CEMENTand CONCRETERESEARCH. Vol. 9, pp. 473-482, 1979. Printed in the U.S.A.

0008-8846/79/040473-I0502.00/0 Copyright (c) 1979 Pergamon Press, Ltd.

ESCA.~ND SI~I STUDIES ON EARLY C3S HYDR%TION

D. M4n4trier, I. Jawed, T.S. Sun and J. Skalny

Martin ~rietta Laboratories
Baltimore, Maryland 21227

(Communicated by H.F.W. Taylor)

(Received April 26, 1979)

ABSTRACT
Electron Spectroscopy for Chemical Analysis CHSCA) and high-
resolution Scanning Electron Microscopy (S~I) have been used to
explore the phenomena occurring on the C3S* surface in the very early
stages of hydration. Definite changes in the surface morphology and
Ca to Si ratio were observed already after a few seconds of hydration.

La spectroscopie de photoelectrons (ESCA) et la microscopie

~lectronique ~ balayage (MKB) ont 6t~ utilise4s pour 6tudier les
ph~nom~nes qui se produisent A la surface du silicate tricalcique,
au cours des tous premiers instants de son hydratation. On observe
des changements de morphologie et du rapport CaO/SiO 2 apr~s
quelques secondes d'hydratation.

Introduction
Physico-chemical changes occurring in the C3S-H20 system in the pre-
induction stage of hydration, although extensively studied, are still not
well understood. This is due, in part, to experimental difficulties en-
countered in the sample preparation as well as to the inability of the
available instrtm~ntation to measure or detect the subtle changes occurring
in the very early stages of hydration. It is for this reason that "early
hydration" in many published reports means, at best, initiation of induction
period - approximately S minutes or more after contact with water, but often
as late as an hour or even longer [1,2).

* Cement nomenclature is used: C = CaO, S = Si02, H = H20

473
474 Vo!. 9, No. 4
D. M~n~trier, e t a ! .

The techniques of ESC~ and S~.I have gained wide application in the
surface studies of metallurgical and inorganic naterials. ~.ere are several
reports on the ESC& studies of silicates inciudin,~ calciL~u silicates 113-6).
However, study of the hydrated calciten silicate surface by memos of ESCq
and ST~[ seems to have received little attention (7-9). It is the purpose
of the present study to explore and establish the applicability of the ESC\
and higi~-resolution SK~I techniques to the surface hydration of C35. The
prelimina~T data reported herein are a part of a long range study, ti~e aim
of which is to explore the mechanism of calcit~ silicates hydration in
general and the early hydration of C3S in particular (I0).

Experimental

C3S was prepared by burning pre-calcined calcium carbonate and silicic

acid at 1650°C for 30 minutes three times, finely grinding the sintered mass
and rehomogenizing after each burn. ~ e sm,~.e batch of C3S was used for all
hydration experiments. XRD and DTA patterns showed the C3S to be triclinic
TII pol>~norph (Ii) with a free lime content below 0.4%.

C3S samples were hydrated both in paste and pellet forms. For paste
hydration, a w/c of 1.0 was used. The pellets, 0.5 mm thick and 12.5 ~n
in diameter, were prepared by pressing 200 mg of C35 powder at 500 kg/cm 2.
Just before hydration, the pellets were sintered at 1000°C for I hour to
remove impurities that possibly could have been adsorbed on the C35 surface
during preparation. This treatment resulted in an almost perfectly clean
and smooth surface as sho~m on S~I micrographs (Fig. i).

'r : ~" ! !
5urn l~m

Fig. 1 - Morphology of .~a~hvdrous

• C,S
.) Surface
Vol. 9, No. 3 475
ESCA, SEM, HIGH RESOLUTION,C3S, HYDRATION

The hydration of pellets does not reproduce the conditions of paste

hydration butwas chosen mainly on the basis of two experimental con-
siderations: (a) it is almost impossible to prepare a hydrated paste and
stop its hydration as early as 2-5 seconds and ~) the sensitivity of the
ESCA spectral peaks was found to be about 3 times higher for hydrated
pellets than for pastes.

