See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/320237720

Effects of Ca-, Mg-, K-, and Na-lignosulfonates on the behavior of fresh

concrete

Article in Construction and Building Materials · December 2017

DOI: 10.1016/j.conbuildmat.2017.09.190

CITATIONS READS

10 1,831

2 authors:

Hasan şahan Arel Ertug Aydin

Izmir University European University of Lefke
34 PUBLICATIONS 208 CITATIONS 37 PUBLICATIONS 135 CITATIONS

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Bottom ash and Marble powder utilization View project

utilisation of bottom ash, marble wastes and glass fiber View project

All content following this page was uploaded by Hasan şahan Arel on 09 October 2017.

The user has requested enhancement of the downloaded file.

 Construction and Building Materials 157 (2017) 1084–1091

Contents lists available at ScienceDirect

Construction and Building Materials

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

Effects of Ca-, Mg-, K-, and Na-lignosulfonates on the behavior of fresh

concrete
Hasan Sß ahan Arel a,⇑, Ertug Aydin b
a _
Faculty of Architecture, Izmir _
University, Gürsel Aksel Bulvarı, No. 14, 35350 Üçkuyular, Izmir, Turkey
b
Faculty of Engineering, Civil Engineering Department, European University of Lefke, Lefke North Cyprus, via Mersin 10, Turkey

h i g h l i g h t s

Lignosulfonates with different cations were investigated for use in concrete.

Cements with various chemical properties were analyzed.

Sugar content and molecular mass counteract negative effects of lignosulfonate.

Calcium lignosulfonate (10% cement mass) gave the best water reduction.

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

Article history: Lignosulfonates are waste products of the pulp and paper industry. The effects of various metal-cation-
Received 25 December 2016 containing lignosulfonate-based plasticizers on the properties of concrete mixtures produced using
Received in revised form 15 April 2017 cements with various Ca(SO4)2H2O, tricalcium aluminate, and tetracalcium aluminoferrite contents
Accepted 28 September 2017
were investigated. A-type cement, which had lower tricalcium aluminate and alkaline contents, greater
fineness, and higher SO3 content than B-type cement, exhibited better water reduction. Setting times of
A-type cement and its lignosulfonate mixtures were shorter than those of B-type cement by 9–11%. The
Keywords:
highest 28-day compressive strength of 41 MPa was found for A-type cement with a calcium-
Lignosulfonate
Fineness
lignosulfonate salt admixture.
Concrete Ó 2017 Elsevier Ltd. All rights reserved.
Cement
Workability

1. Introduction The water-reducing ability of LS in concrete production is well

Lignin is separated from wood using the Kraft process [1]. Wood
pulp and lignin liquor are obtained. Lignin liquor is treated with
SO2 in a sulfonation process, yielding lignosulfonates (LS) as a
byproduct. LS are inexpensive water-soluble anionic polyelec-
trolytes, with a cell structure composed of cellulose (45%), hemi-
celluloses (20–25%), and lignins (27–37%). They are produced
from two main tree types-softwoods and hardwoods [2]. They con-
tain hydroxyl (OH), methoxyl (OCH3), phenyl (C6H5), and sulfonic
acid (SO3H) groups [2–6]. Use of waste LS, which are more environ-
mentally friendly than other water reducers, is gradually becoming
widespread in concrete production, thereby reducing the accumu-
lation of LS as waste materials in nature and improving the effi-
ciencies of concrete production technology.
⇑ Corresponding author.
ß ahan Arel),
E-mail addresses: sahanarel@gmail.com, sahan.arel@izmir.edu.tr (H.S
eraydin@eul.edu.tr (E. Aydin).
known. The availability of sugars (such as glucose and sucrose)
in their chemical composition causes retardation of setting time
[7]. Addition of small amounts of calcium chloride and tri-
ethanolamine minimizes this retardation and early strength loss
[8]. Because they reduce surface tension, LS adsorb easily onto
cement particles [3,4]. Differences in origin, as well as in molecular
masses and chemical compositions, can cause different LS to exhi-
bit a variety of behaviors.
Fig. 1 represents the chemical unit of a generic LS, while Eqs. (1)
and (2) define their main equilibria, where R1 and R2 designate dif-
ferent functionalities of the lignin structure [2]:
R-O-R0 þ Hþ ! Rþ þ R0 OH ð1Þ
Rþ þ HSO3 ! R-SO3 H ð2Þ
+2 +2 +2
Various positive counter-ions (Ca , Na , Mg , etc.) form com-
plex structures with LS. These salts are used as water-reducing
admixtures in concrete production [1,9,10]. LS with different

