Construction and Building Materials 204 (2019) 541–549

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Construction and Building Materials

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

The synthesis of a new chitosan based superplasticizer and investigation

of its effects on concrete properties
Hülya Arslan a,⇑, Uğur Semih Aytaç a, Turhan Bilir b,⇑, Sß adi Sß en a
a
Bülent Ecevit University, Chemistry Department, 67100 Zonguldak, Turkey
b_ _
Istanbul University-Cerrahpasßa, Department of Civil Engineering, Avcılar Campus, 34320 Avcılar, Istanbul, Turkey

h i g h l i g h t s

A new type of renewable and biodegradable superplasticizer based on sulfated graft chitosan copolymer has been proposed.

The workability improved.

The compressive strengths improved.

Contributed to sustainable cement, mortar and concrete.

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

Article history: Chitosan-g-POEGMA (Chitosan-g-poly[oligo(ethyleneglycol) methyl ether methacrylate]) graft copoly-

Received 22 October 2018 mers are prepared by grafting of oligo (ethylene glycol methyl ether) methacrylate (OEGMA) on chitosan
Received in revised form 16 January 2019 via redox free radical polymerization method using ceric ammonium nitrate (CAN) as the initiator at
Accepted 27 January 2019
40 °C. Then the resulting copolymers are sulphated by sulphuric acid, chlorosulfonic acid and fuming sul-
phuric acid (Oleum). The compounds are characterized by FT-IR, NMR, and Elemental analysis. The chi-
tosan homopolymer is also sulphated to compare the results. Taking all characterization results and
Keywords:
water solubility ratios into account, it is decided to conduct tests on concrete specimens containing graft
Chitosan-g-POEGMA graft copolymers
Sulfonation
copolymers sulphated with oleum sulfuric.
Superplasticizers Water-reducing properties in the fresh concrete have been examined. Compared to the reference con-
Cement paste crete; it is observed that water-reducing of sulphonated graft is %6 and sulphonated chitosan is %5. The
Concrete unit weights of the reference concrete is as 2380 kg/m3, sulphonated graft is as 2395 kg/m3 and sulpho-
nated chitosan is as 2388 kg/m3. The air content of the reference concrete is measured as 2%, sulphonated
graft as 1.5% and sulphonated chitosan as 1.6%. 28-day concrete durability results are determined as
30.1 MPa for the reference concrete, 34.7 MPa for sulphonated graft and 33.8 MPa for sulphonated
chitosan.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction repulsion mechanisms. Their use allows the production of concrete

Superplasticizer/high-surface water reducers are admixtures
that provide a high level of consistency to concrete because of
low water/cement (w/c) ratio, maintain consistency and increase
the early or ultimate strengths with respect to the product type.
Superplasticizers are polymeric admixtures used in cementitious
systems in the construction industry in recent years. The role of
superplasticizers is to increase the workability of fresh concrete
by distributing the cement particles through electrostatic or steric
⇑ Corresponding authors.
E-mail addresses: hulya.arslan@beun.edu.tr (H. Arslan), tbilir@istanbul.edu.tr
(T. Bilir).
with special flow properties such as self-compacting concrete. On
the other hand, superplasticizers provide concrete mix designs
with very low water/cement ratios. Thus, high performance con-
cretes with very high strength and durability can be obtained [1].
Polymeric chemical admixtures, i.e., superplasticizers, are
sulfonate or carboxylate polyelectrolytes. First generation super-
plasticizers have been developed in the 60–70 s and are based on
water-soluble polymers containing sulphonated groups such as
sulfated naphthalene-formaldehyde (SNF) condensates, sulfated
melamine-formaldehyde (SMF) condensates and modified
lignosulfonates (MLS). New generation products with further
improved properties are comb-shaped polycarboxylate-based
polymers [2–5].

