Cement and Concrete Research 32 (2002) 789 – 793

Effects of temperature on the hydration characteristics of free lime

Huisheng Shi*, Yujing Zhao, Wenwen Li
State Key Laboratory of Concrete Materials Research, Tongji University, Shanghai 200092, People’s Republic of China
Received 23 January 2001; accepted 10 December 2001

Abstract

The rate of heat evolution of hydrating CaO has been determined quantitatively by means of a conductive microcalorimetry, and the
hydration kinetics of CaO has been studied. Some regularity of the influence of temperature on the hydration characteristics of free lime
(f-CaO) has been discussed as well. Based on the present research, the mechanism of effects of temperature in the calcining process and the
hydration process on the hydration of CaO has been illustrated. D 2002 Elsevier Science Ltd. All rights reserved.

Keywords: Temperature; Calorimetry; Hydration; Kinetics; Microstructure

1. Introduction serious. It demonstrates that the disappearance of f-CaO is

closely related with the ambient temperature.
The most outstanding characteristic of cement-based In this paper, the influence of calcination temperature on
materials is that they need two technology processes (cal- the hydration activity and microstructure of CaO crystals,
cination and hydration) in contrast to glasses, ceramics and the influence of environmental temperature on the hydrating
other inorganic nonmetallic materials. Temperature is of rate of CaO and the hydration kinetics during its hydration
great importance in the calcination of cement clinker, the process have been studied by means of conductive micro-
hydration of cement and the formation of cement stone. Free calorimetry, X-ray diffraction and other techniques. The
lime (f-CaO), as a composition phase of Portland cement mechanism of the effect of temperature on the hydration
clinker, has great effect on some properties of cement, es- characteristics of f-CaO has also been investigated.
pecially on it soundness [1 –7]. Besides the content of f-CaO
in the cement, the soundness of the cement also depends
greatly on the hydration activity of the f-CaO [6,7]. That is, 2. Experimental
it is closely related to the calcination temperature of the
clinker. The hydration activity of f-CaO formed under 2.1. Materials and preparation of samples
different conditions is variable, so the soundness of the
cement must be tested and cannot be predicted reliably from An analytical pure CaCO3 reagent and an industrial
the f-CaO content. Industrial practice has showed that, even limestone powder were used in this work. The powders
when produced in the same kiln and under the same were pressed into cylinders (F 40
5 mm) under a pressure
conditions, the rate of disappearance of f-CaO in cement of 25 MPa, fired at different temperatures for 1 h in a high-
clinker is affected by the ambient temperature. In some temperature electric furnace and then cooled rapidly in air to
factories with shaft kiln operated in China, the clinker provide a series of sample of pure CaO and industrial CaO.
produced in winter has to be stored because the dispelling The chemical composition of the industrial limestone is
rate of f-CaO is very slow. Thus, normal production and shown in Table 1.
working capital are affected. In summer, the matter is not as
2.2. Determination of hydration activity

* Corresponding author. Tel.: +86-216-598-2462; fax: +86-216-598-

The heat of hydration of CaO determined by means of an
5385. improved RD-I conductive microcalorimetry is regarded as
E-mail address: shs@mail.tongji.edu.cn (H. Shi). the characteristic of hydration activity in this research.

0008-8846/02/$ – see front matter D 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 8 - 8 8 4 6 ( 0 2 ) 0 0 7 1 4 - 7
790 H. Shi et al. / Cement and Concrete Research 32 (2002) 789–793

Table 1
Chemical composition of limestone (%)
IL SiO2 Al2O3 Fe2O3 CaO MgO
42.49 0.85 1.12 0.29 54.55 0.82

Generally, the fineness of each specimen was almost the

same, and a fixed w/c ratio (w/c = 2.5), constant hydration
temperature ( ± 0.1
C) and sample mass (1 ± 0.0001 g) and
internal mixing were adopted in the test. Some special cases
would be illustrated separately in this paper.

