 200 — — 0·5 —
10
PCL2 4800 200 — — 1·0 —
PCL3 4800 200 — — 1·5 —
PCL4 4800 200 — — 2·0 — 0
PS1 4800 200 — — — 0·5
PS2 4800 200 — — — 1·0 0 0·01 0·02 0·03 0·04
PS3 4800 200 — — — 1·5 D: %
PS4 4800 200 — — — 2·0
Figure 2. Correlation between the increment of specific surface
Table 3. Proportions of cement samples area (ΔS) and dosage of grinding aids (D)

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 Advances in Cement Research
Volume 28 Issue 7
shows the relationship between ΔS of all the cement samples
shown in Table 3 and the dosage (D) of grinding aid.
Figure 3 shows that all the grinding aids enhanced the grindabil-
ity of cement clinker. As expected, the cement Blaine fineness
substantially improved with the addition of higher concen-
trations of all four kinds of grinding aids. From the perspective
of ΔS, the grindability of the grinding aids was in the order
CLS > TEA > STPP > PG. ΔS was found to increase as an expo-
nential function with an increase of dosage for the four kinds of
grinding aids, and the mathematical model is shown in Table 4.
The R 2 values for the four grinding aids were all higher than
0·97, indicating a very high degree of fitting. In the equation
shown Table 4, ΔSmax, A1 and B1 are fitting constants for the
model. ΔSmax refers to the theoretical maximum value for the
increment of specific surface area after 30 min grinding. A1 rep-
resents the maximum slope of the curve and B1 is the minimum
dosage of grinding aids that led to a remarkable increase in ΔS.
That is to say, the grinding aid dosage should be higher than B1.
According to Table 4, the values of B1 for TEA, CLS and
STPP were lower than 1  104, while the value of B1 for PG
was higher than 5  104. CLS, TEA and STPP obviously
enhanced the ΔS of cement samples. For example, the value of
12
PT1–PT4
PP1–PP4
8 PCL1–PCL4
PS1–PS4
∆η: %
4
0 and B2 is the minimum dosage of grinding aid leading to a
0 0·01 0·02 0·03 0·04
D: %
Figure 3. Correlation between the decrement of sieve residue
(Δη) and dosage of grinding aids (D)
Grinding aid Mathematical model
TEA ΔS = ΔSmax(1 − e−A1 (D−B1))
PG
CLS
STPP
Table 4. Empirical fit constants of the ΔS − D function
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A grindability model for grinding aids
and their impact on cement properties
Sun and Liu
ΔS for PT4, PP4 and PS4 reached 38·2 m2/kg, 27·9 m2/kg and
16·2 m2/kg, respectively. PG showed no obviously grindability:
the ΔS of PP4 was only 5·5 m2/kg. Based on either ΔS or
ΔSmax, the grindability trend of the four kinds of grinding aids
was the same (i.e. CLS > TEA > STPP > PG).
Sieve residue
Some researchers have reported that cement particles of diam-
eter 3 –30 μm play a decisive role in cement performance (Cai
et al., 2005; Jang and So, 2015; Knop and Peled, 2016; Knop
et al., 2014). The grindability of the four grinding aids was
thus also evaluated by comparing the 30 μm sieve residues of
cement samples. The relationship between decrement of 30 μm
sieve residue (Δη) and dosage of grinding aid (D) is shown in
Figure 3. Compared with the reference samples, there was a
significant change in sieve residue for cement samples ground
with grinding aids. The 30 μm sieve residues of the PT, PC and
PS samples were all much lower than that of PC. The sieve
residues decreased with the increasing dosage for the PT and
PC samples, but there was no obvious difference in sieve
residue from PS1 to PS4. For the PP samples, the sieve resi-
dues even showed an increasing trend. According to the 30 μm
sieve residue, the grindability of the four grinding aids was in
the order TEA > CLS > STPP > PG.
As shown in Figure 3, the change in sieve residue (Δη) for the
four kinds of grinding aids showed a similar transformation
rule as ΔS, also demonstrating an exponential function with
an increase in grinding aid dosage. The mathematical model
is shown in Table 5. The R 2 values for TEA, CLS and STPP
were all higher than 0·99, indicating a very high degree of fitting.
However, the R 2 of PG was only 0·33, indicating poor agreement
with the mathematical model. In the equation shown in Table 5,
Δηmax, A2 and B2 are fitting constants for the model. Δηmax
refers to the theoretical maximum value for sieve residue after
30 min grinding. A2 represents the maximum slope of the curve
remarkable increase in Δη. That is to say, the dosage of each
grinding aid should be higher than B1 for better grinding.
Figure 3 and Table 5 demonstrate the good grindability of
TEA, CLS and STPP. The B2 values of these three grinding
aids were almost all 0·8  104. PG showed negative grind-
ability: the 30 μm sieve residues of PP3 and PP4 were lower
ΔSmax: m2/kg A1: m2/kg B1 R2
34·20 43·22 0·2104 0·999
8·85 25·68 5·6104 0·975
45·39 49·21 0·1104 0·986
23·43 29·59 0·6104 0·997
 Advances in Cement Research A grindability model for grinding aids
Volume 28 Issue 7 and their impact on cement properties
Sun and Liu

