7042 Ind. Eng. Chem. Res.

2006, 45, 7042-7049

APPLIED CHEMISTRY

Cement Hydration Inhibition with Sucrose, Tartaric Acid, and Lignosulfonate:

Analytical and Spectroscopic Study
Maximilienne Bishop and Andrew R. Barron*
Department of Chemistry and Department of Mechanical Engineering and Materials Science, Rice UniVersity,
Houston, Texas 77005

The reaction of the cement retarders tartaric acid, sucrose, and lignosulfonate with tricalcium silicate (C3S),
tricalcium aluminate (C3A), and C3A/gypsum have been studied by 27Al and 29Si MAS NMR spectroscopy,
SEM, XRD, and XPS to gain an understanding of the effect on the individual minerals prior to studying a
typical sample of portland cement. Tartaric acid is the most effective at retarding C3A hydration and ettringite
formation, while sucrose and the lignosulfonate accelerate ettringite formation but are more effective at retarding
C3S hydration. We have confirmed that sucrose acts via nucleation poisoning/surface adsorption while
lignosulfonates involve the formation of a semipermeable layer on the cement grains. The formation of calcium
tartrate is clearly the most important step in tartaric acid inhibition; however, tartaric acid only exhibits a
dissolution-precipitation mechanism for C3A. Under conditions of excess calcium, the formation of a calcium
tartrate overlayer does not require the predissolution of the mineral.

Introduction We have recently demonstrated that a fifth mechanism

In the oil industry, boreholes of ever increasing depth are
supported by portland cement. This application requires a high
degree of control over the setting kinetics to allow the cement
to be pumped down in a liquid form. A number of chemical
inhibitors are employed to delay the setting time. The ideal
inhibitor for oil well cementing would predictably delay the
setting of cement, and then suddenly allow hydration to continue
at a rapid rate.
Traditionally, four different cement hydration inhibition
mechanisms have been proposed to explain the action of
different retarders in cement.1 Calcium complexation involves
either removing calcium from solution by forming insoluble salts
or chelating calcium in solution to prevent calcium-silicon-
hydrate gel (C-S-H) formation.2 However, there is no simple
correlation between either calcium binding strength or calcium
salt solubility and retarding ability.3,4 Therefore, although
calcium complexation must play some role in inhibition, other
mechanisms of inhibition must be at work as well. Inhibition
by nucleation poisoning is where the retarder blocks the growth
of C-S-H or Ca(OH)2 crystals through inhibiting agglomerates
of calcium ions from forming the necessary nucleates.5 In a
related manner, surface adsorption of inhibitors directly onto
the surface of either the anhydrous or (more likely) the partially
hydrated mineral surfaces blocks future reactions with water.
Finally, the formation of a semipermeable layer on the cement
grains has been proposed to slow the migration of water and
lengthen the induction period. Osmosis will drive water through
the semipermeable membrane toward the anhydrous mineral,
and eventually the flow of water creates higher pressure inside
the protective coating and the layer bursts, allowing hydration
to continue at a normal rate.6
* To whom correspondence should be addressed. Tel.: (713) 348-
5610. Fax: (713) 348-5619. E-mail: arb@rice.edu.
10.1021/ie060806t CCC: $33.50 © 2006 American Chemical Society
Published on Web 09/07/2006
(“dissolution-precipitation”) occurs with the use of organic
phosphonic acids, in particular nitrilotris(methylene)phosphonic
acid (H6ntmp).7 Dissolution of calcium by extraction with H6-
ntmp exposes the aluminum-rich surface to enhance (catalyze)
hydration, followed by precipitation of a layered calcium
phosphonate that binds to the surface of the cement grains,
inhibiting further hydration by acting as a diffusion barrier to
water as well as a nucleation inhibitor. Based upon these results
we have investigated the analogous reactions of three traditional
inhibitors to determine if this new mechanism is prevalent in
these systems: sucrose, tartaric acid, and a lignosulfonate poly-
mer (Figure 1). Sucrose is widely believed to act as a nucleation
poison for C-S-H formation, whereas tartaric acid is known
to be a good calcium chelating ligand. Lignosulfonates are large,
anionic polymers that it is generally agreed retard hydration by
adsorption onto hydrating mineral phases,8 although intercalation
of large polymers into C-S-H has been proposed.9
The hydration of cement is obviously far more complex than
the sum of the hydration reactions of the individual minerals;
however, we have found that an understanding of the reaction
with the constituent parts assists in the overall understanding
of the system. In this regard, the reactions of sucrose, tartaric
acid, and a lignosulfonate polymer with tricalcium silicate
(3CaO‚SiO2, C3S), tricalcium aluminate (3CaO‚Al2O3, C3A)
in both the absence and presence of gypsum, and cement were
characterized by scanning electron microscopy (SEM), nuclear
magnetic resonance (NMR), X-ray diffraction (XRD), and X-ray
photoelectron spectroscopy (XPS). We have previously shown7
that the chemistry of dicalcium silicate (2CaO‚SiO2, C2S) with
retarders is substantially the same as that of C3S, as is that of
tetracalcium aluminoferrite (4CaO‚nAl2O3‚(2 - n)Fe2O3, C4AF)
similar to that of C3A, and therefore we have not been included
C2S and C4AF in the present study. In addition, the paramag-

