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Article history:
Received 1 August 2013
Accepted 9 June 2014
Available online 12 July 2014
Keywords:
Hydration (A)
Mechanical properties (C)
CaO (D)
Concrete (E)
Pop-out
a b s t r a c t
When nodules of lime are embedded into concrete, the expansion accompanying the transformation of CaO into
Ca(OH)2 induces stresses and strains in both the lime nodule and in the concrete matrix. The concrete cover
thickness, the diameter and the shape of the lime nodule as well as the mechanical characteristics of concrete
and lime are the key parameters inuencing the development of internal pressure and hence controlling the
risk of cracking or pop-out. In order to study the effect of lime into cementitious concretes, laboratory investigations and modelling have been performed and show that the minimum cover thickness necessary to avoid the
development of the pop-out phenomenon is estimated of the order of half the diameter of the inclusion. This
is coming from the observation that expansion happens inside the porosity of the hydrated lime Ca(OH)2:
ESEM and DRX analyses conrm the effect of connement in the development of crystals.
2014 Elsevier Ltd. All rights reserved.
1. Introduction
Lime has been used for a very long time in construction and buildings: Roman cement was already made of a part of lime while it
remained the only binder used until modern cement was designed
during XIXth century [1]. Lime is an industrial product obtained by
calcination of limestone in a lime kiln [2]. This is described as a bright
lime (Table 1), because of its high reactivity with water. The bulk density
of the limestones industrially used for the manufacture of lime usually
offers a lower density than calcite used for ornamental stones: porosity
maybe up to 30% [3]. Quick lime is very reactive with water and
hydrates are quickly formed [4]. Hydration process is accompanied by
a signicant proliferation (Table 1). The formation of Ca(OH)2 yields
in larger volume (expansive reaction). The ratio of volume change
from CaO particle to Ca(OH)2 is 33.1/16.8 2.
The doubling of the molar volume (from 16.8 to 33.1 cm3/mol) is responsible for expansion during hydration [4]. The intensity and speed of
hydration are governed by lime purity, particle size, surface area, etc.
[5]. Burning temperature and kiln technology are also two important
discriminant factors in the case of industrial lime production [3].
An interesting parameter used to quantify the reactivity of lime is
the so-called T60, which is measured in accordance with standardized
method EN 459-2:2001. It gives the speed of lime extinction, or the
Corresponding author at: University of Lige, Civil and Mechanical Engineering
Institute (B 52/3). Chemin des Chevreuils, 1, B-4000 LIEGE, Belgium. Tel.:+32 4 366 93
50; fax: +32 4 366 92 38.
E-mail address: Luc.Courard@ulg.ac.be (L. Courard).
http://dx.doi.org/10.1016/j.cemconres.2014.06.005
0008-8846/ 2014 Elsevier Ltd. All rights reserved.
74
Table 1
Hydration of quick to hydrated lime [2,3].
Property
CaO
+H2O
Ca(OH)2
Molecular weight
Bulk density (g/cm3)
Specic density (g/cm3)
Molar volume (cm3/mol)
56.08
1.401.90
3.33
56.08/3.33 = 16.8
18.01
74.09
0.450.65
2.24
74.09/2.24 = 33.1
from the easier fullling of aggregate cracks by the silica gel which
progressively replaces a part of the initial products present along the
edge of stone material.
With regard to the very poor information coming from literature
reviewing, it clearly appears a lack of knowledge on the behaviour of
quick lime aggregates (up to 20 mm diameter) when mixed into
concrete. A risk evaluation analysis is needed: it will be based on an experimental programme and modelling that will help in understanding
free lime behaviour in conned situation.
Fig. 2. Concrete cover versus diameter of the slag for different concrete types (from [11]).
f c;cube k
f c;cube K0 K0
2
c
with K0 K Rc
cwv
1cm
C
h1
W
1
1:017:
1 3:15 0:512
2cm
75
76
media are assumed to exhibit an elastic behaviour. Although both materials are known to be largely inelastic, this model is however appropriate for low level of stresses and in particular to estimate the initiation
of cracking and can also provide a good understanding of the physical
phenomena with a limited computational effort.