https://doi.org/10.1016/j.conbuildmat.2017.09.190
0950-0618/Ó 2017 Elsevier Ltd. All rights reserved.
 H.Sßahan Arel, E. Aydin / Construction and Building Materials 157 (2017) 1084–1091 1085

Fig. 1. General structural units of lignosulfonates [2].

chemical properties (free sugar ratio, counter-ion type, etc.) react

differently with the chemicals in cement and show various hydra-
tion effects. LS adsorb onto both carboxyl groups (ACOOH), via
Ca2+ ions, and hydroxyl groups, via the oxygen ions [4,5,11]. The
most commonly known LS are those of the Ca and Na salts [12],
shown in Figs. 2 and 3, respectively.
LS are adsorbed at the solid-water interface and function by dis-
persing the cement grains. Opposing charges on adjacent cement
particles can exert substantial electrostatic attraction, thus causing
the particles to flocculate. LS neutralize the surface charges and
cause the particles to repel, rather than attract, each other, and
they remain fully dispersed in the paste [14]. Based on electrical
conductivity results, it is known that less of the sodium salt is
required to maintain the same level of water reduction, when com-
pared with calcium salts; however, calcium LS are less expensive
and are therefore preferred for use in concrete [8,14]. It has fur-
thermore been demonstrated that the chemical composition of
the cement is the main factor influencing the properties of fresh
concrete, rather than those of the ammonium, sodium, or calcium
LS salts [15]. LS have high molecular masses [6,7]: a range of 1000–
140,000 g/mol has been reported for softwood LS; lower values are
reported for those originating from hardwoods [2]. Their ability to
be adsorbed increases with molecular mass [16]. Because their
chemical structures include free sugar, LS exhibit hydration-
retardant properties; however, hydration occurs to a lesser extent
Fig. 3. Sodium lignosulfonate, C20H24Na2O10S2 (i.e., sodium salt of lignosulfonic
acid) [13].

for those with high tricalcium aluminate (3CaOAl2O3, represented

Fig. 2. Calcium lignosulfonate, C20H24CaO10S2 (i.e., calcium salt of lignosulfonic
acid) [13].
as C3A) and SO3 contents [17].
Portland cement is widely used as a binder in the field of civil
engineering [18]. The contents of C3A and tetracalcium aluminofer-
rite (4CaOAl2O3Fe2O3; C4AF) are effective in improving early
hydration of concrete. The tricalcium silicate (3CaOSiO2; C3S)
and dicalcium silicate (3CaOSiO2; C2S) contents, which are effec-
tive for hydration for up to 30 days, affect the mechanism of action
of LS. Transformation of the hexagonal dicalcium aluminate
hydrate (2CaOAl2O38H2O; C2AH8) and tetracalcium alumina
tridecahydrate (4CaOAl2O313H2O; C4AH13) phases into the cubic
tricalcium alumina hexahydrate (3CaOAl2O36H2O; C3AH6) phase
is delayed in C3A pastes [19]. Akman [20] reported that cement
should comply with the correct proportions of C3S and C2S compo-
nents to ensure that the LS provide a stable water-reducing effect;
however, in cements with high (C3A + C4AF) contents, the admix-
ture adheres to these components, resulting in less adherence to
the C3SAC2S components; viscosity of the cement paste therefore
decreases.
In general, the presence of ordinary Portland cement signifi-
cantly affects early hydration of concrete, even though it contains
less than 10% C3A [21]. In the presence of Ca(OH)2 and H2O, mono-
sulfate hydrate and calcium aluminate hydrate react with sulfate
to produce ettringite [22]. The needle-shaped ettringite, formed
by the reaction of C3A in cement (C3A + 3 CaSO4 ? ettringite
1086 H.Sßahan Arel, E. Aydin / Construction and Building Materials 157 (2017) 1084–1091