Figure 1. Structural formulas of sucrose, tartaric acid, and the sodium
lignosulfonate monomer.
netic iron centers in C4AF further complicate NMR spectro-
scopic characterization.10
Experimental Section
Samples of C3S and C3A were obtained from Construction
Technology Laboratories, Inc., Skokie, IL. Class H portland
cement and the sodium lignosulfonate retarder were provided
by Halliburton Energy Services, Duncan, OK. All samples were
used as received and stored in a desiccator to reduce hydration
and carbonation in air. L-Tartaric acid and sucrose were
purchased from Sigma Aldrich (St. Louis, MO) and used as
received without further purification.
Stock solutions of 5 and 2.2 wt % of each retarder were
prepared by dissolving each retarder (2.2 or 5.0 g) in freshly
boiled and cooled water (100 mL). C3S and cement samples
for 29Si magic angle spinning (MAS) NMR were hydrated using
the 2.2 wt % solutions (0.45 mL per 1.0 g of solid) to create
pastes with 1.0 wt % retarder (relative to the weight of the dry
mineral) and were allowed to hydrate for 24 h, 1 week, and 2
weeks. C3A samples for 27Al MAS NMR were hydrated using
the 5 wt % solutions (0.3 mL per 1.0 g of solid) to create pastes
with retarder (1.5 wt % relative to the weight of the dry mineral)
and were immediately packed into ZrO2 rotors and hydrated
during NMR analysis. C3A (0.6 g) and gypsum (0.4 g) were
mixed together and then hydrated with 5 wt % solutions of each
retarder and immediately packed into ZrO2 rotors and hydrated
during NMR analysis. All samples for SEM imaging were
prepared using 5 wt % solutions (0.3 mL per 1.0 g of solid).
These samples were allowed to hydrate for the following
times: C3A, 4 h; C3A and gypsum, 6 h; C3S, 7 h; cement
clinker, 7 h. The differences in hydration times were based on
our prior solid-state NMR results that showed these to be the
optimum times for measurements of consistent hydration.7
SEM images were observed on a Philips XL-30 ESEM. The
samples were attached to a glass slide using carbon tape and
then sputtered with gold to reduce charging effects. Powder
X-ray diffraction studies were performed on a Siemens diffrac-
tometer. XPS analysis was performed at the University of
Houston on a PHI 5700 ESCA system with a 1 mm omnifocus
lens area, an aluminum anode at 400 W, 27-28 mA, and a
base pressure of 10-10 Torr.
NMR Spectroscopy. 13C{1H} CP/MAS NMR was performed
at 50.3 MHz on a Bruker Avance 200 NMR equipped for use
with a 7 mm o.d. ZrO2 rotor and a MAS spin rate of 5 kHz.
Spectra were collected using a 3.5 µs 90° 1H pulse, 1 ms contact
time, TPPM decoupling during the 33 ms flame ionization
Ind. Eng. Chem. Res., Vol. 45, No. 21, 2006 7043
detector (FID) length, and 5 s relaxation delay. Chemical shifts
were externally referenced to the glycine peak at 176 ppm.
Solid-state 29Si MAS NMR spectra were observed at 39.8
MHz on a Bruker Avance 200 spectrometer using a VTN probe
designed for use with a 7 mm o.d. ZrO2 rotor. A MAS spin
rate of 5 kHz was employed. Samples were studied using a 5.5
µs pulse based on 90° pulse width calibrations with hexameth-
ylcyclotrisiloxane. Chemical shifts were referenced to hexam-
ethylcyclotrisiloxane at δ ) -10.9 ppm. Spectra were collected
with a 30-60 s acquisition delay. FIDs were processed with 5
Hz line broadening.
Solid-state 27Al MAS NMR spectra were obtained at 52.1
MHz on a Bruker Avance 200 spectrometer equipped with two
probes designed for use with 7 and 4 mm o.d. ZrO2 rotors.
Samples were studied using 0.5 and 0.3 µs pulses for the 7 and
4 mm probes, respectively, based on 90° pulse width calibrations
with solid aluminum nitrate. MAS spin rates of 5 kHz (7 mm
rotor) and 9 kHz (4 mm rotor) were used. Spectra were collected
with a 0.1-1.0 s acquisition delay. FIDs were processed with
50 Hz line broadening. Samples were externally referenced to
the peak maximum of solid aluminum nitrate at δ ) -1.9 ppm.
The shift of solid aluminum nitrate on this instrument was found
by using an external reference of 1.0 M aqueous aluminum
nitrate at δ ) 0.0 ppm. Solid-state 27Al MAS NMR spectra at
130.3 MHz were obtained on a Bruker Avance 500 spectrometer
designed for use with a probe equipped with a 2.5 mm o.d.
ZrO2 rotor. Spectra were studied using a 0.3 µs pulse based on
90° pulse width calibrations with solid aluminum nitrate. A
MAS spin rate of 33.333 kHz was used. Spectra were collected
with a 0.5 s acquisition delay. FIDs were processed using 13
Hz line broadening.
Results
Reaction with C3S. When C3S is hydrated in the presence
of sucrose or lignosulfonate, the resulting paste is much more
watery than the paste hydrated in the absence of a retarder,
indicating that hydration is significantly inhibited. In contrast,
when C3S is hydrated in the presence of tartaric acid, the
resulting paste is unusually dry, suggesting that all of the water
is allowed to react with C3S and inhibition is not as significant
as for sucrose or lignosulfonate.
The hydration of C3S in the presence of different retarders
was followed by 29Si MAS NMR spectroscopy. All of the
retarders inhibit the hydration of C3S; however, the retarding
effects of sucrose and the lignosulfonate are more dramatic,
which is in agreement with the physical observation. Addition
of lignosulfonate (1% by weight of C3S) to C3S shows no
C-S-H formation after 2 weeks, whereas C3S hydrated with
either sucrose or tartaric acid (1% by weight) shows C-S-H
formation after just 9 days (e.g., Figure 2). The 13C{1H} CP/
MAS NMR of C3S hydrated with tartaric acid reveals that
calcium tartrate is formed (Figure 3). No silicon tartrate species
are seen.11
The Ca:Si ratios at the surface of the hydrating minerals were
determined by XPS (Table 1). C3S hydrated in the absence of
additives has a Ca:Si ratio of 2.6 after 7 h of hydration, which
drops to 2.4 after 1 week. The sample hydrated with sucrose
increases slightly during early hydration but then returns to the
same value as that for the anhydrous C3S. The lignosulfonate
begins with a normal Ca:Si ratio, but after 1 week of hydration
has a higher ratio (Table 1). In addition, a significantly higher
carbon percentage was observed for the lignosulfonate-retarded
samples compared to the other samples.
Reaction with C3A. Hydration of C3A in the presence of
tartaric acid results in a very watery sample relative to the pure
7044 Ind. Eng. Chem. Res., Vol. 45, No. 21, 2006