https://doi.org/10.1016/j.conbuildmat.2019.01.209
0950-0618/Ó 2019 Elsevier Ltd. All rights reserved.
542 H. Arslan et al. / Construction and Building Materials 204 (2019) 541–549
Most of the previous studies are concerned with investigating
the influence of molecular structures on the activity of superplas-
ticizers. There are many studies in the literature concerning
polycarboxylate-type superplasticizers [3–10] and
polysulphonate-type superplasticizers [11–26].
There are only a few studies in the literature concerning the
investigation of the efficiency of sulfated chitosan (SC) as a super-
plasticizer [27,28]. In these studies, it has been observed that the
sulfated chitosan superplasticizer (SCS) exhibits better application
performance, especially with regard to the fluidity of the cement
paste and concrete compared to the polycarboxylate superplasti-
cizers (PCs). In other words, high performance sulfated superplas-
ticizers can be obtained [29]. In addition, Chitosans can be used as
cement additive to modify viscosity, heavy metal retainer and
thickener [30]. Likewise, the effects of LMW and High Molecule
Weight (HMW) chitosans on strength and thickening of oil well
cement was investigated [31]. It was observed that the strength
and thickening of oil cell cement is more intensely affected by
LMW chitosan rather than HMW chitosan [31]. In a previous study,
an eco-friendly coating with both hydrophobic and biocide proper-
ties based on a silane/silocane as water repellent combined with
chitosan and silver nitrate as biocides were attempted to be devel-
oped [32].
On the other hand, the usages of chitosan in construction indus-
try are generally limited to be used as admixtures and coatings
[33]. However, there also are few studies related to the usage of
chitosan in the construction research areas. In one of them,
gypsium-chitosan-gypsium coated superabsorpent polymer (SAP)
was developed for microcrack plugging in well cement [34]. In
another study, it was concluded that methacrylated chitosan com-
bined with dimethylaminopropyl for the production of superabsor-
pent polymer gave very promising self-healing results of mortars
close to commercial SAPs even though this chitosan SAP had more
severe reductions in mortar strengths when compared to the
strengths of commercial SAPs [35]. The effects of non-ionic and
ionic derivatives (chitosan ethers) on fresh mortar properties were
investigated and it was observed that non-ionic did not affect
workability significantly while ionic derivative decreased worka-
bility at the ratio of 50% [36]. In another previous study, LMW chi-
tosan was used as a natural polymer binder for coating rice husk
ash particles in cement paste to provide bonding between carbon
nanofibers and SiO2 from rice husk ash [37].
During literature survey, limited studies have been observed for
the usages of chitosan in construction industry. Furthermore, most
of them were usage of them admixtures and coating in cement
paste or paste ingredients. Finally, it can be mentioned that only
three studies could be seen for the effects of sulfated chitosan as
superplasticizer on workability, setting and strengths of cement
paste and concrete [27–29]. Besides, these authors have reported
that these studies did not only present a new superplasticizer
but also developed a method for preparing such a renewable envi-
ronmental biopolymer [27–29]. However, the chitosan used in
these studies were sulfated chitosan.
Based on these results of literature survey, it was thought that
sulfated chitosan-g-POEGMA graft copolymers could give much
better results due to water-soluble POEGMA side branches as
superplasticizer compared to sulfated chitosan in literature. Sul-
fated chitosan-g-POEGMA graft copolymer has not been used as a