Grinding aids Mathematical model Δηmax: % A2: % B2 R2

TEA Δη = Δηmax (1 − e−A2 (D−B2)) 11·3 66·6 0·8104 0·996

PG Δη = Δηmax (1 − e−A2 (D−B2)) 1·0 −1014·0 31·4104 0·325
CLS Δη = Δηmax (1 − e−A2 (D−B2)) 7·9 53·9 0·9104 0·999
STPP Δη = Δηmax (1 − e−A2 (D−B2)) 6·4 53·9 0·8104 0·999

Table 5. Empirical fit constant of Δη −D function

4 PC 4
PT2 PC
PT4 PP2
3 3
PP4
Volume: %

Volume: %

2 2

1 1

0 0

1 10 100 1 10 100
Diameter: µm Diameter: µm
(a) (b)

4 4
PC PC
PCL2 PS2
PCL4 PS4
3 3
Volume: %

Volume: %

2 2

1 1

0 0

1 10 100 1 10 100
Diameter: µm Diameter: µm
(c) (d)

Figure 4. Particle size distribution of (a) PT samples,

(b) PP samples, (c) PCL samples and (d) PS samples

than the reference sample. Based on Δηmax values, the grind-

ability of the four kinds of grinding aids was in the order
TEA > CLS > STPP > PG, which is in accordance with the
conclusion gained from sieve residue Δη.
In conclusion, TEA, CLS and STPP show good grindability
for cement clinker, whereas PG actually had a negative effect
on the 30 μm sieve residue of the cement samples.
Impact of grinding aids on cement properties
Particle size distribution
The PSDs of the cement samples are shown in Figure 4. With
the same Blaine fineness, Figure 4 demonstrates that the
four kinds of grinding aids can significantly change the PSD of
cement samples. Compared with PC, the PT and PCL samples
showed a higher volume proportion of fine particles of diameter

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 Advances in Cement Research A grindability model for grinding aids
Volume 28 Issue 7 and their impact on cement properties
Sun and Liu