Figure 4. 27Al MAS NMR (52.1 MHz) spectra of C3A hydrated in the
presence of tartaric acid (1.5% by weight) for (a) 10 min and (b) 2 h. The
peak centered at 6 ppm is consistent with the formation of C2AH8 and
C4AH13.

Figure 2. 29Si MAS NMR spectra of C3S hydrated in the presence of (a)
tartaric acid (1% by weight) for 9 days and (b) sodium lignosulfonate (1%
by weight) for 2 weeks, showing the formation of C-S-H in the case of
tartaric acid but not sodium lignosulfonate.

Figure 5. 27Al MAS NMR (52.1 MHz) spectra of C3A hydrated with
sucrose and lignosulfonate for (a) 10 min and (b) 20 h. Spinning sidebands
are marked with asterisks (*).

[Al(OH)6]3- units allowing for hydration to be conveniently

followed by 27Al NMR spectroscopy. Although aluminum is
spin 5/2 and in general exhibits a large quadrupolar coupling
constant, several distinct species can be observed during
hydration.12,13 The chemical shifts of the intermediate hexagonal
phases, 2CaO‚Al2O3‚8H2O (C2AH8) and 4CaO‚Al2O3‚13H2O
(C4AH13), lie within 10 ppm of C3AH6; however, the transition
from the hexagonal phases to the cubic phase can be observed
Figure 3. 13C{1H} CP/MAS NMR spectra of (a) L-tartaric acid and (b) as an upfield shift even on a 200 MHz (27Al observed frequency
calcium tartrate formed from the reaction of C3S with L-tartaric acid. 52.1476 MHz) spectrometer. The highly distorted anhydrous
tetrahedral aluminum is difficult to observe on a 200 MHz
Table 1. Summary of XPS Data for C3S, C3A, and Portland
Cement Hydration after 7 h
instrument. The tetrahedral phase is not observed; however, the
growth of the intermediate hexagonal phases C2AH8 and
C3S C3A portland cement
C4AH13 and the subsequent downfield shift of this peak indicate
retarder Ca:Sia Ca:Al Ca:Si Ca:Al C3AH6 formation.
none 2.6 (2.4) 1.7 1.9 25 The 27Al MAS NMR spectrum of C3A hydrated in the
sucrose 3.6 (2.9) 1.7 2.1 3.0
tartaric acid 1.9 (2.0) 1.2 2.1 • presence of tartaric acid appears very noisy after 10 min (Figure
lignosulfonate 2.6 (7.4) 1.6 1.8 6.0 4a); however, a peak centered near 6 ppm grows in during the
H6ntmp7 1.8 (3.0) 12 3.8 78 first few hours of hydration (Figure 4b). This peak is consistent
a Values in parentheses after 1 week hydration. with the formation of C2AH8 and C4AH13. No signals were
observed for C3AH67,12 even after extended reaction times. 13C-
paste, indicating blocked hydration. Interestingly, C3A pastes {1H} CP/MAS NMR spectroscopy reveals that calcium tartrate
hydrated in the presence of either sucrose or the lignosulfonate is the only carbon-containing species present.
are also initially quite runny; however, after ca. 1 min, the pastes Initially, the 27Al MAS NMR spectrum of C3A hydrated in
set and become quite hard. The paste hydrated in the presence the presence of sucrose and the lignosulfonate polymer are
of sucrose is harder to the touch than the lignosulfonate paste. similar. Both reveal a peak centered at 7 ppm at the early stage
The aluminum coordination in C3A is distorted tetrahedral, of hydration (Figure 5), in addition to a peak centered near 78
whereas the aluminum in the hydration product, 3CaO‚Al2O3‚ ppm due to [Al(OH)4]-.14 In the case of sucrose, this peak does
6H2O (C3AH6) exists in highly symmetrical, octahedral not appear to change much during the first 24 h of hydration;
 Ind. Eng. Chem. Res., Vol. 45, No. 21, 2006 7045

Figure 7. 27Al MAS NMR (52.1 MHz) spectra of C3A hydrated with (a)
Figure 6. 27Al MAS NMR (52.1 MHz) spectra of C3A hydrated with excess gypsum and (b) in the presence of excess gypsum and sucrose (1.5
excess gypsum with tartaric acid (1.5% by weight) for (a) 10, (b) 30, and wt %) for 7 min. In the absence of retarder (a) the peak centered at 16 ppm
(c) 45 min showing the rapid formation of ettringite (δ ) 13 ppm). is due to partially hydrated calcium aluminates (C2AH8 and C4AH13).
Spinning sidebands are marked with asterisks (*).
Table 2. Summary of C3A Hydration in the Presence of Excess
Gypsum and Retarders
time to initial time for > 50%
retarder ettringite formation ettringite formation
none 10 min 15 min
sucrose <7 min <7 min
tartaric acid ∼45 min ∼45 min
lignosulfonate <7 min <7 min
H6ntmp7 <10 min >76 h

