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R e a c t i o n M e c h a n i s m s of C o n c r e t e A d m i x t u r e s
P. Paulini
Institut f~ir Baustofflehre und Materialpri.ifung
Universit~it lnnsbruck, A-6020 Innsbruck, Austria
ABSTRACT
Concrete admixtures influence the kinetic of cement hydration
mainly during the d o r m a n t period. The d o m i n a n t influence of admixtures seems to lie in different bound forces between dissociated ions
in the pore water solution. Repulsive forces characterize the solvation process while attractive forces d o m i n a t e during crystallization.
These changes of ion bound forces lead twice to volume changes
during phase transitions of hydration. Volume changes measured
with an immersion weighing setup show clearly the effect of concrete
admixtures on cement r e a c u o n . Retarder agents produce a volume
swelling while accelerators force an i m m e d i a t e shrinkage behaviour.
A m e c h a n i s m as introduced by Le Chatelier involving a solution-crystallization step seems to describe the hydration process most adequately. As long as repulsive forces dominate, a volume swelling
occurs and no strength gain can take place. The d o r m a n t period is
defined by the length of the swelling process. Hardening and strength
growth start at the point at which volume shrinkage appears.
Concrete admixtures are used to influence concrete hardening mainly in the early
tPrhase of hydration. By adding very small amounts of admixtures, properties of
esh conc~:ete can be influenced in a wide range. The hydraulic reaction can be
accelerated or r e t a r d e d using appropriate agents and workability can be improved
using superplasticizers. Many mechanisms have been suggested to explain all
these effects [1],[2]. There is still no full u n d e r s t a n d i n g of hydration mechanisms
including all these p h e n o m e n a at once. In this contribution emphasis shall be put
at energy transformations occuring during physico-chemical processes of c e m e n t
hydration.
910
9t I
Hydration Mechanisms
Cement hydration evolves in a way which includes two phase transitions. [n contact with water, metastable solid cement phases dissolve into an aqueous solution.
This dissociation leads to an increase of CaO concentration up to 20-40 mmol/I in
the first hours of C3S hydration [3]. Reaching a state of supersaturation in the
pore water solution, crystallization into stable and solid CSH-products can follow.
In both phase transitions a sudden volume change occurs, resulting from changes
in bound forces. Figure l shows this phenomenon in a plot according to the Vander-Waals theory.
iitlransition
Area
m
u)
Figure l
a=
Volume
I ~solid =J)TAtI--
fluid
-J-I
[5].
HYDRATION
VARIATIONS
OF
ALITE : SEQUENCE
Figure 2
Hydration of C3S,
ace.
[5]
TIME :
PERIOD :
H.
-I
HYDRATES - -
CSH
10 H.
1)'1.
II
--III-. . . . .
--
--
CH
100 H.
I
CSH
. . . . . .
912
P. Paulini
t
o
E
c
i.i
la_
AG
Go
m
ZXG
Time
Figure3
913
Figure 4
A d i a b a t i c State F u n c t i o n
P(
VI
v,
V,
914
P. Paulini
~Wrev
= - j
PB
dV
- ~Qrev
= Seq
(Tl
- TO)
~Wrev
~Wirr
~ PB
Vs
S t r u c t u r e f o r m a t i o n and strength growth of a material d e p e n d only on the irreversible part of volume work.
~Wirr
&PB
Vs
+ ~
PB
dV
dQ R
e n d o t h e r m i c reactions
dWir r <_ 0 _ dQ R
Kinetics of Hvdration
Kinetic m e a s u r e m e n t s of chemical reactions can be p e r f o r m e d based on the above
explanations recording either heat energies or v o l u m e work. Until now mostly
c a l o r i m e t r i c recordings have been used i n t e r p r e t i n g hydraulic reactions.
In o r d e r to d e s c r i b e the irreversible v o l u m e work remaining in the material we
would have to record both, b o u n d stresses and shrinkage volumes during a reaction. A direct m e a s u r e m e n t of intermo-}ecular bound stresses is a rather difficult
task. It is much easier to record volume changes during a reaction and to calculate b o u n d pressures. This can be done using
dPB = - K . d V s / V 0
w h e r e K is the bulk modulus, V s the shrinkage v o l u m e and Vf~ the initial volume.
