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A R T I C L E I N F O A B S T R A C T
Keywords: Combined mechanical and environmental actions reduce service life of reinforced concrete structures more than
C. Freezing and thawing each of the participating actions alone. In this contribution, the influence of freeze-thaw cycles on capillary
Capillary absorption water absorption and chloride penetration into ordinary concrete with two different water-cement ratios and air-
D. Chloride entrained concrete was investigated. Water profiles in concrete were quantified by neutron radiography.
C. Durability
Capillary water absorption and chloride penetration are both slowed down considerably by air entrainment.
Neutron radiography
Chloride ions dissolved in water are filtered out of the penetrating salt solution and remain concentrated near the
surface. Capillary water absorption and chloride penetration into ordinary concrete are accelerated considerably
by frost damage. After exposure to freeze-thaw cycles a damage gradient from the surface to the center of the
samples was observed. Transport mechanisms were studied in some detail and the data obtained can serve as a
basis for more realistic prediction of service life of reinforced concrete structures under the influence of com-
bined freeze-thaw cycles and chloride penetration.
⁎
Corresponding author at: Schlierbergstr. 80, D-79100 Freiburg, Germany.
E-mail address: wittmann@aedificat.de (F.H. Wittmann).
http://dx.doi.org/10.1016/j.cemconres.2017.05.018
Received 16 January 2017; Received in revised form 24 May 2017; Accepted 26 May 2017
0008-8846/ © 2017 Elsevier Ltd. All rights reserved.
P. Zhang et al. Cement and Concrete Research 100 (2017) 60–67
Table 1
Composition of the three types of concrete used in these test series.
Type W/C Cement Sand Gravel Water Air-entr. Air content 28 day comp. strength
kg/m3 kg/m3 kg/m3 kg/m3 % % MPa
a water-cement ratio of 0.6 but in this case an air entraining agent was 2.3. Capillary absorption and chloride penetration
added to make the concrete frost resistant. For all three types of con-
crete Portland cement Type 42.5 was used. The coarse aggregates Concrete cubes, which were exposed to 0, 10, 50, and 100 freeze-
consisted of local crushed aggregates with a maximum diameter of thaw cycles, were cut into two halves. All half cubes were then first
20 mm and a density of 2620 kg/m3 and local river sand with a max- dried in a ventilated oven at 50 °C until constant weight was reached.
imum grain size of 5 mm and a density of 2610 kg/m3 from Qingdao Then the four side surfaces (50 × 100 mm) were covered with alu-
area. The exact composition of all three types of concrete is given in minum foil. The cast surface (100 × 100 mm) of the dry concrete
Table 1. specimens was then brought into contact with water. The water surface
From all three fresh mixes prisms with a cross section of was kept constant at approximately 3 mm above the surface of the
100 × 100 mm and a length of 400 mm were produced. In addition, concrete specimens by a special support. The mass of the water ab-
cubes with a side length of 100 mm were produced from the same sorbed by capillary action was determined after 0.5, 1, 2, 4, 8, 12 and
mixes. The fresh concrete was compacted in steel molds and allowed to 24 h by weighing.
harden in the laboratory under plastic sheets. After 24 h, the steel molds In addition, concrete specimens after a certain number of freeze-
were removed and the prisms and cubes were placed in a curing room thaw cycles were put in contact with an aqueous 3% NaCl solution for
with a controlled temperature of T = 20 ± 2 °C and a relative hu- testing chloride penetration. After 3, 10 and 100 days, thin layers of
midity RH > 95%. When the specimens had reached an age of 24 days 1 mm thickness were milled consecutively from the surface, which was
they were placed in water at a temperature of 20 °C until they have in contact with the salt solution. The chloride content of the powder,
reached an age of 28 days. obtained in this way, was finally determined by titration.
beam, which passes through the concrete slice the local moisture con-
10 tent can be obtained. For the quantitative evaluation of the neutron
images, neutron signal transfer analysis was used, in which a scattering
0 correction based on Point Scattered Function (PScF) was applied. More
details on the technique of NR and the quantitative analysis can be
-10
found in references [11–14].
