The influence of humidity on hydration of concrete with fly ash and slag

THE INFLUENCE OF THE HUMIDITY ON THE HYDRATION OF CONCRETE WITH
HIGH CONTENTS OF FLY ASH AND BLAST FURNACE SLAG

Thomas Adam, Peter Grbl

SUMMARY

The aim of the investigation was to find out, how air humidity and duration of curing
influence the hydration. The tests were made on concrete samples with high contents of fly
ash and blast furnace slag respectively. After the curing at 100 % relative humidity the
samples were stored at different climates. The impact of the curing conditions and the
hardening behaviour of the concrete were estimated by the kinetics of the hydration. The
kinetics of the hydration was analysed by the measurement of the non-evaporable water.
Therefore, the Carbon-Water-Analysis was used. The results so far show a increased curing
demand of concrete mixes with fly ash and blast furnace slag. Beyond this, concrete with very
high contents of blast furnace slag exhibits an improved capability of storing mixture water,
which led to the late formation of very stable phases and a good hardening at any external
relative air humidity.

INTRODUCTION

Concrete sets and hardens due to the reaction of the cement with water. Because of the
complex mixture of Portland cement (OPC), various chemical reactions take place. The total
of all these reactions is called hydration. Crucial to the development of a dense
microstructure and high strength is the reaction of the tricalcium silicate (C
3
S) and the
dicalcium silicate (C
2
S) with water. In both cases an amorphous calcium silicate hydrate
(CSH) and calcium hydroxide (CH) are formed. Besides the C
3
S and C
2
S, other inorganic
materials are able to form CSH. Some of them are used for mineral additions in concrete to
partially replace OPC. Among these, fly ash and blast furnace slag are the most important.
Both are waste materials, and concrete made with them can have properties similar to those of
ones made with pure OPC. Beyond this, concretes made using fly ash or furnace slag can
have properties that are desirable in some cases, such as slower heat development and an
improved resistance to chemical impacts. Disadvantages include the very slow hydration rate
of those admixtures and the increased tendency of concrete made by blast furnace slag to
carbonate [8]. For this reason, concretes rich in fly ash and blast furnace slag have a
reputation of requiring an extended curing duration. Due to the increased application of fly
ash and blast furnace slag, it becomes essential to have a closer look at the hydration and
curing demands of concretes containing these inorganic materials.
Adam, Th.: The influence of the humidity on the hydration of concrete with high contents of fly ash and blast
furnace slag. Darmstadt Concrete 17 (2002). http://www.darmstadt-concrete.de/2002/humidity.html
According to TAYLOR [9], curing means storage under conditions such that hydration
occurs. If there are unhydrated cement grain and water present, hydration always takes place
at ordinary temperatures. Therefore, the main task of all curing measures is to prevent an
advanced water loss due to evaporation in the concrete. However, that doesnt mean that the
concrete is to cure till the hydration is almost finished. Instead of this, curing measures are to
sustain until the microstructure of the concrete surface is dense enough to keep the mixture
water inside as long as possible. This ability of the concrete to retain water minimized
evaporation and led to a good hardening at any conditions which occurred. From these
observations, it follows that it is important to know how long the concrete is to be kept under
curing conditions to make sure, that a sufficient hardening of the surface takes place. This
does apply especially to concretes made using fly ash and blast furnace slag. The aim of the
present investigation was to research this fact.

EXPERIMENTAL PROGRAM

The investigations were performed on six concretes, which differed in the type of cement and
the water-cement-ratio. The exact mix-designs are shown in Table 1.