2.3. Determination of crystal microstructure

Based on the X-ray diffraction line-broadening effect,

approximate functional methods were used to determine the
crystal grain size and crystal lattice [8]. Testing conditions
were as follows: Rigaku X-ray diffractometer made in
Japan, CuKa radiation, 40 kV/100 mA, DS 1
, SS 1
, RS Fig. 2. Rate of heat evolution of industrial CaO calcined at 1300 and
1450
C.
0.3 mm, graphite diffracted beam monochromators, step
scanning, step length 0.02
, counting time 2 or 4 s. The
tions. When the CaO in a high-energy state comes in to
diffraction peaks of the following crystalline planes of CaO
contact with water, the following reaction occurs [9]:
were determined: (111), (200), (220), (311), (222), (400),
(331), (420), (511), (440) and (531). All the data were CaO þ H2 O ! CaðOHÞ2
handled by special software. The crystal parameters of CaO
were determined under the same conditions. The Ka1 and
DH296 ¼ 15; 620 cal=mol ð65:40
103 J=molÞ
Ka2 doublets were separated, and the crystalline cell param-
eters of CaO were calculated according to the peak position Figs. 1 and 2 show the heat evolution curves during the
2q of individual peak Ka1 and d of crystalline plane (531). hydration of pure CaO and industrial CaO calcined at various
temperatures, respectively. The magnitude of the peaks and
the times at which they were observed are presented in Table
3. Experimental results and discussion 2. As shown in Fig. 1 and Table 2, with increase of firing
temperature, the rate of heat evolution of pure CaO decreases
3.1. The influences of firing temperature considerably. For the CaO calcined at 1100
C, the highest
rate of heat evolution was reached after only 2 min, the
CaO and other minerals in cement clinker are unstable hydrating reaction would be completed after about 21 min
products of high-temperature physical and chemical reac- and the rate of heat evolution tended towards zero at that
time. In contrast, for the CaO calcined at 1300
C, the
highest rate of heat evolution was reached after 5 min.
The rate of heat evolution tended to zero after 27 min. For
the CaO calcined at 1500
C, the highest rate of heat
evolution is just about 1/6 of that calcined at 1100
C. The
magnitude of the largest heat evolution peak is far lower than
that of the CaO calcined at lower temperature. The heat

Table 2
Rate of heat evolution of CaO fired at various temperatures and time
at which
Heat evolution Time of
Firing Time at hydration
temperature Maximum maximum termination
Sample (
C) rate (w/g) rate (min) (min)
Pure CaO 1100 3.144 2.0 21.1
1300 1.872 5.0 27.4
1500 0.571 18.2 79.2
Fig. 1. Effect of firing temperature on the rate of heat evolution of Industrial CaO 1300 0.754 3.7 > 240
pure CaO. 1450 0.557 5.1 >240
 H. Shi et al. / Cement and Concrete Research 32 (2002) 789–793 791

