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The methodology for assessing the impact of new generation

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DOI: 10.1016/j.conbuildmat.2013.11.092

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Construction and Building Materials 53 (2014) 488–502

Contents lists available at ScienceDirect

Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

The methodology for assessing the impact of new generation

superplasticizers on air content in self-compacting concrete
Beata Łaźniewska-Piekarczyk ⇑
Silesian Technical University, Faculty of Civil Engineering, Department of Building Materials and Processes Engineering, Akademicka 5 Str., 44-100 Gliwice, Poland

h i g h l i g h t s

 Too much air is noticed in SCC that meets the requirements of EN 12350-8.
 Too much air remains in the SCC despite its high liquidity.
 Test compatibility of SP does not recognize the impact of SP on air content in SCC.
 Foam ability, stability index and surface tension tests assess the impact of SP on air content in SCC.

a r t i c l e i n f o a b s t r a c t

Article history: Certain types of the new generation superplasticizers (SP) cause the rise of excessive air content in self-
Received 13 January 2012 compacting concrete (SCC). The influence of different type of SP on air-content in cement paste and fresh
Received in revised form 17 November 2013 SCC are tested in the paper. The qualitative methods (foam ability and stability index), which serves the
Accepted 26 November 2013
best choice of SP not showing the side-effect in the form of an excessive SCC air-entrainment are pre-
Available online 4 January 2014
sented. The surface tension of SP solutions is also analyzed. The results of tests show that we can predict
the influence of SP on air-content of SCC by measuring the surface tension of SP solution, foam ability and
Keywords:
stability index of cement paste.
Self-compacting concrete (SCC)
Superplasticizer
Ó 2013 Elsevier Ltd. All rights reserved.
Air bubble
Foam ability index
Foam stability index
Surface tension

1. Introduction melamine condensates with formaldehyde. These products offer

Superplasticizers are the most important admixtures enhancing
concrete performance. The development of new superplasticizers
during the last decades has determined the most important pro-
gress in the field of concrete structures in terms of higher strength,
longer durability, lower shrinkage and safer placement particularly
in elements with very congested reinforcement [1].
First-generation superplasticizers were primarily derived from
natural organic materials such as sugars and lignins (extracted
from wood pulp). These products had a limited effectiveness and
may have been somewhat variable in performance, depending on
the source material. These water reducers would often retard the
mixture, particularly when overdosed. They are still used as Type
A, B, and D products.
Second-generation (early high-range) superplasticizers were
derived from petroleum feed stocks: sulfonated naphthalene or
⇑ Tel.: +48 032 2372294; fax: +48 032 2372737.
E-mail address: beata.lazniewska@polsl.pl
greater water reduction and are less detrimental when overdosed.
Third generations of superplasticizers often provide only about
20 min of effectiveness before the concrete exhibits significant
slump loss. These products can be re-dosed after this time to main-
tain workability, if required. Third-generation Superplasticizers are
polycarboxylates (PC), which are copolymers synthesized from
carefully selected monomers. These products are currently used
in mid- or high-range Superplasticizers (Type F and G; Admixture
Types Defined by ASTM C 494/AASHTO M 194). These admixtures
can be fine-tuned for a given application, including a range of effec-
tiveness and setting times [2–5]. PCEs are quite sensitive to differ-
ent cement compositions (e.g. because of the sulfate effect) and
they interact strongly with clay which can occur as an impurity
in aggregates and limestone. The first polycarboxylates used as dis-
persants in concrete were found to be very efficient at a dosage
that was often two times lower than that of the most efficient poly-
sulfonates. However, some of these first polymers were found to
entrain an excessive amount of air so that an air detraining agent
had to be mixed with them. As polycarboxylates are less sensitive

0950-0618/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.conbuildmat.2013.11.092
 Author's personal copy
B. Łaźniewska-Piekarczyk / Construction and Building Materials 53 (2014) 488–502
to C3A content and its reactivity, their use is very common in the
European precast industry, which uses fine contents rich in C3S
and C3A to obtain high early strength. Up to now, there exist some
polyacrylates with which it is not easy to develop a stable network
of air bubbles having a low spacing factor to protect concrete
against freeze–thaw cycles and the action of deicing salt, so that
their use is not very popular in the North American ready-mix con-
crete industry. Excessive foaming needs to be controlled by the
addition of defoamers [6].
According to the standard requirements [7,8] superplasticizers
should not cause the rise of the air content in concrete mix higher
than 2%, compared to the control mix. Unfortunately, as already
mentioned above, some types of SP increase the air-entrainment
(Table 1) [9,10,4,5]. Thus in case of non-air-entrained self-com-
pacting concrete (SCC), achieving low air-content might be difficult
[11–15].
Thus, the compatibility test of superplasticizer with cement
should be extended to a test to assess the effect of superplasticizer
on the air content in concrete. Known and used methods of testing
the air content in the paste, mortar and concrete mixture are the
following:
– surface tension measurement [16],
– foam index test [17,18],
– volume density [19],
– pressure measurement of the air content [20],
– Air Void Analyzer (AVA) [21–23],
– laser method on frozen samples [24].
The first and second methods are used for cement paste. For
qualitative methods of air-entrainment evaluation the first two
methods are used. For quantitative assessment methods of air-
entrainment evaluation other methods are used.
In the publication [16] surface tensions of the surfactants in dif-
ferent solutions were measured using the Wilhelmy Plate method
[14]. The test method measures the force between a probe and the
surface of a fluid. A rectangular roughened platinum thin section
plate was used as a probe. The platinum plate was hung vertically
on a balance and lowered until it came in contact with the solution
surface. The plate was dipped 3 mm into the liquid, and raised up
1 mm. At the equilibrium point, the forces acting on the balance
are the weight of the platinum plate, the up-thrust force on the
submerged part of the plate, and the surface tension of the liquid
touching the plate. The forces present in this situation are a func-
tion of the size and shape of the plate, the contact angle of the
liquid/plate interaction, and the surface tension of the liquid. The
contact angle of the liquid/plate interface is zero under
the assumption that the solutions completely wet the plate. Conse-
quently, the surface tension forces act directly downwards and
in-plane on the platinum plate. The surface tension of the liquid
is calculated by dividing the surface tension force (milliNewton,
Table 1
The influence of SP type on the concrete air-entrainment [9].
Plasticizer or SP type Influence on air content of
concrete
Lignosulfonate, LS ++
Sulfonated Naphthalene Formaldehyde +
Condensate, SNF
Sulfonated Melamine Formaldehyde 0 The polar groups in the chain get adsorbed on the surface of the
Condensate, SMF
Polycarboxylate Polyoxyethylenea, PCP ++
Amino Phosphonate Polyoxyethylenea, AAP ++
a
New generation of SP.
489
mN) to the wetted length of the plate (meter, m), which equals
to two times the width of the Wilhelmy thin plate [16].
The foam index test is the method usually employed to deter-
mine the degree of fly ash interference with air entrainment agents
in concrete [25–27]. The foam index test is not a standardized
method. The procedure for the foam index test is similar to that
which others have proposed. 2 g of fly ash, 8 g of Portland cement,
and 25 ml of deionized water were poured into a cylindrical glass
vessel being 6 cm in diameter, which was capped and shaken on
a vortex shaker for 1 min. A 5 vol.% aqueous solution of AEA was
added in small aliquot amounts (20 ll) from a diluter and the ves-
sel was shaken for another 15 s. The foam was observed for stabil-
ity, i.e. defined as no bursting of bubbles within 30 s. In case the
foam was unstable, more AEA was added, and the procedure was
repeated until the foam remained stable. The test involves the
use of commercial air-entraining agents (AEAs) and visual observa-
tion of foam stability. These facts reduce the reproducibility of the
test, because commercially available AEAs vary in strength, and the
criteria for foam stability are operator dependent [28]. The paper
[28] presents efforts toward the development of a new method
based on dynamic surface tension measurements, using the bubble
pressure method, on filtrate from a fly ash and cement suspension.
The purpose of the foam index test is to predict surfactant-ce-
ment compatibility using a simple method and evaluation. The
modified foam index test proposed by Corr et al. [29] was deemed
more applicable to this experiment because it allows a better com-
parison between the three surfactants with and without the effect
of cement [16]. The absolute volume of the foam and the relative
lack of change between the final and the initial volume of the foam
indicate the foam stability. The compatibility between the cement
and each surfactant can be implied by relative change in the foam
stability between surfactant solution and surfactant solution with
cement.
This paper presents efforts toward the development of a meth-
od based on surface tension measurements of superplasticizer sus-
pension, using the stalagmometric method, and new method
verification of foam ability and also foam stability index of superp-
lasticizer suspension.
2. Study on the mechanism causing foaming behavior of
superplasticizer
The two most important mechanisms are linked to polymer
adsorption: steric hindrance through the adsorbed layer thickness
and electrostatic repulsion through the induced electrical charge.
Water-reducing chemicals belong to a group of chemicals known
as ‘dispersants’. The action of the dispersant is to prevent the floc-
culation of fine particles of cement. These dispersants are basically
surface-active chemicals consisting of long-chain organic mole-
cules, having a polar hydrophilic group (water-attracting, such as
–COO, –SO3–, –NH4+) attached to a non-polar hydrophobic organ-
ic chain (water-repelling) with some polar groups (–OH). The elec-
trostatic attractive forces, existing among cement particles and
causing agglomeration, would be neutralized by the adsorption
of anionic polymers negatively charged, such as SNF or SMF, for
the presence of –SO3– groups on the surface of cement particles.
The dispersion of cement particles would be related with the elec-
trical repulsion produced by the negatively charged groups –SO3–
on the other side of the main polymer chain (Fig. 1) [35].
cement grains, and the hydrophobic end with the polar hydrophilic
groups at the tip project outwards from the cement grain. The
hydrophilic tip is able to reduce the surface tension of water, and
the adsorbed polymer keeps the cement particles apart by electro-
static repulsion (The grinding of cement results in the ground
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Fig. 1. Schematic picture of sulfonated polymer (SNF) and its electrostatic repulsion on the dispersion of cement particles [35].

