Construction and Building Materials 23 (2009) 1954–1959

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Construction and Building Materials

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Characterization of various cement grinding aids and their impact

on grindability and cement performance
M. Katsioti a, P.E. Tsakiridis b,*, P. Giannatos a, Z. Tsibouki c, J. Marinos d
a
National Technical University of Athens, School of Chemical Engineering, 9 Heroon Polytechniou Street, 15773 Athens, Greece
b
National Technical University of Athens, School of Mining and Metallurgical Engineering, 9 Heroon Polytechniou Street, 15780 Athens, Greece
c
Hellenic Cement Research Center Ltd., Heracles Group, 15 K. Pateli, 14123 Lykovrissi, Attica, Greece
d
Heracles General Cement Company, 49-51 Soph. Venizelou Street, 14123 Lycovrissi, Attica, Greece

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

Article history: The aim of the present research work was the evaluation of six commercial grinding additives, which
Received 30 July 2008 were used for the production of Portland cement (ground in a ball mill at a laboratory stage). For this pur-
Received in revised form 1 September 2008 pose, a reference sample was also produced without using any admixture. The characterization of the
Accepted 2 September 2008
grinding aids (GA) was carried out by Fourier transform infra-red spectroscopy (FT-IR) and gas chroma-
Available online 10 October 2008
tography/mass spectrometry (GC/MS). All the cement mixtures were tested for initial and final setting
times, consistency of standard paste, flow of normal mortar and compressive strengths after 2, 7 and
Keywords:
28 days. In all cases the addition of grinding aids resulted in improvement of the specific surface and grin-
Cement
Grinding aids
dability index, a fact that was attributed to the additive ability not only to reduce resistance to commi-
FT-IR nution, but also to prevent agglomeration and powder coatings of ball and mill. The mortars made with
GC–MS cements ground with the addition of commercial additives, which contained triisopropanolamine (TIPA),
Physical and mechanical properties exhibited higher strength at any age and higher setting times. On the other hand, the presence of trieth-
anolamine (TEA) on the commercial grinding additives did not affect the mechanical properties of the
produced cements but slightly decreased their setting times.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction
Cement world production currently accounts approximately 1.6
billion ton/year and the grinding process consumes nearly 2% of
the electricity produced in the whole world. The clinker grinding
step consumes about one-third of the power required to produce
1 ton of cement. This refers to an average specific power consump-
tion of 57 kWh/t [1] and specific carbon dioxide emissions inten-
sity for electricity generation of 9.1 kg CO2 per ton [2].
Furthermore, approximately 60–70% of the total electrical energy
used in a cement plant is utilized for the grinding of raw materials,
coal and clinker. As a result, a small gain in grinding efficiency can
have not only a large impact on the operating cost of a plant, but
also a reduction in greenhouse gas emission.
Approximately 95% of the feed to the cement grinding circuit
are clinker and the rest of the feed are ‘‘additives” which includes
grinding aids (GA). The quality of cement is measured by the sur-
face area (Blaine index). It should be noticed that the surface area
of the cement powder depends on size distribution of cement par-
ticles (smaller particles have larger surface area) [3].
* Corresponding author. Tel.: +30 210 772 1761; fax: +30 210 772 2118.
E-mail address: ptsakiri@central.ntua.gr (P.E. Tsakiridis).
The efficiency of most grinding units is very low. The cement
particles can coat the grinding media, can seal the armour plating
and can agglomerate and form small plates which absorb the im-
pact. The action of the grinding media within a rotating mill not
only crushes the existing clinker particles, but also sharply com-
presses them, a fact that leads to the formation of electrostatic sur-
face charges of opposed polarity. The cement particles then
agglomerate as a result of the forces of attraction acting on them.
Consequently, the cement particle agglomeration reduces the effi-
ciency of the mill. This phenomenon is characterized by an in-
crease in energy consumption whilst maintaining constant
Blaine. The extent of agglomeration depends on:
 the specific characteristics of the materials to be ground,
 the operating parameters of the mill,
 the efficiency and distribution of the grinding media,
 the fineness of the cement particles,
 the internal operating conditions of the mill (humidity, temper-
ature, ventilation, condition of the armour plating, etc.).
The agglomeration phenomenon remains one of the priorities of
cement manufacturers, hence the importance of grinding aids. The
latter enables the partial neutralization of surface charges which
have developed during milling. Additives, such as water, organic