superplasticizer and it is aimed to synthesize sulfated chitosan-g-
POEGMA graft copolymers as a new chitosan-based superplasti-
cizer for cement paste and concrete. Thus, the novelty of this study
is to develop a new environmental-friendly biodegradable super-
plasticizer based on sulfated chitosan-g-POEGMA graft copolymer.
Moreover, since the sulfated chitosan-g-POEGMA graft copoly-
mers are produced from natural sources and are biodegradable, it
is important for the future to use it as a concrete admixture in
the ready-mixed concrete production and to bring innovation to
the literature.
2. Experimental procedure
2.1. Materials
Chitosan (Low molecular weight), methanol, sodium hydroxide,
oligo(ethylene glycol) methyl ether methacrylate (OEGMA
Mn:300), amonium cerium (IV) nitrat were supplied from Sigma-
Aldrich and used without purification. Nitric acid, acetic acid, sul-
furic acid, chlorosulphuric acid, sulphuric acid with fume (Oleum),
dimethylformamid, diethyl ether, aceton were supplied from
Merck and used as received.
2.2. The graft copolymerization of OEGMA onto chitosan by redox free
radical polymerization
Firstly, the molecular weight of the low molecular weight Chi-
tosan (LMW) was determined by viscosimetric measurements. Vis-
cosity measurements were made using Ubbelohde viscometer. The
viscosity average molecular weight (Mv) was calculated to be
22875 Da.
5 g chitosan (LMW) is dissolved in 130 ml of 2% acetic acid solu-
tion under stirring at room temperature for 72 h. 0.25 M Oligo
(ethylene glycol) methyl ether methacrylate (OEGMA) monomer
and 0.05 M (Ce (NH4)2 (NO3)6) in 0.5 M HNO3 initiator solution
were added to the chitosan solution. Argon gas was passed through
the obtained mixture for 10 min and then taken at 40 °C for 8 h. At
the end of this period, the reactor was uncovered and allowed to
reach room temperature for 1 h. The solvent was removed by
rotary evaporation, dried in a vacuum oven at 30 °C and the dry
matter was weighed (raw weighing) (Table 1, Fig. 1).
2.3. Purification of the synthesized graft copolymer
Purification was carried out by the soxhlet extraction method
using the appropriate solvent (THF) to dissolve the homopolymer
of POEGMA in the crude polymer. The pure graft copolymer was
dried and weighed in a vacuum oven at 30 °C. The yield calcula-
tions and graft percentages of the obtained products were calcu-
lated (Table 1).
2.4. Sulfonation of the graft copolymer
The sulfonation process was carried out by three different
methods. These; sulfonation with sulfuric acid, sulfonation with
chlorosulphonic acid and sulfonation with fuming sulfuric acid.
Sulfonation with Sulfuric Acid (Sulfonation I) has been made as
followings. 2.355 ml of DMF and 1.134 ml of sulfuric acid are
mixed thoroughly, followed by addition of the Chitosan-g-
POEGMA graft copolymer. The resulting mixture is placed in a
water bath at a certain temperature and mixed for a certain period
of time. Water baths at different temperatures and different dura-
tions such as 30 °C during 4 h, 40 °C during 4 h, 50 °C during 4 h
and 50 °C during 12 h, etc have been examined. At the end of this
run, the mixture was allowed to cool with stirring at room temper-
ature for 1 h at 25 °C, neutralized with 30% by weight of sodium
hydroxide. Precipitation with a 3:1 diethylether-acetone mixture
was carried out, the product was separated by decantation and
washed 2–3 times with methyl alcohol. After dialysis against water
for 48 h, it was dried with freeze dryer [27].
Sulfonation with chlorosulfuric acid (Sulfonation II) has been
made as followings. 0.5 g of Chitosan-g-POEGMA graft copolymer
was mixed with 35 ml of 1% acetic acid until dissolved (3 days).
 H. Arslan et al. / Construction and Building Materials 204 (2019) 541–549 543