[Ca6Al2(SO4)3(OH)1226H2O]), consumes water in the environment 1.1. Research significance

under normal conditions and decreases workability of the cement
paste [23]; plasticizers, however, adhere to the ettringite and delay
the formation of needle-like structures [24,25]. In addition, CaSO4/
C3A in different molar ratios transform C3A into different forms,
affecting setting times. The mechanism of the interaction between
anhydrite and hydration of C3A has not yet been fully clarified [16].
Nawa and Eguchi [26] noted that, in addition to cement’s chemical
properties, its fineness significantly affects plasticizer perfor-
mance; thus, to provide the same workability, additional plasti-
cizer is required with increased fineness. Cements with high
fineness and a spherical particle structure exhibit improved viscos-
ity [27]. In summary, the workability and consistency of fresh con-
crete are influenced by numerous parameters.
Topcu and Atesßin [28] examined the effects of high-dose LS- and
naphthalene sulfonate-based plasticizers on the properties of con-
crete. They reported that, in comparison with a control sample,
when the amount of LS plasticizer added to a fresh concrete mix-
ture was increased from 1% to 5%, the air content increased by
44% and the 28-day compressive strength increased by approxi-
mately 3.8% with 1% LS addition. Danner et al. [10] examined the
effects of calcium (LSc) and sodium (LSn) LS on early hydration
of C3A-gypsum pastes. On the basis of scanning electron micro-
scopy images collected after 24 h, they reported that paste without
LS developed typical needle-like ettringite structures, but such
structures were not observed in C3A–gypsum pastes containing
4% LSc or LSn, with egg-like structures forming instead of needles.
Nicolás et al. [29] reported that LS-based superplasticizers retarded
the setting time of air-ime-based mortar mixtures: when the LS
content was increased from zero to 0.50%, the initial setting time
increased by approximately 71% and the needle-shaped ettringite
particles observed in C3A-paste microscopy images became round
and egg-like at 1% LSc as a result of hydration of C3A. On the basis
of C3A-paste X-ray diffraction measurements, Nagrockiene et al. [3]
observed that using LS at 0.6% of the cement mass increased the
viscosity after 30 min and decreased the compressive strength by
1.2%, relative to the corresponding values for a reference sample.
The increase in compressive strength in Portland Cement (CEM-I)
containing CaCO3 was higher than that in Portland Composite
Cement (CEM-II) containing CaCO3 and CaSO4; the compressive
strength of a CEM-I sample was 19% higher than that of the refer-
ence sample.
Some researchers investigated the relationships between
cements of different chemical compositions and LS [3,4,28,29]. In
general, the use of LSc was preferred in these studies, which
focused on its effects on C3A, rather than on the chemical proper-
ties of the cement. The present study focuses on the relationship
between LS type and the chemical composition of cement (a topic
currently requiring extensive research). The laboratory-based test-
work program was designed to investigate the use of LS in concrete
production over as wide a range as possible. A detailed investiga-
tion of how viscosity and easy settlement of concrete can be
ensured in terms of the addition of various LS, having complex
