Composites: Part B
journal homepage: www.elsevier.com/locate/compositesb
a r t i c l e i n f o a b s t r a c t
Article history: This study examined the effects of antifreeze on the physical and mechanical properties of the concrete
Received 17 November 2012 which are produced in cold weather. 30% Calcium Nitrate and 5% hydroxyethylaminemixture (HEA), Cal-
Received in revised form 17 January 2013 cium Nitrate (KN) and Polyhydroxy Amine (PA) were used as additives in antifreeze. Prepared concrete
Accepted 19 February 2013
samples were placed in a formwork and exposed to the frost at 0 C, 5 C, 10 C, 15 C and 20 C
Available online 27 February 2013
for 2 days. Afterwards, concrete samples in the freezer were cured at the room temperature until the
28th day and permeable pore space volume, water absorption ratio, density, capillarity ratio, imperme-
Keywords:
ability, compressive strength, static modulus of elasticity, Poissons ratio and tensile strength values of
B. Physical properties
B. Mechanical properties
the concrete samples were determined after the curing. In conclusion, 30% Calcium Nitrate and 5%
B. Porosity hydroxyethylaminemixture (HEA) were found to be giving the best performance among the antifreeze
E. Cure types. The physical and mechanical properties of the concrete were negatively affected from all antifreeze
B. Cure behaviour types due to the temperature decrease of the exposed fresh concrete.
2013 Elsevier Ltd. All rights reserved.
1. Introduction penetration of water [5,6]. In cold weather, the water inside these
pores freezes and thus expands. As it is known, approximately a 9%
The method and time of placing the concrete into the formwork increase in volume occurs when water turns into ice. Accordingly,
and the curing conditions signicantly affect the physical and if freezing occurs when 91% or more of the volume of the pores in-
mechanical properties of the concrete, regardless of the materials side the concrete are lled with water, the volume of the water will
used in the composition of concrete [1]. not t in the existing volume when it turns into ice, as it will apply
Portland cement cannot harden under a freezing point without pressure to the surrounding. Since some of the water turns into ice
some thermal protection. For this reason, fresh concrete should be and causes an increase in volume, it pushes the water which has
protected if it is below the freezing point. Protection procedures not yet turned into ice in an outwardly direction and creates a high
can be performed with an insulation material or by increasing level of hydraulic pressure. This hydraulic pressure might cause
the internal temperature of the concrete over 5 C. Temperature hardened cement paste, which surrounds the aggregate and aggre-
should denitely be conserved in emergency conditions. If the con- gate grain inside the concrete causes it to crack [57]. On the other
crete is not protected from the cold, it freezes and might cause a hand, researchers reported that concrete was less affected by frost
disaster [2]. damage when a concrete with high density and an impermeable
Concrete is widely used in buildings, which are constantly ex- surface is obtained [8,9].
posed to temperature and moisture. The mechanical and physical Considerable progresses have been made in the production,
properties of the concrete vary according to environmental condi- placing, curing and protection of concrete under cold air condi-
tions in the production period and in curing conditions [3]. tions. As a result, rms do not need to take a break to place the con-
The literature contains a large body of research to explain the crete in cold weather [10].
freezing mechanism of concretes [4]. Most of the studies showed Since the temperature of the material components of the con-
that aggregate voids and the transitions between cement paste crete will have be low temperature in cold weather, the tempera-
aggregate interfaces affect the freezing of concrete. Concrete is af- ture of the concrete produced also becomes low. The ideal
fected from frost according to the multiplicity of pores on the temperature for casting concrete is 1516 C degrees and the tem-
materials composing the concrete which are large enough to allow peratures which are considered normal when varying between 5
and 32 C. At temperatures lower than +5 C, chemical reactions
between cement and water signicantly decrease. Due to the
Corresponding author. Tel.: +90 456 2337425/6/1133; fax: +90 456 2337427. deceleration of the hydration of cement at low temperatures, the
E-mail address: mcullu@gumushane.edu.tr (M. ullu).