Table 1
The Graft Copolymerization of OEGMA onto Chitosan via redox free radical polymerization method using CAN as the initiator at 40 °C for 8 h.

Run Chitosan OEGMA300 Percent Grafting(a) Grafting Efficiency(a) Grafting Efficiency(b) Yield(c)(%) Raw Weighing Pure Graft Weighing
No (W0) (g) (W2) (g) (G %) (GE%) (GE%) (W3) (g) (W1) (g)
G1 5.00 13.50 260.00 96.30 90.00 97.30 20.00 18.00
G2 2.00 5.12 255.45 99.79 87.77 99.85 8.10 7.11
G3 4.00 10.87 267.50 98.44 95.77 98.86 15.35 14.70
(a)



% G¼ W1W0
W0  100 , % GE ¼ W1W0
W2  100 [38].
(b)


% GE ¼ W1W3  100 [39].
 
(c)
% Yield ¼ W0þW2
W1
 100 .

Fig. 1. Synthesis of Chitosan-g-POEGMA graft copolymers.

Mixtures of HCISO3 + DMF were produced using the ratios indi-
cated in Table 2 and added dropwise to the Chitosan-g-POEGMA
graft copolymer solution. The resulting final mixture was stirred
at the temperatures and times indicated in Table 2 to determine
the optimum conditions for the sulfonation. At the end of the sul-
fonation process, neutralization in 20% NaOH and precipitation in
cold methanol were carried out. After dialysis against water for
48 h, it was dried with freeze dryer [40].
Sulfonation with oleum sulfuric acid (Sulfonation III) has been
made as followings. Dimethylformamide and oleum sulfuric acid
are placed in the balloon. An exothermic reaction occurs. The bal-
loon is mixed in a salt-ice bath to bring it to 0–5 °C (when it cools,
the mixture of oleum sulfuric acid and DMF solidifies). Chitosan-g-
POEGMA graft copolymer is added and placed in a 60 °C water
bath, stirring is continued for 3 h. At the end of the period, the bal-
loon is removed from the water bath and is allowed to reach room
temperature. The obtained mixture is taken into tubes and cen-
trifuged. After precipitation with acetone and washing, the acetone
is completely removed. The sulphonated product is dissolved in
distilled water and immediately neutralized with 20% sodium
hydroxide. After dialysis against water for 72 h, it is dried with
freeze dryer [41].
Table 2
Determination of optimum conditions for the sulfonation.
HCISO3 (ml) DMF (ml) Temperature (oC)
2.5. Characterization
FTIR spectra were recorded on a Perkin Elmer Spectrum 100
spectrophotometer using an ATR attachment between 4000 and
400 cm1. The 1H, 13C, HMBC, HSQC, DEPT, COZY NMR spectra were
recorded on a AGILENT 600 MHz Frekans 14.1 Tesla field power
Premium Compact NMR instrument using % 50 TFA (trifloroaceti-
cacid) as solvent for chitosan-g-POEGMA and chlorosulfonic acid
sulphated chitosan-g-POEGMA graft copolymers, D2O as solvent
for chitosan-g-POEGMA graft copolymers sulphated with oleum
sulfuric acid and Me4Si (TMS) as an internal standard. Elemental
analysis (sulfur analysis) was performed on a LECO CHSN 932
instrument. The viscosities of the polymers were measured using
Conon brand viscometer. For moisture determination, the Presica
XM 60 device with a temperature range of 30–230 °C, weighing
diameter of 100 mm and a maximum weighing capacity of 124 g
was used.
2.6. Cement
In the concrete specimen production, CEM I 42.5R in accordance
with TS EN 197-1 was used [42]. The physical and chemical prop-
erties of the cement used are presented in Tables 3 and 4,
respectively.
Table 3
Time Physical properties of CEM I 42.5R [43].

2.5 15 Room temperature 7 Initial Setting time (minutes) 157 Min 60

2.5 15 50 7 Final Setting Time (minutes) 219 –
2.5 15 70 7 Specific Gravity 3.18 g/cm3 –
5.0 30 30 7 Soundness 1.0 mm Max. 10
5.0 30 50 7 Fineness (Blaine) 3837 cm2/g –
10.0 60 30 7 2-day Compr. Strength 28.7 MPa Min. 20 MPa
10.0 60 50 7 28-day Compr. Strength 60.3 MPa Min. 42.5- Max. 62.5 MPa
544 H. Arslan et al. / Construction and Building Materials 204 (2019) 541–549

Table 4 Table 6
Chemical Composition of CEM I 42.5R [43]. Water absorption test results.

