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The Influence of Some Surfactants on Porous Concrete Properties

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 ISSN 1392–1320 MATERIALS SCIENCE (MEDŽIAGOTYRA). Vol. 13, No. 4. 2007

The Influence of Some Surfactants on Porous Concrete Properties

Modestas KLIGYS∗, Antanas LAUKAITIS, Marijonas SINICA, Georgijus SEZEMANAS

Vilnius Gediminas Technical University, Institute of Thermal Insulation, Linkmenų 28, LT-08217 Vilnius, Lithuania
Received 19 September 2007; accepted 16 October 2007
Expanded polystyrene is used as packing material in various industrial fields in the world. A large quantity of expanded
polystyrene is consumed, and is disposed as a waste. On purpose to utilize packing tare waste of expanded polystyrene,
composite material is created. The matrix in this composite material is porous concrete and insertion – crushed tare
waste. The properties of composite matrix are analyzed comprehensively in this article. As it is known, porous concrete
is one of types of lightweight concrete. One of ways to get porous concrete is the usage of surfactants in the formative
mixtures. It has been widely used to decrease the density of concrete and to improve its thermal properties. The
surfactant molecules help entrain air bubbles and stabilize them in the fresh cement paste. Researches with
6 different types of surfactants were made. The Ufapore TCO surfactant was chosen for the further research as the most
suitable for production of composite material.
Keywords: porous concrete, surfactants, contact angle, surface tension.

INTRODUCTION∗ to exceed the concentration in the interfacial surface and

than micelles are formed. The concentration of surfactant
The use of lightweight concrete has been increasing solution at which remarkable changes of its properties
especially in the construction of high rise buildings, off- begin because of micelle formation is called the critical
shore structures and long span bridges due to the advantage micelle concentration (CMC) [6]. Then all the coaligative
of its low density, which results in a significant benefit in properties of the solution fluctuate. The ionic surfactants
terms of load bearing elements of smaller cross section and modulate into micelles when moll concentration is ten
a corresponding reduction in the size of the foundation [1]. times higher than nonionic surfactants [5]. Rosen [7] fixed
There are two ways to reduce the density of concrete: us- that the value appearing first to decrease with the tem-
ing light porous fillers or forming air voids. These air voids perature to some minimum and then to increase with
are entrained in a fresh cement paste using surfactants [2]. further increase in temperature, so the effect of temperature
Surfactants are substances, which have a tendency to con- on the CMC in aqueous solutions of surfactants is very
centrate at the surface or interface. They often carry a complex.
charge and thus they impart a charge to the surface that It is known that formed air bubbles in fresh concrete
they attach to. To understand the role of surfactants play in are unstable and have a limited lifetime. The interfaces
this process, it is important to learn their chemical proper- between the dispersed air and the surrounding matrix con-
ties. The most common chemical classification of tain free surface energy, and the thermodynamic tendency
surfactants is based on the nature of the hydrophilic group, is to reduce the interfacial surface areas [8]. Diffusion of
i. e., anionic (the surface-active portion of the molecule air from a bubble, bubble coalescence due to capillary
exhibits a negative charged), cationic (the surface-active flow, and rapid hydrodynamic drainage of liquid from the
portion bears positive charge), zwitterionic (both, positive bubbles show that pure liquid cannot form stable air bub-
and negative charges are presented in the surface-active bles [9]. Girniene et al. [10] investigated the influence of
portion), nonionic (the surface-active portion bears no different surfactants and stabilizers on the foam stability in
apparent ionic charge) [3]. The first three classes create the porous concrete production technology and fixed that this
group of ionic surfactants. As Shenfeld [4] prescribes, stability is the main factor affecting the selection of sur-
hydrophilic and hydrophobic nature of surfactant mole- factants. Most of modern surfactants have anionic nature,
cules determines their solutions behaviour. Temperature because the stability of air voids is generated in assistance
also affects the solubility of surfactants. The solubility of with them [11]. The stability of air voids is questionable
ionic surfactants increases rising the temperature while when they are formed using the cationic and nonionic sur-
nonionic – decreases [5]. factants [8]. Fagerlund [12] described three mechanisms of
Micelle formation is an important parameter due to a air-void instability in the concrete. Mielenz et al. [13]
number of important interfacial phenomena, such as deter- proposed four origins of air in the concrete, which include
gency and solubilization, depend on the existence of air contained in the system and air entrapped during the
micelles in surfactant solution [3]. If the concentration of mixing. Bruere [14] specified factors affecting the air en-
surfactants in a volume of the system does not exceed the trainment in cement and silica pastes, Powers [15]
concentration in the interfacial surface, molecules and ions described how air is entrained into concrete mixture during
are the monodispersic conformation. Increasing the con- the mixing, Diamond [16] analyzed how mixing time af-
centration of surfactants in a volume of the system, it starts fecting microstructure in concrete and Monteiro et al. [17]
examined air void morphology in the fresh cement pastes.
∗ Authors [18] analyzed adsorptive behavior of the
Corresponding author. Tel.: +370-5-2752642; fax.: +370-5-2752629.
E-mail address: termo@aiva.lt (M. Kligys)