Fig. 1. Temperature T in the cooling box and at the center of the concrete specimens as Compressive strength was determined by means of a servo-con-
function of time t. trolled testing machine. The results obtained for all three types of
61
P. Zhang et al. Cement and Concrete Research 100 (2017) 60–67
60 100
Compressive strength, MPa
40
20 A
A 20 C
C CA
CA 0
0 0 20 40 60 80 100
0 20 40 60 80 100 Freeze-thaw cycles N
Freeze-thaw cycles N Fig. 4. Elastic modulus of concrete A, C and CA as function of the number of imposed
Fig. 3. Compressive strength of concrete A, C and CA as function of number of imposed freeze-thaw cycles.
freeze-thaw cycles.
the pore size distribution of the two other types of concrete in the range
concrete are shown in Fig. 3. As expected concrete A has a significantly between 30 and 60 μm in particular. This is the characteristic range of
higher compressive strength as compared to concrete C and CA. Com- artificial pores in concrete. In the range of smaller pores the distribution
pressive strength of air-entrained concrete CA is slightly reduced if function of concrete C and CA remain at nearly the same distance. That
compared with concrete type C. Compressive strength of all three types means the distribution of smaller pores is not influenced by adding the
of concrete decreases with increasing number of freeze-thaw cycles. But air entrainment agent.
it is obvious that the air-entrained concrete CA is significantly more
frost resistant than concrete A and C in particular. 3.3. Capillary absorption
The influence of the number of freeze-thaw cycles on the elastic
modulus of the three types of concrete is shown in Fig. 4. While frost Capillary absorption was measured first in the undamaged state
damage as observed on concrete type CA is comparatively small, con- (N = 0) and then after 10, 50 and 100 freeze-thaw cycles. Results are
crete C can be considered to be destroyed after 100 freeze-thaw cycles. shown in Fig. 6.
If gravity can be neglected, that means if water is absorbed hor-
3.2. Porosity and pore size distribution izontally or vertically for a short time only, the amount of capillary
absorbed water as function of time can be described by the following
Porosity and pore size distribution of concrete A, C and CA was simple equation [15,16]:
determined by mercury intrusion porosimetry (MIP). Results are shown
∆W (t ) = A t (1)
in Fig. 5 and Table 2. The pore size distribution changes moderately
only in both concretes type A and CA, but it changes considerably in In case water is vertically absorbed the mass of the already absorbed
concrete Type C. Porosity of concretes A and CA moderately increased water slows down further absorption and finally a constant value is
after 50 and 300 freeze-thaw cycles, respectively. But porosity of con- reached when the mass of absorbed water compensates the capillary
crete C increased substantially after 25 freeze-thaw cycles only. Fig. 5 pressure. This process can be described in a simplified way by the fol-
shows us that the pore size distribution of concrete CA deviates from lowing empirical equation:
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P. Zhang et al. Cement and Concrete Research 100 (2017) 60–67
tribution.
0.0 0.00
10 100 1000 10000 100000 10 100 1000 10000 100000
Diameter, nm Diameter, nm
5000
A (N=0) C (N=0) CA (N=0)
A (N=10) C (N=10) CA (N=10)
4000 A (N=50) C (N=50) CA (N=50)
A (N=100) C (N=100) CA (N=100)
3000
2000
1000
0
0 1 2 3 4 5 0 1 2 3 4 5 0 1 2 3 4 5
Square root of time, h0.5 Square root of time, h0.5 Square root of time, h0.5
Fig. 6. Water capillary absorption of ordinary concrete A (left), C (center), and air-entrained concrete CA (right) after a certain number of freeze-thaw cycles.
63
P. Zhang et al. Cement and Concrete Research 100 (2017) 60–67
2000 0
C (N=0)
A(t), g/(m2.h1/2)
C (N=10)
1500 C (N=50) 0 CA (N=0)
A (N=0)
A (N=10) C (N=100) CA (N=10)
1000 A (N=50) 0 CA (N=50)
A (N=100) CA (N=100)
500 0
0 0
0 1 2 3 4 50 1 2 3 4 50 1 2 3 4 5
Time, h1/2 Time, h1/2 Time, h1/2
Fig. 7. Time-dependent coefficient of capillary absorption (see Eq. (3)) of ordinary concrete A (left), C (center) and air-entrained concrete CA (right) after increasing number of freeze-
thaw cycles. Fitted lines were obtained from experimental results shown in Fig. 6.