SO3 2.59% Maks. 4% Property (gr) Crushed sand Crushed stone I Crushed stone II
MgO 1.30% –
Tare 588.1 587.6 578.1
Loss on Ignition 2.53% Max. 5%
Dry weight + Tare 864.7 874.2 1018.6
Insoluble Matter 0.39% Max. 5%
Saturated + Tare 869.4 876.1 1021.3
CI 0.01>% Max. 0.1%
Dry weight 276.6 286.6 440.5
Total Alkali (N2O + 0,658 * K2O) 0.43% –
Saturated 281.3 288.5 443.2
Free CaO 1.73% –
Water absorption 1.7 0.7 0.6

2.7. Aggregates Table 7

Specific gravity test results (g/cm3).
2.7.1. Sieve analysis
Saturated 2.69 2.70 2.70
Sieve analysis has been conducted according to TS EN 933-1 and Mean 1.34 1.35 1.35
the results have been presented in Table 5 [44].

2.7.2. Specific gravity and water absorption test Table 8

The tests have been conducted according to TS EN 1097-6 [45]. Mixture Proportions (kg/m3).
Water absorption and specific gravity test results have been given Reference 1.2% Sulfonated 1.2% Sulfonated
in Tables 6 and 7. Graft Chitosan Chitosan
Cement 280 280 280
2.7.3. Methylene blue test Water 192 180 182
The procedure of TS EN 933-9 + A1 [46] has been applied and Crushed Sand 1067 1080 1075
methylene blue value has been observed as 1.50 g/kg. Crushed Stone I 287 290 289
Crushed Stone II 554 561 559
Total 2380 2395 2388
2.8. Mixing water
Slump (cm)
5 min 16 16 16
_
Istanbul City tap water was used as mixing water. 30 min 14 13 13

2.9. Investigation of the efficiency of sulfated chitosan-g-POEGMA graft

copolymers as superplasticizers 3. Results and discussion

Slump test has been conducted in compliance with TS EN
12350-2 [47]. Fresh concrete unit weights have been observed in
accordance with TS EN 12350-6 [48]. Air quantity in fresh concrete
has been obtained according to TS EN 12350-7 [49]. Compressive
strength test has been made according to TS EN 12350-2 and TS
EN 12350-4 [47,50]. The cubic concrete specimens with the dimen-
sions of 150 mm have been used to obtain compressive strengths.
The real mixture proportions after water reduction for reference
concrete specimens, concrete specimens produced with 1.2% sul-
fonated graft chitosan polymer and produced with 1.2% sulfonated
chitosan polymer, respectively, are presented in Table 8.
3.1. Synthesis and characterization of chitosan-g-POEGMA graft
copolymers
The synthesis of Chitosan-g-POEGMA graft copolymers was per-
formed by grafting of OEGMA monomers onto chitosan via redox
free radical polymerization method using CAN as the initiator at
40 °C (Fig. 1).
The initial conditions and results of the graft copolymerization
of OEGMA onto chitosan are listed in Table 1.
Purification was carried out by the soxhlet extraction method
using the appropriate solvent (THF) to dissolve POEGMA

Table 5
Granulometry of Crushed sand, Crushed Stone I and Crushed Stone II.

Fine Materials Specimen Crushed sand Crushed stone I Crushed stone II

Dry weight (gr) 1005.1 1224.2 1485.7
Washed dry weight (gr) 921.5 1222.2 1481.1
Passing (%) 8.3 0.2 0.3
Sieve Analysis Sieve Passing (%)
63.0 100 100 100
31.5 100 100 100
22.4 100 100 95
16.0 100 100 48
11.2 100 89 4
8.0 100 49 0
5.6 100 10 0
4.0 94 1 0
2.0 64 0 0
1.0 45 0 0
0.50 31 0 0
0.25 23 0 0
0.125 18 0 0
0.063 8 0 0
Fineness Module 4.2
 H. Arslan et al. / Construction and Building Materials 204 (2019) 541–549 545