1359-8368/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.compositesb.2013.02.012
M. ullu, M. Arslan / Composites: Part B 50 (2013) 202209 203
setting time becomes longer. Since low hydration speed deceler- samples were taken according to the principles specied in EN
ates the formation of calciumsilicatehydrate (CSH) gels, which 706 EN 12620 + A1 in such a way as to represent an aggregate heap
is the most important component of hydration and has a bonding [17].
property, it results in a delayed resistance acquisition. Acquiring
the desired resistance at a delayed time negatively affects the 2.1.3. Antifreeze
properties of concrete and delays the time taken for the removal Three different antifreezes were used in the study. Antifreezes
of the mold [11]. are chemical additives in compliance with ASTM C 494 and TS
When water inside the concrete completely turns into ice with- 11746 standard [18,19]. Some of the properties of the antifreezes
out setting, there will be no water adequate for hydration, as are presented in Table 2.
hydration completely stops and concrete volume expands. After a
certain time, if the ice inside the concrete dissolves and turns into 2.1.4. Super plasticizer
water due to temperature increase, concrete can set and harden. An additive which is in compliance with ASTM C 494 Type F and
However, in such cases, since void volume which occurs due to EN 934-2 standards and provides high range water reducer and
melting of ice will be quite large and gels which are the products early high resistance was used in fresh concrete samples [1820].
of hydration, it will fail to ll these voids adequately, causing a de-
crease in the resistance of the concrete, and thus water imperme- 2.2. Method
ability increases [12].
However, if the concrete which set does not gain enough resis- Antifreeze ratios which will be used for concrete samples for
tance when it freezes, then a cracked and low-resistant concrete is each type were determined by a preliminary work. Basically, the
obtained as the water in capillary voids freeze and expand. Various antifreeze amount in the concrete mix is approximately 12% of
researchers suggest 514 MPa as an adequate compressive the total mass of the cement. The antifreeze ratios are presented
strength. Another method is to determine how many days later in Table 3 [21].
concrete samples, which are kept at different temperatures, remain After placing the prepared concrete samples in formwork, the
undamaged by frost. However, in cases where the concrete which samples were put in a deep freezer within 15 min. They were ex-
started setting did not reach a sufcient level of resistance, a loss of posed to frost at 0 C, 5 C, 10 C, 15 C and 20 C degrees
resistance is expected in the concrete. The freezing of water in a in a deep freezer for 2 days. The samples, which were taken out
concrete with adequate resistance for once does not cause cracks of the freezer, were then removed from the formwork 1 day later.
and does not affect resistance. This is explained by the fact that They were cured in water at room temperature until the 28th day.
water inside the concrete with a sufcient degree of resistance is At the end of the curing period, the permeable pore space volume,
used for hydration and thus the amount of water decreases. water absorption ratio, unit volume weight, capillarity ratio,
According to ACI 306R-88 (Cold Weather Concreting), to avoid a impermeability, compressive strength, static modulus of elasticity,
concrete which was exposed to frost once from being damaged, Poissons ratio and tensile strength values of the concrete samples
its resistance should reach a minimum of 3.5 MPa. A concrete with were determined.
a good mixture ratio at +10 C can reach 3.5 MPa resistance 2 days
after placing it [1215]. 2.2.1. Identication of permeable pore space volume
As an alternative, antifreeze additives can be used in cold Permeable pore space volume (B0) was calculated on ve
weather. These chemical additives repress the freezing point of 100 200 mm cylindrical concrete samples according to ASTM
water under 0 C degrees and accelerate the hydration of cement; C642 principles. Eq. (1) was used to calculate B0 [22].
however, the long-term effects of these additives remain unknown
[2]. Concrete antifreeze additives are an indispensable component CA
B0 100 1
of concrete, particularly in winter and in areas with a cold climate. CD
The overall effects of these additives, which are thought to have where B0 is the permeable pore space volume, %, A is mass of oven-
overall positive effects, should be determined and these effects dried sample in air, g, C is mass of surface-dry sample in air after
should be taken into account in the design process [16]. immersion and boiling, g, D is the apparent mass of sample in water
In parallel to these advancements, the present study examined after immersion and boiling, g [22].
the physical and mechanical properties of the concrete with anti-
freeze additives which were exposed to frost. To achieve this goal, 2.2.2. Identication of water absorption
the permeable pore space volume, water absorption ratio, density, Water absorption ratio (m) was calculated on ve
capillarity ratio, impermeability, compressive strength, static mod- 100 200 mm cylindrical concrete samples according to ASTM
ulus of elasticity, Poissons ratio and tensile strength values were C642 principles. Eq. (2) was used to calculate m [22].
all measured.