particles having a surface charge (zeta potential). The adsorption
of the admixture leads to a decrease of the zeta potential, and
eventually causes like charges (negative) on the cement particles).
With the progress of hydration, the electrostatic charge diminishes
and flocculation of the hydrating product occurs. Lignosulfonates
(normal, and sugar-refined), SMF, and SNF based superplasticizers
work on the mechanism of lowering zeta potential that leads to
electrostatic repulsion.
The dispersion mechanism performed by the PC-based superp-
lasticizers could be related more to a steric hindrance effect (pro-
duced by the presence of neutral side long graft chains) rather
than to the presence of negatively charged anionic groups (COO–
) which are responsible for the adsorption of the polymers on the
surface of cement particles (Fig. 2). In other words, the graft chains
of the polymer molecules on the surface of cement would hinder
by themselves from flocculating into large and irregular agglomer-
ates of cement particles (Fig. 2) [35].
The molecular structure of polycarboxylate (PC) superplasticiz-
er admixtures is shown in Fig. 2. Their ‘comb-type’ molecule con-
sists of one main linear chain with lateral carboxylate and ether
groups [30]. According to the literature [31], the carboxylate
groups are instrumental in the adsorption of these admixtures to
cement particles. Dispersion is due to electrostatic repulsion (as
in melamine and naphthalene admixtures) owing to the carboxyl-
ate groups, but primarily to the steric repulsion associated with the
long lateral ether chains. The high degree and duration of the flu-
idity that this admixture affords concrete are related to structural
factors; hence, the shorter the main chain and the longer and more
numerous the lateral chains, the greater and more long lasting is
the fluidity induced [30,32]. The molecular weight of these admix-
tures likewise has a substantial effect on their performance:
according to Magarotto et al. [33] adsorption and system fluidity
are proportionally higher in polymers with large molecular weight
[30].

Fig. 2. Schematic picture of the polycarboxylate (PC) superplasticizer and its steric hindrance effect on the dispersion of cement particles [35,31].
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B. Łaźniewska-Piekarczyk / Construction and Building Materials 53 (2014) 488–502
Fig. 3. Types of superplasticizer action: (a) creating ‘‘grease’’ layer, (b) surrounding
grains of cement with negative charge, (c) decreasing of surface water tension and
(d) long chains of polymer, physically precluding the grains of cement to approach
each other [9].
Deflocculating and dispersion of the cement particles are the
net result and allow better use of the available water for more uni-
form lubrication and hydration.
Additional mechanisms of SP action include dispersion of ce-
ment particles by reduction in surface tension of mixing water
(Figs. 3 and 4) and a decrease in frictional resistance because of
the line-up of linear polymers along the concrete flow direction
and lubrication properties produced by low molecular weight
polymers. Unfortunately, many PC entrain as much as 2% [36].
The presence of functional groups (oxygen in form of etheric
group (–O–), hydroxyl group (–OH) and carboxyl group) produce
water surface tension decrease, producing flocculation of associ-
ated molecules and increase in moisture of not only grains of ce-
ment but also the whole mineral framework [38]. The research
[34] results show that the surface tension changed considerably
with time depending on the combination of powder and superp-
lasticizer. The change seems to be caused by the sorption, which
includes chemical adsorption, physical adsorption and absorption.
Among three kinds of sorption, the absorption of superplasticizer
by powder obstructs the function of superplasticizer. The tendency
was indicated that the absorption could occur in paste according to
fluidity test of paste.
In the SPs group there are ones that show only dispersion func-
tioning not decreasing surface tension [39]. They are: hydrocarb-
oxylen acid salts, sulphonic melamine-formaldehygenic resins,
formaldehygenic picodensats salts of beta-naphtalensulphonic
acid.
The foaming capacity of a surfactant depends primarily on its
effectiveness to reduce the surface tension of the solution, its
diffusion characteristics, its properties with regard to disjoining
pressure in thin films, and the elastic properties it imparts to
interfaces [40]. Fig. 5 shows a free-body diagram for the right half
Fig. 4. Water conglomerates deflocculating under the influence of superplasticizer as the effect of surface tension diminution [37].
491
of the bubble, on which two forces act. First, there is the force due
to the surface tension in the film. This force is exerted on the right
half of the bubble by the left half. The surface tension force points
to the left and acts all along the circular edge of the hemispherical
film. The magnitude of the force due to each surface of the film is
the product of the tension c and the circumference (2pR) of the cir-
cular edge, or c(2pR). The total force due to the inner and outer
surfaces is twice this amount or 2c(2pR). We have included the
minus sign to denote that this force points to the left in the draw-
ing. We have also assumed the film to be sufficiently thin enough
that its inner and outer radii are nearly the same. Second, there is a
force caused by the air pressure inside the bubble. At each point on
the surface of the bubble, the force due to the air pressure is per-
pendicular to the surface and is directed outward. Fig. 1b shows
this force at six points on the surface. When these forces are added
to obtain the total force due to the air pressure, all the components
cancel, except those pointing to the right. The total force due to all
the components pointing to the right is equal to the product of the
pressure Pi inside the bubble times the circular cross-sectional area
of the hemisphere, or Pi(pR2). Using these expressions for the
forces due to the surface tension and air pressure, we can write
P
Newton’s second law of motion as F = 0, or 2c(2pP) + Pt
(pR2) = 0, where: 2c(2pR) force due to surface tension; Pi(pR2)-
force due to pressure inside bubble. Solving this equation for the
pressure inside the bubble gives Pi = 4c/R. In general, the pressure
P0 outside the bubble is not zero. However, this result still gives the
difference between the inside and outside pressures, consequently
that we have (see Fig. 5).
Pi  P0 ¼ 0 ðSpherical air bubbleÞ ð1Þ
This result tells us that the difference in pressure depends on
the surface tension and the radius of the sphere. What is surprising
is that a greater pressure exists inside a smaller air bubble (smaller
value of R) than inside a larger one (compare with Fig. 5c). Thus,
the force due to the surface tension is only one-half as large as that
in a bubble. Consequently, the difference in pressure between the
inside and outside of a liquid drop is one-half of that for a soap
bubble [42].
Pi  P0 ¼ 2c=R — Laplace’slaw ð2Þ
The rate of surface tension decrease by surface active com-
pounds is followed in accordance with Gibbs Eq. (3) [43]. This
equation shows that the change of surface tension results from
substance absorption on given surface (Fig. 2).
dr Cs
 ¼ RT i ð3Þ
dc c
where dd is the change of surface tension; dc the change of given sub-
stance concentration in the solution; Csi the surface concentration
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492 B. Łaźniewska-Piekarczyk / Construction and Building Materials 53 (2014) 488–502

Fig. 5. (a) The forces pointing to the left are due to the surface tension, (b) the forces pointing perpendicular to the hemispherical surface are due the air pressure inside the
bubble [41] and (c) the inner and outer pressures on the spherical air bubble ale Pi and P0, respectively [42].