Table 1: Mix designs

C1-FA-0,6 C1-FA-0,4 C2-A-0,6 C2-A-0,4 C3-B-0,6 C3-B-0,4
CEM I
32,5 R
CEM I
32,5 R
CEM III/A
32,5 R
CEM III/A
32,5 R
CEM III/B
32,5 N
CEM III/B
32,5 N
w/c-ratio 0,66 0,44 0,60 0,40 0,60 0,40
w/(c+0,4*f)-ratio 0,60 0,40 - - - -
Cement 325,0 kg/m 487,5 kg/m 357,5 kg/m 537,5 kg/m 357,5 kg/m 537,5 kg/m
Fly ash 82,5 kg/m 122,5 kg/m - - - -
Water 215 l/m 215 l/m 215 l/m 215 l/m 215 l/m 215 l/m
Aggregates 0/2 962,5 kg/m 890 kg/m 962,5 kg/m 890 kg/m 962,5 kg/m 890 kg/m
2/8 727,5 kg/m 670 kg/m 727,5 kg/m 670 kg/m 727,5 kg/m 670 kg/m
1690 kg/m 1560 kg/m 1690 kg/m 1560 kg/m 1690 kg/m 1560 kg/m

The test samples were produced as follows: First, 100-mm cubes were moulded. The concrete
was left in the forms for one day. After that, the cubes were sawed into small slices of 15 mm-
thickness. The test samples were cured according to the specification in Table 2.
Table 2: Type and duration of the curing

curing of the samples
Type
in form conserved under
water
test
climate
I 1 d until test - -
II 1 d 1 d - until test
III 1 d 2 d - until test
IV 1 d - 2 d until test
V 1 d - 6 d until test

After curing under conserved conditions or under water the samples were stored under
different climatic conditions. The effect of the subsequently listed relative air humidity on the
hydration was explored:

100 % r. h.
92 % r. h.
85 % r. h.
75 % r. h.
50 % r. h.
0 % r. h.

The test-temperature was set at 20 C.

The measurements were taken on the following days:

1
st
day
2
nd
day
3
rd
day
7
th
day
14
th
day
28
th
day
91
st
day

Having reached the measuring day, the sample was taken from the storage climate. The
weight was measured and the hydration of the cement was stopped by evaporating the water
at 105 C. After no changes of weight had taken place anymore the sample was weighed
again. The difference of both values resulted in the content of evaporable pore water. Before
the sample was further worked on, it was cooled in a desiccator.

The CWA-measurement was used to evaluate the non-evaporable water. In order to
accomplish this, the complete dried sample was milled to a fineness less than 0,125 mm. Next
a few grams of the powder were brought to a red-hot glow in the CWA-unit at about 950 C.
The percentages of carbon dioxide and water were displayed. By deduction of the carbon
dioxide and water content of the unhydrated cement the quantum of non-evaporable water in
the sample was calculated.

RESULTS AND DISCUSSION

The replacement of OPC by fly ash or blast furnace slag has a striking effect on the course
and the degree of hydration. Based on the development of non-evaporable water, Figures 1,2
and 3 illustrate this in comparison with results of GRBL ET AL. [1].

0,0
5,0
10,0
15,0
20,0
25,0
30,0
0 10 20 30 40 50 60 70 80 90 100
Age (d)
n
o
n
-
e
v
a
p
o
r
a
b
l
e

w
a
t
e
r

[
m
a
s
s
-
%

o
f

c
e
m
e
n
t
]
CEM I w/c=0,6 [1]
C1-FA-0,6
CEM I w/c=0,4 [1]
C1-FA-0,4

Fig. 1: Non-evaporable water content of concretes containing fly ash compared to
ones made with pure OPC
0,0
5,0
10,0
15,0
20,0
25,0
30,0
0 10 20 30 40 50 60 70 80 90 100
Age (d)
n
o
n
-
e
v
a
p
o
r
a
b
l
e

w
a
t
e
r

[
m
a
s
s
-
%

o
f

c
e
m
e
n
t
]
CEM I w/c=0,6 [1]
C2-A-0,6
CEM I w/c=0,4 [1]
C2-A-0,4

Fig. 2: Non-evaporable water content of concretes containing medium amounts of
blast furnace slag (CEM III/A) compared to ones made with pure OPC