evolution curve becomes smoother and flat, and the duration

of heat evolution becomes longer. The time for the whole
heat evolution process is almost four times longer than that
of CaO calcined at 1100
C. It shows that the CaO calcina-
tion temperature has a great effect on its hydration activity.
Similar to the f-CaO in clinker, the industrial CaO contains
small amounts of SiO2, Al2O3, Fe2O3 and other oxides.
Consequently, the hydration activity is lower than that of
pure CaO [7]. Nevertheless, the regularity of the influence of
firing temperature on hydration activity is similar, which can
be seen from Fig. 2 and Table 2. The highest rate of heat
evolution of industrial CaO calcined at 1450
C is remark-
ably lower than that calcined at 1300
C. The study shows
whether pure CaO or industrial CaO is considered. Their
hydration activities have been greatly affected by the firing
temperature. Raising the calcination temperature decreases Fig. 3. Crystalline cell parameter of CaO vs. firing temperature.
the hydration activity of CaO.
The hydration activity and other properties of Portland structure of CaO. The CaO when first decomposed from
cement depend on the microstructure of the clinker, that is, CaCO 3 retains the typical rhombohedral structure of
they depend on the microstructure of each phase in the CaCO3, and the crystal lattice is rather imperfect. There
clinker. The clinkers with identical chemical or mineral are more vacancies and defects in the crystal structure, so
composition may have very different hydration activities the structure is loose and the crystallite size is small. With
and hydraulic characteristics because of their various micro- rise of temperature, the crystals of CaO grow and change to
structures. It can be seen from the study of the crystal the cubic structure.
microstructure of pure CaO that the microstructure of CaO The essence of crystal growth is atomic transition. Grain
crystals is closely related to the calcination temperature. As growth results from grain boundary removal. The difference
shown in Table 3, when the firing temperature is raised, the in the free enthalpy of material on the two sides of a grain
crystallite size of CaO increases rapidly. It is almost by an boundary is the driving force that makes the boundary move
order of magnitude greater at 1500
C than that at 1100
C. toward its center of curvature. Raising calcination temper-
Moreover, when the firing temperature is increased, the ature increases the average atomic vibration energy and
growth rate of CaO crystallites also increases. Over the accelerates the transition of atoms, resulting in a faster speed
temperature range of 1100 – 1300
C, the crystallite size of migration of the grain boundaries. At the same time, the
only increases by about 150 nm, but over the temperature array of atoms in the crystal lattice tends to become more
range of 1300– 1500
C, it increases by about 500 nm. In regular and the imperfections become less. Therefore, the
addition, with the increase of firing temperature, the array of lattice distortion and cell parameter reduce. The smaller the
atoms in the crystal becomes more regular, the defects crystallite, the more crystal imperfections, the larger the area
present in the crystal are evidently reduced and the lattice of crystal boundaries and the lattice distortions and the
distortion also decreases. As shown in Fig. 3, the higher the higher the free energy in the crystal surfaces, so the more
calcining temperature, the denser the crystal structure and
the more perfect the crystal lattice, so the smaller the cell
parameter of CaO. Furthermore, from the slope of the curve
in Fig. 3, one can see that the curve over the range of
1300 – 1500
C is steeper than that over the range of
1100– 1300
C. It shows that the changing rate of the cell
parameter increases with the rise of temperature, which is in
accordance with that of the crystallite size. The higher the
firing temperature, the greater the influence on the micro-

Table 3
Crystallite size and lattice distortion of CaO
Firing Lattice
temperature Firing Crystallite distortion
(
C) time (h) size (nm) (%)
1100 1 86 0.09
1300 1 233 0.06
1500 1 738 0.04 Fig. 4. Rate of heat evolution of pure CaO at various temperatures.
792 H. Shi et al. / Cement and Concrete Research 32 (2002) 789–793

Fig. 6. Plot of maximum rate of heat evolution (ln W) vs. 1/T.

purities is larger than that of pure CaO. With the increase of

Fig. 5. Rate of heat evolution of industrial CaO at various temperatures.
hydrating temperature, the duration of heat evolution
decreases remarkably. The duration of the total heat evolu-
unstable the crystal structure. When it reacts with water, the
tion of pure CaO during hydration decreases from 0.83 h at
CaO with such structure shows higher reactivity. The essence
12
C to 0.36 h at 50
C, whereas that of industrial CaO
of the effect of firing temperature on the hydration activity of
decreases from 7.1 h at 12
C to 2.0 h at 50
C.
CaO is to change its microstructure. The difference in the
The rate of heat evolution of CaO increases with the rise
microstructure of CaO fired at various temperatures results in
of reaction temperature, which shows that the hydration
its different hydration activity. The hydration activity of CaO
reaction rate also increases with the rise of hydrating
is a macroscopic reflection of its microstructure.
temperature. According to the Law of Boltzmann distri-
bution, the rate in a physical or chemical reaction process
3.2. Hydrating temperature and hydration kinetics
has a relationship with temperature, as follows (Eq. (1)):
 