Fig. 6. (a) Rapid change of surface tension over a relatively small concentration range [44]. (b) Rapid change of surface tension and foam production over a concentration
range [42].

(mol/m2), c the constituent concentration; R the gas constant; T is
the temperature.
The combined Gibbs–Marangoni effect is the theory derived to
explain the function that surfactant played in foam film formation
and persistence. From Gibbs adsorption Eq. (3), the surface tension
of a liquid will decrease as the concentration of the monomer sur-
factant in solution increases (assuming positive adsorption) up to
the point of surface saturation (Fig. 6). The instantaneous (dy-
namic) surface tension at a newly formed surface is always higher
than the equilibrium value. There is a finite time requirement dur-
ing which the surfactant in the solution must diffuse to the inter-
face in order to lower the surface tension. The time lag in reaching
the equilibrium surface tension due to diffusion is generally known
as the Marangoni effect, which explains why the diffusion proper-
ties and concentration of a surfactant is important. These two
surface tension effects are usually complementary. Because the
disturbance of air bubbles in concrete is unavoidable, the Marang-
oni effect is essential to maintain the integrity of air bubbles [44].
The hydrophobic tails of surfactant molecules stick out of the
solution to reduce the distortion of water molecules by the hydro-
phobic sections and thus lower the overall free energy of the sys-
tem. Relationship between surface tension, solid tension and
phase-to-phase voltage according to equation Younga–Dupre’a
was presented in Fig. 7.
The mutual repulsion between the hydrophilic heads of surfac-
tant molecules reduces the attraction of the bulk liquid phase and a
lower surface tension is resulted. Because of the electrostatic com-
ponent of the repulsion force of ionic surfactants, their effective-
ness to reduce surface tension is more significant than nonionic
surfactants. The nature and concentrations of the surfactants
determine the physical and chemical properties of the interface
at the air bubble surfaces, including surface tension (equals to free
surface energy) and stability. The electrostatic and steric repul-
sions between surfactants help stabilize air bubbles in the paste
phase. Ions, organics, and polymers in the bulk solution also affect
the properties of the interfaces through complex interactions with
the orientated surfactant molecules [44]. Air-entraining admix-
tures molecules in the solution help entrain air-bubbles and stabi-
lize them in the fresh concrete. Most of the modern AEAs are
anionic because of the stability of air voids entrained [44]. The
anionic surfactants include: n-alkylcarboxylates (n-RCOO),
   
n-alkylsulfonates n-RSO 3 and n-alkylsulfates n-RSO 4 , with
hydrocarbon chain lengths between C7 and C12. The two main fea-
tures of the AEAs are their composition and size of hydrophobic
chain and the nature and size of their hydrophilic head group
affecting surface activity and their solubility in cement paste solu-
tion. Maximum air entrainment is obtained with surfactants of
intermediate chain length because their surface activity and solu-
bility vary in opposite directions. The hydrophilic head group in-
creases the air entrainment in the order carboxylate, sulfonate,
sulfate in line with the respective solubility of surfactants [45].
Unfortunately, there is still little information on the influence of
the type and characteristics of the new generation superplasticiz-
ers on the air content of concrete.
3. Experimental
The experimental investigation was carried out in three phases. In Phase 1, tests
were carried out on various aqueous plasticizers and SP solution. Phase 2 investi-
gated the properties of the cement paste with SP. In Phase 3, tests were carried
out on self-compacting concrete mixes.
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B. Łaźniewska-Piekarczyk / Construction and Building Materials 53 (2014) 488–502 493

Fig. 7. Relationship between surface tension, solid tension and phase-to-phase voltage according to equation Younga–Dupre’a [42].

3.1. Materials Table 3

The composition of SP aqueous solution.
In Phase 1, the surface tension of aqueous plasticizers and SP solution was
determined (Tables 2 and 3). It should be noted that the exact composition of tested Type of SP SP (%m.c.)
plasticizer and SP and the presence of other possible compounds is not well known, PCP 1 0.77
because it is restricted by the manufacturer. PCP 2 0.77
Phase 2 investigated the properties of the cement paste with SP. For cement PCP 3 0.77
paste and concrete manufacturing, the following materials were used: CEM III/A PCE 1 0.77
42.5N-HSR/NA, gravel aggregate 2/8 mm and 8/16 mm, pit sand 0/2 mm, tap water PCE 2 0.56
and chemical admixtures (Table 3). Standard cement properties determined using PCE 3 0.16
EN standard methods are presented in Table 4. AP 0.77
In Phase 2, the effect of SP type on air-entrainment of cement paste was verified SF 0.77
(Table 5). Because the author’s research methodology of paste requires it to be
highly liquid, w/c = 1.0 was intentionally used. m.c. – In relation to mass of cement.
In Phase 3, tests were carried out on self-compacting concrete mixes. The mix
design of concrete, according to requirements of [47] is given in Table 6. A principal
criterion for applied dosage of SP was its ability to provide a maximum slump flow
Table 4
without segregation of self-compacting mixture (SCC). Since the effectiveness of the
Standard properties of applied cement.
plasticizers and SP used is varied, in order to obtain self-compacting mix, their var-
ious quantities should be used. SP was introduced after approximately 30 s, after Properties CEM III/A 42.5N-HSR/NA
mixing the dry ingredients with water. The ingredients of the mixture were mixed
Le Chatelier, mm 0.3
for 5 min.
Beginning of setting time, minutes 229
The doses of admixtures in the aqueous solution and in cement pastes (Tables 3
Compressive strength after 2 days, MPa 17.5
and 5) correspond to doses of superplasticizer used in the SCC (see Table 6). Alter-
Compressive strength after 7 days, MPa 32.7
natively, the same manufacturer’s recommended dosage of superplasticizers can be
Compressive strength after 28 days, MPa 55.1
used to verify the effect on the air content in the SCC.
Specific surface, cm2/g 4205
Water demand, % 32.1
3.2. Test methods Loss on ignition, % 0.4
Insoluble residue, % 0.5
3.2.1. Test methods of surface tension SO3, % 2.5
The stalagmometric method (drop counting method) is one of the most com- CL, % 0.050
mon methods for measuring surface tension. The principle is to measure the weight
of the drops of the fluid falling from the capillary glass tube, and then calculate the
surface tension of the specific fluid which we are interested in. We know the weight
of each drop of the liquid by counting the number of the drops falling out. From this Table 5
we can determine the surface tension [43]. The composition of cement paste.
There are two line marks on the stalagmometer: top line above the wide part
CEM III/A 42.5N – LH/HSR/NA (kg/m3) w/c Type of Dosage of SP
and bottom line bellow it (Fig. 8). The volume between these two lines is V, and li-
SP (%m.c.)
quid with density q contained in this volume has a mass m
510 1.0 PCP 1 0.77
m¼V q ð4Þ
510 1.0 PCP 2 0.77
Such a volume V corresponds to n drops, which are released from the stalag- 510 1.0 PCP 3 0.77
mometer upon the decrease of liquid level from top to bottom line mark. Here, 510 1.0 PCE 1 0.77
the average mass of one drop is 510 1.0 PCE 2 0.56
510 1.0 PCE 3 0.16
m V q 510 1.0 AP 0.77
¼ ð5Þ
n n 510 1.0 SF 0.77
surface tension of the other liquid can be calculated from the equation
m.c. – In relation to mass of cement.