We have t h e r e f o r e used a setup b a s e d on the i m m e r s i o n weighinz m e t h o d (Fig. 5).
In this way v o l u m e shrinkages during c e m e n t reaction can be effsily and a c c u r a t e
r e c o r d e d [8].
915
Figure5
(~ Balance
(~) DataLoggingUnit
(~) TherrnmCmt
(~ Sample
Shrinkage
0,01
. :
Typ
TypN
-0,01
-0,02
Sw~'~
-0,05
-O,04
0
Figure 6
TypS
i
6
Time(h)
6
I
10
'12
14
Type L cements have a low initial reaction and were found by finer ground cement
types. Type N cements show no clear initial reaction and were found in normal
portland cements and sulhpate resistant cements. Swelling processes of type S
cements were observed especially in slag cements, old cements and fresh ground
cements.
In o r d e r to prove that the time during which swelling occurs can be defined as
d o r m a n t pertod, accelerated cement reactions with different isothermal temperatures are represented in Figure 7. Leaving out the swelling phase, Figure 7 shows
916
P. PafiLi.ni
only volume contractions, starting at the time where chemical shrinkage appears.
We note the well known behaviour of temperature-accelerated cement reactions
which have shorter dormant periods, react faster at the beginning, and reach
lower degrees of hvdration at the end.
0,00
~ m k , ~ l e Volume (cm,3/,~
0.03
0.04
0,03
0.O2
0.01
20
40
Figure7
60
T i m e (h)
80
100
120
The following plots give an insight into the working mechanisms of concrete
admixtures. Adding accelerator agents leads to an increase of early volume shrinkage. This is illustrated in Figure 8 using 5% accelerators of different brands and
a rather fast reacting CE II S cement. Figure 9 shows the same result with a slowreacting sulphate-resistant portland cement, Both, dry and fluid agents have been
used.
0,01
vca (cm3/g)
0,03
v~e (crib/g)
0,008
0.02 ~
O,OOe
0.01
0,004
Q
0,002
oo
CE !I-
Ace.
-0,02
0,002
0.5
t,3
2,5
3,11
4.5
II
5.1l
T i m e (h)
i
2
J
4
I
6
L
8
I
10
L
12
~
14
h
le
L
18
Time (h)
On the other hand, the use of retarders leads [o an increase of volume swelling.
Figure 10 shows this, using 0.4% retarder with an ordinary CE I cement and a CE
II S slag cement. Increasing the dosage of retarder leads to a higher propagation
of swelling volumes. This is shown in Figure 11 with an ordinary PC 3 5 F c e m e n t
using a retarder based on hydroycarboxilic acid.
,
20
v~
0,03
(cm3/;d
...........
0.02
veo
0.06
917
(m3/0)
, , . . - - - ' - " - - - " ~ n~roCo
n t rol
0.04
0.5%
J
0.03
Control CE II S
0.01
1.0%
O.02
O.01
0
k ~ " ~" C
~
II S * 0.4% Ret.
-0.01 [
*0,01
"0.021
0
10
20
Time (h)
30
40
Retarder
PC 3 5 F
-0.02
10
F i g u r e 10 C e m e n t Reaction with
0.4% Retarder
20
Figurell
30
Time (h)
40
OO
so
C e m e n t Reaction with
incr. Retarder Dosage
0.04
0,06
v=~ (om,,~o)
~ t o ~
0,03
0.02
_
"
Yea
(m3/g|
0.04
2.5%
o
Control
0.5%
0.03
0,01
0
0.02
-0.01
0.01
-0.02
0.04
PC 3 5 F + CaCI 2
CaCJ2
o0,03
I
10
20
30
40
50
60
70
Time (h)
..+.
80
o0.01
0
to
t4
20
30 36
Time (hi
25
40
411 50
54
F i g u r e 13 CaCI9 influence on
PC 35F reaction
Picture 13 shows the reaction influence of CaCI 2 on a fast reacting PC 35F. Increasing the dosage up to 2.5% leads to declining shrinkage volumes and to a
swelling period. A dosage of 5% shows again a faster reaction.
60
9].8
P. Paulini
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