The effect of free lime on the hydration kinetics and rheology of

cement mortar

O. Wallevik1, P. Sandberg2, K. Kjellsen3, H. Svavarsson4, S. Kubens1

1
IBRI, Reykjavik, Iceland; 2W. R. Grace, Cambridge, USA; 3Norcem,
Brevik, Norway; 4Reykjavik University, Iceland

Abstract
The effect of free lime on the hydration kinetics and rheology of cement
mortar was investigated by the addition of CaO “fresh” and “aged” to a
portland cement with and without fly ash. The rheology of fresh cement
mortar was measured using the Rheomixer, a novel rheometer that mixes
and measures rheology in a single operation. The cement hydration
kinetics was monitored using an isothermal conduction calorimeter. The
effect of added free lime on the pore solution was measured on parallel
samples. The results indicate that free lime can have substantial effect on
the cement hydration kinetics while the effect on rheology measured on
fresh cement mortar was less. However, the reactivity of free lime is
sensitive to ageing.

1. Introduction
The introduction of carbon dioxide taxes in Europe has accelerated the
development of low clinker blended cements. A common performance
issue with fly ash blended cements is longer setting times in concrete and
mortar compared to mixtures with straight portland cement, especially
during the winter season. The free lime (CaO) content of cement is known
to influence the setting time [1] and could potentially be used to offset the
longer setting times caused by increased clinker substitution. This paper
presents results on the use of elevated levels of free lime (burned lime) as
a setting time accelerator in an experimental blended fly ash cement and
the corresponding effect on hydration kinetics and rheology in mortar with
different concrete admixtures.

1.2 Equipment and methods used in this study

Rheomixer
The Rheomixer is a novel rheometer that mixes and measures rheology of
mortar in one operation. It logs the torque (T) values at various rotation
velocity (N). As cement based particle suspensions are non-Newtonian
fluid, the simplest relation between torque (or stresses) and rotation
velocity (or shear rate) is the linear with an intercept at the torque axes.
This is often named Bingham behavior of the mortar or concrete.
Generally, with few exceptions, mortar and concrete can be characterized
as Bingham materials [2]. The relation between the torque, T and velocity,
N is, Eq.1:

T = G + H·N. . . . . . . . (1)

Where the G and H values [2,3] are the intercept on the torque axes and
the “slope of the line”, respectively. These two parameters are also called
Tattersall values and will be here named:

Ø G-yield or G-yield value [Nm]

Ø H-viscosity or H-viscosity value [Nm·s]

There is a linear relation between the G-yield value and H-viscosity to the
(Bingham parameters) yield value and plastic viscosity, respectively, Eq.2:

τ = τ 0 + µ ⋅ γ&. . . . . . . . (2)

Where:
τ = shear stress [Pa]
τ0 = yield value [Pa]
μ= plastic viscosity [Pa·s]
γ˙ = shear rate [1/s]

The new equipment is based on similar principle as for the Tattersall two-
point test where an impeller is rotating in the testing material [3].

Fig. 1. The Rheomixer including 10” Tablet PC for data processing.

Isothermal conduction calorimeter

A novel isothermal calorimeter designed to test relatively large samples of
mortar or even concrete was used for testing of mortar at 20 C. The
calorimeter is a prototype manufactured by Thermometric AB in Sweden,
based on a design by Lars Wadso [4]. The calorimeter was kept at
constant temperature in a portable thermostat manufactured by Sable
Systems, Las Vegas, U.S.

4
Heat Flow (mW/g dry binder)

3
D

A
2
C

B
0
0 4 8 12 16 20 24
Time (hrs)
Fig. 2: Example of normal hydration of an ASTM Type II portland cement,
water-to-cement ratio of 0.45.