0950-0618/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.conbuildmat.2008.09.003
 M. Katsioti et al. / Construction and Building Materials 23 (2009) 1954–1959
liquids and some inorganic electrolytes have been used to reduce
the surface free energy of the material being ground with a view
to improving grinding efficiency [4]. Although the prime use of
grinding aids are to reduce agglomeration of cement particles, their
use will also assist in:
 the total or partial elimination of the ‘‘coating” effect on the
media,
 an improvement in the separator efficiency due to increased flu-
idity of fine particles,
 a decrease in pack-set problems in storage silos and bulk deliv-
ery trucks,
 an increased bulk and bag cement quality,
 improved materials-handling (blowing into silos, off-loading
trucks etc) due to an improved fluidity,
 improved grinding production capacity.
What make GA application even more desirable are their signif-
icant effects on mechanical properties of cement, whose particle
size distribution results narrower and shifted towards shorter
diameters [5]. The greater the surface of the hydraulically active
components, and therefore the higher the Blaine fineness, the fas-
ter does the cement harden. Nevertheless, the Blaine value only
gives an indication and not an absolute value, as it does not ade-
quately reflect the fine fraction which is an important parameter
for the grinding process and for the properties of the binder pro-
duced. When cement clinker is ground using grinding aids a nar-
rower particle size range is generated, as the percentage of very
fine particles, which only influence the setting time, is reduced.
This is why the strengths at equal Blaine values are higher than
when grinding without grinding aids. With closed-circuit grinding
plants it was also noted that cements ground with heavy circulat-
ing loads often contain smaller amounts of both ultra fine and
coarse particles. To some extent the grinding aids force the mill
to work with a higher circulating load [6].
In the grinding process, a variety of grinding aids have been
used. There are aliphatic amines such as triethylenetetramine
(TETA), tetraethylenepentamine (TEPA) and aminealcohols such
as diethanolamine (DEA), triethanolamine (TEA) and triisopropa-
nolamine (TIPA). Glycol compounds are represented such as ethyl-
eneglycol (EG), diethyleneglycol (DEG) [7]. In addition, there are
more complex compounds such as aminoethylethanolamine
(AEEA) and hydroxyethyl diethylenetriamine (HEDETA). Phenol
and phenol-derivates are also used as grinding aids, whereas, other
compounds, such as amine acetate, higher polyamines and their
hydroxyethyl derivates, are used, but these are undefined in GA
data sheets.
Generally, the concentration range of grinding aids added is
from 50 to 500 ppm. After the grinding process the additives might
not be any longer in their original chemical form. In addition,
grinding aid composition might not consist of mixtures of pure
compounds, but rather more complex raw materials [8].
Triethanolamine (TEA), a low tertiary alkanolamines, is used for
various reasons in cement industry. The action of TEA in the hydra-
tion of cement is not understood. It is not yet even resolved
whether it is an accelerator or a retarder. At an addition of 0.02%
to Portland cement, TEA acts as a set accelerator, at 0.25% it acts
as a mild set retarder, at 0.5% TEA acts as a severe retarder, and
at 1% it is a very strong accelerator [9]. TEA is a weak base and in
an aqueous phase it is mostly in the molecular state. TEA has the
ability to chelate with certain metallic ions such as Fe3+ in highly
alkaline media [10].
Triisopropanolamine (TIPA) is a tertiary amine. The cement
industry uses TIPA as a grinding aid, and it is also used in concrete
admixtures. The addition of small amounts of TIPA can result in
significant increase in the strength of cement pastes at different
1955
ages [11]. Perez et al. proposed that triisopropanolamine (TIPA)
does not improve the mechanical properties of hydrated Portland
cement paste, but rather improves mortar and concrete strength
by acting on the interfacial transition zone (ITZ) between the Port-
land cement paste and sand or aggregate [12]. However, Sandberg
and Doncaster recently presents the compressive strength data for
10 Portland cements (with TIPA) tested as cement paste, as well as
two different kinds of mortar after 28 days hydration [13]. The
average strength improvement with TIPA was 10% in the hydrated
Portland cement paste and 9% in the mortar, clearly showing
that the strength enhancement is not dependent on an ITZ
mechanism.
The aim of the present research work was the evaluation of six
commercial grinding aids, which were used for the production of
Portland cement. One reference and six cements were prepared
by interground 0.015% of each grinding aid with gypsum and a
Portland cement clinker (95% clinker, 5% gypsum). The character-
ization of the grinding aids was carried out by Fourier transform
infra-red spectroscopy (FT-IR) and gas chromatography/mass spec-
trometry (GC/MS). Water demand, setting time, flow of normal
mortar and compressive strength were also measured.
2. Experimental
Six samples of commercial grinding aids were supplied from Heracles General
Cement Company of Greece. They were first characterized by a Nicolet 560 IR Mag-
na Fourier transform spectrophotometer, in the range of 4000–400 cm1 with 200
successive scans. The spectrometer was equipped with a deuterated triglycine sul-
fate (DTGS) detector and with an attenuated total reflectance (ATR) unit. The spec-
tra rationed against a potassium bromide (KBr) background. The ATR sampling
compartment is a ZnSe crystal (refractive index 2.4) with an angle of incidence of
45° oriented horizontally. The size of the rectangular surface area of the ATR crystal
is 60 mm  10 mm.
The profile of the compounds contained in the grinding aids were determined
with a Hewlett Packard gas chromatograph HP 6890 equipped with a mass
spectrometry detector HP 5973 (GC–MS). The constituents of the mixtures were
separated using an HP-5 MS column, with 30 m length and internal diameter of
250  106 m. It was operated at 323 K for 5 min, then its temperature was
raised to 473 K with a rate of 10 K/min and finally to 553 K with 20 K/min. He-
lium was used as carrier gas with total flow of 9.7 ml/min in pulsed split
(1:10) mode. The temperature of the injector and the detector was 523 and
423 K, respectively.
The evaluation of the grinding aids (GA) was carried out by interground 0.015%
of each grinding aid with gypsum and a Portland cement clinker (95% clinker, 5%
gypsum), in a 1 kg laboratory rotating ball mill, using steel balls as grinding med-
ium, to a Blaine surface area of about 4000 cm2/g (according to the Blaine air per-
meability method) [14]. The composition of the clinker used is reported in Table
1. Its mineralogical phases, which were determined by XRD analysis, using a Sie-
mens D5000 diffractometer with nickel-filtered Cu Ka1 radiation (=1.5405 Å,
40 kV and 30 mA), are given in Fig. 1.
The standard consistency and the setting times of the cement pastes were
determined according to the European Standard EN 196-3 [15]. The determination
of the normal mortar flow was carried out according to ASTM C1437 [16]. Compres-
sive strength measurements were conducted at the ages of 2, 7 and 28 days on mor-
tar prisms (dimensions 40  40  160 mm), prepared and tested in accordance with
European Standard EN 196-1 [17].
Table 1
Chemical analyses and physical characteristics of the Portland cement clinker used
Oxides Chemical analysis (%)
CEM I-42,5
SiO2 21.21
Al2O3 5.10
Fe2O3 3.61
CaO 66.34
MgO 1.89
K2O 0.54
Na2O 0.24
SO3 0.39
free CaO 0.85
LOI 0.62
1956 M. Katsioti et al. / Construction and Building Materials 23 (2009) 1954–1959