however, for the lignosulfonate sample a large amount of

C3AH6 is seen after 20 h.12,13
XPS analysis was performed on C3A hydrated in the presence
of sucrose, tartaric acid, and the lignosulfonate polymer (Table
1). Similar ratios are observed for pastes hydrated with sucrose
and lignosulfonate and for the C3A paste hydrated in the absence
of any additives. However, the Ca:Al ratio for tartaric acid is a
little low, indicating that there is more aluminum at the surface
of these particles.
Reaction with C3A in the Presence of Gypsum. The
hydration of C3A with excess gypsum in the presence of each
retarder was monitored by 27Al MAS NMR. In particular, time
to formation of ettringite [3CaO‚Al2O3‚3CaSO4‚32H2O] was
investigated. Table 2 summarizes the effect of the different
retarders on ettringite formation.
Tartaric acid is the most effective retarder at shutting down
ettringite formation (Figure 6). The spectrum of C3A hydrated
with tartaric acid (1.5% by weight) shows no octahedral complex
Figure 8. Powder X-ray diffraction pattern of C3A hydrated with excess
formation (characteristic of ettringite) during the first 30 min. gypsum for 3 h (a) without any additives and (b) with sucrose (1.5% by
After 45 min, an ettringite peak suddenly appears (Figure 6c). weight). Peaks due to ettringite (*), gypsum (φ), and anhydrous C3A (∆)
This sudden appearance of ettringite may indicate that all of are marked.
the tartaric acid has been consumed.
crystalline, but quantification in comparison to pastes hydrated
Hydration of C3A with excess gypsum with either sucrose without sucrose does not suggest a significant increase (Figure
or lignosulfonate reveals accelerated ettringite formation (Figure 8).
7). 27Al MAS NMR spectra observed after about 7 min hydration The SEM images of each sample support the 27Al MAS NMR
shows almost exclusively ettringite; there are no partially data and reveal needlelike ettringite formation in the presence
hydrated calcium aluminates (C2AH8 or C4AH13) as is of sucrose and lignosulfonate, but not in the presence of tartaric
observed for C3A/gypsum in the absence of a retarder (Figure acid (Figure 9). The ettringite formed in the presence of sucrose
7a). The amount of ettringite continues to increase with time. does not appear uniform in size, and is associated with much
Powder X-ray diffraction confirms that the ettringite formed is smaller particles.
7046 Ind. Eng. Chem. Res., Vol. 45, No. 21, 2006
Figure 9. SEM images of C3A and gypsum hydrated with (a) tartaric acid,
(b) sucrose, and (c) lignosulfonate after 4 h. The formation of needlelike
ettringite crystals is clearly seen for the samples containing (b) sucrose and
(c) lignosulfonate.
Reaction with Cement. Cement samples hydrated with
sucrose, the lignosulfonate, or H6ntmp form watery pastes
relative to cement hydrated without any additives. In contrast,
cement hydrated with tartaric acid is far less runny, and
maintains a consistency similar to the uninhibited paste. 29Si
MAS NMR confirms that all of these retarders inhibit C-S-H
formation, resulting in spectra that look like dry cement.
XPS was used to analyze the surface composition of cement
after 7 h of hydration in the presence of sucrose, tartaric acid,
and the lignosulfonate, all at 2.5 wt %. Table 1 summarizes the
XPS data from these samples and from the cement sample
hydrated with H6ntmp.7 The Ca:Si ratio for the uninhibited
cement paste is 1.9. The Ca:Si ratios for the samples hydrated
with sucrose, tartaric acid, and the lignosulfonate are all close
to this value, while a high Ca:Si ratio is observed for H6ntmp
Figure 10. SEM images of portland cement hydrated in the presence of
(a) sucrose, (b) tartaric acid, and (c) lignosulfonate.
inhibition.7 The Ca:Al ratio for the uninhibited hydrated cement
paste is high (Table 1), consistent with the low content of C3A
and C4AF in portland cement (ca. 20%). The Ca:Al ratios for
the samples hydrated with sucrose and the lignosulfonate
indicate that a far greater amount of aluminum is present at the
surface of these samples. In contrast, the sample hydrated with
tartaric acid has no detectable aluminum at the surface.
The SEM images of cement samples hydrated with each
retarder also emphasize the very different behavior of these
additives. The images of cement hydrated in the presence of
sucrose show regions where broad, flat ettringite rods are
growing out of a more amorphous grain coating (Figure 10a).
Images of cement hydrated in the presence of tartaric acid
show smooth regions with small, needle-shaped features and
round features on top of the grains (Figure 10b). Other re-
gions show evidence of a coating. In contrast, cement grains
hydrated in the presence of the lignosulfonate contain several