ranging from 1 μm to 30 μm. Meanwhile, the volume pro-
portions of coarse particles (diameter greater than 30 μm) of
the PT and PCL samples were lower than that of PC. Contrary
to the PT and PCL samples, the PP samples had a lower volume
proportion of fine particles (diameter 1–30 μm) and a higher
volume proportion of coarse particles (diameter > 30 μm).
The PS samples presented a higher volume proportion of par-
ticles of diameter 1–10 μm and a lower volume proportion of
20–60 μm particles. Furthermore, the PSDs of the PT and PP
samples showed a more drastic change with increasing dosage,
while there was no remarkable difference in the PSDs of the
PCL or PS samples with different dosages.
Water demand for normal consistency and setting time
of cement samples
The experimental results obtained for the water demand for
normal consistency and setting time of the cement pastes are
shown in Figures 5 and 6.
PT1–PT4
27·0
PP1–PP4
PCL1–PCL4
26·5
Water demand: %
Figure 5 illustrates that the four kinds of grinding aids all
had obvious effects on water demand for normal consistency.
Compared with the PC paste, the PT and PS pastes had larger
water requirements, while the PP and PCL pastes showed a
lower water requirement. With increased dosage of grinding
aids, the water demand of the PT and PS pastes presented a
similar slowly changing trend. Increasing additions of CLS
(i.e. PCL pastes) clearly reduced the water requirement, while
increasing the PG dosage in the PP pastes showed no further
significant effect on water demand beyond a dosage of 0·02%.
According to Schiller and Ellerbrock (1992), water demand
is composed of three fractions: a low proportion of chemical
water needed to form the initial hydration products, a second
proportion needed to lubricate the initial hydration products,
and a large amount of water to lubricate the surfaces of the
cement grains. PG and STPP are usually used as retarders, so
both can help lubricate the surface of cement grains. The water
demand of the PP and PS pastes would be certainly lower
than that of PC paste. CLS is used as a kind of efficient water
reducer. To obtain the same consistency, the water demand
of PCL pastes would be much lower than that of PC paste.
However, TEA, which generally serves as a kind of cement
accelerator at small dosages, can significantly accelerate the

PS1–PS4
initial hydration of cement pastes, thus consuming larger
amounts of water.
26·0

The results presented in Figure 6 indicate that the setting times

25·5 of the PT and PCL pastes were shorter than that of the PC
paste. With increased dosage of these two grinding aids, both
the initial setting time and final setting time of the cement
25·0 pastes were reduced. This can be attributed to the higher
volume proportion and fast hydration rate of fine particles. PG
0 0·01 0·02 0·03 0·04
showed no effect on the initial setting time of the PP pastes,
D: %
but it delayed the final setting time of the pastes remarkably.
Figure 5. Water demand for normal consistency of cement pastes The final setting time also increased with increasing PG
dosage. This could be due to two reasons. On the one hand,