chemical structures, without reducing the amount of cement
required or compromising the concrete strength, was undertaken.
Previous research studies have shown that LS are highly effec-
tive in medium-strength concrete applications [3,4,28–31]. This
can be largely explained by the fact that their surface friction char-
acteristics are reduced by their ready adsorption onto cement
grains. In addition, LS salts convert the single electrostatic ion to
a complex species with the same charge as the cement particles,
LS with different positive counter-ions and chemical composi-
tions were investigated with respect to their compatibility with
cements of different chemical compositions and fineness. The
cements that can be optimally used with a given type of LS were
determined. The most significant contribution of this study is to
demonstrate that problems such as air entrainment and an exces-
sive setting retarding effect, which are considered the main nega-
tive effects of LS even when small amounts are used, are
eliminated by changing the sugar content and molecular mass of
the LS. Moreover, the results demonstrate that desirable properties
in the same fresh concrete are achievable with the use of multiple
admixtures using a particular LS containing anionic-type colloidal
tension-active compounds. In other words, this study determined
whether an LS can be simultaneously employed as a setting retar-
dant, a plasticizer, and an air-entrainment agent, without causing a
negative effect. The results of this work will enable the negative
effects caused by the use of multiple admixtures with different
chemical properties to be avoided, thereby achieving the desired
concrete functionality and promoting the more widespread use
of LS obtained as a waste product from the pulp and paper indus-
try. Magnesium, potassium, and the more commonly used sodium
and calcium salts of LS were investigated with respect to their
effects on the production of concretes with a wide range of chem-
ical properties.
2. Experimental
2.1. Materials
2.1.1. Cement
CEM-I Portland cements with two different C3A/CaSO42H2O
contents were used. Their physical and chemical properties are
presented in Table 1. Different C3A/CaSO4 ratios were used to
demonstrate changes in the mechanism of LS action by determin-
ing how the various LS responded. The C3S and C2S proportions
affect early and late strength, respectively, so cements with differ-
ent contents of these components were also selected.
2.1.2. Aggregate
Granulated crushed limestone aggregates of sizes 0–2, 2–4, and
4–16 mm were used to produce the concretes. The 0–2 mm aggre-
gates had a fineness modulus of 1.40 and a water absorption value
of 1.15%. The corresponding values for the 2–4 mm fine and 4–16
mm coarse aggregates were 2.51 and 1.35% and 2.70 and 1.40%,
respectively. The specific gravities of the three aggregate classes
were 2.65, 2.63, and 2.6 g/cm3, respectively. The distributions of
the fine and coarse aggregates used in the mixtures were selected
Table 1
Physical and chemical properties of cements.
Chemical properties A-type (%) B-type (%)
C3S (tricalcium silicate) 58.1 63.1
C2S (tricalcium silicate) 7.40 7.10
C3A (tricalcium aluminate) 2.83 5.57
C4AF (tetracalcium aluminoferrite) 12.33 13.17
CaSO42H2O (calcium sulfate dihydrate) 2.10 2.76
C3A + C4AF 15.16 19.74
C3A/CaSO4 1.34 2.38