Model 1 (Fig. 3) is based on the assumption that the swelling of the
nodule is partially prevented by pressure developing at the interface
between concrete and lime and conning the nodule. This pressure depends on the mechanical properties (elastic modulus and Poisson's
ratio) of the two materials, as well as on the amplitude of the swelling
as it would be observed if the nodule was perfectly free to expand
upon hydration. Assuming a spherical symmetry of the problem and a
perfect compatibility of the displacements at the interface between
lime nodule and concrete matrix, the pressure can be calculated using
Eq. (3), on the base of the relations proposed in [19] for spherical
containers under internal or external uniform pressure:
R
R
p
CL CC
with
CL
1 2L
EL
D=2
r p
3
D
2z
and
12C
EC
s
3 Vfinal
1:
Vinitial
3
p D=2
D
3 :
2 z
where EL and EC are the elastic modulus of hydrated lime and concrete,
respectively; L and C are the Poisson's ratio of hydrated lime and
concrete, respectively; R is the initial radius of the nodule and R is
the variation of the radius of the nodule due to hydration process.
R/R ratio can be directly related to volume variation by means of
Eq. (6):
R
and
CC
pR
#
t "
2
R e
RR e
tg
3tg2
where R is the radius of the nodule, p is the pressure induced at the interface between nodule and concrete, e is the thickness of concrete
Table 2
Evaluation of the contact pressure vs lime and concrete properties.
EC
(MPa)
R/Rmean
(%)
R/Rmax
(%)
Pmean
(MPa)
Pmax
(MPa)
2000
4000
15,000
22
16
7
24
19
12
32
24
11
35
29
19
covering and is the angle of the ejection cone with respect to the concrete surface. Eq. (9) simply translates the fact that the resultant of
swelling pressure acting on the bottom part of the nodule is directly balanced by the vertical resultant of tensile stresses acting at the surface of
the ejection cone and that the pop-out effect is initiated when the local
tension stresses exceed the tension resistance of the concrete matrix.
Based on the evaluation of the swelling pressure obtained from
model 1, tensile stress can be calculated from model 2 and compared
to the tensile strength of concrete to assess the risk of pop-out.
Table 3
Evaluation of the contact pressure vs E modulus of lime (EL) and concrete (EC) and volume
(radius) variation of lime.
EL
(MPa)
V/V
(%)
R/R
(%)
p [EC = 7000]
(MPa)
p [EC = 15,000]
(MPa)
p [EC = 30,000]
(MPa)
100
10
20
30
40
50
10
20
30
40
50
10
20
30
40
50
3
6
9
12
14
3
6
9
12
14
3
6
9
12
14
6
12
18
23
28
9
18
27
35
42
12
24
35
46
56
6
12
18
24
29
10
19
27
35
43
13
25
36
47
57
6
12
18
24
29
10
19
27
35
43
13
25
36
47
57
150
77
200
78
thus metallized with Pt before being introduced into the vacuum chamber
of a scanning electron microscope ESEM. The electron beam gives a view
of topography and shape of hydrated lime. EDAX (Philips) system,
coupled with ESEM, allows the detection of elements identied on a
spectrum according to their energy dispersion.
These analyses allow obtaining a good identication of different
forms of calcium hydroxide crystals under connement.
4. Results and discussions
4.1. Stress calculation and modelling hypothesis
In order to feed the proposed models, data needed are:
Elastic modulus of hydrated lime and concrete,
Poisson's ratio of hydrated lime and concrete,
Variation of volume of nodule during hydration.
The elastic modulus and Poisson's ratio of lime are estimated from
[20]: the value used for the elastic modulus of 100 MPa and Poisson's
ratio is 0.25. Results obtained from the experimental programme running
Fig. 10. Evolution of tensile stresses vs contact pressure and nodule diameter.