For hydration, the pellets were placed on a wire holder, submerged in

2 ml water, withdrawn after selected periods of time ranging from 2 seconds
to 3 hours, and then immersed in acetone followed by drying in a vacuum
oven at 30°C. To avoid carbonation and further hydration, the samples,
thus obtained, were immediately sealed into the vacuum chamber of the ESCA
spectrometer. For SEM examination, they were stored in inert and dry
atmosphere.

A Physical Electronic Model $48 Auger/ESCA spectrometer featuring a

double pass cylindrical mirror analyzer and an ultra-high vacut~n system
(<5 x 10 -10 mm) was used (12). The X-ray source is a magnesium anode. The
sample is placed on an indium sheet. First, a low resolution spectrum
(2.5 eV)was recorded and then, for quantitative measurements, high resolu-
tion (0.6 eV) was used. X-ray photoelectron spectroscopy, commonly termed
ESCA, was preferred over Auger electron spectroscopy because the electron
beam used in the latter technique drastically damages the specimen surface.
Recent works by Hercules (13), Carriere and Deville (14) and Braun et al.
(15) have discussed this problem in detail; the latter two studies show a
progressive reduction of silicate ions by electron beams. The possibility
of some surface transformation even by X-ray irradiation cannot be com-
pletely ruled out as we did observe a color change in some samples. However,
this effect was almost negligible when compared to that caused by the electron
beam in Auger electron spectroscopy.

In order to quantitatively monitor the variation in Ca/Si ratio on

the hydrating C3S surface, a suitable calibration curve is necessary. Peak
areas of Ols, Ca2p and Si2p, located at 533, 345, and 103 eVrespectively,
were measured and a calibration curve of Ca2p/Si2p peak area ratio versus
chemical Ca/Si of CaSiO3, Ca2SiO4 and Ca3SiO S was constructed (Figure 2).

15- Fig. 2 - Calibration curve of

Ca2p/Si2p intensity ratio
0
m vs. Ca/Si chemical ratio

10-

5-

I I I
1 2 3
Ca I Si CHEMICAL RATIO
476 Vol. 9, No. 4
D. M4n~trier, et al.

The calibration was found to be linear only when the sample surfaces were
sputtered by an argon beam. It is well known that surface composition of a
"homogeneous" compound can be very different from the bulk composition,
depending on factors such as the thermodynamic properties of the compound,
the surface preparation, etc. (16). However, the composition of a sputtered
surface is generally proportional to the bulk composition and is relatively
independent of the initial surface condition (16,17).

For morphology studies, a JEOL J194-I00 CX Scanning Transmission Electron

Microscope (STIr) with bright and dark fields, microprobe and electron
diffraction capabilities was used. The unit can operate in scanning trans-
mission (STIr), transmissiono(TEM), and scanning (SE~0 modes. In the present
study, the SEM mode with 40 A resolution was used. Portions of the same
pellets were used for SEM and ESCA measurements.

Results and Discussion

ESCA Studies

High resolution ESCA spectra show definite changes on the C3S surface
upon contact with water. This is indicated by (a) the changes in the position
and the shape of the Ols peak, and Co) the intensity change in the Ca2p and
Si2p peaks.