310
surfactants on a surface of Portland cement. It is widely ments are made with all rising contents solutions of
known that the pore structure of concrete strongly surfactants. The measurements are made three times, the
influences its physical properties [19, 20]. average of data is used in the calculations. The surface
The aim of this work is to investigate the properties of tension was calculated in following way:
aqueous solutions of some surfactants and the influence of σ 0 ⋅ hX
different surfactant type, concentration and mixing time on σX = , (1)
the density of fresh cement paste and hardened specimens. h0
Depending on research results to choose the most suitable where σ0 is the surface tension of distilled water, σX is the
surfactant type from several ones, its optimal content and surface tension of surfactant solution, h0 is the difference
mixing time. between heights in a manometer offsets of distilled water,
hX is the difference between heights in a manometer offsets
EXPERIMENTAL of surfactant solution.
Portland cement of mark CEM I 42,5R from the com- It is impossible to determine the contact angle of a
pany JSC “Akmenės cementas”, which met requirements drop of surfactant solution onto the surface of crushed
of the standard [21], was used as a binding material. Port- expanded polystyrene waste. Accordingly these angles
land cement setting time is 140 min and final setting time – were measured onto the surface of metallic plate coated
190 min [22]. The specific surface area according to Blaine with the paraffin wax. The position of a drop was fixed
was 420 m2/kg. The chemical and mineral compositions of with the VARIMEX projector. The variation of contact
Portland cement were determined in accordance with the angle was measured depending on the content of surfactant
methods [23] and [24], respectively, and are presented in solution.
Table 1. After determination of surface tension and contact
For the determination of surfactant solution properties, angle it is possible to fix the wetting of surfactant solution.
aqueous solutions from distilled water and following Wetting is also characterized in terms of a “work of
surfactants (air entraining agents are also called surfactants adhesion” denoted by WAd, and calculated in the following
in this article) were studied: (a) Ufapore CC 85; (b) way:
Ufapore TP 707; (c) Upafore CC; (d) Ufapore TCO; (e) W Ad = σ lv (1 + cos θ ) , (2)
PB-2000 and (f) Sulfonol-bone glue. These surfactants
were used in contents: 0.025, 0.050, 0.075, and 0.100 %. where WAd is the work of adhesion, σlv is the surface
Key properties of surfactants are presented in Table 2. tension of the liquid, θ is the contact angle at the solid-
The measure of surface tension was made with Re- liquid-vapor contact region.
binder apparatus. The distilled water was poured into the For the formation of the fresh cement pastes the same
test – tube and the capillar of pipe was contacted to the surfactants, mentioned above, were used (W/C ratio = 0.3).
surface. Dripping the distilled water from aspirator the These surfactants were used in contents: 0.01, 0.03,
maximal difference between liquid heights was fixed in the 0.05, 0.07 and 0.09 % (calculating from Portland cement
manometer offsets. Then the mostly attenuated solution of mass).
surfactant is poured not varying the speed of water drip- For materials mixing, the round plastic container of 20
ping from aspirator and the difference between heights is liters and the vertical mixer MXP1602E was used. During
measured in the manometer offsets again. The measure- the whole mixing, the speed of a mixer was 225 r.p.m.
Table 1. Chemical and mineral compositions of Portland cement

Chemical
SiO2 Al2O3 Fe2O3 CaO K2O + Na2O SO3 Others
composition
In % 20.76 6.12 3.37 63.50 1.03 0.80 0.30
Mineral
C3S C2S C3A C4AF
composition
In % 58.54 15.29 10.40 10.17

Table 2. A summary of the major physical properties of the surfactants used in this study

Ufapore CC 85 Ufapore TP 707 Ufapore CC Ufapore TCO PB-2000 Sulfonol-bone glue

Mixture of anionic
Chemical Air entraining Anionic Air entraining
and non-ionic Foamer Anionic surfactant
description agent surfactant agent
surfactants
pH 7.8 10.7 8.8 8.0 7.0 – 10.0 8.0
Molecular
– 382 – – – 290
mass, g/mol
Appearance White colored Pale straw paste Clear mobile liquid White colored Brown colored Yellow colored
Active
85.3 27.2 30.1 92.0 – 96.0 – 75.0
content, %