Fig. 2. FT-IR spectra of (A) Chitosan homopolymers, (B) POEGMA homopolymers, (C) Chitosan-g-POEGMA graft copolymers.

homopolymers in the crude polymer. The pure graft copolymer The graft copolymers were characterized by FT-IR. The FT-IR
was dried and weighed in a vacuum oven at 30 °C. The yield calcu- spectrum of the graft copolymers contains characteristic peaks of
lations and graft percentages of the obtained products were calcu- homopolymers of chitosan and POEGMA. This indicates that the
lated according to literatures [38,39]. graft copolymer is successfully synthesized (Fig. 2).
546 H. Arslan et al. / Construction and Building Materials 204 (2019) 541–549
3.2. Sulfonation of the graft copolymers
The sulfonation process was carried out by three different
methods. These are sulfonation with sulfuric acid (Sulfonation I),
sulfonation with chlorosulphonic acid (Sulfonation II) and sulfona-
tion with fuming sulfuric acid (Sulfonation III) (Fig. 3). When
choosing the methods; Chitosan, POEGMA homopolymer and
Chitosan-g-POEGMA graft copolymers were confirmed to be free
from degradation due to sulfonation reaction.
The sulfated graft copolymers were characterized by spectro-
scopic methods such as FT-IR, NMR and elemental (sulfur) analysis.
Analysis results and solubility tests showed that the best sulfona-
tion results were obtained with oleum sulfuric acid (Table 9, Fig. 4).
Solubility tests were applied to the sulphated samples and the
oleum-sulphated sample showed better solubility, especially in
water, than the others. This is due to the higher amount of sulfur,
depending on the amount of sulphate entering the structure in the
oleum-sulphated sample.
Fig. 4 shows the FTIR spectra of Chitosan-g-POEGMA graft
copolymer and sulfated graft copolymers. In the spectra (B,C,D)
in addition to the characteristic peaks of chitosan and POEGMA,
there are peaks in the spots indicating that the sulfation process
can be carried out. And it is clear that these peaks are more promi-
nent in the spectra of sulfated graft copolymer with oleum sulfuric
acid sample (D).
NMR tests (1H, 13C, HMBC, HSQC, DEPT, COSY) were applied to
all samples, but since sufficient solubility could not be obtained,
only peaks of POEGMA homopolymers could be observed in the
spectra.
3.3. Investigation of the efficiency of sulfated chitosan-g-POEGMA graft
copolymers as superplasticizers
Slump test of concrete with graft chitosan plasticizer has been
shown in Fig. 5. Slump values of all series have been shown in
Fig. 6. Sulfonated graft (11.6 lt/m3) and sulfonated chitosan
(9.7 lt/m3) can reduce water. The water reducing effect also has
been verified with the 1, 3, 7 ve 28 days compressive strength
results. It has seen in Fig. 6 that reference concrete series have
maintained better consistencies with respect to the ones produced
with chemical admixtures during 45 min (Sulfonated graft and chi-
tosan). Besides, it can be concluded that water reducing capability,
Fig. 3. Sulfonation of the graft copolymers.
Table 9
Sulfur analysis results of sulfated graft copolymers.
Name of the product Amount of sulfur (%)
sulfated graft copolymer with sulfuric acid 0.59
sulfated graft copolymer with chlorosulphonic acid 4.04
sulfated graft copolymer with oleum sulfuric acid 6.66
thus, the workability of concrete is better for sulfonated graft
copolymer chitosan. This means that the new superplasticizer
based graft chitosan has higher performance than the sulfated chi-
tosan which also has been used previously in other studies [27–
29].
In addition, it has been obtained that reference series have the
fresh unit weight of 2380 kg/m3, sulfonated graft series have the
value of 2395 kg/m3 and sulfonated chitosan series have the unit
weight of 2388 kg/m3 when Fig. 7 is examined. The new graft chi-
tosan superplasticizer increases the unit weight of fresh concrete
compared to sulfonated chitosan.
The air content of fresh reference concrete series has been
obtained as 2%, the one of fresh sulfonated graft concrete series
has been measured as 1.5% and the air content of fresh sulfonated
chitosan concrete series has been measured as 1.6 value. These
results support the unit weight test results. When air contents
increase, the fresh unit weights decrease. The air contents of all
concrete series can be seen in Fig. 8. In compliance with the unit
weight results, it is observed that graft copolymer chitosan has
decreased air content in fresh concrete.
Reference concrete series has the unit weight of 2380 kg/m3, air
content of 2% and 28 day compressive strength of 30.1 N/mm2
(Fig. 9). Additionally, sulfonated graft concrete series has the unit
weight of 2395 kg/m3, air content of 1.5% and 28 days compressive
strength of 34.7 N/mm2. Finally, sulfonated chitosan concrete ser-
ies has the unit weight of 2388 kg/m3, air content of 1.6% and
28 days compressive strength of 33.8 N/mm2. As expected, it can
be seen that compressive strengths of concretes with lower unit
weights and higher air contents are greater than the ones with
higher unit weights and lower air contents. In addition to these,
it can be concluded that sulfonated graft and sulfonated chitosan
lead to higher compressive strengths because of their significant
water reducing property (Figs. 6–9). Both superlasticizers lead to
close concrete strength test results to each other. Furthermore,
 H. Arslan et al. / Construction and Building Materials 204 (2019) 541–549 547

