SP-288.

16

Understanding the Effectiveness of

Polycarboxylates as Grinding Aids
by Ratan K. Mishra, Hendrik Heinz,
JrgZimmermann, Thomas Mller, and Robert J.
Flatt
Synopsis: Over recent years, polycarboxylate superplasticizers have found their way into
grinding aids used in cement production to reduce the electrical energy consumption. The
effectiveness of these large molecules challenges the pre-existing theories concerning the
factors that govern the performance of grinding aids. This paper reports on molecular
dynamics simulations to examine a physical property believed to control the effectiveness of grinding aids, namely their adsorption energy. The molecules selected are TIPA
(Triisopropanol amine), TEA (Triethanol amine) and glycerine. The surfaces examined are
dry and hydroxylated C3S surfaces, which are believed to be more representative of reality,
since some humidity is always present during the grinding. Detailed results of this part of
the work show that glycerine interacts relatively more with dry as well as hydroxylated
surfaces of C3S both at 25C, ambient temperature and 110C, grinding temperature with
respect to TIPA and TEA. These result help to better understand the specific interaction of
these molecules with cement surfaces. In the second part of this work oligomers of some
PCE superplasticizers are examined with similar numerical tools on dry and hydroxylated
surfaces of C3S. Results for different types of these oligomers, together with the previous
results, shed light onto the reasons why polycarboxylate superplasticizers have found to
also be effective grinding aids in cement production.

Keywords: adsorption; agglomeration; hydroxylated (Hyd); molecular

dynamics (MD); TEA (Triethanol amine); TIPA (Triisopropanol amine);
tricalcium silicate (C3S).
235

236 Mishra et al.

Ratan K. Mishra holds a BE degree in chemical engineering from Visveswaraya Technological University and worked as a research assistant at IISc Bangalore. He currently
pursues a Ph.D. degree at the Department of Polymer Engineering, University of Akron,
Akron, OH, with Prof. Hendrik Heinz. He investigates the interactions of polymers with
inorganic surfaces at the nanoscale and confined fluids using molecular simulation. He
received a best presentation award for his work on surface properties of C3S at the 13th
ICCC Madrid 2011.
Hendrik Heinz received a MS in Chemistry and a PhD degree in Materials Science
from ETH Zurich in 2003. After postdoctoral work at the Air Force Research Laboratory
at Wright-Patterson Air Force Base, he joined the University of Akron, as an Assistant
Professor. His research interests include the simulation of cement materials, biomineralization, and inorganic-organic interfaces using advanced simulation tools. He received
an NSF Career Award, an ACS HP Outstanding Junior Faculty Award, and the Giovanni
Novelli Prize of the Italian Clay Group.
Jrg Zimmermann obtained his PhD thesis at the Institut fr Makromolekulare Chemie,
Albert-Ludwigs-Universitt Freiburg (Germany). He is manager of the Polymer Synthesis
Department within the Construction Chemicals and Mortars division at Sika Technology
AG (Zrich, Switzerland).
Thomas Mller received a Diploma in Chemistry and a PhD degree in Chemistry from
FSU Jena, Germany in 2008. Directly after he joined Sika as Corporate responsible for
fundamental development of cement additives like grinding aids and quality improver.
Robert J. Flatt is Professor of Building Materials at ETHZ. Before that he was Principal
Scientist at Sika Technology AG and postdoctoral researcher at the Princeton University. He owns a master in Chemical Engineering and a PhD from EPFL. In 2003, he
received the RILEM Robert LHermite Medal for his contributions to the understanding
of chemical admixtures. In 2007, he received the Ross C. Purdy award from the basic
science division of the American Ceramic Society.
INTRODUCTION
Grinding of clinker is a highly energy intensive process during cement production. On
its own, it consumes about one third of the entire electrical energy used in cement production.1 Apart from this, it should be noted that mainly due to the decarbonation of limestone,
but also to the major use of carbon based fuels, cement production contributes 5%-7% of
global CO2 emissions.2,3 Presently the most used approach to mitigating this is the partial
replacement of cement by supplementary cementitious materials. This however, generally
leads to a lower initial reactivity that may be compensated by finer grinding.4 In order to
reduce energy consumption in the cement production, grinding can therefore be expected
to be of growing importance.5,6 In particular, there is certainly a greater potential for saving
reasonable amount of energy using chemical grinding. These products limit agglomeration
of fine particles, which enhances the separator efficiency as less fine material gets fed back