Figure 11. Schematic representation of the formation of calcium tartrate
during the hydration of C3A with tartaric acid showing the absorption of
tartaric acid onto the C3A surface, the release of calcium and aluminum
ions into solution, and the reaction of calcium ions with tartaric acid on the
C3A surface to form calcium tartrate.
regions that appear to have an amorphous, weblike coating
(Figure 10c).
Discussion
Sucrose. Sucrose has been reported to be the most powerful
retarding agent for a range of sugars,15 and an atomic force
microscopy study on its effects as an inhibitor has been recently
reported.16 The addition of too much sucrose will indefinitely
delay cement setting, which is undesirable in oil well cementing.
It is generally agreed that sucrose acts as a nucleation poisoner
in order to delay C-S-H formation, but the pathway by which
this occurs is less well understood. From our 29Si and 27Al MAS
NMR studies it is clear that sucrose reacts with C3S but not
directly with C3A, although, in the presence of gypsum, sucrose
catalyzes the hydration of C3A (see Table 2). Potentially either
a nucleation poisoning/surface adsorption or calcium chelating
mechanism may explain the inhibition of hydration.
Sucrose is known to undergo ring-opening reactions at high
pH,17 and some of these ring-opened complexes are capable of
coordination to ions such as Ca2+. However, Thomas and
Birchall found that sugars with pentose units (such as sucrose)
were more effective retarders than reducing sugars that are more
prone to ring-open to form calcium chelating agents.5 Since C3S
reacts with water to form calcium hydroxide, in addition to
C-S-H (eq 1),18,19
2(3CaO‚SiO2) + 7H2O f 3CaO‚2SiO2‚4H2O + 3Ca(OH)2
(1)
hydration would be enhanced by complexation of the liberated
calcium by sucrose, as is observed for tartaric acid (see Figure
2 and Table 1). Such a reaction would also result in the reduction
of the Ca:Si ratio, and this result is not observed (Table 1).
Thus, we may propose that sucrose does not inhibit hydration
through the formation of soluble calcium complexes.
Thomas and Birchall reached the same opinion,5 but based
their conclusion on the suggestion that sucrose binds calcium
in a monodentate fashion (i.e., Ca-OR) rather than the more
normal multidentate complexation.20 It was proposed that
monodentate Ca-OR moieties were more likely to incorporate
Ind. Eng. Chem. Res., Vol. 45, No. 21, 2006 7047
Figure 12. Schematic representation of cement hydration in the presence
of tartaric acid. The aluminate (and aluminate ferrate) phases surround the
silicate phases (C3S and C2S). Tartaric acid adsorbs onto the aluminum
surfaces and reacts with calcium ions from gypsum to deposit a thick calcium
tartrate coating on the cement grain.
into growing Ca-O crystallites than the bi- or tridentate
complexes and thus poison the nucleation of C-S-H. Based
upon the known coordination chemistry of calcium, we must
disagree with this proposal. Calcium alkoxides (Ca-OR) are
only observed to be monodentate where the ligands are of
sufficient steric bulk to inhibit further coordination.21 However,
as is observed for other multidentate ligands,20,21 calcium will
readily form complexes with both 1,2-diols and 1,3-diolssboth
of which are present in sucrose (see Figure 1a). Furthermore,
calcium alkoxides are ordinarily oligomeric and insoluble rather
than simple soluble monometallic complexes.22 Given the
foregoing, we propose that the hydration inhibition activity of
sucrose is most likely a surface adsorption/nucleation poisoning
mechanism through the formation of surface-bound oligomeric
calcium alkoxides. If surface adsorption were the only reaction
occurring, then inhibition of C3A should happen to the same
extent as that of C3S since their surfaces should not be
differentiated; however, this is not observed.
In the absence of any additives, C3A reacts with water to form
two intermediate hexagonal phases, C2AH8 and C4AH13 (eq 2),
