International Journal of Biological Macromolecules 70 (2014) 381384

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International Journal of Biological Macromolecules

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

Improvement of reinforced concrete properties based on modied

starch/polybutadiene nanocomposites
Amin Saboktakin a , Mohammad Reza Saboktakin b,
a
b

Faculty of Architecture Engineering, Islamic Azad University, Tabriz, Iran

Nanostructured Materials Synthesis Lab., ArianchemieGostar Research Company, Tabriz, Iran

a r t i c l e

i n f o

Article history:
Received 9 June 2014
Received in revised form 26 June 2014
Accepted 4 July 2014
Available online 16 July 2014
Keywords:
Reinforced concrete
Carboxymethyl starch
Polybutadiene
Mechanical properties

a b s t r a c t
A novel polymer-modied cement concrete with carboxymethyl starch (CMS) and 1,4-cis polybutadiene
(PBD) system by mixing polymer dispersions or redispersible polymer powders with the fresh mixture
have been examined. In this paper, the addition of CMS-PBD powders in an aqueous solution is studied.
Polymeric molecules are supplied on a molecular scale, improving the approach of the relatively large
cement grains by the polymers. The chemical and mechanical properties of CMS-PBD-modied cement
concrete have been studied. The additions of very small amounts of CMS-PBD polymeric system results in
an improvement of the durability and the adhesion strength of the cementitious materials, which makes
them appropriate as repair materials.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Polymer modication is a frequently used technique to overcome some of the shortcomings of conventional concretes such as
poor tensile and impact strength, limited resistance to corrosion,
poor behavior under severe conditions and poor adhesion of fresh
concrete to old concrete [1]. Polymer-modied concrete are prepared by mixing a small amount of polymer with the fresh concrete
mixture [2,3]. These modied concrete contain two types of binder:
the system based on hydraulic cement and the polymer system. An
interpenetrating network of polymer and cement hydrates is generated in which the aggregates are embedded. Polymer-modied
cement concrete is produced by mixing polymer dispersions, redispersible powders, water-soluble polymers and polymeric bers
with the fresh mixture [48]. Even monomers can be added to the
mixture on the assumption that polymerization and adequate lm
formation take place in combination with the cement hydration
process [9]. The polymers are added to the fresh mixture as an
aqueous dispersion or as a redispersible powder [10,11]. Watersoluble polymers are supplied on a molecular scale, improving the
approximation of the relatively large cement grains by the polymers. In the absence of surface active agents, the lm formation
on the hydrate crystals will proceed more easily and uniformly

Corresponding author at: International Research Institute of Arian Chemie

Gostar, Tabriz, Iran.
E-mail address: saboktakin123@gmail.com (M.R. Saboktakin).
http://dx.doi.org/10.1016/j.ijbiomac.2014.07.020
0141-8130/ 2014 Elsevier B.V. All rights reserved.

and the material properties can be better tuned and modeled [12].
The various classes of water-soluble polymers are that can be used
for the modication of concrete. The important class consists of
modied polysaccharides such as cellulose derivates, as methylcellulose (MC) and starch derivates, carboxymethyl starch (CMS),
can be added to the fresh mixture. In this paper, the use of twocomponents polymers in cement concrete is discussed [13,14]. The
st component of this system is the carboxymethyl starch (CMS).
The second component of polymeric system is 1,4-cis polybutadiene. For many applications, it is becoming increasingly popular to
reinforce the concrete with small.
Randomly distributed bers. Their main purpose is to increase the
energy absorption capacity and cracking resistance of the material.
But also the increase in tensile and exural strength is often the
primary objective [15]. Fiber reinforcements increase concretes
toughness and ductility (the ability to deform plastically without fracturing) by carrying a portion of the load in the case of
matrix failure and by arresting crack growth. While steel bers
are probably the most widely used and effective bers for many
applications, other types of ber are more appropriate for special
applications [16]. For example, architectural and decorative concrete products will call for bers with a minimum of visual impact,
so that nylon or polypropylene bers may be called for. Properties
of a brous concrete as composite material depend on properties
of its components from which the major are steel or nonmetallic
bers [17]. Because the Youngs modulus of steel bers is 48 times
that of concrete it is possible to increase strength of concrete and its
crack resistance. According to lab tests, small diameter steel bers