311
 The density of the fresh cement paste was fixed after low, the surface energy of solid is high, and the liquid-
every 2 mixing minutes. The round metallic can of 0.5 liter solid interfacial tension is low [25]. The solid is wet by the
was used for that purpose. Density of fresh cement paste liquid, if θ < 90° and if θ > 90°, the solid is not wet by the
was fixed by weighting empty and filled with fresh cement liquid. Research results showed that Ufapore CC 85
paste metallic can. The density of the fresh cement paste surfactant solution has the lowest θ value (41º) in content
was fixed till 34 mixing minute. 0.025 %, Ufapore TCO (32º and 33º ) in contents 0.050 %
The density of hardened specimens of the porous con- and 0.075 %, and PB-2000 (36º) in content 0.100 %. The
crete was fixed after 4, 8, 14 and 24 mixing minutes. The highest θ value (62º) was fixed with PB-2000 surfactant
prepared cement paste was poured into molds (size solution in content 0.025 %, and Ufapore TP 707 (from 61º
(10×10×10) mm) and slightly compacted to have the paste to 59°) in contents from 0.050 % to 0.100 %.
evenly distributed. The following day the molded speci- 110

mens of porous concrete with different densities were

taken out of molds, covered by polyethylene film and kept 100

for 27 days at temperature of 20 °C. Afterwards, the speci- 90

mens were conditioned in the ventilated oven until
constant mass was achieved. After that specimens were 80

Contact angle, °
measured and the density of hardened specimens was
fixed. 70

The pore structure of the hardened specimens was

60 2
determined by an optical microscope, connected to a
computer, which can enlarge the image up to 100 times. 50
5
3

RESULTS AND DISCUSSIONS 40

6
1

Low surface tension of the liquid phase helps to en- 4

30
train air bubbles in fresh cement paste during the mixing. 0,000 0,025 0,050 0,075 0,100
In many liquid – solid systems, wettability is also im- Surfactant solution content, %
proved lowering the surface tension of the liquid phase. Fig. 2. The dependence of surfactant solution contact angle on its
Research results showed that all surfactant solutions in all content and type: 1 – Ufapore CC 85; 2 – Ufapore TP
contents reduced the surface tension comparing with pure 707; 3 – Ufapore CC; 4 – Ufapore TCO; 5 – PB-2000;
distilled water (0.073 N/m). Ufapore CC 85 surfactant 6 – Sulfonol-bone glue
solution has the lowest values of surface tension (from A high value of WAd indicates good wetting, and low
0.051 N/m to 0.035 N/m) in all contents. PB-2000 surfac- value – poor wetting. Good wetting means that the strong
tant solution has the highest value of surface tension adhesion between the liquid and the solid will develop.
(0.051 N/m) in 0.025 % content, and Ufapore CC has the Research results (Fig. 3) showed that Ufapore TCO
highest values (from 0.048 N/m to 0.036 N/m) in contents surfactant solution has the highest work of adhesion values
from 0.050 % to 0.100 %. (from 0.078 N/m to 0.070 N/m) in contents (from 0.025 %
0,075 to 0.050 %) and PB-2000 the highest values (from
0.066 N/m to 0.063 N/m) in contents (from 0.075 % to
0,070
0.100 %). The Ufapore TP 707 surfactant solution has the
0,065 lowest values (from 0.060 N/m to 0.053 N/m) in all
contents.
0,060
Surface tension, N/m

0,085

0,055
0,080 4

0,050
5
5 0,075

0,045
Work of adhesion, N/m

3 3
4 0,070
0,040 6
6
0,065
0,035 2 1
1 0,060
0,030 2
0,000 0,025 0,050 0,075 0,100
0,055
Surfactant solution content, %

Fig. 1. The dependence of surfactant solution surface tension on 0,050

its content and type: 1 – Ufapore CC 85; 2 – Ufapore TP

707; 3 – Ufapore CC; 4 – Ufapore TCO; 5 – PB-2000; 0,045
0,000 0,025 0,050 0,075 0,100
6 – Sulfonol-bone glue
Surfactant solution content, %
The angle of contact θ is measured through the liquid
Fig. 3. The dependence of work of adhesion on surfactant
at the solid-liquid-vapor contact region after the liquid has solution content and type: 1 – Ufapore CC 85;
attained an equilibrium configuration on the solid. Low 2 – Ufapore TP 707; 3 – Ufapore CC; 4 – Ufapore TCO;
values of θ will be obtained if the liquid surface tension is 5 – PB-2000; 6 – Sulfonol-bone glue