2(3CaO‚Al2O3) + 21H2O f 4CaO‚Al2O3‚13H2O +
2CaO‚Al2O3‚8H2O (2)
both of which are metastable phases and spontaneously trans-
form into the fully hydrated, thermodynamically stable cubic
phase, C3AH6 (eq 3).
4CaO‚Al2O3‚13H2O + 2CaO‚Al2O3‚8H2O f 2
(3CaO‚Al2O3‚6H2O) + 9H2O (3)
In neither eq 2 nor eq 3 is calcium liberated, suggesting that
free calcium is important to the inhibition of hydration for C3S.
Thus, we can propose that for the inhibition of C3S an initial
hydration occurs, yielding Ca2+ which complexes with sucrose
7048 Ind. Eng. Chem. Res., Vol. 45, No. 21, 2006
Table 3. Summary of the Behavior of Various Hydration Retarders
retarder
sucrose Ca binding, acts directly on silicates, accelerates ettringite formation
tartaric acid acts via calcium complexation and calcium tartrate coating, inhibits ettringite formation
lignosulfonate accelerates ettringite formation, calcium becomes incorporated into the polymer matrix during hydration, forms a diffusion barrier
H6ntmp7 promotes Ca dissolution, forms [Ca(H4ntmp)], heterogeneous nucleation on aluminates creates a protective coating around the grain
to form oligomeric calcium alkoxides, which act via poisoning
the nucleation of C-S-H.
As has been previously reported,23 we have observed that in
the presence of sucrose C3A reacts directly with gypsum to form
ettringite. In fact, the reaction rate is significantly increased by
the addition of sucrose (Table 2). The ability of sucrose to com-
plex calcium may explain the accelerated ettringite formation
in C3A/gypsum pastes hydrated with sucrose, since complex-
ation of soluble calcium would liberate sulfate that could in
turn react with C3A to initiate ettringite formation (eq 4).
3CaO‚Al2O3 + 3(CaSO4‚2H2O) +
26 H2O f 3CaO‚Al2O3‚3CaSO4‚32H2O (4)
It should be noted that the accelerated formation of crystalline
ettringite should not delay the setting of cement, and therefore
it is the direct interaction of sucrose with the silicate phases
that causes hydration inhibition.
Tartaric Acid. The behavior of tartaric acid is very different
from that of sucrose. Tartaric acid is a known calcium chelating
ligand, and the resulting complex is only sparingly soluble in
water (0.266 g‚L-1).24 In the solid state the structure is that of
an extended network in which each tartrate is coordinated to
four calcium ions, while the coordination sphere of each calcium
ion consists of four tartrate ions and two water molecules.25 It
should be noted that unlike the dense layered structure of [Ca-
(H4ntmp)(H2O)]∞,7 which limits water diffusion, the structure
of calcium tartrate is a relatively open three-dimensional
structure. In addition to chelating calcium, tartaric acid has a
high affinity for aluminum, and is capable of coordinating to
octahedral aluminum in moderately acidic solutions and tetra-
hedral aluminum in moderately basic solutions. Above pH 11.5,
the tetrahedral aluminum tartrate complex dissociates into the
free ligand and [Al(OH)4]-.26 Tartaric acid also forms a 3:1
complex with octahedral aluminum in basic solutions. This
complex is stabilized by calcium ions in solution.27 Despite the
possibility of aluminum tartrate, calcium tartrate is the only
complex formed in both C3S and C3A pastes.
In contrast to sucrose, tartaric acid does not completely inhibit
the hydration of C3S. The liberated calcium from the hydration
of C3S (eq 1) is acquiesced by tartaric acid, and the formation
of calcium tartrate is confirmed by 13C{1H} CP/MAS NMR.
Calcium tartrate is also formed from the reaction of C3A with
tartaric acid. However, in this case, the hydration only proceeds
partway. While C2AH8 and C4AH13 are formed, there is no
evidence for the formation of C3AH6, suggesting that the
blocked hydration of the aluminate phase must be due to the
presence of calcium tartrate at the surface of the aluminate
particles. Calcium complexation would also explain the apparent
initiation period for the formation of ettringite. Once the gypsum