10
20
30
40
50
0.19 D
0.36 D
0.48 D
0.57 D
0.64 D
0.11 D
0.26 D
0.37 D
0.45 D
0.51 D
0.07 D
0.21 D
0.30 D
0.37 D
0.43 D
10
and
CC
1 C
:
EC
11
79
One might conclude from the values in Table 2 that the pressure required to conne the reaction varies with the material. It must however
be noted that the model assumes an elastic behaviour of the conning
material whatever the value of the pressure, while an evaluation of
the stresses developed in the conning medium for the cellular concrete
block case (i.e. c,max = p and t,max = p/2) concludes that they exceed
by far the resistance of the blocks. Calculations show that, for a sample
of 18 mm diameter, the resistance is actually exceeded on a thickness
approximately equal to the diameter of the sample. It can therefore be
estimated that the effective stiffness of the zone of the conning
medium directly surrounding the inclusion is reduced with respect to
its reference undamaged value, thereby increasing the value of the
coefcient CC and reducing consequently the pressure so as to reach a
balanced situation between effective stiffness and pressure. A rened
modelling of this phenomenon would however require advanced tools
that are considered out of the scope of the present study. One must
also note that cracks were indeed observed in the zone surrounding
the inclusion for some of the cellular concrete blocks used for connement tests, which is in accordance with the above conclusions. On the
other hand, for an ordinary concrete containment, the calculated level
of pressure is such that the stress remains at a level below the resistance
of the material. The model reproduces thus correctly the experimental
trends.
The range of parameters considered for the upcoming parameter
studies is dened by:
EC: 7000, 15,000 and 30,000 MPa, which corresponds to concrete
connement ranging from poor characteristics to ordinary
concrete;
EL: 100 to 200 MPa, ranging from a normal value to a value doubled
to take into account densication of lime during hydration. Experimental tests shows actually that, for the samples corresponding to
hydration in heavy concrete blocks, and thus with the highest
densication rate, the value of the measured elastic modulus is
about 150 MPa;
L and C are equal to 0.25 and 0.20 (values from the technical
literature), respectively;
Change in volume of the spherical inclusion varying from 10 to
50%, which corresponds to changes in radius of 3 to 15%, respectively. This range roughly sweeps the radius variation observed
Fig. 11. Evolution of the minimal thickness of concrete cover vs nodule diameter (minimum pressure).
80
Fig. 12. Evolution of the minimal thickness of concrete cover vs nodule diameter (mean pressure).
between the inclusion and the matrix; the real pressure should
therefore be associated with only a fraction of the volume change;
The model assumes that the elastic modulus of lime is constant
throughout the swelling phase, whereas it is in fact a phenomenon
whose parameters vary with time. The mechanical characteristics of
hydrated lime at the initiation of the swelling (ini) are corresponding
to an unconned environment and progressively evolve to those of
hydrated lime properties in conned environment (fin). The model
conservatively considers the stiffer situation (fin) throughout the
entire swelling process.
The level of conservatism of the chosen modelling assumptions is
however quite impossible to quantify.
4.2. Model exploitation and parametric study
4.2.1. Evaluation of the contact pressure
Results of the calculation of the contact pressure are presented on
Table 3. It is showed that pressure is roughly independent from the
Fig. 13. Evolution of the minimal thickness of concrete cover vs nodule diameter (maximum pressure).
Ca(OH)2 content
[%]
8
9
12
17
24.2
23.9
23.6
23.7
99.6
98.1
96.9
97.4
quality of concrete. However, results are clearly inuenced by the rigidity of the lime and the variation of the volume: estimated pressure
ranges from 6 to 57 MPa (this latter value is clearly unrealistic but
denes an absolute upper bound that would never be overtaken even
for the worst conditions). It has also to be mentioned that a possible variation of the Poisson's ratio of the lime could induce signicant variation
81
of the pressure: e.g. for an elastic modulus equal to 100 MPa, a variation
of volume corresponding to 30% and Poisson's ratio equal to 0.2, 0.25
and 0.3, resulting pressure is equal to 15, 18 and 23 MPa respectively.
For the reasonable average values of the parameters (EL = 150 MPa
and volume variation of 20%), pressure is up to 19 MPa, which is however
a clearly conservative estimate of the real pressure, as illustrated on Fig. 8.