Mixtures with fly ash exhibit a rapid hardening until the 3
rd
day. The hydration kinetics is as
fast as those of pure OPC-mixtures. Some authors [6][8][9] even describe an accelerated
initial strength development of those concretes. The reason for this behaviour is the elevated
water supply due to the dilution with fly ash. Therefore, the complete water is provided to the
reaction of the OPC at the beginning. But, after the 3
rd
day the content of non-evaporable
water lags behind the pure OPC-mixtures. The available cement particles are surrounded by a
relatively dense layer of hydration products, which inhibit a further reaction. Furthermore,
the puzzolanic reaction of the fly ash starts only very hesitatingly. The non-evaporable water
content rises slightly but steadily. According to HTTEL [4], countable hydration rates of
fly ash happens only beyond the 28
th
day. If the evaporation is not prevented during this
period, the puzzolanic reaction can not take place. In this case the fly ash act merely
physically due to their effect on the package density of the concrete.

The partial replacement of OPC by blast furnace slag modifies the course of hydration too.
According to Figures 2 and 3, the upper limit of chemical water due to the formation of CSH-
phases is slowed down until the 28
th
day. After that, mixtures with CEM III/A do not exhibit
any significant changes in the non-evaporable water. Mixtures with slag-rich CEM III/B
react completely different than the above mixtures. As shown in Figure 3, such mixtures start
to hydrate again after a pause between the 14
th
and 28
th
day.

0,0
5,0
10,0
15,0
20,0
25,0
30,0
0 10 20 30 40 50 60 70 80 90 100
Age (d)
n
o
n
-
e
v
a
p
o
r
a
b
l
e

w
a
t
e
r

[
m
a
s
s
-
%

o
f

c
e
m
e
n
t
]
CEM I w/c=0,6 [1]
C3-B-0,6
CEM I w/c=0,4 [1]
C3-B-0,4

Fig. 3: Non-evaporable water content of concretes containing high amounts of blast
furnace slag (CEM III/B) compared to ones made with pure OPC

Due to the denser microstructure, the compressive strength of concrete made with fly ash or
blast furnace slag could be higher than those of concrete with pure OPC. This can happen,
although these concretes contain less chemical bound water and as a consequence have a
lower degree of hydration. Table 3 shows this explicitly.

Table 3: Compressive strength and non-evaporable water on the 28
th
day of
concretes with different contents of mineral additions under
conserved storage

w/b-value
non-evaporable
water at 28
th
day
[mass-%]
Compressive
strength at 28
th
day
[N/mm]
0,40 18,64 51,7
CEM I 32,5 R
0,60 21,47 35,9
0,40 14,34 70,0
CEM I 32,5 R +
25 % fly ash
0,60 15,35 42,4
0,40 14,04 55,8
CEM III/A 32,5 R
0,60 16,32 33,2
0,40 11,60 63,5
CEM III/B 32,5 N
0,60 14,59 41,7
The diffusion, caused by the gradient of the steam pressure, has the main effect on the loss of
water and on that score on the hydration. Figures 4 and 5 exemplary show the influence of
changes in the air humidity on the hydration of two concrete mixes.

0
2
4
6
8
10
12
14
16
18
20
0 20 40 60 80 10
Age [d]
n
o
n
-
e
v
a
p
o
r
a
b
l
e

w
a
t
e
r

[
m
a
s
s
-
%

o
f

c
e
m
e
n
t
]
0
II-100 %
II-92 %
II-85 %
II-75 %
II-50 %
II-0 %

Fig. 4: Non-evaporable water of concrete mix C1-FA-0,6 after curing two days under
conserved conditions

0
2
4
6
8
10
12
14
16
18
20
0 20 40 60 80 100
Age [d]
n
o
n
-
e
v
a
p
o
r
a
b
l
e

w
a
t
e
r

[
m
a
s
s
-
%

o
f

c
e
m
e
n
t
]
II-100 %
II-92 %
II-85 %
II-75 %
II-50 %
II-0 %

Fig. 5: Non-evaporable water of concrete mix C3-B-0,4 after curing two days
under conserved conditions
Concrete mixes with fly ash exhibit a significant sensibility to the storage conditions. Below
85 % relative air humidity the puzzolanic reaction becomes severely restricted. But even at 92
% the hydration rate is considerably reduced. A previous moist curing up to the 7
th
day
benefits the OPC-hydration, but apparently has no effect on the reaction of the fly ash.