Table 6
Table 2
Self-compacting concrete mixture design (kg/m3).
Type of plasticizers and SPs.
CEM III/A w/c Sand (kg/m3) Gravel Type Dosage
Symbol The basic polymers included in the content of Form
42.5N – LH/HSR/NA aggregate (kg/m3) of SP of SP
SPs 3
(kg/m ) (%m.c.)
0/2 mm 2/4 mm 4/16 mm
PCP 1 PCP, polycarboxylates Liquid form
PCP 2 PCP, polycarboxylates Liquid form 510 0.38 800 400 505 PCP 1 0.77
PCP 3 PCP, polycarboxylates and modified Liquid form 510 0.38 800 400 505 PCP 2 0.77
phosphates 510 0.38 800 400 505 PCP 3 0.77
PCE 1 PCE, polycarboxylic ethers Liquid form 510 0.38 800 400 505 PCE 1 0.77
PCE 2 PCE, polycarboxylic ethers Liquid form 510 0.38 800 400 505 PCE 2 0.56
PCE 3 PCE, polycarboxylic ethers Solid form/ 510 0.38 800 400 505 PCE 3 0.16
powder 510 0.38 800 400 505 AP 0.77
AP AP, acrylates Liquid form 510 0.38 800 400 505 SF 0.77
SF SF, modified phosphonates compounds Liquid form
m.c. – In relation to mass of cement.
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Table 7
The test results of foam formation of examined plasticizers and SPs.

SP type rR p0 h0 p45 h45 FA FS

(mN/m) (mm) (mm) (mm) (mm)
Distilled water 72 – – – – – –
PCP 1 41 7 59 4 60 10 6
PCP 2 48 7 58 3 63 10 4
PCP 3 42 8 66 2 65 11 3
PCE 1 45 6 61 5 62 8 6
PCE 2 42 9 64 3 64 13 4
PCE 3 45 9 65 1 65 13 1
AP 53 4 54 4 60 6 6
SF 39 8 66 3 66 12 4

Table 8
Tests results of mixtures properties.
Fig. 8. Schematic picture of stalagmometer.
SP type Ac (%) SF (mm) T500 (sec.) q (kg/m3)
PCP 1 4.5 630 3.0 2.216
m PCP 2 4.0 750 3.0 2.264
r ¼ rw  ð6Þ
mw PCP 3 3.0 700 2.0 2.288
PCE 1 6.0 730 6.0 2.190
Substituting the mass m in the Eq. (6) with the mass of one drop then yields
PCE 2 4.0 710 5.0 2.261
q nw PCE 3 0.9 700 2.0 2.310
r ¼ rw   ð7Þ
qw n AP 5.6 620 3.0 2.201
SF 3.5 630 3.0 2.283
Finally, the solution surface tension was measured using the dependence (8). A
model liquid used in the measurements was distilled water, which surface tension
calculated from the formula (9).

rR nW qR of paste and foam were reported, using millimeters located on the surface of the
¼ ð8Þ
rW nR qW flask. Differences in the levels were marked as p0 After 45 s the paste and foam lev-
els located on the surface determined and differences in levels were marked as p45.
r ¼ ½72:9  0:155ðt  18Þ  103 ð9Þ
3.2.3. Test methods of fresh self-compacting concrete
where is the rR is the paste surface tension (N/m); rW the water surface tension (N/
The flow test of mixtures (Table 5) was carried out according to [50], density
m); nR the waste drops amount; nW the water drops amount; qR the density of tested
according to [19], the air content in the mixture according to [20].
paste (kg/m3); qW the water density (kg/m3); t the environment temperature (°C).

3.2.2. Test methods of foam ability index and stability index 4. Test results
In order to determine the effect of the plasticizer or SP type on the quantity and
stability of foam generated by its operations, the author adopted the following val- The results of the SP water solutions and cement pastes proper-
ues: FA – foam ability index (10) and FS – foam stability index (11).
ties are summarized in Table 7. While the research results of mix-
p0 tures properties are presented in Table 8.
FA ¼  100 ð10Þ
hp

p45 5. The analyze of the research results

FS ¼  100 ð11Þ
hp
where p0 is the difference in the levels of paste and the top surface of the foam in the
flask (after 60 s of vigorous mixing) (mm), (Fig. 9); p45 the difference in the levels of
paste and the top surface of the foam in the flask (after 45 s from stopping the paste
mixing). The higher p45 value, the higher foam formation is, (mm), (Fig. 9); FA the
foam ability index of plasticizer or superplasticizer. The higher the FA value, the
more plasticizer or superplasticizer has the ability to foam generation; FS is the foam
stability index of plasticizer or superplasticizer. The higher the FS value, the more
stable foam is.
Pastes were shaken vigorously for 60 s in a closed glass flask with internal
diameter 3.0 cm and a volume of 100 cm3 (Fig. 9), volume of the grout (Table 5)
in the flask was always 65 cm3. Immediately after the cessation of mixing the levels
Fig. 9. The method of indicating the parameter values of hp, h0, h45, p0, p45.
5.1. The influence of surface tension of water solution of
superplasticizer on foam ability index
The surface tension of pure water was found at 72 mN/m
(Table 7), which is close to the literature value of water at 23 °C.
The research results indicate that investigated superplasticizer de-
crease the surface tension of the water. In Fig. 10 the relationship
between the surface tension of aqueous solution of SPs and foam
ability index is presented. Considering the results shown in
Fig. 14 it can be concluded that the superplasticizers cause exces-
sive increase in the air content in concrete because they reduce the
surface tension of water.
With the addition of polycarboxylic ethers (PCE) much more
water can be bound to the solid particles (Fig. 11). The molecules
of the PCE contact the particles with their backbone and adsorb
water molecules at their side chains [49]. With this effect the film
of bound water around the particles becomes thicker, the propor-
tion of bound water increases and the remaining cross-section
for the flow of unbound water decreases. The back pressure rises.
A similar effect can be achieved by the addition of very fine parti-
cles. Due to their immense largeness of surface they can bind a lot
of water and they down size the remaining cross-section for water
flow, too [49].
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Fig. 10. The effect of surface tension of SP solution on the air content in the fresh
self-compacting concrete.
Another possibility to bind the water is the use of organic stabi-
lizers. These are large organic molecules. They can adsorb a lot of
water molecules. These emerging molecule packages are more in-
ert and immobile. If their long molecule chains intertwine they can
even evolve into a sort of net-structure, which limits the mobility
of both the bound and the free water molecules. As a result of all
these three effects the drainage cannot be stopped completely,
but it can be significantly slowed down [49]. This is the basis for
a foamed cement paste being stable until hardening with minimal
symptoms of decline. The before mentioned ideas are combined
and illustrated in Fig. 12.
On the basis of the research results [49] it becomes apparent
that the type and dosage of the organic stabilizer decide about
the foam stability. It is obvious that the dependency is not linear.
There is a material related marginal dosage which is necessary to
keep the foam stable. The influence on the density of the fresh
and hardened (stable) foamed cement pastes is small. This sort of
analysis does not detect changes of the pore structure inside the
foam. They were reviewed by means of fracture surfaces [49].
In the study [48], the mechanism behind the foaming action of
an allyl ether-based polycarboxylate was investigated. Allyl ether-
based PCE was chosen because it possesses a well defined chemical

Fig. 11. Options to control the drainage [49].