Fig. 2 shows an example of hydrating Portland cement in the absence of

admixture, a water-to-cement ratio of 0.45, monitored at 20 oC by an
isothermal conduction calorimeter. Portland cement mixed with water
initially displays a strong exotherm (A) caused by rapid dissolution and
initial hydration of mainly the aluminate phase. If sufficient calcium sulfate
is available in solution, the hydration rate rapidly decreases (B) as
aluminate reacts with calcium and sulfate to form ettringite like phases.
After some time the strength generating alite hydration takes off, which
results in a broad exotherm. Set usually occurs at the steepest part of the
alite exotherm (C). The alite and aluminate hydration continue in parallel
until the mixture runs out of soluble sulfate, indicated by the “sulfate
depletion” peak (D) [5].

2. Experimental

2.1 Materials

A low alkali portland cement conforming to CEN CEM I and ASTM Type I
was used “as is”, and interblended with quick lime (CaO) and an ASTM
Type F fly ash.

Free lime was prepared as freshly burned CaO and cooled to room
temperature in a dessicator. It was either blended with the cement
immediately before mortar testing or two months prior to mortar testing.

A commercially available polycarboxylic acid (PCE) high range water

reducer with no co-additives was used as dispersing agent, Table 1.
2.2 Mortar Mixtures

Mortars were prepared by adding dry materials gently into water

previously added to the Rheomixer. Mixing and rheology testing
commenced immediately after loading, Fig. 3. The mixing part can be
divided into three regimes: The first one account for the time interval of 30
seconds and consists of three 10s cycles of alternating forward and
reverse rotations of the impeller at a speed of +/- 1.5 revolutions per
seconds (rps). The second regime consists of alternating rotations of short
cycles (2s) for the next 120s. In this regime a constant rotation speed is
maintained for each mix at 5 rps. The third regime account for the last 55s
where a constant unidirectional speed of 1.5 rps is maintained. After the
mixing process is completed the mortar is left at rest for several minutes
during which at least three measurements on the rheological parameters
G-yield value and H-viscosity are measured.

Table 1, Mortar mixtures

Mix w/c Cem. Type Cement Water Sand CaO PCE Note
no. (g) (g) (g)
1 0,5 Cem I 582 291 1350
2 0,5 Cem I 582 291 1350 +1,7% CaO aged
3 0,5 Cem I 582 291 1350 1,70%
4 0,42 Cem I 643 270 1350 0,10%
5 0,42 Cem I 643 270 1350 0,10% +1,7% CaO aged
6 0,42 Cem I 643 270 1350 1,70% 0,10%
7 0,50 35% FA 570 285 1350
8 0,50 35% FA 570 285 1350 1,70%
9 0,42 35% FA 657 276 1350 0,10%
10 0,42 35% FA 657 276 1350 1,70% 0,10%

Regime 1 Regime 2 Regime 3 Resting and measurement period

120 s
Revolutions 2s
per second [rps]
1.33 1.33 1.33
12 1.17 1.17 1.17
1.00 1.00 10 s 1.00 10 s
10 s
10 0.83 0.83 0.83
0.67 0.67 0.67
8 0.50 5s 0.50 5s 0.50 5s

6
10 20 30 40 10 20 30 40 10 20 30 40
4
5s
2
0
55 s
-2
30 s 150 s 35 s 390 s 35 s 85 s 35 s
-4
-6
1. meas. 2. meas. 3. meas.
-8
-10
-12

10 20 30 40 150 200 360 390 780 815 900 935

Time [s]
Fig 3. Rheomixer mixing and testing sequence. The mixing is carried out
in regimes 1-3 whereof the variable mixing speed is executed in regime 2.

An environmental temperature of 22 +/- 1°C was maintained during the

tests. If used, the chemical admixture was added with the mixing water.
The volume of each mixture was kept constant or 1.0 liter (not including
air). The volume of sand was constant in all mixtures. The mixture
proportions are given in Table 1.

All mixtures were prepared and tested in the Rheomixer during the first
hour of hydration. After 70 minutes hydration, approximately 50 g of
mortar (the exact mass was recorded for each mix) was removed from the
Rheomixer and placed in the isothermal calorimeter at 20°C. Since all
mixtures were prepared externally, non-isothermal conditions exist in the
beginning of each calorimetry test. A set of eight duplicate blank mixtures
were prepared and tested for the purpose of measuring the time needed
for the results to converge, Fig. 4. The result was used as an estimate of
the time required to reach isothermal conditions in the calorimeter, e.g.
approximately 60 minutes was needed to reach isothermal conditions after
placing a 50 g mortar sample in the calorimeter.