Figs. 4 and 5 show the rate of heat evolution of pure CaO N Ei
and industrial CaO calcined at 1500
C at various hydrating Ni ¼ exp  ð1Þ
Z KT
temperatures, respectively. Table 4 gives the magnitude of
the peaks and the times at which they were observed. From where N is the total number of molecules, Ni is the number
Figs. 4 and 5 and Table 4, one can see clearly that whether of molecules with energy Ei, K is Boltzmann’s constant, T is
pure CaO or industrial CaO containing certain impurities. the absolute temperature and Z is the partition function.
Their rate of heat evolution accelerates with the increase of For CaO + H2O ! Ca(OH)2, the reaction rate also fol-
hydrating temperature. The maximum rate of heat evolution lows the Arrhenius equation:
of pure CaO increases from 1.736 w/g at 12
C to 4.585 w/g
at 50
C. The increase is even more obvious for industrial k ¼ AeEa =RT ð2Þ
CaO from 0.144 w/g at 12
C to 0.905 w/g at 50
C. An where k is the reaction rate constant, A is the Arrhenius
increase of more than sixfold is observed. The experimental factor, Ea is the activation energy, R is the universal gas
results show that the influence of hydrating temperature on constant and T is the absolute temperature.
the rate of heat evolution of industrial CaO containing im- Suppose the reaction rate is in direct proportion to the
rate of heat evolution. That is
Table 4
Maximum rate of heat evolution of CaO at various temperatures k ¼ BW ð3Þ
Maximum rate Time at
Temperature of heat evolution maximum where B is a proportionally constant and W is the rate of heat
Sample (
C) (w/g) rate (min) evolution. Substituting Eqs. (2) and (3) and taking the
Pure CaO 12 1.736 7.1
25 2.892 5.9 Table 5
40 3.694 3.4 Parameters of hydration kinetics of CaO at heat evolution reaction
50 4.585 1.5
Industrial CaO 12 0.144 72.0 Sample Ea (R) ln C Ea (J/K mol)
30 0.688 13.7 Pure CaO 14.25 1.710 1.714
50 0.905 6.9 Industrial CaO 29.64 0.546 3.565
 H. Shi et al. / Cement and Concrete Research 32 (2002) 789–793 793

logarithm, we have Eq. (4): the crystallite size of CaO crystals increases, while the
lattice distortion and crystal cell parameters decrease. The
Ea more perfect the lattice of CaO and the denser its structure,
lnW ¼ lnC  ð4Þ
RT the lower the free energy of the crystal surfaces and the
where C = A/B. lower the hydration activity of CaO. The hydration activity
According to the maximum rate of heat evolution of CaO of CaO is a macroscopic reflection of its microstructure.
in Table 4, taking linear regression (see Fig. 6), we can The hydration rate of CaO is closely related to the
calculate the activation energy of the hydrating reaction of hydration reaction temperature. Raising the hydration reac-
CaO (see Table 5). Table 5 shows that, for the hydration tion temperature can make the reactant obtain enough
reaction of CaO, the activation energy of industrial CaO energy to surmount reaction the potential barrier, thus
containing impurities is twice as much as that of pure CaO. increasing reaction rate effectively. The effect of the hydra-
For the material with high activation energy, higher energy tion reaction temperature on CaO with high activation
is needed for the creation and continuation of reaction. At energy and some impurities is more obvious than that on
the same temperature, the hydration rate of industrial CaO pure CaO. The f-CaO in Portland cement clinker forms in
with high activation energy is lower than that of pure CaO coexistence with many other oxides coexists. Thus, it has
with low activation energy. Rising reaction temperature higher hydration activation energy, so the ambient temper-
increases the average kinetic energy of Ca2 + and OH  ature has a great influence on the disappearance and
(or CaO and H2O molecules), accelerates their diffusion rate hydration rate of CaO.
in solution and increases their mutual collision frequency.
Besides, at higher temperature, more ions have enough
energy to form an activated complex when they collide Acknowledgments
with other ions. Therefore, raising temperature can increase
both collision energy and collision frequency. Thus, the This research is supported by the University Key Studies
reaction rate increases greatly, which has been confirmed by protects of Shanghai.
our experiment. With the increase of reaction temperature,
the rate of heat evolution of CaO increases rapidly and the
duration of the maximum rate of heat evolution and the References
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