800
1. C3S - Alite
2. C2S - Belite 1,2
3. C3A - Calcium Aluminate
4. C4AF - Ferrite
5. CaOf - free Lime
600 6. MgO - Periclase

1,2
1,2
Intenstity (cps)

400 1

1,2

1,2

200
4
1
3 1,2 2
4 1,2 1,4
1 4
1 1,2 1 1
2 5 2
4 1 2 6 1,2
0
5 10 15 20 25 30 35 40 45 50 55
2θ
Fig. 1. X-ray diffraction of the clinker used.

GA6 300

GA5 250

GA4
200 % Transmittance

GA3
150
GA2

100
GA1

50

0
4000 3600 3200 2800 2400 2000 1600 1200 800 400
Wavenumbers (cm-1)
Fig. 2. FT-IR spectra of the examined grinding aids.
 M. Katsioti et al. / Construction and Building Materials 23 (2009) 1954–1959 1957

3. Results and discussion Table 2

Components of the grinding additives as identified by GC–MS analysis

3.1. Grinding aids characterization Sample RT (min) Area (%) Component

GA1 7.38 23.13 Triethanolamine hydrochloride
Fig. 2 presents the FT-IR spectra of the examined grinding addi- 7.60 5.06 Triethanolamine hydrochloride
tives. IR spectroscopy is generally used in order to give information 7.81 7.32 Triethanolamine hydrochloride
8.06 8.39 Triethanolamine hydrochloride
as far as the composition of a sample and its structure. The bands
8.34 8.66 Triethanolamine (TEA)
occurring in the FTIR spectra of the examined additives can be 8.50 14.42 Triethanolamine hydrochloride
characterized as follows: 8.80 6.14 Triethanolamine (TEA)
9.22 8.95 Triethanolamine hydrochloride
 The distinct broad band at 3600–3200 cm1 attributes O–H. The 10.47 1.04 Triethanolamine hydrochloride
10.70 16.89 Triethanolamine hydrochloride
O–H stretching vibration is normally observed at about
3300 cm1. The O–H in-plane bending vibration is observed in GA2 10.67 84.71 Triethanolamine (TEA)
10.75 4.93 Triethanolamine hydrochloride
the region 1440–1260 cm1.
10.83 10.36 2,4(1H,3H)-Pyrimidinedione
 The band at 2925 cm1 is due to the presence of C–H stretching
GA3 10.78 46.16 Triethanolamine hydrochloride
vibration in aliphatic structures, where as the corresponding at
10.89 53.00 Triethanolamine hydrochloride
2840 cm1 attributed to the symmetrical CH stretching vibra- 12.07 0.85 2-Propanol, 1-[bis(2-hydroxyethyl)amino]-
tions in –CH2. The band ranging from 1450 to 1500 cm1 stands
GA4 10.78 23.10 Triethanolamine hydrochloride
for C–H3 and C–H2 distortion in all samples. The aliphatic C–H 10.89 70.82 1,10 ,100 -Nitrilotri-2-propanol (TIPA)
out-of-plane bending at 810 cm1 (together with the corre- 11.28 4.01 1,10 ,100 -Nitrilotri-2-propanol (TIPA)
sponding C–H stretching at 2840 cm1) suggested the presence 11.32 2.07 1,10 ,100 -Nitrilotri-2-propanol (TIPA)
of hydrocarbon species. In aromatic compounds, CH stretching GA5 10.38 17.41 1,10 ,100 -Nitrilotri-2-propanol (TIPA)
frequencies appear in the range of 3000–3100 cm1. 10.43 7.83 1,10 ,100 -Nitrilotri-2-propanol (TIPA)
10.57 19.31 1,10 ,100 -Nitrilotri-2-propanol (TIPA)
 The band observed at 1650–1600 cm1 was assigned to C@O
10.64 5.52 1,10 ,100 -Nitrilotri-2-propanol (TIPA)
stretching vibrations in aromatic groups, where as the narrow 10.70 10.11 1,10 ,100 -Nitrilotri-2-propanol (TIPA)
band around 1000 cm1 is attributed to the C–OH stretching 10.76 1.67 1,10 ,100 -Nitrilotri-2-propanol (TIPA)
vibration. Aromatic C@C stretch was observed at 1597 and 10.88 14.63 4-hydroxy-1,8-naphthyridine
1495 cm1. 11.00 19.52 1,10 ,100 -Nitrilotri-2-propanol (TIPA)
11.10 0.85 1,10 ,100 -Nitrilotri-2-propanol (TIPA)
 The absorption observed at the range of 1200–1000 cm1 corre-
11.14 0.61 1,10 ,100 -Nitrilotri-2-propanol (TIPA)
sponds to the C–O stretching vibration. The C–N stretching is 11.33 1.74 1,10 ,100 -Nitrilotri-2-propanol (TIPA)
appeared at 1320 cm1. 11.37 0.80 1,10 ,100 -Nitrilotri-2-propanol (TIPA)