Time of approximately
isothermal conditions.
Each sample was 70
minutes old when placed
in the calorimeter

Fig. 4. Estimation of the time needed for isothermal conditions. 8 duplicate

50 g mortar samples w/c 0.50 placed in the calorimeter after mixing and
rheology testing in the Rheomixer.

The rate of heat evolution was normalized to the dry content of binder, e.g.
mW/g dry binder.
2.3 Paste mixtures for Pore water extraction and analysis

Separate tests with cement paste w/c 0.50 were prepared in order to
evaluate the effect of free lime on the calcium concentration in porewater.
The cement paste was mixed at room temperature for 120 seconds and
the porewater was extracted at different hydration times using vacuum
filtration. The extracted porewater was immediately acidified using 1.0 M
nitric acid to pH 1 to prevent precipitation followed by analysis for Calcium
and Sulfur content by atomic adsorption spectroscopy.

3. Results

The effects of adding freshly burned CaO cooled to room temperature on

the rheology, hydration kinetics and selected pore water ions are shown in
Fig. 5-11. For the calorimetry results, note that all mixtures were 70
minutes old at time zero. The first 60 minutes calorimetry data omitted due
to non-isothermal conditions.
400 160
Blank
.

+1.7% CaO aged

.

120 +1.7% CaO fresh

H-viscosity (a.u.)

300
G-value (a.u.)

200 80

100 Blank 40
+1.7% CaO aged
+1,7% CaO fresh
0 0
0 15 30 45 60 0 15 30 45 60
Time (min)
Time (min)
Fig. 5. Effect of free lime on the relative yield value and viscosity as
function of time (CEM I, w/c 0.50, no chemical admixture).

400 160
Blank + 0,1% PCE
+1.7% CaO aged
.
.

300 +1.7%CaO fresh 120

H-viscisity (a.u.)
G-value (a.u.)

200 80

Blank +0.1%PCE
100 40
+1.7% CaO fresh
+1.7% CaO aged

0 0
0 15 30 45 60 0 15 30 45 60
Time (min)
Time (min)
Fig. 6. Effect of free lime, both aged in cement and added fresh on the G-
and H-value as function of time (CEM I, w/c 0.42, PCE 0.1%).
 400 160
35% FA
+1,7%CaO, 35%FA
.

.
300 35%FA +0,1%PCE 120
+1,7%CaO, 35%FA +0,1%PCE
G-value (a.u.)

H-value (a.u.)
200 80

100 40

0 0
0 15 30 45 60 0 15 30 45 60
Time (min) Time (min)
Fig. 7. Effect of added fresh free lime in cement (CEM II/B, 35% fly ash)
on the G- and H-value as function of time in mixes without (w/c: 0.5) and
with (w/c: 0.42) 0.1% PCE.

+ 1.7% CaO
CEM I CEM II/B 35% FA

+ 1.7% CaO
Setting
indicator Setting
indicator

Fig. 8. Effect of added free lime on cement hydration kinetics tested at 20

C, EN mortar without chemical admixture – Left: CEM I portland cement,
w/c 0.50. Right: CEM II/B, 35% fly ash, w/c 0.50.
 + 1.7% CaO CEM I CEM II/B 35% FA
repeated 0.1% PCE 0.1% PCE
twice + 1.7% CaO

Setting
indicator
Setting
indicator

Fig. 9. Effect of added free lime on cement hydration kinetics tested at 20

C, EN mortar with 0.1% s/s PCE added with mix water – Left: CEM I
portland cement, w/c 0.50. Right: CEM II/B, 35% fly ash, w/c 0.42.