has consumed all tartaric acid, any remaining gypsum is free
to react with the C3A.
Calcium tartrate has a low solubility in water and is expected
to adsorb onto the surface of any mineral particles. To explain
why tartaric acid is more effective at blocking C3A hydration
than C3S hydration, we propose that tartaric acid appears to
have a greater affinity for hydrated aluminate surfaces than for
hydrated silicate surface. Calcium tartrate growth from an
characteristic behavior
aluminate surface would also explain the lack of aluminum at
the surface of hydrating cement pastes, as the aluminum would
be buried under a layer of calcium tartrate (Table 1). Conversely,
XPS of C3A hydrated with tartaric acid reveals extra aluminum
at the surface (Table 1). We propose the following models to
explain the observed analytical and spectroscopic data.
In C3A, the mineral must be partially dissolved before
calcium can react with tartaric acid. Tartaric acid may be more
likely to directly adsorb onto the surface of hydrating C3A under
these conditions, blocking the reaction with water and making
C3A pastes very runny. A simple schematic of this process is
shown in Figure 11. This process is clearly related to the
“dissolution-precipitation” mechanism proposed for organic
phosphonic acids.7 That is, dissolution of calcium by extraction
with tartaric acid (exposing the residual aluminum) is followed
by precipitation of a layered calcium tartrate that binds to the
surface of the C3A grains, inhibiting further hydration. The Ca:
Al ratio will be reduced compared to the C3A since not all the
calcium dissolved by tartaric acid will be precipitated on the
grains.
As represented, as a schematic form, in Figure 12 cement
grains generally consist of smaller C3A and C4AF particles
surrounding C3S and C2S particles. In cement pastes, there are
more calcium ions available to react with tartaric acid, from
both gypsum and C3S, which would increase the rate of calcium
tartrate formation. This would result in a thicker layer of calcium
tartrate being formed on the mineral particles and the observed
XPS analysis.
Lignosulfonates. Lignosulfonates have been used as oil well
cement retarders for many years. Although the exact mechanism
of lignosulfonates retarding the set of portland cement is not
well understood, it has been postulated that the mechanism is a
combination of adsorption and nucleation.28,29 Studies have
shown sulfonate and hydroxyl groups adsorb onto the C-S-H
gel layer of the hydrating cement. This fact has led to the
hypothesis that the sulfonate and hydroxyl groups present in
lignosulfonates allow them to adsorb onto and, consequently,
incorporate into the C-S-H gel layer, causing a change in the
morphology of the C-S-H gel and leading to a more
impermeable structure. This causes a type of waterproofing
effect slowing further hydration. Our observed data are con-
sistent with this model. The SEM images and the high amount
of carbon at the surface of the C3S particles (as measured by
XPS) indicate that adsorption of the polymer onto the particles
is likely. We can also postulate that the increase in the observed
Ca:Si ratio at the surface of the hydrated mineral grains is
indicative of increased calcium incorporation into the lignosul-
fonate polymer matrix through the formation of the calcium
(as opposed to the sodium) salt of the lignosulfonate.
Although lignosulfonates have been shown to adsorb very
strongly to hydrated C3A, there is a large amount of C3AH6
seen after 20 h. Thus, while the effect of lignosulfonates on the
C3A hydration should not be discounted, lignosulfonates
predominantly affect the hydration kinetics of C3S.30 The
observation of catalyzed formation of ettringite is presumably
a function of the templating ability of the lignosulfonates, since
it is known that small anions can substitute for sulfate anions
in ettringite,31 and also that small organic sulfonates form