 The bands between 700 and 900 cm1 were attributed to the GA6 3.34 0.78 Benzene
presence of aromatic groups. 8.57 2.49 1,10 -Iminobisi-2-propanol (DIPA)
10.92 38.10 1,10 ,100 -Nitrilotri-2-propanol (TIPA)
11.05 32.99 1,10 ,100 -Nitrilotri-2-propanol (TIPA)
Gas chromatography/mass spectrometry (GC/MS) is one of the
11.16 18.12 1,10 ,100 -Nitrilotri-2-propanol (TIPA)
best identification systems because it combines the high separa- 11.25 1.38 Benzenamine
tion efficiency of capillary GC with the selectivity and relatively 11.37 1.88 1,10 ,100 -Nitrilotri-2-propanol (TIPA)
high sensitivity of MS. The cement grinding additives were ana- 11.45 3.95 1,10 ,100 -Nitrilotri-2-propanol (TIPA)
lyzed by GC/MS and the identified compounds are presented in Ta- 11.93 0.07 Benzenamine
12.59 0.24 Acetamide
ble 2. The retention time (RT) and the typical mass fragments were
applied as the criteria for its identification. The chromatograms of
the different samples showed the presence of two major com-
pounds: triethanolamine (TEA) and triisopropanolamine (TIPA). It Table 3
is apparent that the main component of the GA1, GA2 and GA3 Main components of the commercial grinding additives used
grinding aids was triethanolamine (TEA). A group of peaks with Active component (%) GA1 GA2 GA3 GA4 GA5 GA6
retention times between 7.38–8.06 min and 9.22–10.70 min corre-
Triethanolamine (TEA) 100 89.64 99.15 23.10 –
spond to triethanolamine hydrochloride with very significant
Triisopropanolamine (TIPA) – – – 76.9 85.37 95.04
amount. In case of GA2 a small amount of pyrimidinedione
(RT = 0.83 min, 10.36%) was detected, whereas traces of N,N-
bis(2-hydroxyethyl) isopropanolamine were found in GA3
(RT = 12.07 min, 0.85%). On the other hand, 1,10 ,100 -Nitrilotri-2-pro- requirement for grinding the clinker to a given fineness and can be
panol (TIPA) was identified as the most abundant component of given in relation to the revolutions of the mill necessary to produce
GA4, GA5 and GA6 grinding aids. It should be noticed the presence the cement with specified specific surface area. As it was men-
of 23.10% of triethanolamine (TEA) (RT = 10.78 min) in case of GA4, tioned in the experimental section, gypsum and a Portland cement
a fact that indicates that GA4 is a mixture of TIPA and TEA. Finally, clinker (95% clinker, 5% gypsum) were interground together with
an important peak (14.63%) appearing at 10.88 min has been iden- 0.015% of each grinding aid to a Blaine surface area of about
tified as a 4-hydroxy-1,8-naphthyridine in GA5 grinding aid. As it is 4000 cm2/g. The results of the specific surface, as well as those of
shown in Table 3, among the last three grinding aids triisopropa- the cement grindability are given in Table 4. The reference sample
nolamine (TIPA) is the most abundant component of the GA6 (clinker with gypsum) originally presented a grindability index of
(about 95%). 0.781. It is observed that all the grinding aids studied were effec-
tive in varying degrees in the improvement of grinding. In all cases,
the presence of the additive resulted in higher specific surface and
3.2. Grindability study in higher grindability index, in comparison with those of the
reference (nonadditive) cement, a fact that was attributed to the
Clinker grindability is the measure of the ability of a clinker to elimination or retardation of the caking and agglomeration phe-
resist grinding forces. It is an indicator for the estimation of energy nomena during the grinding process. During grinding in rotating
1958 M. Katsioti et al. / Construction and Building Materials 23 (2009) 1954–1959