312
 2100 1 2100 1
2000 2000
2
1900 1900
3
1800 1800

3
3

Fresh cement paste density, kg/m

4
Fresh cement paste density, kg/m

1700 1700
1600 5
1600
1500 2
6 1500
1400 1400
3
1300 1300
1200 1200
4
1100 1100 5
1000 1000 6
900 900
800 800
700 700
600 600
500 500
400 400
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34
Mixing time, min Mixing time, min

a b
2100 1 2100 1
2000 2000
1900 1900
1800 1800
3
Fresh cement paste density, kg/m
3
Fresh cement paste density, kg/m

1700 1700
1600 1600
1500 1500
2
1400 1400
1300 1300
1200 1200
1100 2 1100
3
1000 1000
900 3 900
800 4 800 4
700 5 700
5
600 6 600

500 500 6
400 400
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34
Mixing time, min Mixing time, min

c d
2100 1 2100 1
2000 2000
2 2
1900 1900
1800 1800 3
3

3
Fresh cement paste density, kg/m

Fresh cement paste density, kg/m

1700 1700
4
1600 1600
5
1500 1500
1400 1400 6
1300 1300
1200 1200
3
1100 1100
1000 1000
900
4 900
800 5 800
700 700
600
6 600
500 500
400 400
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34
Mixing time, min Mixing time, min

e f
Fig. 4. The changes of fresh cement paste densities depending on surfactant type, content and mixing time: a – Ufapore CC 85,
b – Ufapore TP 707, c – Ufapore CC, d – Ufapore TCO, e – PB-2000, f – Sulfonol-bone glue. 1 – test, 2 – 0.01 %, 3 – 0.03 %,
4 – 0.05 %, 5 – 0.07 %, 6 – 0.09 %

313
 After the analysis of surfactant solution properties the then the content of surfactant is enlarged. The density
density of the fresh cement pastes was fixed. There is no values of the fresh cement paste with mentioned surfac-
sense in mixing the fresh cement paste longer than for 10 tants vary from 1684 kg/m3 to 996 kg/m3 (Ufapore CC),
minutes in the technological processes of this composite and from 1812 kg/m3 to 973 kg/m3 (Ufapore TCO) when
material type, so the effectiveness of surfactants must be mixing time was till 10 minutes. It was found that the less
estimated depending on this factor. It was established that effective are Ufapore CC 85 and Sulfonol-bone glue
the most effective are Ufapore CC and Ufapore TCO sur- surfactants (Fig. 4, a and f) in all contents and through all
factants in all contents (Fig. 4, c and d). Although primary mixing ranges. The density values of the fresh cement
decrease of the density of fresh cement paste with Ufapore paste with mentioned surfactants through all mixing ranges
CC surfactant is more significant, the density of cement vary from 2044 kg/m3 to 1554 kg/m3 (Ufapore CC 85) and
paste with Ufapore TCO surfactant decreases more rapidly from 2040 kg/m3 to 1477 kg/m3 (Sulfonol-bone glue).
1700

3
3

Fresh cement paste density, kg/m

Fresh cement paste density, kg/m

2000
1600

1900 1500

1400
1800
1300
1700 0.01 %
0.01 % 1200 0.03 %
0.03 % 0.05 %
0.05 % 1100 0.07 %
1600
0.07 % 0.09 %
0.09 % 1000
1500 1500 1400 1300 1200 1100 1000
1900 1800 1700 1600 1500 1400 3
Hardened specimens density, kg/m
3 Hardened specimens density, kg/m

a b

1500 1700
Fresh cement paste density, kg/m3

1600
Fresh cement paste density, kg/m

1400
1500
1300 1400
1200 1300
1200
1100
1100
1000 1000
0.01 %
900 900 0.01 %
0.03 %
800 0.03 %
0.05 %
800 0.07 % 0.05 %
700
0.09 % 0.07 %
700 600 0.09 %
500
1200 1100 1000 900 800 700 600 500 1400 1200 1000 800 600 400
3 3
Hardened specimens density, kg/m Hardened specimens density, kg/m

c d

1900 2050
3
3

Fresh cement paste density, kg/m

Fresh cement paste density, kg/m

1800 2000
1700 1950
1600 1900
1500 1850
1400 1800
1300 1750
1200
1700
1100 0.01 %
1650 0.01 %
1000 0.03 %
0.05 % 1600 0.03 %
900
0.07 % 1550 0.05 %
800 0.07 %
0.09 % 1500
700 0.09 %
1450
1800 1600 1400 1200 1000 800 600
3 1900 1800 1700 1600 1500 1400 1300
Hardened specimens density, kg/m 3
Hardened specimens density, kg/m

e f
Fig. 5. The dependence of hardened specimens density on the fresh cement paste densities: a – Ufapore CC 85, b – Ufapore TP 707,
c – Ufapore CC, d – Ufapore TCO, e – PB-2000, f – Sulfonol-bone glue