Mixes using CEM III/B contain high amounts of blast furnace slag. Therefore, their properties
are different from mixes with CEM III/A. As shown in Figure 5, the late hardening of those
mixes isnt appreciably influenced by the exogenous moisture conditions. Even if the curing
measurements would be extended, the gradient of the non-evaporable water after the 14
th
day
would stay almost the same. This led to the conclusion, that only the hydration of the OPC is
influenced by the evaporation but not the hydraulic reaction of the blast furnace slag. Thats
why, moist curing has merely an effect on the OPC-reaction, which is important, because CH
is formed in this case. The formation of CH guaranteed an acceptable resistance to
carbonation, wherein slag-concrete otherwise is weak. Because of the low influence on the
hydration of blast furnace slag, temporary curing measurements effect the hydration rate only
minimally. On that score, the curves of Figure 6 run tightly together. Only a longer storage
above 85 % relative air humidity led to an enhanced hydration rate.

0,0
0,2
0,4
0,6
0,8
1,0
0 20 40 60 80 10
relative humidity [%]
r
e
l
a
t
i
v
e

h
y
d
r
a
t
i
o
n

k
i
n
e
t
i
c
s

[
v
(
x
%
)
/
v
(
1
0
0
%
)
0
]
I (restorage at the end of the 1st day)
II (restorage at the end of the 2nd day)
III (restorage at the end of the 3rd day)
IV (restorage after 1 day in form and 2 days under water)
V (restorage after 1 day in form and 6 days under water)

Fig. 6: Relative hydration kinetics based on the conserved storage of concrete mix
C3-B-0,4 calculated for the 14
th
day

During the hydration, parts of the mixing water will be tightly bound in the hydration
products. This water is called chemical bound water and can be only evacuated by
temperatures above 105 C. Water physically bound or free is evaporable till 105 C. If no
diffusion can occur, then the total water amount results in the original water content of the
mixture. Three examples of water balances are shown in Figures 7, 8 and 9.
0
5
10
15
20
25
30
35
40
45
0 20 40 60 80 10
Age [d]
w
a
t
e
r

[
m
a
s
s
-
%

o
f

c
e
m
e
n
t
]
0
evaporable water
nonevaporable water
total water

Fig. 7: Changes in the water content of concrete mix C1-FA-0,4 in the course of
time under conserved storage conditions

0
5
10
15
20
25
30
35
40
45
0 20 40 60 80 10
Age [d]
w
a
t
e
r

[
m
a
s
s
-
%

o
f

c
e
m
e
n
t
]
0
evaporable water
non-evaporable water
total water

Fig. 8: Changes in the water content of concrete mix C2-A-0,4 in the course
of time under conserved storage conditions

0
5
10
15
20
25
30
35
40
45
0 20 40 60 80 10
Age [t]
w
a
t
e
r

[
m
a
s
s
-
%

o
f

c
e
m
e
n
t
]
0
evaporable water
non-evaporable water
total water

Fig. 9: Changes in the water content of concrete mix C3-B-0,4 in the course of
time under conserved storage conditions