200 200
PT1–PT4
PP1–PP4
175 PCL1–PCL4 175
Initial setting time: min

Final setting time: min

PS1–PS4
150 150

125 125 PT1–PT4

PP1–PP4
100 100 PCL1–PCL4
PS1–PS4
75 75

0 0·01 0·02 0·03 0·04 0 0·01 0·02 0·03 0·04

D: % D: %

Figure 6. Initial and final setting times of cement pastes

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 Advances in Cement Research
Volume 28 Issue 7
hydroxy (–OH) in PG molecules is easily absorbed onto the
surface of cement particles and hydrates to form a layer of
hydrogen-bonding membrane, thus retarding the hydration rate
of cement. On the other hand, the higher volume proportion
of coarse particles in the PG samples also led to a decrease
in hydration rate. Zhu et al. (2012) and Kong et al. (2012)
indicated that STPP could bond with Ca2+ in solution phase
to form complexes, thus retarding the hydration of C3A. Due
to the retarding effect of STPP, the setting times of the PS
pastes were a little longer than those of the PC paste.
The standard specifications of GB/T 1346 (CNS, 2011) limit
the initial setting time to a minimum of 45 min and the final
setting time to a maximum of 420 min. As shown in Figure 6,
all the cement samples met these requirements.
Heat release
Figure 7 presents the heat release curves of the PC, PT4, PP4,
PCL4 and PS4 pastes. According to these, compared with
the PC paste, the use of TEA (paste PT4) and PG (paste PP4)
caused a higher amount of heat release in the initial hydration
period, with a small sharp heat release peak for PT4.
Meanwhile, the use of CLS (PCL4) and STPP (PS4) caused a
delay in the hydration peak, with the delay effect of STPP
being more obvious than that of CLS.
The differences in heat release for all the cement samples were
attributed to two factors. On the one hand, as noted earlier,
TEA accelerates the hydration of C3A thus increasing the heat
release rate, while the retarding effect of PG, STPP and the
sulfonate ions in CLS would usually cause a delay in heat
release. On the other hand, differences in the PSD would also
lead to a remarkable change in heat release. Ghiasvand et al.
(2015) indicated that finer cement particles hydrated faster and
released larger amounts of heat at early ages than coarse
15
PC
PT4
12
PP4
Heat release: J/g
PCL4
9 on mortar strength. PG decreased the compressive strength by
PS4
6 flexural strength.
3
0 attributed to acceleration of the C3A reaction. Depending on
0 300 600 900 1200
Time: min
Figure 7. Heat release of cement samples
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A grindability model for grinding aids
and their impact on cement properties
Sun and Liu
cement particles. Based on the PSDs of the cement samples,
TEA and CLS would accelerate the initial heat release of
cement pastes, while PG would have the opposite impact.
In conclusion, the changes in heat release shown in Figure 7
are influenced by both the chemical action of the grinding aids
and the PSD of the cement samples. The anomalous change of
paste PP4 may be due to the fact that with too many coarse
particles, there may exist more free water for the dissolution
of cement grains and for the initial hydration of minerals, thus,
on the contrary, accelerating the initial heat release rate.
Compressive strength and flexural strength of cement
mortars
The differences between compressive (flexural) strengths of the
cement mortar samples and the reference mortar sample were
calculated, with Rc and Rf defined as the ratios of compressive
and flexural strength of the mortars with grinding aids com-
pared with the respective strength values of the PC mortar.
Rc and Rf thus reflect the impact of grinding aids on mortar
strength. Figure 8 shows the Rc and Rf values at 3 d and 28 d
for all cement mortar samples.
Figure 8 illustrates the different and significant influences
of TEA, PG, CLS and STPP on mortar strength. According
to the 3 d Rc and Rf values, compared with the PC mortar, PT
mortars and PCL mortars presented higher early compressive
and flexural strength. For example, at a grinding aid dosage
of 0·04%, the compressive strength of PT4 mortar and PCL4
mortar increased by 23% and 18%, respectively. The strengths
of the PS mortars were close to that of the PC mortar. The use
of PG i.e. PP samples) significantly decreased the compressive
strength of the mortar, with the compressive strength of PP4
mortar 23% lower than that of the PC mortar. However, the
flexural strengths of the PP mortars were much higher than
that of the PC mortar. For example, the flexural strength of
PP1 and PP2 mortars was nearly 40% higher than that of the
PC mortar.
The 28 d Rc and Rf values demonstrated that TEA showed
some negative effect on late mortar strength. CLS played a
positive role on mortar strength, increasing mortar compressive
strength by nearly 8%. STPP presented no obvious influence
as much 12%, while there was a little positive effect on mortar
As noted earlier, TEA has been used for many years as a com-
ponent of additives and admixtures for Portland cements,
usually being added at low dosages as a set accelerator – a fact
1500
the chemical and mineralogical composition of the cement and
the amount of TEA added, it can accelerate the hydration of
C3A to the hexagonal aluminate hydrate and its conversion to
the cubic aluminate hydrate, thus raising the development of
481
 Advances in Cement Research A grindability model for grinding aids
Volume 28 Issue 7 and their impact on cement properties
Sun and Liu

20 20

10 10

Rc, 28 d: %
Rc, 3 d: %

0 0

–10 –10

TEA PG TEA PG
–20 CLS STPP –20 CLS STPP

0·01 0·02 0·03 0·04 0·01 0·02 0·03 0·04

D: % D: %
(a)