The Ols line in sputtered C3S specimens is a symmetric peak, 2.7 eV

wide, with a binding energy of 532.9-+ 0.2eV. In unsputtered, anhydrous C3S
samples, it is slightly asy~netric and broader (3.2 eV), but with the same
binding energy. Upon hydration, the maximum of the Ols peak shifts toward
the higher binding-energy side and its line width increases. At about
I0 minutes of hydration, it becomes symmetrical and broader (3.5 eV), and
its binding energy increases to 533.5 +-0.2 eV. Afterwards, even up to 3
hours of hydration, the position and shape of the peak remain unchanged.
These observations are attributed to the fact there are more than one oxygen
species on the hydrated surface, and the new oxygen-containing species has
a higher binding energy prestmmbly due to the O-H bond (6). The broadening
of the Ols peak and the shift in its binding energy, therefore, reflect the
initiation and progress of C3S hydration. From this, the hydration is seen
to have taken place as early as 2 seconds after contact with water. In
fact, no matter how carefully the unhydrated specimen is prepared, its
surface always shows minute traces of hydrated species, as indicated by the
asymmetric shape of the Ols peak. Furthermore, formation of a hydrated
surfa&e layer with a depth approximately equal to the ESCA probing depth
(~20 •) appears to occur after about I0 minutes of hydration. Afterwards,
no more changes in the shape and binding energy of the Ols peak can be
observed because the hydrate layer is greater than the ESCA probing depth.

Fig. 3 shows typical results of the variation of Ca/Si on C3S

surface as a function of hydration time. As early as 2 seconds, the Ca/Si
drops to about 2.6-2.7. It then passes through a minimum at about 2.2-2.5
and increases to a maximum at about 2.8-2.9. From then on it continuously
decreases to a value of about 2.0 in 10 minutes and i. 5 at 30 minutes.
Afterwards, there is very little change even up to 3 hours. The times of
appearance of minima and maxima in the Ca/Si curves are not exactly
reproducible and probably depend, to a large extent, on the fineness and
change in reactivity of C3S. Qualitatively, similar data were reported
recently by Regourd et al. (7). The drop in Ca/Si in early seconds of
Vol. 9, No. 4 477
ESCA, SEM, HIGHRESOLUTION,C3S, HYDRATION

)20

2.75

_o 2.501

2.25

2.00

1.75

1.50 m

! t I i / / ~ I ,,L , I I ! ..... I
5 15 30 6o " 2 5 10 15 20 ~
(mint
TIME OF HYDRATION

Fig. 5 - Change in Ca/Si versus time of hydration

t
'E

m
v

.9

4Oc

l J * ,, , I I i
5 ]3 30 60 120 180 (sec)
TIMEOFHYDRATION

Fig. 4 - Effect of temperature on the Ca/Si versus time relationship

478 Vol. 9, No. 4
D. Menetrier

hydration does not confirm the views that first hydrates have aoCa/Si of 3
(18,19,20). Admittedly, the probing depth of ESCA is about 20 A and the
thickness of hydrated C3S , a~ least in the early seconds of hydration, is
believed to be less than 20 A. However, even with this uncertainty in the
Ca/Si, it is less than 3 in C-S-H according to present data, which is in
agreement with some recent views (21,22,23).

Fig. 4 shows the changes in the Ca/Si of the C3S surface as a function
of hydration time for two temperatures, 4 ° and 25°C. It is interesting
to note the differences in the position and shape of the Ca/Si curves at
these two temperatures. There are insufficient data to prove it but the
differences are believed to be related to the C3S solubility in water at
the temperatures studied and to the rate of nucleation of the initially
formed hydration products. The solubilities of Ca(OH) 2 and C-S-H, the
hydration products of C3 S, differ with temperature. For example, the pos-
sibility of nucleation and precipitation of Ca(OH) 2 at low temperatures is
reduced due to its higher solubility, and may account for a lower Ca/Si
at 4°C than at 250C.

Morphological Studies

Fig. 1 presents micrographs of unhydrated C3S surface at two magnifi-

cations. The absence of any particles or a leached (corroded) surface should
be noted. Fig. 5 shows the typical microstructures formed during the first
i0 minutes after contact of the C3S surface with water at 25°C. At'.30
seconds, formation or deposition on the surface of minute hydration products
is already visible and, at several places, "corrosion" of the surface
initiates. After 1 minute, the surface becomes much more damaged and a
larger amount (but not larger size) of hydration product forms. Subsequently,
after 5 and I0 minutes, the surface of C3 S particles is progressively leached
to greater depths. New hydration products are not seen, and those formed in
the initial stages do not appear to grow and are now barely visible on the
damaged background.