+ 1.7% fresh CaO CEM II/B 35% FA

+ 1.7% aged CaO

Setting
indicator

Fig. 10. Effect of ageing of free lime on cement hydration kinetics tested at
20 C, EN mortar without chemical admixture –CEM II/B, 35% fly ash, w/c
0.50.
 80
w/c=0.5 w/c=0.5
60 Sulphur
w/c=0.5 1.1% CaO w/c=0.5 0.1%PCE
70
w/c=0.5 1.7% CaO w/c=0.5 1.1% CaO
50 w/c=0.5 0.1% PCE w/c=0.5 1.7% CaO
60
w/c=0.5 1.7% CaO 0.1% PCE w/c=0.5 1.7% CaO 0.1%PCE
.

.
40 50
[Ca] mM

[S] mM
40
30

30
20
20

10
10

0 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time [m] Time [m]

Fig. 11. Calcium and sulfate (measured as sulfur) concentration in

extracted porewater.

4. Discussion

4.1 Rheology by Rheomixer

Addition of 1,7% freshly burned CaO cooled to room temperature

influenced the rheology more than if the same amount of CaO was added
and allowed to age in the cement for 2 months. However, the effect of
adding fresh free lime is small compared to the effect of changing the w/c-
ratio. The effect of addition of fresh 1.7% CaO to the cement increased the
yield-value approximately 80 a.u. or approximately 50 Pa, Fig. 5. The
measured increase in the yield value corresponds to a change in w/c ratio
of approximately 0.01.

A similar trend was observed in the mixes containing 0.1% PCE (w/c:
0.42), Fig. 6. The fresh CaO increased the relative yield value
approximately 80 a.u. while the aged CaO increased the relative yield
value approximately 40 a.u. However, the rate of change in the rheological
parameters was relatively unaffected by the addition of CaO.

The effect of addition of fresh CaO to the blended cement with 35% fly ash
was smaller compared to the CEM I portland cement, ~25 Pa, Fig. 7. This
is expected, as the clinker fraction of the cement is smaller. It is
noteworthy that the change in G-yield-value as a function of time (e.g.
“workability loss”) is significantly smaller in the mixes containing FA. The
influence on the addition of fresh free lime on the H-viscosity is
insignificant.

4.2 Hydration kinetics by isothermal calorimetry

The calorimetry results indicated as strong accelerating effect of added
free lime on the onset of the alite hydration peak, or approx. 1 hr shorter
setting time. The free lime content could be adjusted by intergrinding
quicklime if not feasible by adjusting the clinkering process. However, the
accelerating effect was reduced with ageing of the free lime.

4.3 Porewater composition

The addition of free lime did not significantly affect the concentration of
calcium in the extracted porewater. The results indicate that the free lime
addition accelerates cement hydration probably by increased nucleation
without changing the amount of calcium in solution. Therefore, the
measured effect of free lime addition on rheology is primarily due to the
effect on cement hydration and not due to a change in calcium ion
concentration. The effect of free lime addition on the ionic strength is
probably also minor.

5. Conclusion

The results obtained indicate the possibility of shortening the setting time
of blended fly ash cement by means of increasing the free lime content
without detrimental effects on rheology of mortar or concrete. However,
the benefit of the added free lime is sensitive to cement ageing.

6. References

[1] Uchikawa, H, Ogawa, K, Uchida, S, Influence of the character of clinker

on the early hydration process and rheological property of cement paste,
Cement and Concrete Research (1985), 15(4), 561-72.
[2] O.H. Wallevik, Description of fresh concrete properties by use of two-
point workability test instrument, Ph D thesis, NTH, Trondheim, 1983, p.
136.
[3] G.H. Tattersall, P.F.G. Banfill, The rheology of fresh concrete, Pitman,
London, 1983, p. 356.
[4] Wadso, L, Unthermostated Multichannel Heat Conduction Calorimeter,
Cement, Concrete and Aggregates, Dec. 2004, Vol. 26, No. 2, available
online at www.astm.org.
[5] W. Lerch, The influence of gypsum on the hydration and properties of
portland cement pastes, Proceedings, Vol. 46 (1946), of the American
Society for Testing Materials.