4.2.2. Stress distribution
Compressive and tensile stress distributions are given in Figs. 9 and
10 for several values of pressures and nodule diameters. Curves are
corresponding to 3 levels of pressure taken from Table 3:
Pmin = 6 MPa (pressure calculated on the base of minimalistic
hypotheses),
Pmean = 19 MPa (pressure conservatively calculated on the base of
most probable hypotheses),
(e) Free lime nodule at 5 mm depth : pop out but no internal crack
Fig. 14. Sections of concrete blocks and free lime nodules.
82
(a)
(b)
Fig. 15. Free lime nodule at 5 mm depth (a) and 10 mm depth (b).
Fig. 10 shows that, except for the minimum conditions, there exists a
region around the nodule where tensile forces are potentially present
and thus likely to initiate micro-cracking. No signicant cracking has
however been observed in tests performed in the laboratory for lime hydration in heavy concrete blocks (chapter 4). Table 4 gives the thickness
of the potentially cracked area corresponding to a module of lime E =
150 MPa for different values of the volume change and of the tensile
strength of the concrete (corresponding to percentiles of 5, 50 and 95,
respectively, for standard concrete C25/30).
One must be reminded that the values of radial swelling measured
in the laboratory (chapter 4) are of the order of 7% (so corresponding
to a volume variation V/V about 15%). However, in the worst case
(V/V = 50%) and for a very low concrete tensile strength (1.8 MPa),
the thickness of the cracked area is potentially of the order of 64% of
the diameter. Under these conditions, if these cracked zones are fully assimilated to non-resistant inclusions with a diameter equivalent to 2.28
times the diameter of the nodule (i.e. 1 D + 2 0.64 D), the calculation
of the effect of voids on the compressive strength of concrete according
to Section 1 of the present paper shows that, even in the case of cracking
around all the nodules included in the concrete (for a reasonable concentration of such lime nodules), the overall strength of the concrete
would hardly be affected.
4.2.3. Pop-out risk estimation
Figs. 11, 12 and 13 represent the results obtained by using the Eq. (9)
to estimate the risk of pop-out. These gures actually represent the
Table 6
Measurements of conned lime cylinders in concrete blocks (D is the distance between the nodule and the surface and d is the diameter of the nodule).
Test
Maximal connement
Restricted connement
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
Initial lime
Observations
Characteristics of hydrate
Density
(g/cm3)
D/d
Pop-out
(Y/N)
Cracking
(Y/N)
Density
(g/cm3)
Volume expansion
(%)
Radial expansion
(%)
Longitudinal expansion
(%)
1.38
1.58
1.44
1.44
1.38
1.49
1.47
1.39
1.43
1.40
1.41
1.46
1.50
1.39
1.45
1.51
1.41
1.50
4.5
4.5
4.5
4.5
4.5
4.5
2
2
1
1
1
0.5
0.5
0.5
0.25
0.25
2
0.25
N
N
N
N
N
N
N
N
N
N
N
Y
N
N
Y
Y
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
1.39
1.71
1.62
1.67
1.47
1.54
1.66
1.50
1.49
1.55
1.52
Unrecovered
1.50
1.46
Unrecovered
Unrecovered
1.14
1.31
32
22
18
14
24
28
17
23
27
20
23
10
5
7
3
6
8
8
6
8
8
6
8
11
4
6
11
9
1
8
8
3
9
32
25
12
7
5
10
64
51
24
27
76
73
83
1.84
Fig. 16. Evolution of the density of hydrated lime vs volume expansion (conned (tests 1 to 16) and less conned (tests 17 and 18)).
Table 7
Rigidity modulus and compressive strength of hydrated lime cylinders (MPa).