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added to concrete mixture reduce its visible shrinkage cracking by

more than 80%, increase toughness and atmospheric durability [18].
Chemical action of corrosive environments changes the structure
of polymeric materials and results in irreversible deterioration of
compositions. Chemical stability and water absorption of ber reinforced concrete in acid and alkaline media are studied in the present
work [19,20].
2. Materials and methods
2.1. Materials
The cornstarch was purchased from Merck Co., Germany. 1,4PBD was prepared from our previous research project and other
required materials were purchased from Sigma Chemical Co. All
other solvents and materials were of analytical grade. Deionized
water (Milli-Q water) was used in the preparation of buffers and
standard solutions. All other chemicals and reagents used in this
study were of analytical grade. Sodium hydroxide and chloroacetic
acid were used as received. A grey cement PMES 42.5 according to
the European standards were selected.
2.2. Instruments
Melting points were obtained on a Mel-Temp melting point
apparatus. Analytical TLCs were run on commercial Merck plates
coated with silica gel GF250 (0.25 mm thick). The samples were
examined to determine the mean diameter and size distribution.
The powder morphology nanoparticles in the form of pellets (to
measure grain size) was investigated using Philips XL-30 E SEM
scanning electron microscope (SEM) at 30 kV (max.). The samples
were prepared by physical vapor disposition method. The gold layer
thickness was about 100 A at these samples. Mooney viscometer,

Shimadzu SMV-201, was used for Mooney viscosity characterization and measurements.
2.3. Preparation of carboxymethylstarch (CMS)
Firstly, the 0.5 g corn starch and 120 ml 2-propanol were placed
in a 500 ml vessel and stirred fro 2 h. The 5 g sodium hydroxide
was added and reacted for 1 h at 7880 C. After that, the 10 g
chloroacetic acid was added to the vessel and stirred for another 2 h
at 50 C. The product was ltered and washed several times with
ethanol, then dried under vacuum. The resulting CMS was crushed
in a mortar [degree of substitution (DS) = 0.49].
2.4. Preparation of CMS-PBD-cement concrete
Cement, CMS and PBD powders were mixed together for 2
periods of 2 min using a shaker-mixer. Unless otherwise stated,
polymers matrix-to-cement ratio (P/C) was equal to 0.50.6% (w/w)
and experiments were carried out in triplicate, also, The CMS-PBD
ratio is 0.1. The conductivity equipment consists of a 25 C thermostated reactor that contains 1 l of deionised water, a platinum
electrode and a conductimeter. Previous to each experiment a calibration was performed with a 0.1 M KCl solution.
2.5. Scanning electron microscopy
Surface and shape characteristics of CMS-1,4-PBD-cement concrete were evaluated by means of a scanning electron microscope
(FEI-Qunta-200 SEM, FEI Company, Hillsboro, OR). The samples for
SEM were prepared by lightly sprinkling the samples on a bouble
adhesive tape, which stuck to an aluminum stub. The stubs were
than coated with gold to a thickness of 300 A using a sputter coater
and viewed under the scanning electron microscope.

Fig. 1. (a) Morphology of CMS-PBD-modied cement concrete by emission scanning electron microscopy eld.
(b) The size distribution of CMS-PBD-modied cement concrete was determined from the SEM picture.