Table 4 Table 6
Results of grindability tests Mechanical properties of tested cements according EN-196

Mixture Ref GA1 GA2 GA3 GA4 GA5 GA6 Sample Compressive strengths (MPa)
Mill revolutions 5056 4450 4600 4500 4200 4150 4000 2 days 7 days 28 days
Specific surface 3950 3960 3955 3980 3945 3970 3935
Ref 25.5 39.0 55.0
(Blaine – cm2 g1)
GA1 26.0 41.0 57.2
Grindability index 0.781 0.890 0.860 0.884 0.939 0.957 0.984
GA2 25.8 40.5 56.0
GA3 26.0 41.2 57.0
GA4 26.5 41.5 58.1
GA5 27.1 42.5 59.3
Table 5 GA6 30.2 43.0 63.0
Physical properties of tested cements according EN-196

Sample Water demand for standard Setting time (min) Flow of normal
consistency (% w/w) mortar (%) 3.3. Physical and mechanical properties of the produced cements
Initial Final
Ref 27.1 120 150 110
GA1 28.0 115 150 105 Table 5 presents the cement water demand, the setting time
GA2 27.6 110 140 105 and the normal mortar flow of the tested samples. The water de-
GA3 27.6 115 150 110 mand of the produced cements varies from 27.6% to 28.1%, while
GA4 28.0 130 160 115 the corresponding value for the reference Portland cement was
GA5 28.1 135 160 120
GA6 28.0 140 170 120
27.1%. The slightly increase in water demand should be attributed
mainly to the higher fineness of the cement that were interground
with the examined additives.
mill, electrostatic surface charges of opposed polarity are devel- The initial and final setting times were slightly decreased in
oped among cement particles, whereas the presence of the grind- case of GA1, GA2 and GA3 (triethanolamine). TEA has been known
ing additives enables their partial neutralization. The maximum for many years as a component of additives and admixtures for
growth of the grindability index (up to 20–26%), in comparison Portland cements, usually being added at low dosages as a set
with the reference one, was achieved when triisopropanolamine accelerator, a fact that is attributed to the C3A reaction accelera-
(TIPA) grinding aids (GA4, GA5 and GA6) were used, whereas in case tion. Depending on the chemical and mineralogical composition
of triethanolamine (TEA) grinding aids (GA1, GA2 and GA3) the in- of the cement and the amount of TEA, it can accelerate the hydra-
crease of grindability index varied between 10% and 14%. The max- tion of C3A to the hexagonal aluminate hydrate and its conversion
imum increase in grindability index was observed in case of GA6, to the cubic aluminate hydrate [18]. On the other hand, compared
which contained about 95% triisopropanolamine. with control mix, in case of GA4, GA5 and GA6 the presence of