40 40

20 20
Rf, 28 d: %
Rf, 3 d: %

0 0

–20 –20

TEA PG TEA PG
–40 CLS STPP –40 CLS STPP

0·01 0·02 0·03 0·04 0·01 0·02 0·03 0·04

D: % D: %
(b)

Figure 8. Rc values (a) and Rf values (b) at 3 d and 28 d for all

cement mortar samples

early mortar strength (Albayrak et al., 2005). However,
because of the coverage of large amounts of fine AFt on the
surface of hydration products, the later hydration of C3S and
C3A is delayed, resulting in a loss in later mortar strength
(Aggoun et al., 2008). CLS plays the role of a water reducer;
sulfonate ions (–SO32−) in CLS can be easily absorbed onto
cement particles and thus increase the zeta potential (Zhang
et al., 2007). It can enhance paste flowability and mortar
strength at the same w/c ratio. Meanwhile, with the dissolution
of CLS, the concentration of Ca2+ ions in solution phase
would increase, which would accelerate the cement hydration
rate (Jian et al., 2012), thus improving early mortar strength.
PO43− ions in STPP can bond with Ca2+ in solution phase
to form complexes (Kong et al., 2012; Zhu et al., 2012), thus
retarding the hydration of C3A and C3S, leading to a negative
effect on the development of early mortar strength. Meanwhile,
Abdelrazig et al. (1999) indicated that Na+ in STPP would
reduce the solubility of Ca2+ to have an adverse influence
on the formation of crystalline C-S-H, which would cause a
negative effect on the development of mortar strength.
Hydroxy (–OH) in PG molecules easily forms a hydrogen
bond with the O2− ions of hydrates and other –OH can form
hydrogen bonds with water, which finally forms a membrane
layer on the cement particles (Heathman et al., 2003), thus re-
tarding the hydration rate of the cement and the development
of mortar strength. Late mortar strength would be improved
through a better combination of hydration products.
A variation in PSD can also lead to a change in mortar
strength. Cement ground with TEA or CLS had a higher pro-
portion of fine particles, and the development of mortar
strength increases with the rapid hydration of fine particles.
However, cement ground with PG presented a lower proport-
ion of fine particles that contribute to the development of
mortar strength, so the strength of the PP mortars decreased.
The abnormal increase in flexural strength of the PP mortars
is presumed to be due to the filler effect, heterogeneous nuclea-
tion and the dilution effect, but this requires further study.

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 Advances in Cement Research
Volume 28 Issue 7
Conclusion
Based on the test results and analysis, the following con-
clusions can be made.
The increment in specific area (ΔS) and decrement in 30 μm
sieve residue (Δη) both presented an exponential function
with increasing dosage for the four kinds of grinding aids
studied (triethanolamine (TEA), propylene glycol (PG),
calcium lignosulfonate (CLS) and sodium tripolyphosphate
(STPP)). TEA, CLS and STPP showed significant grindability
for cement clinker, while PG had a negative impact on cement
grindability.
The four kinds of grinding aids were found to have a remark-
able influence on cement particle size distribution (PSD). For
the same specific surface area, samples ground with TEA and
CLS had a higher proportion fine particles, while samples
ground with PG showed the opposite result. The use of STPP
had only a little effect on PSD.
The four kinds of grinding aids had different influences on the
water demand and setting time of cement, but all the cement
samples satisfied the requirement of GB 175-2008 (CNS,
2008a).
The results of heat release and mortar strength indicated
that the grinding aids influenced cement properties through
both the chemical action of the grinding aids and their effect
on the PSD. TEA accelerated the heat release rate and
enhanced the early mortar strength. CLS delayed heat release,
but increased both early and late mortar strength. STPP also
retarded the heat release, but showed no remarkable impact on
mortar strength. PG accelerated heat release and decreased
mortar strength at the same time.
Acknowledgements
The authors appreciate the financial support of Projects in
the National Science Foundation (grant 51178339) and the
National & Technology Program during the Twelfth Five-year
Plan Period (grant 2012BAJ20B02).
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