Fig. 12. Model of the influence of different components of cement paste on foam processing and foam stability [49].
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496 B. Łaźniewska-Piekarczyk / Construction and Building Materials 53 (2014) 488–502
Fig. 13. Chemical structures of PC and EPBE-PC [46].
structure with a fairly narrow molecular weight distribution [11].
At first, the foaming action of the PCE as obtained from the synthe-
sis was compared to that of the PCE after purification which re-
moved unreacted monomers and impurities. Foaming tendency
of PCE was determined by measuring surface tension and foam de-
cay times of aqueous PCE solutions and the air void content of a
standard mortar formulation. It was found that both purified allyl
ether-co-maleic acid PCE and individual allyl ether macromono-
mer possess moderate surfactant properties but do not cause the
excessive foaming known from industrially manufactured PCEs.
Whereas, a mixture of purified PCE polymer and only small
amounts (P10%) of allyl ether macromonomer shows very strong
foaming. This combination exhibits similar foaming action like
industrially manufactured PCE superplasticizers. Apparently, the
allyl ether macromonomer acts as a co-surfactant (foam stabilizer)
to PCE which already presents a macro tenside. Minimizing the
amount of unreacted allylether monomer in commercial PCEs pro-
vides a solution to obtain a less foaming product.
We can find that the effect of superplasticizers with a low
molecular weight on the reduction in surface tension is not strong.
In accordance with the results [40] lignosulfonate has a character-
istic of being strong hydrophilic. Its hydrophobic skeleton appears
spherical in shape, so it cannot form a regular arrangement at the
interfacial phase. This is common with certain surfactants of low
molecular weights. The surface tension of calcium lignosulfonate
solutions decreases with increasing molecular weight. This may
be related to the fact that the charged hydrophilic groups decrease,
relatively, with a molecular weight increase. The adsorption
amount thus increases leading to that calcium lignosulfonate with
a high relative molecular weight has higher surface activity, i.e.,
lower surface tension [40]. The lower surface tension of the liquid
solution is, the easier the wetting of solid particles may be because
this helps the cement particles more readily disperse into water.
Sugiyama et al. [46] synthesized a new series of superplasticizers
in which functional groups of EPBE acting as shrinkage reducing
agent (SRA), capable of reducing surface tension, were attached
to the structure of various polycarboxylate polymers (Fig. 13).
5.2. The influence of foam ability index and stability index on air-
content in SCC
Figs. 14 and 15 show the relationship between FA index and FS
index and the content of the air in the mixture. Research results,
presented in these figures show that FA and FS index correlate well
with air-entrainment of mixture.
7
6 PCE1
AP
5
PCP1
4 PCP2 PCE2
Ac, %
R² = 0.6417 SF
3 PCP3
2
1 PCE3
0
0 2 4 6 8 10 12 14
FA
Fig. 14. The effect of FA index on the air content in the mixture.
7
6 R² = 0.9351 PCE1
AP
5
PCP1
Ac , %
4 PCP2; PCE2
SF
3 PCP3
2
1 PCE3
0
0 1 2 3 4 5 6 7
FS
Fig. 15. The effect of FS on the air content in the mixture.
Interesting that the value of the FS index corresponds to the air
content in concrete mix (see Fig. 15). However, this observation re-
quires further study, because it deepens on composition of SCC.
Reassuming, there is good correlation between these test re-
sults of surface tension of different type of superplasticizers solu-
tion and air-content in SCC. The influence of plasticizer and SP on
air-content in SCC can be quickly and easily verified on the basis
of FA index or FS index tests, which correlate well with the air con-
tent found in the self-compacting mixture. The foam ability and
stability index test is not a standardized method. The described
method is at present stage not a finished procedure, but needs fur-
ther work to fulfill our goal of having a reproducible method. These
tests should be based on using a pure surfactant instead of a
superplasticizer, where commercial products show variation in
chemical nature and concentrations. In the next stages of research,
the effect of cement type, temperature and modifications SCC by
admixtures on the air content will also be taken into account.
5.3. The influence of SP type on rheological properties of SCC
Analyzing the effect of the SP type on the air content in concrete
mix, one should keep in mind that in case of self-compacting mix-
ture the air content remains in its volume and it depends on its rhe-
ological properties. Each type of the SP effects differently on the
modification of SCC rheological properties, and moreover its imple-
mentation may be different, therefore the analysis of the effect of
the SP type on the air content in SCC is very complicated. Due to
the varying effectiveness of SP, in order to obtain the minimum flow
of the mixture according to [50], i.e. 550 mm, it was necessary to
use substantially different amounts of SP. Due to different SP type
used in the research, it is not possible to analyze directly the effect
of the flow of mixture diameter or the flow time on the air content
in its volume. Fig. 16 shows the effect of the amount and type of SP
on the flow of mixture. Barfield and Ghafoori’s [51] study indicated
that a polycarboxylate-ester (PCE) SP needed a larger dosage to im-
part the same flowability to SCC than a polycarboxylate-acid (PCA)
SP. The research results presented in Fig. 16 indicate that it is some-
times otherwise. This depends on the type of SP. More effective in
realization of the mixture used with a small amount of admixture,
are SPs characterized by sequence based on acrylates, modified
phosphates (AP and PCE3). However, the most effective in this area
are SPs characterized on the basis of polycarboxylates (PCP2). Be-
sides a lower slump loss, AP-based superplasticizers perform better
than the traditional sulfonated polymers even in terms of either
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800 – a modified PE-based superplasticizer where a great number of

750 PCP 2 carboxylic groups are replaced by a slump-loss controlling
PCE 1 agent (SLCA) to achieve a still higher slump retention with min-
700 PCE 3 PCE 2 PCP 3
SF, mm

imal setting retardation: indeed, due to the relatively low num-

650 PCP 1 ber of carboxylic groups in SLCA (Fig. 18) the initial adsorption
SF
AP
600 and dispersing effect are negligible as well as the setting retar-
dation; however, subsequently to the hydrolytic effect related
550
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
with the OH– presence in the aqueous phase of the cement
SP, % m.C. paste, the number of carboxylic units increases and the slump
can still increase by prolonging the mixing time due to the
Fig. 16. The effect of the amount and the type of SP on the flow of mixture. increasing adsorption of the polymer on the surface of the
cement particles.
higher reduction in the w/c at a given workability or higher slump
level at a given mixture composition. However, the AP superplast- The behavior of fresh concrete in the presence of PC and SLCA-
icizers appear to be more expensive than others [52]. based superplasticizers is schematically shown in Fig. 19.
Hanada et al. [53] developed a new family of acrylic polymers Polymers with backbone and graft chains, such as PCEs, acrylic
based on the following changes with respect to the PC-based esters, and cross-linked acrylic polymers, cause dispersion of ce-
superplasticizer [35]: ment grains by steric hindrance [54–56]. This phenomenon relates
to the separation of the admixture molecules from each other due
– a polyether (PE) based superplasticizer with much longer side to the bulky side chains. Steric hindrance is more effective mecha-
chains of ethylene oxide (EO): 130 moles of EO instead of 10– nism than electrostatic repulsion. The side chains, primarily of
25 moles as in traditional PC-based superplasticizer (Fig. 17); polyethylene oxide extending on the surface of cement particles,
this change produces a lower adsorption speed and reduces migrate in water and the cement particles are dispersed by the ste-
the typical retarding effect related to the early adsorption; ric hindrance of the side chains. Electrostatic repulsion depends on
the composition of the solution phase and adsorbed amount of the
SP (greater the adsorption, better the repulsion) [57]. On the other
hand, steric repulsion depends on the length of main chain, length
and number of side chains [58]. In case of PCE based admixtures,
for fluidity retention, the main chain should be short, with large
numbers of long side chains [58]. Because of the steric repulsion
mechanism, PCEs are generally more effective than the sulfonate
based admixtures, and generally do not experience much problems
at low water to cement ratios. However, they are more sensitive to
overdosing, and can lead to problems like excessive air entrain-
ment and retardation.

5.4. The influence of rheological properties of SCC type on air-content

of mixture with different SP type

The determining factor for the bubble-stability in a fluid is the

Fig. 17. The chemical structure of polycarboxylate type (PC), polyether type (PE)
and slump-loss-controlling agent superplasticizer (SLCA); q and p are the number of
moles of EO in PC and PE or SLCA polymers [35].
balance between the internal pressure of the bubble, being always
a bit higher than the ambient pressure, and tensile stresses ab-
sorbed by the bubble shell (Fig. 20). The maximum size of these
tensile stresses depends on the inner cohesion of the fluid and
interfacial tension [49].
The stability of foams depends not only on the stability of its
single bubbles but also on other effects. The most important one,
especially for the production of cement-bound foams, is drainage.
This means that air and fluid separate. The air bubbles up while
the fluid flows out under the influence of the gravitation