without increasing or decreasing (as in high- or low-strength con- Physical Properties

crete applications, respectively) the cement dosage. The aim of the Retained on 32 lm screen 29.1 33.8
Retained on 45 lm screen 10.2 19.03
present study was to investigate the effects of various LS on the Blaine specific surface (cm2/g) 3.254 4.115
properties of concrete for medium-strength applications.
 H.Sßahan Arel, E. Aydin / Construction and Building Materials 157 (2017) 1084–1091
between the A–B curves, in compliance with the Turkish TS 706 EN
12620 + A1 standard [32], which is exactly compatible with the
ASTM C 136-96 standard. The grain-size curve is shown in Fig. 4.
Water absorption values were determined according to the TS EN
1097-6 standard [33].
2.1.3. Lignosulfonates
LS with cations of sodium, potassium, calcium, and magnesium
were used as chemical admixtures. Samples from different sources
were examined to see how the lignin structure and source varia-
tion created differences in the LS characteristics. Four different LS
samples were mixed into the concretes (as 40% solutions). The
chemical characteristics of the admixtures are given in Table 2.
The readily available free sugar content in LS affects the cement
hydration process. The sugar contents of LS obtained from different
manufacturers varied, enabling a wide range of contents to be
tested for their effect on setting time. pH values of the LS also var-
ied, depending on the cation. Although the complex cause of this
effect is not discussed here, it was noted that pH did not have a
noticeable effect on the results.
2.2. Preparation and production of concrete mixtures
Concrete mixtures were prepared using calcium (LSc), magne-
sium (LSm), potassium (LSk), and sodium (LSn) LS at concentra-
tions of 0.5% of the cement mass, while keeping the slump values
constant. The mixtures were designated as x-LSy, where x refers
to the cement type and y refers to the plasticizer type. For example,
a mixture designated A-LSc indicated A-type cement with LSc,
whereas A-LSn indicated A-type cement with LSn.
To maintain the same level of workability as measured in the
reference sample, the water/cement ratio was kept constant in
all mixtures. This was achieved by determining the amount of
water-reducing plasticizers required for the different metal ions
to achieve the same level of slump. In an attempt to maintain a
slump value of 135 mm for all mixtures, test mixtures were first
prepared. LS were used at concentrations of 0.4 and 0.8 mass% in
cement; the mixtures were labeled as z-LSx, where z was the
0,1 1 10
Sieve size
A 16 B 16 Aggregates
Fig. 4. Grain-size distributions for individual components (Dmax = 16 mm) and
aggregates used in mixtures, determined according to the TS 706 EN 12620+A1
standard [32].
Table 2
Chemical characteristics of additives.
Lignosulphonate type Code pH Solid (%)
Ca-LS LSc 4.11 41.1
Mg-LS LSm 4.93 40.1
Na-LS LSn 8.21 39.3
K-LS LSk 4.33 40.1
1087
cement type and x the LS type. The mixture ratios are given in
Table 3. The slump value measured for each amount of water grad-
ually decreased as the amount of A-LSc in the formulation
increased.
2.3. Curing and testing
Samples were demolded one day after the casting process and
soaked in a curing pool filled with limewater at room temperature
(22 ± 1 °C). The samples were cured in accordance with the TS EN
12390-2 standard [34]. A total of 240 concrete samples were pro-
duced and, on average, six samples were used for each test. Cubes
of 150 mm each side were used for the compressive strength tests,
the standard deviation of which was calculated as 1.37 MPa.
Setting time, viscosity, air content, slump, and slump loss tests
were performed for fresh concrete samples. Setting times were
determined according to the TS 2987 standard [35] for mixtures
prepared with the A- and B-type cements. Viscosities were mea-
sured at a frequency of 30 Hz using a BGD 152/2 digital viscometer
(Biuged Laboratory Instruments (Guangzhou) Co., Ltd., China)
within the range of 0.01–100 Pas. Dynamic viscosity values were
measured at the onset (0 min), after 5 min, and after 15 min. Air
contents were measured by passing air of a known pressure and
volume over fresh concrete samples in an airtight cup in accor-
dance with the TS EN 12350-7 standard [36]. Slump values were
measured in accordance with TS EN 12350-2 [37]; slump-loss val-
ues were measured after times of 0, 30, and 60 min. The compres-
sive strengths of the hardened concrete samples were determined
in accordance with TS EN 12390-3 [38], measured on days 3, 7, 14,
and 28 for samples produced using both A- and B-type cements
with LS admixtures.
3. Results and discussion
3.1. Fresh concrete experiments
Setting-time tests were conducted to determine the effects of
varying the amounts of sugar contained in the LS and of LS-
induced water reduction on hydration and, therefore, on setting
100 time. The results for initial and final setting times are shown in
Fig. 5.
Cumulative passing (%)
80 Retardation in setting occurred because the non-ionized hydro-
xyl groups formed hydrogen bonds with oxygen and the adsorp-
60 tion capability of LS increased. Wang et al. [16] reported that the
CaSO4 saturation ratio decreased in the presence of calcium LS.
40 Considering mixtures prepared using A-type cement and LSc as
plasticizer, the initial setting times were extended by 8.6%, 34%,
20 and 21.5%, when compared with LSm, LSn, and LSk plasticizers,
respectively. The corresponding values were 3.56%, 28%, and
0 17.6% when B-type cement and LSc were used.
100
Cement grains tend to adsorb more LS-type plasticizer when
C3A > C4AF, so the retardation effect was expected to be greater
for A-type cement, which had lower amounts of C3A and C4AF;
however, greater retardation was observed in B-type cements in
this study. As an example, A-LSc and B-LSc mixtures showed
40.7% and 42% longer initial setting times, respectively, compared
Density (g/cm3) Insoluble matter (%) Average molecular mass (g/mole) Inverted sugars (%)
1.125 0.051 54.000 25–30
1.131 0.428 57.000 16
1.217 0.043 55.000 3
1.188 0.763 43.000 8
1088 H.Sßahan Arel, E. Aydin / Construction and Building Materials 157 (2017) 1084–1091