Effectiveness of Polycarboxylates as Grinding Aids 237

into the mill.7,8 They also prevent the milling media from getting covered by a compacted
layer of powder, which also reduces grinding efficiency.
Despite the reasonable amount of research work in the area of chemical admixtures, still
the understanding of molecular level mechanisms of grinding aids remains poorly understood. As of now, a few mechanisms have been suggested to explain the action of various
grinding aids. These include7-10:
(a) Preventing agglomeration of the freshly cleaved mineral surfaces
(b) Preventing minerals particles from sticking to the milling media and mill wall
(c) Adsorption-induced mobility
(d) Reduction in surface free energy due to adsorption on freshly cleaved surface.
In order to critically examine some of these hypotheses, there would be a need to access
physio-chemical properties such as adsorption energy on freshly cleaved surfaces, agglomeration energy in the presence of grinding aids and driving forces for adsorption. Unfortunately, these properties are very difficult to access experimentally, which is why we find the
necessity of using molecular modeling to get access to some of them.
In particular, we are interested in comparing the behavior of classical grinding aids as
TIPA, TEA and glycerol with the more recently introduced polycarboxylates. These are
large comb copolymers that are largely used in concrete for their ability to improve workability, strength and durability of concrete through mechanisms that have largely been
studied.5,11-14 Their effectiveness as grinding aid is more surprising as their volatility is low,
which is one parameter that (in the past) has been considered important for grinding aids.
However, mobility may also take place on the surface and can be expected to be affected
by the strength of the bond formations between the grinding aids and the cement particle
surfaces. This is why we focus in the present study on determining adsorption energies and
examining the nature of these bonds.
More specifically, we used a molecular model of tricalcium silicate (3CaOSiO2, noted
C3S) to examine some important questions of direct practical relevance such as adsorption energy of grinding aids on C3S in the presence of grinding aids.15 The C3S was
selected among the various clinker phases because it is a primary constituent of cement
clinker (50-70%) and also due to its abundance and main role in strength development,
C3S frequently serves as a model system for both alite and cement.16 Kundu et al.17 also
described the atomistic simulation approach to simulate the surface of another calcium
silicate, wollastonite (CaSiO3). They studied the adsorption of water and organic additives,
finding that the simulations predicted the well-established trend of experimental findings.
Our present study is limited to the hydroxylation of oxides ions of C3S surface due to presence of humidity in the grinding process, but in this study we have not considered the extra
amount of water, which may be present at clinker surfaces as a result of the dehydration
of gypsum.
RESEARCH SIGNIFICANCE
The present research work methodically uses atomistic simulations to understand the
working mechanisms of grinding aids. It proposes new insights into the working mechanisms of these admixtures and accesses information that is not or barely accessible experimentally. Thereby it contributes to the global efforts devoted to improving grinding effi-