Fig. 18. The schematic molecular structure of polycarboxylate type (PC), polyether type (PE) and slump-loss-controlling agent superplasticizer (SLCA) [35].
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Fig. 19. Schematic trend in the slump loss behavior with different acrylic
superplasticizers (PC, PE, SLCA, PE + SLCA) in concrete mixtures with CEM II A/L
32.5R (340 kg/m3), w/c = 0.45 [35].
Fig. 20. Schematic diagram of a bubble [49].
(Fig. 21). The most important influences on the drainage are the
density and viscosity of the fluid. If the fluid film between two bub-
bles thins out so far that the tensile stresses corresponding to the
internal pressure can no longer be absorbed, the fluid film breaks
and the bubbles affiliate. This is called coalescence [49]. Provided
that the air entrainment works as well as possible, the maximum
air content of the foam depends on geometrical aspects, like bubble
diameter distribution and the minimum thickness of the fluid films
between the bubbles. For this a higher viscosity of the fluid would
be better. Nevertheless, the viscosity has to be limited, because a
high viscosity interferes with the air entrainment and the disper-
sion of the air in the fluid [49].
On single bubble located in cement paste the following forces
act [65]: the force of gravity G, the buoyancy force, the force caused
by the fluid vortex C, the force caused by the existence of the elec-
tric field E. Resultant of these forces is thus equal to S: [59]:
S¼W þGþCþE
When a mixture of self-compacting concrete is already at rest,
for a single air bubble forces act: gravity G and buoyancy W
forces. Thus, the resultant will be equal: S = G + W. If the force S
is larger than zero, the particle begins to move relative to the
stationary fluid at a certain flow velocity w. Then drag force
formed center R in the same direction and opposite to the
resultant force S. The balance of forces acting on a single bubble
is shown in Fig. 22.
Fig. 21. Schematic diagram of drainage and coalescence [49].
Flow speed of bubbles in the cement grout can be described by
relationship [59,60]:
2
d ðqz  qp Þg
w¼ ð13Þ
18gz
when w is the bubble flow velocity; d the diameter of the bubble; qz
the density of the grout; qp the air density; gz the viscosity of the
grout.
Thus, the bubble outflow velocity increases with increasing
bubble volume, and decreases with increasing viscosity of the
grout. However, for describing the behavior of the bubbles, the
physical and chemical interactions between the components of
the concrete mix must be taken into account, modified by chemical
admixtures. The molecules of SP should also modify the surface of
solid particles in order to keep its hydrophilic character. Air bub-
bles can adhere only to hydrophobic surfaces. The surfactant mol-
ecules in the solution help entrain air bubbles and stabilize them in
the fresh concrete (Fig. 23a) if cement paste does not implicates
another admixtures, especially superplasticizers (Fig. 23b) [61–
63]. The effect of superplasticizers on air content of the mixtures
can be estimated using FA and FS indexes.
The SP type significantly influences the air-content in self-com-
pacting mix with similar slump diameter and time flow value (for
example, SF = 700, T500 = 3.0: PCP2, PCE1, PCE2, PCP3 and PCE3).
The air-content amounts to 6.5% in spite of the fact that the flow
diameter amounts to 750 mm (Fig. 24). Viscosity also slows down
the potential coalition of adjacent air bubbles by working as a bar-
rier [44]. The yield stress of cement paste prevents the escape of
small air bubbles whose buoyancy forces are not large enough to
break the bulk paste phase. The viscosity of the paste and diameter
of bubbles determine how fast the air bubbles move upward
according to Stokes’ law. High viscosity can provide a cushion ef-
fect for air bubbles to absorb shocks from disturbances. The effect
of viscosity of the mixture on air-content depends on the type of SP
(Fig. 25). The superplasticizer type significantly influences the air-
content in self-compacting mix, regardless of the yield stress and
viscosity of SCC. Therefore, it is difficult to create a statistical model
that describes the influence of the rheological properties of SCC on
the effect of the self-compaction, finally air-content, regardless of
the superplasticizer type. Due to the volume of air voids, the type
of SP is essential [2,8]. FA index and FS index.
The foaming behavior of PCs was investigated by the foam vol-
ume, the surface tension of PCs aqueous solution, and the air con-
ð12Þ
tent of concrete were analyzed in the research [48]. According to
the results, the hydrophobic side chains of PCs may affect the
hydration reaction of cement resulting in better workability. In
SPs group, which action was caused by the flow over 60 cm
(Fig. 24), acrylate SP (AP) characterizes with the greatest side air-
entraining effect, involving the formation of an excessive amount
of the air in the mixture. SPs based on the modified phosphate
(SF) did not cause an excessive air-entrainment although the mix-
ture also achieved the flow over 600 mm. The smallest side effect
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B. Łaźniewska-Piekarczyk / Construction and Building Materials 53 (2014) 488–502 499

Fig. 22. Schematic of the balance of forces acting on a single bubble [59].

Fig. 23. (a) Adsorption of the flux molecules framework in the grains of cement and the negative effect of the anion final group; (b) diagram of arrangement of cement–water
and aggregate–cement–water arrangement, with the use of air-entraining mean (surface active anion substance) [64].