Remarkable is, that Figure 9 shows a vital deviation from Figure 7 and 8. It can be seen from
the graph, that the evaporable water declines dramatically after the 28
th
day. The content of
non-evaporable water rises slightly against it. That means, the concrete is loosing water
between the 28
th
and 91
st
day and probably beyond. The question is now, where the water is
gone and why? Because of the storage under conserved condition, it is quite improbable that
the loss is caused due to diffusion. Either the water disappears in another way or it is still
there but can not be measured. This leads one to assume that CSH-phases were formed,
which may be resistant up to 950 C. In this case, it would be impossible to detect this water
with the available equipment. As a consequence the real non-evaporable water content must
be higher than the measured one. If this turns out to be true, then the degree of hydration of
concretes made with high contents of blast furnace slag was underestimated up to now. As a
result, the known excellent resistance of those concretes against chemical attacks is not only
caused by the high package density of the particles but also by the formation of very stable
CSH-phases. The empirical knowledge [6] with binders containing more than 90 % blast
furnace slag seem to verify this hypothesis. So called activated slag cements maintain
acceptable strength and performance up to 1000 C. According to ODLER [6], this
temperature may be extended to even higher values.

Important in this connection is, that the formation of those suspected stable CSH-phases
occur only if the amount of slag is above 60 % of the cement. Therefore, CEM III/A-mixes
do not exhibit the same behaviour.
CONCLUSION

Fly ash cement concrete undergoes hydration much more slowly than pure OPC-mixes.
Therefore, moist conditions influencing the hydration of those mixes last. A decrease in the
humidity led to a restriction of the puzzolanic reaction, no matter how long the concrete was
moist cured before. Thats why, a relative air humidity above 85 % is vital for the late
hardening. Otherwise fly ash acts primarily as a filler. However, an intensive curing benefits
the OPC-hydration in any case. That applies to mixes where the OPC was partially replaced
by blast furnace slag, too. Those concretes exhibit a strongly reduced hydration rate but a
quite good late hardening. Thereby, the amount of blast furnace slag in the mix has a relevant
effect on the hydration. Contents below 60 % turned out to have no substantial influence on
the late hardening compared to pure OPC. On the other hand concrete mixes with very high
amounts of blast furnace slag show a relevant hydration after the 28
th
day, which occurs
independent of the preceding curing conditions. This is probably due to the formation of very
stable hydrate phases. The statements which were made in the paper are valid for the test
conditions, where this investigation was executed.

REFERENCES

[1] Grbl, P.; Becker-Roes, D.: Hydration under reduced water availability; Darmstadt
Concrete; Vol. 15; Institut fr Massivbau, TU Darmstadt; Darmstadt 2000
[2] Hinrichs, W.: Untersuchung zur Hydratation von Schlackeportlandzementen;
Dissertation; TU Clausthal 1987
[3] Ho, D. W. S.; Cui, Q. Y.; Ritchie, D. J.: The Influence of Humidity and Curing
Time on the Quality of Concrete; Cem. And Con. Res., Vol. 19, S. 457-464;
[4] Httel, R.: Wirkungsmechanismus von Steinkohlenflugasche als Betonzusatzstoff;
Dissertation; TU Berlin 2000
[5] Kern, R.: Der Einfluss der Austrocknung auf die Wasserbindung und Eigenschaften
des Betons; Dissertation; TU Darmstadt 1998
[6] Odler, I.: Special Inorganic Cements; E & FN Spon; London 2000
[7] Paque, T.: Charakterisierung der Hydratation von Betonen mit hohem Httensand-
oder Steinkohleflugascheanteil im frhen Stadium der Erhrtung; Diplomarbeit;
TU Darmstadt 2002
[8] Stark, J.; Wicht, B.: Zement und Kalk; Birkhuser Verlag, Basel 2000
[9] Taylor, H.F.W.: Cement Chemistry; 2
nd
edition; Thomas Telford Ltd., London 1997

Contact to the authors:
adam@massivbau.tu-darmstadt.de
gruebl@massivbau.tu-darmstadt.de
Homepage of Darmstadt Concrete:
http://www.darmstadt-concrete.de

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THE INFLUENCE OF THE HUMIDITY ON THE HYDRATION OF CONCRETE WITH

HIGH CONTENTS OF FLY ASH AND BLAST FURNACE SLAG

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