lamellar structures when incorporated into hydrated calcium
aluminates.32 Thus, the larger polyanionic lignosulfonates may
be capable of enhancing ettringite formation by providing a large
anionic template around which the calcium aluminate columns
can form.
Conclusions
Table 3 summarizes the data for hydration in the presence
of sucrose, tartaric acid, and the lignosulfonate in comparison
with the results previously reported for H6ntmp.7 Tartaric acid
is the most effective at retarding C3A hydration and ettringite
formation. In contrast, sucrose and the lignosulfonate accelerate
ettringite formation but are more effective at retarding C3S
hydration. All are effective at stopping cement hydration;
however, each appears to act by a different mechanism.
Our study confirms the previous proposals on the mechanism
by which sucrose and lignosulfonates retard cement hydration.
Thus, sucrose acts via nucleation poisoning/surface adsorption
while lignosulfonates involve the formation of a semipermeable
layer on the cement grains. However, we propose that sucrose
relies on calcium complexation to initiate the formation of
calcium-sucrose complexes that provide surface adsorption and
nucleation poisoning.
The formation of a calcium complex is clearly the most
important step in tartaric acid inhibition. However, in a manner
similar to that observed for the organic phosphonic acids (e.g.,
H6ntmp),7 the calcium tartrate forms a semipermeable layer on
the cement grains, inhibiting further hydration. However, in
contrast to the phosphonic acids, tartaric acid only exhibits our
dissolution-precipitation mechanism for C3A (or cement in the
absence of gypsum). Under conditions of excess calcium, the
formation of a calcium tartrate overlayer does not require the
predissolution of the mineral surface.
Acknowledgment
Financial support for this work was provided by Halliburton
Energy Services. The Bruker CCD Smart System Diffractometer
of the Texas Center for Crystallography at Rice University was
purchased with funds from the Robert A. Welch Foundation.
The Bruker Avance 200 and 500 NMR spectrometers were
purchased with funds from ONR Grant N00014-96-1-1146 and
NSF Grant CHE-9708978, respectively.
Nomenclature
C-S-H ) calcium-silicon-hydrate gel
C3A ) tricalcium aluminate (3CaO‚Al2O3)
C4AF ) tetracalcium aluminoferrite (4CaO‚nAl2O3‚(2 - n)-
Fe2O3)
C2S ) dicalcium silicate (2CaO‚SiO2)
C3S ) tricalcium silicate (3CaO‚SiO2)
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ReceiVed for reView June 23, 2006
ReVised manuscript receiVed August 7, 2006
Accepted August 10, 2006
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