Fig. 5. Slump Test.

18
16 16 16
16
14
14 13 13
12

Slump, cm
10
8
6
4
2
0
Initial Slump 45 Minutes Slump

Reference Sulfonated Graft Sulfonated Chitosan

Fig. 6. Slump Results of (C25/30) Reference Concrete Series and Concrete Series
Produced with Chemical Admixtures.

2,400.00

2,395.00 2395
Unit Weigths, kg/m3

2,390.00
2388
2,385.00

2,380.00 2380

2,375.00
Reference Sulfonated Graft Sulfonated Chitosan

Fig. 7. Fresh Concrete Unit Weights.

2.20

Fig. 4. FT-IR spectra of (A) Chitosan-g-POEGMA graft copolymer, (B) sulfated graft 2.00 2
copolymer with sulfuric acid, (C) sulfated graft copolymer with chlorosulphonic
Air Content, %

acid, (D) sulfated graft copolymer with oleum sulfuric acid. 1.80

1.60 1.6
1.5
the same effect of graft copolymer chitosan also can be observed 1.40
from compressive strength test results. Graft copolymer increases
the unit weight of fresh concrete, decreases the air content of fresh 1.20
concrete, reduces water content at higher amounts and thus, it also
1.00
increases the compressive strengths. Reference Sulfonated Graft Sulfonated Chitosan
If the compressive strength increases are considered in Fig. 10,
it can be said that the increase rate in compressive strength of sul- Fig. 8. Air Contents.
fonated graft and sulfonated chitosan have been obtained as 9.1%
and 5.5% for 1 day compressive strengths, 13.4% and 10.2 for 3 days tosan superplasticizer can increase compressive strengths of con-
compressive strengths, 8.3% and 4.1% for 7 days compressive crete at the ratios between 3% and 4% with respect to sulfonated
strengths and, finally, 13.3% and 10.9% for 28 days compressive chitosan superplasticizer. This results can be said as a desired
strengths, respectively. Consequently, new graft copolymer chi- improvement in the means of superplasticizer usage.
548
40
Compressive Strength, N/mm2
35
30
25
19.4
20
15 12 13.2 12.7
10
5 tosan has a little bit higher compressive strength than sul-
0 fonated chitosan. However, it has significant strength increase
1 Day
Reference Sulfonated Graft
Fig. 9. Compressive strengths.
16
Compressive Strength Increase Rate,
14 13.4
12
10 9.1
8
%
5.5
6
4
2
0 produced from natural renewable sources and are biodegradable,
1 Day
Sulfonated Graft
Fig. 10. Compressive strength increase rates of sulfonated graft and chitosan
concrete series compared to reference concrete series.
It can be observed that both chemical admixtures can reduce
water consistency and increase compressive strengths of concrete
series. Sulfonated graft can be said as a little bit better than sul-
fonated chitosan for reducing water content. This leads to a little
bit more aggregate content increase in sulfonated graft series. Fur-
thermore, this effect has led to higher unit weights, lower air con-
tents and higher compressive strengths for the sulfonated graft
copolymer concrete series when compared with the ones of sul-
fonated chitosan copolymer concrete series. This significant effect
also can be observed in Fig. 10.
4. Conclusions
Chitosan and POEGMA based chitosan-g-POEGMA graft copoly-
mers were synthesized with high efficiency by grafting OEGMA
monomers onto chitosan by means of redox free radical polymer-