CA 0.08 CA (N=0)
1500 0.06
0.04
1000
A: y=685.6+3.21x 0.02
CA: y=728.4+2.85x
0.00
500 0 5 10 15 20 25 30 35 40 45
Penetration depth, mm
0 20 40 60 80 100
Freeze-thaw cycles Fig. 10. Moisture profiles in the central part of the three types of concrete as marked by a
red rectangle in Fig. 9. (For interpretation of the references to colour in this figure legend,
Fig. 8. Initial coefficient of capillary absorption (Ai) of the three different types of con- the reader is referred to the web version of this article.)
crete after a given number N of freeze-thaw cycles and results obtained by fitting the
experimental data with linear functions.
is clear evidence that the induced frost damage as obtained in a cooling
box with a thermal cycle of < 2.5 h is not equally distributed in the
the position of the aggregates can be visualized. They do not absorb
exposed samples. The temperature difference near the surface is 40 °C
water and hence the area where they are situated appears as dry zones.
during one cycle, while the temperature difference in the center is
But from Fig. 9 it can also be seen that the matrix consisting of har-
approximately 22 °C (see Fig.1) only. Depending on the size of the
dened cement paste in concrete type C absorbs significantly more water
specimens to be tested, the duration of each cooling cycle should be
than the matrix in concrete Type CA. Air entrainment not only reduces
significantly longer. Otherwise an important damage gradient is gen-
the penetration depth it also reduces the water content in the matrix.
erated in the concrete block and the damage is size dependent. The
In Fig. 11 similar neutron radiographies are shown but in this case
gradation of the temperature inside the specimen is inevitable for the
three different layers of concrete Type C were investigated. As shown in
frost test, it also imposes damage to concrete besides the damage caused
Fig. 2, layer 1 of concrete Type C (C-1) is close to the surface of the
by freezing and thawing cycles by thermal stress. How the size of
specimen during exposure to freeze-thaw cycles, while layers 2 and 3
specimens affect the final result needs to be investigated, then we can
are more and more remote from the surface which is exposed to tem-
reach a conclusion if it is necessary to prolong the freezing and thawing
perature cycles.
duration.
Moisture profiles in the three slides C1, C2 and C3 were determined
Slides CA-1 and CA-2 were cut from a block of air entrained con-
in the same way as described above for the radiographs shown in Fig.9.
crete and exposed to 200 freeze-thaw cycles. The resulting neutron
Results obtained are shown in Fig. 12. It can be seen that the pene-
images and the quantified humidity distributions are shown in Fig. 13.
tration into the surface near slide C1 is highest, while the penetration
It can be seen that in agreement with data shown in Fig. 11 and 12 the
depth and the maximum amount of absorbed water in the slide C3,
damage near the surface CA-1 is again more serious as compared to
taken from the center of the specimen, are both significantly lower. This
damage in the deeper layer CA-2. The water content in the cement
Fig. 9. Neutron images (upper part) and the quantified moisture distributions (lower part) in the three types of concrete after 4 h of capillary water absorption from the bottom surface.
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P. Zhang et al. Cement and Concrete Research 100 (2017) 60–67
Fig. 11. Neutron images and the quantified moisture distributions in different layers of concrete type C after exposure to 10 freeze-thaw cycles after 4 h of water absorption from the
bottom surface.