At approximately 15 minutes after the initiation of hydration, a

striking change occurs (Fig. 6). As seen in this sequence of stereo photo-
micrographs, a large number of minute particles, similar to but somewPmt
smaller than those formed during the initial seconds of hydration (Fig. 5),
form in ~he "corroded" surface. Their typical diameter is approximately
200-300 A, and the whole surface resembles the Type IV C-S-H morphology of
Diamond (24). At the same time, the formation of a "honeycomb" morphology
initiates. Higher magnification pictures (e.g., x 50,000) clearly show that
the layers forming this "honeycomb" do contain some of the small particles.
A f t e r 20 m i n u t e s , t h e s u r f a c e i s c o m p l e t e l y c o n v e r t e d t o t h e Type II o r
"honeycomb" C-S-H. This morphology is predominant up to 3 hours (extent of
present investigation) and is similar to that observed for C3S hydration in
the presence of CaCI 2 (2~,26). The typical "pore" in the "honeycomb"
structure is about 2000 A. At no time did we detect the formation of
acicular Type I C-S-H. It is of interest (even if not of direct consequence)
that the morphology of a hydrated aluminum surface very closely resembles
that obtained with C3S (27).
Vol. 9, No. 4 479
ESCA, SEM, HIGH RESOLUTION, C3S, HYDRATION

rl
30 sec I min

S min I0 min
Fig. S - High-resolution SI~;micrographs of
hydrated C3S surface; I t
0.5 um

The dramatic changes in the morphology of the hydrating C3S surface

at about 15 minutes are not associated with any sudden changes in the Ca/Si.
This is clearly seen from the ESCAdata showing only a minor decrease in
Ca/Si between i0 and 30 minutes of hydration. Rather, it seems, the
"honeycomb" is formed by layers peeling off the surface -- possibly from the
pressure of hydration products forming beneath. It is estimated that, at
30 minutes of hydration, the "honeycomb" layer is already several micrometers
thick.

The times given here for the various transformations at ZS°C are
typical for the particular C3S batch studied. However, it is probable that,
under different conditions, these will change somewhat.
480 Vol. 9, No. 4
D. M~n~trier, et al.

Fi~. 6
High-resolution stereo
S~Imicrographs of hydrated
C~S surface

10.S 1~m !

15 minutes

20 minutes

180 minutes
Vol. 9, No. 4 48l
ESCA, SEM, HIGH RESOLUTION,C3S HYDRATION

Conclusions

i. Present work demonstrates the applicability o r E SCA in the

hydration studies of cement systems. New information is obtained regarding
chemical changes on the C3S surface in the very early stages of hydration.
However, these changes are not well understood. The appearance of a minimum
and maximtln in the Ca/Si versus time curve is difficult to explain.
Nevertheless, the observed decrease in Ca/Si in the early seconds of
hydration does not indicate a first hydrate layer with Ca/Si = 3.
Significant differences in the Ca/Si on the hydrated C3S surface at two
different temperatures are observed. The influence of temperature on the
solubilities of C3S and its hydration products is indicated.
2. High resolution SI~4 has provided new information on the morphology
of C3S surface in the very early stages of hydration. After 30 seconds,
significant changes in the surface texture of C3S are observed. During the
time of present investigation (3 hours), a "honeycomb" morphology of the
Diamond Type II C-S-H is observed. However, at no time was acicular Type I
C-S-H morphology found.
Acknowledgements
The authors would like to acknowledge financial support by the
U.S. Army Research Office. One of the authors (D.H.) wishes to thank
NATO for a research grant. Experimental support by M. Meyerhoff and
D.K. McNamara, and critical review of the manuscript by H.F.W. Taylor and
W.A. Klemmis greatly appreciated.
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D. M~n~trier

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