238 Mishra et al.

ciency. This is needed in order to compensate for the loss of early age reactivity in cement
containing larger amounts of SCMs (Supplementary Cementitious Materials).
Approaching this problem by a molecular level understanding of grinding aids is a clear
originality of this work. It makes it possible to obtain information that would not be accessible otherwise. For example it is shown for the first time that grinding aid adsorption
involves hydrogen bonds to the C3S surface. We also examine the differences in behavior
between classical grinding aids as TIPA or TEA with respect to polycarboxylate polymers
more recently introduced in this area.
COMPUTATIONAL MODELS AND METHODS
Computer simulation provides a direct route from the microscopic details of a system (the
mass of the atoms, interactions between atoms, molecular geometry etc.) to macroscopic
properties of experimental interest (the equation of state, transport coefficients, structural
order parameters and so on).18 The simulation of interfacial processes can be done at the
small scale (<1000 atoms) using quantum-mechanical methods while larger scale dynamic
processes require simplified classical energy models. The present study requires an accurate molecular model of C3S, which was first derived from the X-ray crystal structure by
Mumme19 and Jeffery.20 In this paper we will not discuss the force-field parameterizations and validation of structural and surface properties of C3S. More details on C3S forcefield validations and other minerals, can be found in the extensive work done by Heinz et
al.15,21-23
Molecular models of pure and hydroxylated tricalcium silicate
A model of the pure tricalcium silicate was derived from X-ray data (Fig. 1)19 using the
Materials Studio graphical interface.24 We decided to use the structure given by Mumme
due to its high precision and the observation of possible local disorder of silicate tetrahedra. During the calculation of adsorption, we employed tricalcium silicate super cells
of dimensions near 2.5 x 2.8 x 2.5 nm3 and 2.5 x 2.8 x 5 nm3 respectively. We used the
energy expression of the polymer consistent force field (PCFF) to approximate the potential energy of the mineral and included terms for quadratic bond stretching, quadratic angle
bending, Coulomb interactions, and van-der-Waals interactions.21
A molecular model of dry C3S surfaces has been obtained by cleavage of the minerals
along a given cleavage plane. In the supercell of C3S illustrated, we see the calcium ions
on the top of the xy plane. Their minimum energy configuration can be obtained using a
temperature gradient technique.25 Under the influence of humidity, the reaction of pure
tricalcium silicate with water molecules can cause different extents of reaction of the tricalcium silicate surface. The first of these is most certainly a superficial hydroxylation as
depicted in Fig. 2 and Eq. (1). Superficial oxide ions react with a water molecule to form
two hydroxide ions on the surface.

H 2 O + O 1.50 O 1.05 H 0.30 + O 1.05 H 0.30 (1)

Effectiveness of Polycarboxylates as Grinding Aids 239

Fig. 1Structure of tricalcium silicate (1 x 2 x 1 supercell).

Fig. 2Single step dissolution mechanism for C3S based on Barret et al.26,27

Fig. 3Adsorption energy approach: molecules adsorbed on

the surface and reference state away from surface.28

240 Mishra et al.

Fig. 4Chemical structure of grinding aids used.

Semiempirical classical simulation
Classical molecular dynamics simulations were performed using the polymer consistent
force field. The adsorption energy calculations of grinding aids on the dry and hydroxylated C3S surfaces were done with 12-16% surface coverage. Here the surface coverage
defines that how much cross-sectional area is occupied by grinding aids molecules on the
C3S surface. We carried out MD simulations in the NVT (N = number of atoms, V =
volume of the simulation box and T = temperature of the system) ensemble with a time step
of 1 fs, and a temperature of 298.15 K maintained by the Andersen thermostat with high
accuracy (106 kcal/mol) for Coulomb interactions of the Ewald summation in periodic
boundary condition in all three directions. For the adsorption energy calculations, a simulation approach was applied using the concept developed by Heinz28 as shown in (Fig. 3) and
also formulated in Eq. (2). Adsorption energies (Eads) were calculated using the Discover
program24 and LAMMPS29 by comparing the energy (Eclose) of adsorbed molecule close to
the surface (on the surface) and energy (Efar) of adsorbed molecule far from the surface (20
nm away from the surface) at two temperature 298.15 K and 383.15 K. Simulation run for
adsorption energy calculation was total of 4 ns time where the first 2 ns time were used for
equilibrium of the system and the remaining 2 ns data were used for calculation.
Eads = Eclose Efar (2)
Simulations with standard grinding aids
The classical grinding aids that we have considered are triethanol amine (TEA), triisopropanolamine (TIPA) and glycerine as shown in Fig. 4. They were deposed on the dry
C3S surface, (040) crystal plane and adsorption energies in vacuum were calculated for
the dosage referred to above. This was done both at ambient temperature and at 110C,
which is representative of average conditions in a ball mill. At such a temperature and for
a material coming out of the kiln (1450C) the humidity is low. However, it is not fully dry
because of small amounts of water available from different sources such as the grinding
aid solution, cooling water (used occasionally to avoid overheating), some humidity, partial
dehydration of gypsum etc. For this reason, we also examined the situation in which the
C3S surface is partially hydroxylated as has been discussed in the molecular model section.