314
 The dependences of hardened specimen densities on The pore structure analysis of hardened specimens
fresh cement paste densities showed that lower value of showed that after 8 mixing minutes Ufapore CC surfactant
fresh cement paste density will cause the decrement of in content 0.03 % formed pores of very large diameter,
hardened specimen density values in all contents and mix- comparing with other surfactants in the same content
ing ranges. It was fixed that the less effective surfactant is (Fig. 6, c). This determination explains why the density of
Ufapore CC 85 (Fig. 5, a). The density values of hardened fresh cement paste and hardened specimens, formed with
specimens of mentioned surfactant vary from 1925 kg/m3 this surfactant, has the lowest values. The thin partitions
(0.01 %) to 1531 kg/m3 (0.09 %). The most effective sur- between pores were formed and this leaded to the coalition
factant in contents (from 0.01 % to 0.05 %) is Ufapore CC. of adjacent air bubbles. Analogous phenomenon was fixed
Its values vary from 1228 kg/m3 to 644 kg/m3. Moreover, in Ufapore TP 707 and PB-2000 surfactants (Fig. 6, b and
surfactants PB-2000 and Ufapore TCO had the lowest e). In contrast with surfactants mentioned above, Ufapore
density values of hardened specimens (from 942 kg/m3 to CC 85 and Sulfonol-bone glue formed pores of small
608 kg/m3 and from 1150 kg/m3 to 500 kg/m3) in contents diameter (Fig. 6, a and f), as a result the density of fresh
(from 0.07 % to 0.09 %) accordingly. It is important to cement pastes and hardened specimens had the highest
mention, that there is no big difference between the values values. However, Ufapore TCO formed pores of larger
of hardened specimens of both Ufapore CC and TCO diameter comparing with Ufapore CC 85 and Sulfonol-
surfactants. Both of them are more effective even in low bone glue surfactants. It determined lower density values
contents comparing with other ones. of fresh cement pastes and hardened specimens. Thicker

a b

c d

e f

Fig. 6. The character of pores after 8 mixing minutes, when surfactant content is 0.03 %, (×24): a – Ufapore CC 85, b – Ufapore TP 707,
c – Ufapore CC, d – Ufapore TCO, e – PB-2000, f – Sulfonol-bone glue

315
partitions between pores helped to avoid their coalition, so 7. Rosen, M. J. Surfactants and Interfacial Phenomena, 3rd ed.
formed air bubbles were more stable and the existence of New Jersey, John Wiley & Sons, 2004: 464 p.
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CONCLUSIONS 9. Myers, D. Surfaces, Interfaces, and Coloids: Principles and
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contents reduced surface tension and contact angle of Surfactants on the Foam Properties Materials Science
distilled water. It means that all surfactants improve the (Medžiagotyra) 6 (4) 2000: pp. 316 – 320.
wetting ability of crushed expanded polystyrene waste with 11. Dodson, V. H. Concrete Admixtures. New York, Van
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hardened specimens densities showed that the most Concrete Properties Nordic Concrete Research 9 1990:
effective surfactants are Ufapore CC and Ufapore TCO. pp. 39 – 52.
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The usage of these surfactants in higher contents is not Flack, H. L. Origin, Evolution, and Effects of the Air Void
economically effective. System in Concrete: Part 1. Entrained Air in Unhardened
3. Research results showed that mixing time with Concrete Journal of American Concrete Institute 30 (1)
mixer MXP1602E should not exceed 10 minutes. Almost 1958: pp. 95 – 121.
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primary densities till that time. Longer mixing time is Journal of American Concrete Institute 26 (9) 1955:
useless economically and technologically. pp. 905 – 920.
4. Although surfactant Ufapore CC reduces the value 15. Powers, T. C. The Properties of Fresh Concrete. New York,
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surfactant Ufapore TCO, but analysis of the structure 16. Diamond, S. The Patch Microstructure in Concrete: Effect
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surfactant is used. This type of voids can influence the 17. Corr, D. J., Lebourgeois, J., Monteiro, P. J. M.,
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further research, surfactant Ufapore TCO will be also used alization of Pore Structure in Hardened Cement Paste by the
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