0.06 0.06
0.04 0.04
0.02 0.02
0.00 0.00
0 5 10 15 20 25 30 35 40 45 0 5 10 15 20 25 30 35 40 45
Penetration depth, mm Penetration depth, mm
Fig. 12. Moisture profiles as determined on the basis of data shown in Fig. 11 on three Fig. 14. The moisture profiles as determined in two different slides of concrete type CA
different layers of concrete C-1, C-2, and C-3 after 10 freeze-thaw cycles and after contact after exposure to 200 freeze-thaw cycles after contact with water for 4 h.
with water for 4 h.
diffusion process begins due to the great concentration difference of
matrix and the penetration depth are higher in specimen CA-1. chloride ions in the pore solution near the surface and the pore solution
The moisture profiles were also determined form the data shown in in deeper zones. A certain part of the chloride ions will be adsorbed at
Fig. 13. Results are shown in Fig. 14. As can be seen the penetration the huge surface of hardened cement paste and another part reacts
depth and the maximum absorbed amount of water are significantly chemically with the hydration products. This fixed part of chloride ions
higher in CA-1 as compared to CA-2. This is again clear evidence for a does not participate in the diffusion process. Altogether this is a rather
damage gradient, with highest damage near the surface. complex process, which needs to be treated separately. In this context,
we will consider the chloride profiles and the influence of freeze-thaw
cycles on chloride profiles in a rather phenomenological way. But more
3.5. Chloride penetration detailed investigations have to follow. It is clear, however, right now
that application of a simple diffusion equation is an oversimplicfication
It has been shown in the preceding sections that the porous struc- of acomplex process.
ture of concrete is gradually damaged if exposed to an increasing The surface of samples of the three types of concrete A, C and CA
number of freeze-thaw cycles. As a consequence, the amount of water, were put in contact with 3% NaCl solution for 3, 10 and 100 days.
absorbed by capillary action per unit time, increases. In case the surface Samples of all different types of concrete were exposed to 0, 10, 50 and
of concrete gets in contact with an aqueous NaCl solution the solution 100 freeze-thaw cycles before contact of the surface with the salt so-
will also be absorbed by capillary action. But the nano-pores of the lution. The chloride profiles obtained in this way are shown in Fig. 15.
hardened cement paste act like a molecular filter and dissolved chloride The molecular filter effect is obvious. While water penetrated within
is hindered to penetrate into the pore space. As a consequence, a high a short period of a few hours 30 to 40 mm into the pore space, chloride
chloride concentration is reached in the surface near zone, while the ions remain essentially concentrated within a range of few mm from the
water penetrates much deeper into the porous material. Then a slow
65
P. Zhang et al. Cement and Concrete Research 100 (2017) 60–67
surface. From Fig. 15 it can be seen that the amount of chloride and the characteristic way. As a consequence, the coefficient of capillary ab-
penetration depth of chloride both increase slowly with increasing ex- sorption is reduced. This modification leads to a change of damage
posure time. It also becomes obvious that chloride penetration is ac- gradient which can be visualized by neutron radiography. For practical
celerated by an increasing number of freeze-thaw cycles. Much more applications, it follows that structural elements which are exposed to
chloride penetrates into concrete type C. As concrete type C must be freeze-thaw cycles in permanent or temporary contact with NaCl so-
considered not to be frost resistant, chloride content increases en- lution, frost resistant concrete has to be applied. For realistic prediction
ormously after exposure to 50 and 100 freeze-thaw cycles. The cement- of service life, it is necessary to take the combination of freeze-thaw
based matrix in concrete C is severely damaged after exposure to freeze- cycles and aggressive environment into consideration.
thaw cycles. Service life of a reinforced concrete structure built with
concrete type C under harsh weather conditions will be very short. The Acknowledgment
microstructure of concrete is severely damaged by frost action. As a
consequence the efficiency of the filter is reduced. Air entrained con- The authors would like to thank Mr. P. Vontobel and Mr. J. Hovind
crete Type CA allows a small amount of chloride to enter the pore space from PSI, Switzerland, for the help during the neutron radiography test.
only. But, most important, even after exposure to 100 freeze-thaw cy- Financial support by Natural Science Foundation of China
cles the chloride profile after three days of contact with the salt solution (51420105015, 51278260), Basic Research Program of China
remains very low. Even after 100 days of contact with the salt solution (2015CB655100) and China Foreign Affairs Office (2016, 111 Program)
the penetration depth remains modest and the material is not really are gratefully acknowledged.
sensitive with respect to exposure of freeze-thaw cycles up to N = 100.
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