Research results presented in Fig. 24, SPs based on polycarbox-

Fig. 24. The effect of mixtures flow volume, considered in terms of the type and
amount of SP used, on the air content in its volume.
Fig. 25. The effect of mixtures flow time, considered in terms of the type and
amount of SP used.
in the form of the excessive air-entrainment of the mixture
(Fig. 24), and liquidizing the mixture in the greatest degree, is a
SP based on polycarboxylates and modified phosphates (PCP3).
Without a doubt it is the most effective SP from the tested ones.
In case of the SP based only on the polycarboxylates (PCP1 and
PCP2), the effect of the excessive air-entrainment of the mixture
occurs.
ylate ethers (PCE1, PCE2 and PCE3) were characterized with a rad-
ically different effect on the ‘‘air-entrainment’’. The type of
superplasticizer is crucial regarding the size and proportions of
the air pores participation, gained as a result of its functioning,
although the time of concrete hardening is of no importance on
further changes of these proportions [27]. The publication [66]
indicates that the superplasticizer causes reduction in total air-
void surface areas and increases in air-void spacing factors. The
bubbles are slightly bigger than those formed as a result of air-
entraining admixture functioning, but their stability is lower. Air
bubbles formed as a result of air-entraining admixtures function-
ing, reach the size of 20–250 lm. Moreover, they adhere to the sur-
face of particles of cement (Fig. 19a) [4]. During concrete’s
hardening, formed pores are not fulfilled with the products of
hydration. With the use of polycarboxylate superplasticizers, the
air pores characterize with smaller diameters than pores formed
as a result of lignosulphonic or naphthalene superplasticizers func-
tioning [67]. The inclusion of SP (sodium salt of a sulfonated nap-
thalene-formaldehyde condensate) in cement paste, leads to a
reduction in the total pore volume and to a refinement of the pore
structures [68]. The dominant pore size is unaffected and the
threshold diameter is reduced in the presence of SP. According to
Sakai et al. [67], superplasticizers type is crucial regarding the size
and share of air pores trapped under their influence (Fig. 26),
although with time of concrete hardening further changes of these
proportions mainly take place (Fig. 27). The addition of polycar-
boxylate superplasticizers, the air pores have smaller diameters
than pores trapped in case of lignosulfonate or naphthalene
superplasticizers addition. The research results [69] indicate that
total air content, the content of micropores less than 0.3 mm in
diameter, total porosity, specific pore volume and specific pore sur-
face in concrete modified with superplasticizer based on polycarb-
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Fig. 26. Influence of some SP, namely; naphthalene sulfonate (b-NS), refined lignin
sulfonate (LS) and polycarboxylate (P32, S34) on pore structure in 28-days old
concrete [67].
Fig. 27. Influence of the same superplasticizers as in Fig. 26 but after 90 days of
curing [67].
oxylans are considerably lower than in concrete modified with
superplasticizer based on polycarboxylic ether. Whereas air voids
spacing factor L, average pore radius and specific air pore surface
are higher for concrete with superplasticizer based on polycarb-
oxylans. It can be concluded from the results that the polycarboxy-
lic ether contained in superplasticizer based on polycarboxylic
ether causes considerable aeration of the self-compacting concrete.
Research results [70] indicate that the air-content in hardened
SCC, as a side effect of PCE acting, may amount to 5.0%, and in some
cases of PCP, even 8.0% [71]. Therefore, it is important to study
their compatibility, also because of the air content in the concrete.
From the point of view of mechanical self-compacting concrete
characteristics (SCC), the most favorable situation is when the
mix characterizes with the lowest air content. The problem of
too high air content becomes more fundamental when the con-
crete’s design class is higher, because with the cement content in
concrete mix the content of the caught air increases. Research re-
sults [67,71,70,72] proved that size of pores arising from the action
of SP in hardened concrete are characterized with overly large
diameters. In effect, concrete’s mechanical parameters are sub-
jected to considerable deterioration 1% of air-entrainment,
depending on its type, may reduce up to 5% of concrete’s compres-
sion strength.
The side effect of some type of SPs on air content in concrete
was used in case of air-entraining superplasticizers (high range
water reducers) in Japan. Polycarboxylic acid based superplasticiz-
ers (Comb-type polymers with grafted pendant polyethylene oxi-
des) influence on air content of concrete. The air entraining high-
range water reducing agents (AEHRWRAs), which boast excellent
water reducing ratios and slump retention abilities, were devel-
oped in the mid-1980s, and first marketed in 1987 [73]. The main
component of AEHRWRA is a copolymer with grafted pendant
groups of polyethylene oxide. Because these have a carboxyl group
in the main chain, they are generically called polycarboxylic acid-
based superplasticizers. Fig. 28 shows a typical chemical structure
of PC-AEHRWRA (PC-based superplasticizers). AEHRWRA ad-
vanced rapidly in association with the development of high-perfor-
mance concrete (self-compacting concrete) as proposed by
Professor Okamura in 1986 [74] and high-strength concrete was
applied to New RC (New reinforced concrete) projects between
1988 and 1992. AEHRWRA containing retarded and standard types
were added in the JIS revision of 1995. AEHRWRA is especially use-
ful for producing self-compacting and high-strength concretes. On
Fig. 28. Chemical structure of main dispersant of PC-based superplasticizer
(Molecular model was drawn with CS Chem. 3D; hydrogen (gray) and oxygen
(dark gray) over carbon.) [73].
the other hand, the worsening situation with respect to aggregate
resources has tended to increase the water demand of concrete,
comb-type polymers, which are also the main component of AEHR-
WRA, are used to reduce the contents of water for secure durability
of ordinary concrete. The development of many types of comb-type
polymers that enable better performance has also continued,
resulting in highly durable and high strength concretes [75].
6. Conclusion
On the basis of the scope of the research it can be concluded
that:
1. SCC characterized with to excessive air content, which was the
effect of functioning of superplasticizer despite fulfilling the
requirements according to EN 12350-8. The effect of type of
superplasticizer is essential because of its ‘‘air-entraining’’
effect of the self-compacting concrete. Therefore, the necessary
complement of superplasticizer compatibility test is to verify
the effect of ‘‘air-entrainment’’.
2. The superplasticizer type significantly influences the air-con-
tent in self-compacting mix, regardless of the yield stress and
viscosity of SCC. Therefore, it is difficult to create a statistical
model that describes the influence of the rheological properties
of SCC on the effect of the self-compaction, finally air-content,
regardless of the superplasticizer type.
3. The influence of SP on air-content in SCC can be verified on the
basis of FA foam ability index or FS foam stability index tests,
which correlate well with the air content found in the self-com-
pacting mixture.
4. There is good correlation between these test results of surface
tension of different type of superplasticizers solution of superp-
lasticizer and air-content in SCC. When surface tension of aque-
ous solution of superplasticizer is low then FA foam ability
index has high value. In turn, high value of FA foam ability index
causes high volume of air-content in SCC.
References
[1] Ramachandran VS. Concrete admixtures handbook. In: Ramachandran VS,
editor. Properties, science and technology. Park Ridge, New Jersey, USA: Noyes
Publications; 1995.
[2] Szwabowski J, Łaźniewska-Piekarczyk B. The requirements for porosity
parameters of frost-resistance self-compacting concrete (SCC). Cem Wapno
Beton 2008;3:155165.
[3] Kamura HO, Ouchi M. Self-Compacting Concrete. J Adv Concr Technol
2003;1(1):515. Japan Concrete Institute.
[4] Thomas DA, Wilson L. Admixtures for use in concrete. CD-ROM-CD039. Skokie,
IL: Portland Cement Association; 2002.
 Author's personal copy
B. Łaźniewska-Piekarczyk / Construction and Building Materials 53 (2014) 488–502
[5] Taylor CP, Kosmatka SH, Voigt GF et al. Integrated materials and construction
practices for concrete pavement: a state-of-the-practice manual. FHWA
Publication No. HIF-07-004.
[6] Aïtcin PC. Performance-based specification for high performance concrete; 2012.
<http://www.watancon.com/documentation/technical/Aitcin_-_Performance-
based%20specifications%20for%20HPC.pdf>.; Lei L, Plank J. Synthesis, working
mechanism and effectiveness of a novel cycloaliphatic superplasticizer for
concrete. Cem Concr Res 2012;42(1):118–23.
[7] EN 934-1:2009. Admixtures for concrete, mortar and grout – Part 1: common
requirements; 2009.
[8] EN 934-2:2010. Admixtures for concrete, mortar and grout – Part 2: concrete
admixtures – definitions, requirements, conformity, marking and labeling;
2010.
[9] Mosquet M. The new generation admixtures. In: Budownictwo Technologie
Architektura. Special Publication; 2003.
[10] Rougeau P, Maillard JL, Mary-Dippe C. Comparative study on properties of self-
compacting and high performance concrete used in precast construction. In:
Proceedings of the first international RILEM symposium on self-compacting
concrete (PRO 7);1999. p. 251–61.
[11] Kamal H, Khayat KH, Assaad J. Air-void stability in self-consolidating concrete.
ACI Mater J 2002;99(4):408416.
[12] Khayat KH. Optimization and performance of the air-entrained self-
consolidating concrete. ACI Mater J 2000;97(5):526535.