Effectiveness of Polycarboxylates as Grinding Aids 241

Fig. 5(a) Structure notation shown with an example of PCE with four side chains; and
(b) chemical structure of PCE1 and (c) PCE2 grinding aids. The figures (b) and (c) were
prepared in Materials Studio.24
The simulations were performed with amounts of grinding aids per unit surface compatible with what is fine ultimately in cement. Values are obtained considering that typical
dosages are of about 500 g/ton of solutions containing 40% of grinding aid by solid mass.
For specific surface ranging from 0.3 m2/g by Blaine to 1 m2/g by BET, this gives on
average an effective grinding aid dosage 0.44 mg/m2.
Simulations with polycarboxylate oligomers
As a reminder, polycarboxylate esters are composed of comb copolymers with an
adsorbing linear anionic backbone (typically a polyacrylate or polymethacrylate) as well
as non-adsorbing side chains (typically polyethylene oxides).
In order to reduce computational time, we have reduced the size of the PCEs and talk
rather of oligomers. We have used a methacrylate backbone of 696 and 2056 g/mol with
two side chain lengths of 220 and 440 g/mol. The notations used for these oligomers follow
the one introduced by Gay and Raphals model30 for comb-homopolymers and extended
by Flatt et al.31 for comb copolymers. In this notation, n is the number of side chains in the
polymer, P is the number of monomers in a side chain, and N is the number of backbone
monomers per side.
This means that the total number of monomers in the backbone is given by: n N and the
used notation of PCE has been shown in Fig. 5(a).
The simulations were performed with these PCEs on dry and hydroxylated C3S surfaces.
We have used four PCE for the calculation of adsorption energy. Details of all the PCEs are
listed in Table 1. We have shown the chemical structure of PCE1 and PCE2 in the Fig. 5 (b)
and (c). Other structures have been drawn in similar way.
We have used a similar method to calculate the adsorption energy of PCE, which is
shown in Fig. 3. Here we have just selected the grinding temperature for computation. Due
to the different backbone lengths, two different sizes of the simulation box have been used.
For the smaller (PCE1 and PCE3) and larger backbone (PCE2, PCE4 and PCE5), we used
surface area of 2.5 x 2.5 nm2 and 4.8 x 7.5 nm2 respectively. In this case we get surface
coverage of approximately 30%, which is higher than the coverage of smaller molecules
used above.

242 Mishra et al.

Table 1Details of PCE-based grinding aids

Abbreviation

Nn

No. of Ca++

Molecular weight, g/mol

PCE1

1315

PCE2

1774

PCE3

10

1756

PCE4

10

2655

PCE5

24

10

5236

Fig. 6Adsorption energies data for TEA, TIPA, and Glycerine on the dry C3S surface and hydroxylated C3S surface at
two temperatures 298 K and 383 K.
SIMULATION RESULTS
This section is divided into two parts. The first one deals with standard grinding aids
and the second with polycarboxylates. In the first part, in addition to adsorption energy, we
present results about the mechanism that controls the grinding aid adsorption.
Classical grinding aids
We introduced classical grinding aids term earlier in this paper. These are the standard
and older products, which are used in cement industry. Below we have discussed the
adsorption energy results and mechanism of the triethanol amine (TEA), triisopropanolamine (TIPA) and glycerine on different types of C3S surface.
Adsorption energy
The results of these calculations are summarized in Fig. 6. Values are given per unit
mass because, in practice, grinding aids are compared at equal mass dosage and not equal
number of molecules. The main conclusions that can be drawn are that:

Effectiveness of Polycarboxylates as Grinding Aids 243

Fig. 7Chemical Snapshot of glycerine on the Hyd C3S

surface, showing the hydrogen bonds between hydroxyl
groups and silicate ions as well as hydroxyl group and
hydroxide ion at 298 K.
1. Adsorption energies are lower at 110C, but remain nevertheless quite high, in the
range of 20-50 kcal/mol.
2. Surface hydroxylation reduces adsorption energies, but only by about 20%.
3. The trend of adsorption energy of grinding aids is as follows: Glycerine > TIPA ~
TEA. This does not follow the ranking of boiling points.
4. Hydrogen bonding is responsible for better adsorption on the surface.
5. Adsorption energies of TIPA and TEA on C3S surface show different trends, when
expressed per mole or per unit mass. For example, at 298 K, adsorption energies of TIPA
and TEA on hydroxylated C3S surface are respectively 39 and 32 kcal/mol when
expressed per mole and 0.20 and 0.21 kcal/g when expressed by mass.
Adsorption mechanism
We have found that the adsorption is hydrogen bond driven and does not follow the
boiling points trend of grinding aids. TIPA (boiling point = 306C) and TEA (boiling point
= 335.4C) are much more sensitive to temperature (~50%) than glycerine (~15%). The
percentages given refer to the change in adsorption energy of TIPA and TEA between the
grinding temperature and room temperature. It was also found that the adsorption energy
varies within the range of 1 to 2 kcal/mol per molecule with different position of grinding
aids on the surface. Glycerine (boiling point = 290C) has strong interactions with the
hydroxylated surface compared to TIPA/TEA, due to difference in hydrogen bond lengths.
As an example, we show in the (Fig. 7) that hydrogen bonds form between alcoholic groups
of glycerine with silicate ions, and hydroxide ions on the hydroxylated C3S surface.
Polycarboxylate grinding aids
The results of PCE adsorption energy calculations are summarized in Fig. 8. These show
that the oligomer is more affected by changes in the charge density on the backbone (N)

244 Mishra et al.

Fig. 8Adsorption energy of PCEs on dry and hydroxylated

C3S surface.
than on the length of the side chains (P). The reasons for this are discussed more extensively at the end of the next section.
Data also show that the PCEs have higher adsorption energy on dry C3S with respect to
hydroxylated C3S surface. Counter ions also has an effect. Calcium ions tend to stay with
the oligomer, so that to some extent it gets repelled from the surface as shown in the Fig. 9.
Longer simulation time will give a much better picture of side chain conformations as well
as backbone orientation towards surface. In the longer side chains, we also see excluded
volume interactions. There is also a minor surface reconstruction on the top of the surface
due to the adsorption of PCE on the surface. We also found that the silicate ion also comes
out from the top layer of surface.
DISCUSSION
Various types of chemicals are or have been considered as grinding aids. The most widely
used today are triethanolamine (TEA), and triisopropanolamine (TIPA). These products
identified as efficient grinding aids due to their volatility and resulting ability to diffuse
faster from one freshly cleaved surface to another through the gas phase.7,32-34 Diffusion
occurs due to the adsorption-induced mobility of grinding aids. While this concept is
appealing, it lacks solid evidence and also suffers from the fact that less volatile products
as polycarboxylate comb-copolymers with much lower volatility have also been shown
to be very effective grinding aids.5,6,11,12 In this paper we have used the possibility offered
by molecular modeling to calculate adsorption energies of grinding aids and therefore
examine the claim concerning the importance of their gas phase mobility.
The results of adsorption energies on classical grinding aids show that values are high
even on hydroxylated surface and at the highest temperature. This is a first point that questions the notion that volatility is an essential factor for the performance of these products. In addition, TIPA and TEA show similar adsorption energies but not perform equally