65
Reference
GA1
GA2
GA3
GA4
GA5
55 GA6
Compressive Strengths (Mpa)

45

35

25
0 5 10 15 20 25 30
Age (Days)
Fig. 3. Strength development of the cements.
 M. Katsioti et al. / Construction and Building Materials 23 (2009) 1954–1959
triisopropanolamine increases initial and final setting times about
15%. As a result, TIPA partially acts as a retarder of hydration at
early stages, probably because it diffuses into pores and cracks,
of the cement particles, during grinding [19]. The lower hydration
rate means lower rate of heat evolution, a fact that is of great
importance in mass concrete constructions.
The flow tests confirmed the above results and showed that in
case of triisopropanolamine the mortar workability was improved,
whereas the presence of triethanolamine did not negatively affect
the produced cement. The mortar flow is connected with cement
particles, which always are agglomerated in water suspensions.
This fact can lead to a viscosity increase by an apparent particle
volume increase. A part of the water is entrapped in the porosity
of the agglomerates and does not contribute to the flowability.
Consequently, the workability increase should be attributed to
the presence of triisopropanolamine, which breaks down these
the cement agglomerates by modifying the balance of interparticle
forces.
The mortars of the cements under investigation were tested for
compressive strengths after 2, 7 and 28 days of curing. The obtained
results are shown in Table 6 and Fig. 3. The addition of triethanola-
mine TEA (GA1, GA2 and GA3) slightly affected the compressive
strengths of the produced cements at all hydration ages. However,
the presence of triisopropanolamine in cement (especially in case
GA6, whose main component is TIPA – about 97.5%) improved sig-
nificantly the compressive strengths at 2 days by about 18,5% and
moderately at 7 days by 10%. The compressive strengths increase
was also significant after 28 days of curing (about 15%).
The above results clearly showed that the commercial grinding
additives, which contain triisopropanolamine (GA4, GA5 and GA6)
improve the mechanical properties of the hydrated Portland ce-
ment, a fact that can be attributed to the hydration enhancement
of alite and ferrite clinker phases [20]. Triisopropanolamine, re-
mains in solution for a sufficient time, and catalyzes the hydration
of C4AF after all of the free gypsum has been consumed to form cal-
cium sulfoaluminate hydrates [11]. In contrast, the lower alkanol-
amine, triethanolamine, is mostly adsorbed by the cement within
the first hours of hydration. The adsorption of TEA is taken place
mainly on the Portlandite surface, during the silicate phase hydra-
tion, while TIPA does not adsorb [12]. These observations could ex-
plain the differences between TEA and TIPA on the mechanical
properties of the produced cements.
4. Conclusions
The aim of the present research work was the evaluation of six
commercial grinding additives, which were used for the produc-
tion of Portland cement. Their characterization was carried out
by Fourier transform infra-red spectroscopy (FT-IR) and gas chro-
matography/mass spectrometry (GC/MS). It was found that the
main component of the GA1, GA2 and GA3 grinding aids was trieth-
anolamine (TEA). On the other hand, 1,10 ,100 -Nitrilotri-2-propanol
(TIPA) was identified as the most abundant component of GA4,
GA5 and GA6 grinding additives.
The examined grinding aids were very effective in the grinding
of Portland cement clinker, increasing the specific surface and the
1959
grindability index. The presence of TEA (GA1, GA2 and GA3), in-
creased the grindability index up to 14%. The corresponding value
for TIPA grinding aids (GA4, GA5 and GA6) reached at 26%.