ization using CAN as the initiator.
Sulfation experiments of the resulting chitosan-g-POEGMA
graft copolymers with sulfuric acid, chlorosulfonic acid and fuming
sulfuric acid were carried out. The products were characterized by
FT-IR, NMR and elemental (sulfur) analyzes. The analysis results
showed that the best sulfolanation was achieved with oleum sulfu-
ric acid. When the solubility ratios in water were examined, it has
been found that oleum sulfuric acid sulfated chitosan-g-POEGMA
graft copolymers were much more soluble in water than other sul-
fated graft copolymers. Based on all characterization results and
water solubility ratios, it has been decided to conduct concrete
tests on oleum sulfuric acid sulfated chitosan-g-POEGMA graft
copolymers. In this manner, following conclusions can be drawn.

Sulfonated graft chitosan and sulfonated chitosan causes to
slump losses when compared the reference concrete series.
H. Arslan et al. / Construction and Building Materials 204 (2019) 541–549

Both chemical admixtures increase the fresh unit weights. In
34.7 33.8 addition, sulfonated graft chitosan has a little bit higher fresh
30.1 unit weight than sulfonated chitosan.

Both chemical admixtures decrease the air contents. In addition,
25.3 24.2
22.4 21.6 23.2
sulfonated graft chitosan has a little bit lower fresh air content
than sulfonated chitosan.

Likewise, both chemical admixtures increase the early and later
age compressive strengths. In addition, sulfonated graft chi-
3 Days 7 Days 28 Days rate than sulfonated chitosan when compared to the reference
Time
concrete series.
Sulfonated Chitosan
Concrete series produced with chitosan-g-POEGMA graft
copolymer has reduced water content at the amount of 6%
(11.6 lt/m3) with respect to reference concrete series.

Consequently, it can be reported that sulfonated chitosan-g-
POEGMA graft copolymer reduces higher water contents com-
pared to sulfonated chitosan copolymer as the ratio of 1% and
13.3 it leads to a more workable fresh concrete compared with the
workability of sulfonated chitosan copolymer concrete.
10.9
10.2
Besides, it also can be presented that sulfonated chitosan-g-
8.3 POEGMA graft copolymer is classified as water reducing/plasti-
cizer chemical admixture in compliance with TS EN 934-2 + A1
4.1 [51].
Since the sulfated chitosan-g-POEGMA graft copolymers are
3 Days 7 Days 28 Days
Time
it is important for the future that they can be used as a concrete
Sulfonated Chitosan
admixture in the ready-mixed concrete industry. Usage of sulfated
chitosan-g-POEGMA graft copolymers as new kinds of superplasti-
cizers in concrete production are the main novelty, the contribu-
tion and the innovation for this study in the terms of literature.
In this manner, such natural chemical admixtures will decrease
the cost of concrete. Because, they do not require higher amounts
of energy to be produced. Besides, they also contribute to the
efforts to decrease the effects green gas emissions and climate
change on humanity and world. Therefore, it can help the sustain-
able concrete for developing a sustainable way of future.
Conflict of interest
None.
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