Effectiveness of Polycarboxylates as Grinding Aids 245

Fig. 9(a) Snapshot of the system PCE2-Hyd C3S; and (b) snapshot of the system PCE4Hyd C3S after 700 ps simulation time.
as grinding aid. On the other hand both TIPA and TEA are reported to be clearly better
grinding aids than glycerol, which has higher adsorption energy. In contrast, this would
support the argument about the importance of gas phase mobility.
The proven efficiency of polycarboxylates as grinding aids also challenges the classical
prevailing theory that stands that mobility in the gas phase is important. However, surface
mobility may play an important role and this may be relevant for polycarboxylates. In more
general terms, grinding aid mobility, must involve the coexistence of diffusion (surface or
gas phase) with the breaking and making of bonds, which are hydrogen bonds for classical
grinding aids and electrostatic interactions for PCEs. In the case of classical grinding aids,
we must critically examine the making and breaking of hydrogen bonds. For this we can
refer to the extensive studies by Luzar and Chandler35,36 on hydrogen bond dynamics in
liquid water as well as water-dimethyl sulfoxide systems. They showed that diffusion can
persist at random with average lifetimes of hydrogen bond making and breaking. For pure
water, the hydrogen bond lifetime is 1 ps. In the present study, we are not concentrating
on the hydrogen bond lifetimes, as our main intention is to know the criterion of diffusion
of adsorbed molecules on the C3S surface and the strength of the hydrogen bonds that
lead to adsorption. The length and strength of hydrogen bond are discussed by Steiner37
and Smallwood et al.38 for weakly and highly polar groups respectively. For highly polar
groups, where short and strong hydrogen bonds form, their lengthening by 0.5 leads
to decrease of approximately 6 kcal/mol in the strength of the ionic hydrogen bond.39
Such issues would require further investigation in order to properly assess the mobility of
grinding aids on the surface of cement particles.

246 Mishra et al.

Other factors may however play more important roles. For example, grinding aids may
play their greatest role in preventing agglomeration. An approach to evaluate this would
be to calculate the re-agglomeration energy, but other approaches may prove more relevant. The first step is therefore to determine the most relevant property in influencing the
grinding performance. After that it is possible to use molecular modeling to understand
how specific factors of the molecular structure affect this property.
Concerning the adsorption of PCE oligomers, we found that the PCE1 and PCE3 (two
side chains, n = 2) has higher adsorption than PCE2 and PCE4 (four side chains, n = 4) due
to higher anionic charge of backbone respectively. Plank et al.39 also described the similar
trend of polycarboxylates as a superplasticizers. They also reported that the higher anionic
charge density of PCE gives stronger adsorption. In the case of PCE2 (P = 5) and PCE4
(P = 10), the only difference is in the length of side chains, which also plays an important
role due to the interactions between side chains. PCE4 has slightly less adsorption energy
than PCE2 due to the steric hindrance effect, caused by the extension of graft chains of
PEO (polyethylene oxides) as shown in Fig. 9. As the length of the backbone increases
from n N = 8 to 24 then adsorption of oligomers also increases due to the increase in
anionic charge of backbone. We found that the adsorption of PCE on C3S surface happens
mainly due to electrostatic interactions and negligible contributions from van der Waals
interactions.
CONCLUSIONS
We calculated the adsorption energy of TIPA (Triisopropanol amine), TEA (Triethanol
amine) and glycerine on the dry and hydroxylated C3S surfaces at room temperature 298 K
(25C) and grinding temperature 383 K (110C). Simulation results show that the adsorption of grinding aid is weaker on the hydroxylated surface than on the dry C3S surface. The
trend of the adsorption energy of grinding aids is as follows: Glycerine > TIPA ~ TEA.
We have also shown that the adsorption is hydrogen bond driven and it does not follow
the boiling points trend of grinding aids. Adsorption strength depends on the lengths of
the hydrogen bond. Interactions of glycerine with C3S have shorter hydrogen bond lengths
than TIPA and TEA. Glycerine is much less sensitive to temperature than TIPA and TEA
on the hydroxylated surface. From the adsorption energy results of PCEs on the hydroxylated surface, we found that some of the PCE oligomers have identical adsorption energy
values like TIPA and TEA. This could explain that PCE are also effective grinding aid,
as they would maintain more mobility on the surface that might be expected. However, it
should be pointed out that PCEs used are generally larger and that the effect of PCEs of
more realistic structures would have to be investigated. On the other hand we also can note
that PCEs adsorption energy reduces on hydroxylated surfaces in comparison to dry C3S.
PCEs with higher anionic charge backbone have higher adsorption energy on C3S as could
be expected. It is also found that there is a dependence on the length of grafted chains,
but to a much lower extent. We hope that this work will motivate further research relating
atomistic simulations to problems of industrial relevance where clear opportunities for
innovation can be seen.

Effectiveness of Polycarboxylates as Grinding Aids 247

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