The initial and final setting times were slightly decreased in
case of GA1, GA2 and GA3 (triethanolamine), a fact that was attrib-
uted to the C3A reaction acceleration. However, the presence of tri-
isopropanolamine (GA4, GA5 and GA6) increases the initial and final
setting times about 15%, acting as a retarder of hydration at early
stages. Furthermore, TIPA improved the mortar workability.
The addition of triethanolamine TEA (GA1, GA2 and GA3) slightly
affected the compressive strengths of the produced cements at all
hydration ages. On the other hand, triisopropanolamine improved
significantly the compressive strengths, increasing them by 18.5%
at 2 days and by 15% after 28 days of curing.
References
[1] Seebach MV, Schneider L. Update on finish grinding with improved energy
efficiency. World Cem 1986;17(8):336–46.
[2] Worrel E, Martin N, Price L. Potentials for energy efficiency improvement in the
US cement industry. Energy 2000;25:1189–214.
[3] Jankovic A, Valery W, Davis E. Cement grinding optimization. Miner Eng
2004;17(11–12):1075–81.
[4] Sohoni S, Sridhar R, Mandal G. The effect of grinding aids on the fine grinding of
limestone, quartz and Portland cement clinker. Powder Technol
1991;67(3):277–86.
[5] Bathia JS. Use of grinding aids in ball mill grinding. World Cem Technol
1979;10(10):413–7.
[6] Magistri M, Presti AL. Influence of grinding aids. World Cem 2007;38(6):39–41.
[7] Teoreanu I, Guslicov G. Mechanisms and effects of additives from the
dihydroxy-compound class on Portland cement grinding. Cem Concr Res
1999;29(9):9–15.
[8] Jeknavorian AA, Barry EF, Serafin F. Determination of grinding aids in Portland
cement by pyrolysis gas chromatography–mass spectrometry. Cem Concr Res
1998;28(9):1335–45.
[9] Dodson VH, editor. Concrete admixtures. New York: Van Nostrand Reinhold;
1990.
[10] Yilmaz VT, Menek N, Odabasoglu M. Quantitative determination of
triethanolamine in cements. Cem Concr Res 1993;23(3):603–8.
[11] Gartner E, Myers D. Influence of tertiary alkanolamines on Portland cement
hydration. J Am Ceram Soc 1993;76(6):1521–30.
[12] Perez J, Nonat A, Garrault-Gauffinet S, Pourchet S, Mosquet M, Canevet C.
Influence of triisopropanolamine on the physico-chemical and mechanical
properties of pure cement pastes and mortars. Proceedings of the 11th
international congress on the chemistry of cement, vol. 2. Durban (South
Africa): The Cement and Concrete Institute of South Africa, Document
Transformation Technologies; 2003. p. 454–63.
[13] Sandberg PJ, Doncaster F. On the mechanism of strength enhancement of
cement paste and mortar with triisopropanolamine. Cem Concr Res
2004;34(6):973–6.
[14] ASTM C204. Standard test method for fineness of hydraulic cement by air
permeability apparatus. ASTM International; 2000. Document Number: ASTM
C204-00.
[15] TN 196-3. Methods of testing cement – determination of setting time and
soundness; 1994.
[16] ASTM C1437. Standard test method for flow of hydraulic cement mortar. ASTM
International; 1999. Document Number: ASTM C1437-01.
[17] TN 196-3. Methods of testing cement – determination of compressive
strength; 1994.
[18] Ramachandran VS. Action of triethanolamine on the hydration of tricalcium
aluminate. Cem Concr Res 1973;3(1):41–54.
[19] Albayrak AT, Yasar M, Gurkaynak MA, Gurgey I. Investigation of the effects of
fatty acids on the compressive strength, of the concrete and the grindability of
the cement. Cem Concr Res 2005;35(2):400–4.
[20] Ichikawa M, Kanaya M, Sano S. Effect of triisopropanolamine on hydration and
strength development of cements with different character. In: Proceedings of
the 10th international congress on the chemistry of cement, Gothenburg,
Sweden; 1997 [Paper 3iii005].