Specimen reference
a
13 centred
14 centredb
17 centred
2C20
4C10
5C40
10C10
a
b
Compressive strength
[MPa]
Rigidity modulus
[MPa]
5.1
5.1
5.4
8.3
3.8
5.3
5.4
150
164
189
168
129
180
144
84
Lin (Counts)
Portlandite
220
210
200
190
180
170
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
0
NC1
d=2.62351
Portlandite
d=4.89551
Portlandite
d=3.10515
d=23.80000
d=26.83630d=16.23526
10
20
30
40
2-Theta - Scale
NC1 - File: NC1.raw - Type: 2Th/Th locked - Start: 2.000 - End: 45.000 - Step: 0.020 - Step time: 0.6 s - Temp.: 25 C (Room) - Time Started: 8 s - 2-Theta: 2.000 - Theta: 1.000 - Chi: 0.00 - Phi: 0.00 - X: 0.0
Operations: Background 0.000,0.000 | Smooth 0.150 | Import
04-0733 (I) - Portlandite, syn - Ca(OH)2 - Y: 86.46 % - d x by: 1. - WL: 1.5406 - 0 - I/Ic PDF 1.4 -
When depth was higher than 1 times the free lime nodule diameter,
no pop-out was observed.
4.3.3. Analysis of densication phenomenon and nodule expansion
As described in 3.2, the blocks are cut with a diamond saw (dry) at
the right and the edge of the nodule and hydrated lime cores are then
recovered, measured and weighed. As a reminder, in unconned
conditions, when quicklime CaO (bulk density about 1.5 g/cm3) is
transformed into Ca(OH)2 hydrate, it is in the shape of a powder of
low density (about 0.5 g/cm3). The measurements show (Table 6), in
conned situation, a densication process of the hydrate which
offers a density much higher than in unconned case. During these
tests, the hydrates obtained in conned environment showed a density
varying from 1.4 to 1.7 g/cm3, with an average value of 1.55 g/cm3
(Table 6).
This densication process logically implies a volume expansion
factor much lower than what is generally known when unconned
(300% as calculated from the ratio of 1.5 g/cm3 for lime divided by
0.5 g/cm3 for Ca(OH)2 hydrated lime). Expansion factors measured
here are in the range from 15 to 30% (23% average). Fig. 16 shows the
experimental values in the case of a high conned situation (tests 1 to
16, rhomb dots) and in the case of a partial connement (tests 17 and
18, square dots).
The positive expansion that is observed in the case of conned
samples (rhumb dots) means that these connements are not perfect,
leaving a free space for expansion. This imprecision is statistically distributed across different samples. These expansions are not related to
a deformation of the concrete block. It is possible to estimate the density
of the core hydrate in the case of perfect connement by extrapolating
the regression line. This extrapolation (82% correlation) allows to
calculate that, in the case of perfect connement (no volume expansion), the hydrate, formed from lime industrial bulk with a density of
1.5 g/cm3, will have an equivalent density of 1.84 g/cm3: this remains
less than the absolute density of the hydrate (2.2 g/cm3).
85
86
(a) NC1
in grain size, this is not the case with regard to their crystallinity: only
C110 and C115 are characterized by the presence of euhedral crystals
(Fig. 23). Grain size is ner for sample type C120.
The scanning electron microscopy allowed observing the structures
of lime processed under various conditions of connement, both on site
and in the laboratory. The comparison of samples generated in the laboratory shows the difference between unconned and conned, and, for
conned samples, the evolution of structures versus rates of expansion.
Structure and porosity may be compared with the densities of cylinders
(Table 6).
5. Conclusions
A simple model based on the theory of elasticity, on duly validated
experimental data and on reasonable engineering judgement has been
(b) C115
(c) C120
Fig. 22. Comparison of the samples under ESEM (low magnication).
(a) NC1
(b) C110
(c) C115
(d) C120
87
nodule and its impact on the strength of the concrete at the macroscopic level is proven as negligible;
for the most probable values of the swelling pressure, the minimum
concrete cover thickness allowing the prevention of the pop-out
phenomenon is of the order of half the diameter of the inclusion. In
other words, under the assumptions considered in this study, no
nodule located at a depth of more than half its diameter should
cause pop-out even when hydrated;
The following conclusions can be drawn from the experimental
programme:
hydration of quicklime in a conned environment, leads to the
production of completely hydrated portlandite nodules;
hydrate formed in a conned environment occupies the available volume and, in present cases, may reach very high densities (average
value = 1.55 g/cm3);
the rate of volume expansion of the quicklime, depending on the free
volume, is very low (average 23% expansion) compared to an
unconned and is the result of a non-full connement;
88
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