BA
m 100 2
A
2. Materials and methods
where m is the water absorption ratio by weight, %, A is mass of
oven-dried sample in air, g, B is the mass of surface-dry sample in
2.1. Material
air after immersion, g [22].
2.1.1. Cement
CEM I 42.5R Portland cement was used in the study. The chem- 2.2.3. Identication of density
ical, physical and mechanical properties of the cement are pre- Density (D) was calculated on ve 100 200 mm cylindrical
sented in Table 1. concrete samples according to EN 12390-7 principles. Eq. (3) was
used to calculate D [23].
m
2.1.2. Aggregate D 3
Limestone aggregate, which is used in the production of normal V
resistance concretes in concrete facilities among (05, 512, 12 where D is the density of concrete sample, gr/cm3, m is mass of the
22) aggregate groups were used in the samples. The aggregate concrete sample depending on its condition during the experiment,
204 M. ullu, M. Arslan / Composites: Part B 50 (2013) 202209
Table 1
Chemical, physical and mechanical properties of CEM I 42,5R.
Table 2
Antifreeze type and properties.
HEA 1 1 1 1 1
fc F=Ac 5
KN 1 1 2 2 2
PHA 1 1 1 1 1
where fc is the compressive strength, MPa, F is total maximum load,
N, Ac is the area of loaded surface, mm2 [26].
2.2.9. Identication of tensile strength capillarity ratios of concrete samples decrease. In addition, the
Tensile strength (T) was calculated on ve 100 200 mm cylin- graph of mean capillarity ratio is presented in Fig. 4.
drical concrete samples according to ASTM C496 principles. Eq. (8)
was used to calculate E [28]. 3.5. Impermeability
T 2P=pld 8
The impermeability value increases in parallel to the decrease
where T = splitting tensile strength, MPa, P = maximum applied load of temperature to which the concrete is exposed. The reason for
indicated by the testing machine, N, l = length, mm, d = diameter, this increase is the increasing void structure due to the decrease
mm [28]. in temperature to which the concrete is exposed. If pressurized
water is applied to porous concrete, water penetration depth in-
creases. The graph for the mean impermeability values are pre-
3. Results and discussion
sented in Fig. 5.
3.4. Capillarity ratio The Poisson ratio values decrease in parallel to the decrease in
temperature which the concrete is exposed. The reason for the de-
The capillarity ratio value decreases in parallel to the decrease crease of Poissons ratio is observed due to the decrease of temper-
in temperature value to which the concrete is exposed. The reason ature of the exposed concrete. The temperature decrease of the
for this decrease is the increased void structure due to decrease in fresh concrete yields a decrease of the compressive strength and
temperature to which the concrete was exposed. Accordingly, the static modulus of elasticity of the concrete specimens. The decreas-
ing compressive strength also yields a greater deformation of the Considering the effects of all antifreeze types used in concrete
specimens hence Poissons ration is increased. The graph for the mixtures on the physical and mechanical properties of the con-
mean Poissons ratio values is presented in Fig. 8. crete, 30% Calcium Nitrate and 5% hydroxyethylaminemixture
(HEA) gave the best performance.
If fresh concrete is exposed to frost, water is required to achieve
3.9. Tensile strength the hydration of cement and thickness of concrete freezes and
creates a porous structure inside the concrete (Turhan [12]).
The tensile strength values decrease in parallel to the decrease The permeable pore space volume value increases in accordance
in temperature values to which the concrete is exposed. The reason with the decrease in temperature value to which the concrete is
for this decrease is the decrease of the tensile strength value of the exposed.
specimens due to the decreasing temperature of the exposed con- It was observed that water absorption ratio of porous concrete
crete specimens. The graph for the mean tensile strength values is increased regarding to the permeable pore space volume value.
presented in Fig. 9. It was observed that, porous structures inside the concrete also
decreased the unit volume weight of the concrete.
The amount of capillary absorbed water decreases in accor-
4. Conclusion dance with the decrease in temperature to which fresh concrete
is exposed. The reason for this might be that the voids which are
The following results were obtained according to the frost con- formed due to the freezing of the water inside the concrete dur-
ditions to which fresh concrete was exposed.
M. ullu, M. Arslan / Composites: Part B 50 (2013) 202209 209
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