A. Saboktakin, M.R. Saboktakin / International Journal of Biological Macromolecules 70 (2014) 381384

383

0.06
0.05

X (%)

0.04
Scheme 1. The chemical structure of 1,4-cis polybutadiene.

0.03
0.02

Table 1
The characteristics of CMS/PBD/Cement nanoparticles.
Variables

Values

Average particles size (nm)

CMS/PBD/Cement

0.1
0.2
0.3
0.4
0.5
0.6

1.59
1.63
1.54
1.78
2.01
2.27

0.10
0.03
0.40
0.12
0.10
0.04

0.01
0
0

50

100

150

200

250

300

Time (days)

1.001
1
0.999

After drying at 37 C for 48 h, the mean diameter of the sample

was determined by a sieving method using USP standard sieves.
Observations are recorded (Fig. 1).

X(%)

2.6. Particle size

0.995
0.994

3.1. Morphology of CMS-PBD-modied cement concrete

50

100

150

200

Time (days)
Fig. 3. Water absorption of CMS-PBD-modied cement concrete and exposure time.
X%: Mass of sample before and after immersion in water.

1.2
1
1
2

0.8

3.2. Inuence of curing conditions

Cement hydration requires a wet or moist curing, while a dry
curing promotes CMS-PBD lm formation. Fig. 2 shows the exural
strength for concrete subjected to the standard curing. The results
show that the exural strength of the modied concrete with CMSPBD nanocomposite is increased with 30% if a dry curing period is
included (standard curing). This is an indication of the formation
of a CMS-PBD lm which contributes to the exural strength of the
concrete. The standard curing and wet curing have been performed in
2days wet and 5 days moisture, respectively.

0.997
0.996

3. Results and discussion

Fresh fracture surfaces of the concrete beams, cured as above

method, are investigated. Samples are coated with gold to a thickness of 300 A using a sputter coater and viewed under the
scanning electron microscope. The presence of CMS-PBD lm is
expected because of their strong afnity to the gaswater phase.
During mechanical mixing, they become attached to the air void
interface and start to stabilize the entrained air void and wet
cement paste may be detected, depending on the surface activity
of the polymer (Scheme 1, Table 1).

0.998

0.6
0.4
0.2
0
0

50

100

150

200

Time (days)

0.9
0.8
0.7
0.6

0.5
0.4
0.3
0.2
0.1
0
0

20

40

60

80

100

120

140

160

Time (days)

Fig. 2. Inuence of the curing conditions on the exural strength of unmodied

concrete (1) and modied concrete (2).

Fig. 4. The coefcient of chemical resistance of CMS-PBD-modied cement concrete

and exposure time in (1) water, (2) 70% H2 SO4 , (3) 25%NH4 OH solutions.

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3.3. Inuence of moisture and water on CMS-PBD-modied

cement concrete
Film of water-soluble CMS component of polymeric matrix is
quite hygroscopic. The equilibrium moisture content of a CMS
lm increases exponentially with increasing relative humidity. The
mechanical properties of this lm are again very much a function
of the water content of the lm. At high relative humidities, the
mechanical properties of CMS lm decrease dramatically. Additionally, splitting tensile tests are carried out on concrete before
and after vacuum saturation and storage under water for 7 days.
The results are shown that in Fig. 3. The splitting tensile of CMSPBDmodied concrete decreases with almost 45% after storage
under water.
3.4. Chemical resistance of CMS-PBD-modied cement concrete
Tests of chemical resistance of samples of 4 4 16 cm size
was carried out into water, 70% H2 SO4 and 25% NH4 OH solution.
The results show that an increase of compressive strength in an
initial stage of exposure is directly related to the adsorption by surface micro defects and surface seal. The CMS-PBD-modied cement
concrete has a good chemical resistance in inorganic acid environments. Figs. 3 and 4 show water absorption and coefcient of
chemical resistance of samples and exposure time, respectively.
4. Conclusions
Adding CMS-PBD polymeric system dispersions or redispersible
powders to the fresh mixture produces polymer-modied cement
concrete with improved chemical and mechanical properties. By

studying the inuence of the curing conditions and the inuence of

moisture and water on the mechanical properties, polymer lm
formation is assumed in concrete modied with CMS-PBD. The
presence of polybutadiene in polymeric system increases the chemical properties such as chemical resistance of concrete for strong
inorganic acids or bases solutions.
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