[13] Kobayashi M, Nakakuro E, Kodama K, Negami S. Frost resistance of
superplasticized concrete. ACI 1981; SP-68: 269282.
[14] Litvan G. Air entrainment in the presence of SPs. ACI J 1983;80(4):326331.
[15] Felekoğlu Burak, Türkel Selçuk, Baradan Bülent. Effect of water/cement ratio
on the fresh and hardened properties of self-compacting concrete. Build
Environ April 2007;42(4):1795–802.
[16] Atahan HN, Carlos Jr C, Chae S, Monteiro PJM, Bastacky J. The morphology of
entrained air voids in hardened cement paste generated with different anionic
surfactants. Cement Concr Compos 2008;30(7):566–75.
[17] Kulaots I, Hsu A, Hurt RH, Suuberg EM. Adsorption of surfactants on unburned
carbon in fly ash and development of a standardized foam index test. Cem
Concr Res 2003;33:2091–9.
[18] Gebler SH, Klieger P. Effect of fly ash on the air void stability of
concrete. Skokie, IL: Portland cement Association; 1986. 40p.
[19] EN 12350-6:2001. Testing Fresh Concrete – Part 6: Density; 2001.
[20] EN 12350-7:2001 Testing Fresh Concrete – Part 7: Air Content – Pressure
Methods; 2001.
[21] The Air Void Analyzer manual instruction by German Instruments.
[22] Mohsen JP, Lane DS, Zhiyong Z. Measuring spacing factor of the air voids
system in fresh concrete. In: Transportation Research Board Annual Meeting,
Washington; 2004. p. 9 [CD-ROM].
[23] Giergiczny Z, Glinicki MA, Sokołowski M, Zielinski M. Air void system and
frost-salt scaling of concrete containing slag-blended cement. Constr Build
Mater 2009;23:2451–6.
[24] Hansen W. Quantitative and rapid measurement of air-void system in fresh
concrete. SHRP-ID/UFR-91-519, Washington; 2001. p. 33.
[25] Helmuth R. Fly ash in cement and concrete. 1st ed. Illinois: Portland Cement
Association; 1987. p. 80–2.
[26] Külaots I, Hsu A, Hurt RH, Suuberg EM. Adsorption of surfactants on unburned
carbon in fly ash and development of a standardized foam index test. Cem
Concr Res 2003;33(12):2091–9.
[27] Dodson VH. Concrete admixtures. 1st ed. New York: Van Nostrand Reinhold;
1990. p. 129–64.
[28] Pedersen KH, Andersen SI, Jensen AD, Dam-Johansen K. Replacement of the
foam index test with surface tension measurements. Cem Concr Res
2007;37(6):996–1004.
[29] Corr DJ, Monteiro PJM, Bastacky SJ, Gartner EM. Air void morphology in fresh
pastes. Cem Concr Res 2002;32(7):1025–31.
[30] Puertas F, Santos H, Palacios M, Martı ´ nez-Ramı´rez S. Polycarboxylate
superplasticiser admixtures: effect on hydration, microstructure and
rheological behaviour in cement pastes. Adv Cem Res 2005;17(2):
77–89.
[31] Yamada K, Takahashi T, Henahara S, Matsuhira M. Effects of the chemical
structure on the properties of polycarboxylate-type superplasticizer. Cem
Concr Res 2000;30(2):197–207.
[32] Sugiyama T, Ohta A, Uomoto T. The dispersing mechanism and applications of
polycarboxylate-based super-plasticizers. In: Proceedings of the XI
international conference on the chemistry of cement, Durban; 2003. p. 560–
68.
[33] Magarotto R, Torresan I, Zeminian N. Influence of the molecular weight of
polycarboxylate ether superplasticizers on the rheological properties of
fresh cement pastes, mortar and concrete. In: Proceedings of the XI
international conference on the chemistry of cement, Durban; 2003. p.
514–26.
[34] Jiang D, Tetsuya Oyamada, Tadashi Fujiwara. Influence of properties of powder
on action of superplasticizer. In: JCA proceedings of cement and concrete, vol.
53, 1999, p. 403–8.
[35] Collepardi M. Chemical admixtures today. In: Proceedings of second
international symposium on concrete technology for sustainable february –
development with emphasis on infrastructure, Hyderabad, India; 27 February–
3 March 2005. p. 527–41.
501
[36] Uchikawa H, Sawaki D, Hanehara S. Influence of kind and added timing organic
admixture type and addition time on the composition, structure, and property
of fresh cement paste. Cem Concr Res 1995;25:353–64.
[37] Rudnicki T. Natural and synthetic plasticizers and mechanisms of their
interaction in concrete mix. Magazyn Autostrady 2004;4:22–5.
[38] Kucharska L. Traditional and modern water reducing concrete admixtures.
Cem Wapno Beton 2000;2:4661.
[39] Ley MT, Folliard KJ, Hover KC. The physical and chemical characteristics of the
shell of air-entrained bubbles in cement paste. Cem Concr Res 2009;39:
417425.
[40] Ouyang Xinping, Qiu Xueqin, Chen. Physicochemical characterization of
calcium lignosulfonate – a potentially useful water reducer. Colloids
Surfaces 2006;5:489–97.
[41] http://higheredbcs.wiley.com/legacy/college/cutnell/0471713988/ste/ste.pdf.
[42] Atkins PW. Physical chemistry. Warszawa: PWN; 2003.
[43] Szczeniowski Sz. Eksperimental physics, Part 2. Warszawa: PWN; 1982.
[44] Du L, Folliard JK. Mechanisms of air entrainment in concrete. Cem Concr Res
2005;35:1463–71.
[45] Jolicoeur C, Cong To T, Soan Nguyen T, Hill R, Page M. Mode of Action of
Anionic Surfactants for Air Entrainment in Cement Pastes w-w/o Fly Ash.
World of Coal Ash (WOCA) Conference, Lexington, KY, USA; 2009.
[46] Sugiyama T, Ohta A, Tanaka Y. Shrinkage reducing type of advanced
superplasticizer. In: Proceedings of the CANMET/ACI symposium on
‘‘Advances in, Concrete Technology’’; 2000. p. 189–200.
[47] EN 206-9:2010. Concrete additional rules for self compacting concrete (SCC);
2010.
[48] Lange A, Plank J. Study on the foaming behaviour of allyl ether-based
polycarboxylate superplasticizers. Cem Concr Res 2012;42(2):484–9.
[49] Pott JU, Lohaus L. Development strategies for foamed cement paste. In:
Walraven, Stoelhorst, editors. Tailor made concrete structures. London: Taylor
& Francis Group; 2008. p. 457–60.
[50] EN 12350-8:2010. Testing fresh concrete. Self-compacting concrete. Slump-
flow test; 2010.
[51] Barfield M, Ghafoori N. Air-entrained self-consolidating concrete: a study of
admixture sources. Constr Build Mater 2012;26:490–6.
[52] Collepardi S, Coppola L, Troli R, Collepardi M. Mechanisms of action of different
superplasticizers for high-performance concrete. ACI Special Publication;
1999.
[53] Hamada D, Sato H, Yamamuro H, Izumi T, Mizunuma T. Development of
slump-loss controlling agent with minimal setting retardation. In: Proceedings
of seventh CANMET/ACI international conference on superplasticizers and
other chemical admixtures in concrete, ACI SP 217, Berlin, Germany; 20–24
October 2003. p. 127–42.
[54] Uchikawa H, Hanehara S, Sawaki D. The role of steric repulsive force in the
dispersion of cement particles in fresh paste prepared with organic
admixtures. Cem Concr Res 1997;27:37–50.
[55] Uchikawa H, Hanehara S, Shirasaka T, Sawaki D. Effect of admixture of
hydration of cement, adsorptive behaviour of admixture and fluidity and
setting of fresh cement paste. Cem Concr Res 1992;22:1115–29.
[56] Uchikawa H, Hanehara S, Sawaki D. The role of steric repulsive force in the
dispersion of cement particles in fresh paste prepared with organic admixture.
Cem Concr Res 1997;27:37–50.
[57] Nakajima Y, Yamada K. The effect of the kind of calcium sulfate in cements on
the dispersing ability of poly ß-napthalene sulfonate condensate
superplasticizer. Cem Concr Res 2004;34:839–44.
[58] Sugiyama T, Sugamata T, Ohta A. The effects of high range water reducing
agent on the improvement of rheological properties. In: Proceedings of the
seventh CANMET/ACI international conference on superplasticizers and other
chemical admixtures in concrete, ACI SP-217; 2003. p. 343–60.
[59] Bandrowski J, Merta H, Zioło J. Sedimentation of suspended solids, principles
and design. Gliwice: Wydawnictwo Politechniki Śla˛skiej; 1995.
[60] Szwabowski J. Rheology of cementitious compositions, Gliwice, Wydaw.
Politechniki Śla˛skiej; 1999. p. 239.
[61] Saucier F, Pigeon M, Plante P. Air-void stability. ACI Mater J 1990;87(1):3–11.
[62] Neville AM. Properties of concrete. Kraków: Polski Cement; 2000. p. 874.
[63] Persson B. Internal frost resistance and salt frost scaling of self-compacting
concrete. Cem Concr Res 2003;33:373–9.
[64] Kurdowski W. Chemistry of building materials. Kraków: Uczelniane
Wydawnictwa Naukowo-Techniczne AGH; 2003.
[65] Wang LY, Wang YW, Gao GB, Chu ZP, Liu YS, Wang KY, et al. Synthesis and
performance of polycarboxylate superplasticizers with hydrophobic side
chains. Appl Mech Mater 2013;357–360:1124–9.
[66] MacInnis C, Racic D. The effect of superplasticizers on the entrained air-void
system in concrete. Cem Concr Res 1986;16(3):345–52.
[67] Sakai E, Kasuga T, Sugiyama T, Asaga K, Daimon M. Influence of SPs on the
hydration of cement and the pore structure of hardened cement. Cem Concr
Res 2006;36:2049–53.
[68] Khatib JM, Mangat PS. Influence of superplasticizer and curing on porosity and
pore structure of cement paste. Cem Concr Comp 1999;21:431–7.
[69] Gorzelańczyk T, Hoła J. Pore structure of self-compacting concretes made
using different superplasticizers. Arch Civil Mech Eng 2011;11(3):611–21.
[70] Łaźniewska-Piekarczyk B. The influence of selected new generation
admixtures on the workability, air-voids parameters and frost-resistance of
self compacting concrete. Constr Build Mater 2012;31:310–9.
 Author's personal copy
502 B. Łaźniewska-Piekarczyk / Construction and Building Materials 53 (2014) 488–502
[71] Szwabowski J, Łaźniewska-Piekarczyk B. The increase of air-content in SCC
mixes under the influence of carboxylate superplasticizers. Cem Wapno Beton
2008;4:205–15.
[72] Tazawa E, Mtasiwa B, Takahasi M. Effect of types of SPs and mixing method on
the properties of cementitious systems. In: 5th CANMET/ACI international
conference ‘‘SPs and Other Chemical Admixtures in Concrete’’, Rome, Italy;
1997. p. 637–56.
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[73] Sakai E, Ishida A, Ohta A. New trends in the development of chemical
admixtures in Japan. J Adv Concr Technol June 2006;4(2):211–23.
[74] Okamura H, Ouchi M. Self-compacting concrete. J Adv Concr Technol
2003;1:5–15.
[75] Sakai E, Yamada K, Ohta A. Molecular structure and dispersion–adsorption
mechanisms of comb-type superplasticizers used in Japan. J Adv Concr
Technol 2003;1:16–25.