Table 3
Concrete mixture compositions.

Code Cement Water Sand Aggregate PS PS Slump w/c

(kg/m3) (%) (mm)
Ref. 350 176.5 635 1220 – – 135 0.5
A-LSc 350 162 645 1240 1.79 0.5 135 0.46
A-LSm 350 164 645 1240 1.79 0.5 135 0.47
A-LSn 350 166 640 1235 1.79 0.5 134 0.47
A-LSk 350 166 640 1235 1.79 0.5 135.5 0.47
B-LSc 350 165 645 1240 1.79 0.5 134.5 0.47
B-LSm 350 166 640 1235 1.79 0.5 135 0.47
B-LSn 350 167 640 1230 1.79 0.5 134.5 0.47
B-LSk 350 166 640 1235 1.79 0.5 135 0.47

*PS = plasticizer; PS (%) = plasticizer by mass of cement; w/c = water/cement ratio; A-LSc = A-type cement and calcium lignosulfonate.

Topçu and Atesßin [28] reported that the presence of LS delayed

450
the hardening and setting time of cement. This finding is consistent
400
with literature claims that, in addition to the type of LS, the chem-
Setting time (min)

350 ical and physical properties of cement affect the setting time. In
300 agreement with studies described in the literature, this study
250 demonstrates that setting times depended on the LS ion type and
200
on the chemical structure of the cement.
The working principle of LS activity in cement is based on
150
reducing surface tension, which causes air entrainment as a side
100 effect. Resulting stable air bubbles increase workability. Fig. 6
I nit ial Fin al
Ref.A 13 5 21 5 shows dynamic viscosity values measured at 5, 10, and 15 min
A-LSc 19 0 42 0 for the A- and B-type cements and concrete pastes produced in
A-LSm 17 5 40 5 combination with various LS.
A-LSn 14 0 31 0 Viscosity increased with curing time. For both types of cement,
A-LSk 15 5 37 0 the highest and lowest values were observed for mixtures prepared
using LSm and LSc, respectively. At 15 min, the A- and B-type
Fig. 5. Effect of lignosulfonate cation on initial and final setting times of mixtures cements with LSm showed the highest viscosity values, at 5.220
prepared with A- and B-type cements.
Pas and 5.555 Pas, respectively; the lowest values were observed
with LSc, at 5.510 Pas and 5.535 Pas, respectively. For both
5560
cements, the increase in the viscosity measured between 5 and
10 min was statistically significant. B-type cements showed higher
5540 overall viscosities.
Viscosity (mPa.s)

This phenomenon can be explained in three ways. Firstly, B-

5520
5500
5480
5460
5440
0 min 5 min
Fig. 6. Viscosities of mixtures produced with A- and B-type cements with different
cation salts of lignosulfonate for different curing times.
with the reference. This is attributed to the finer grain size distri-
bution of the B-type cement. The B-type cement also contained
6% more C4AF.
The retardation effect of the plasticizers used in this study
seemed not only to result from the chemical compositions of the
cement and plasticizers, but also the physical properties of the
cement composites. Arel [4] reported similar findings: when
cement fineness increased from 2254 cm2/g to 5108 cm2/g, the ini-
tial setting time increased from 43.3% for the reference to 46%
when using LSc-type plasticizer. Similarly, Hu et al. [39] reported
that, for mortar mixtures prepared using cements with Blaine sur-
face areas of 399, 364, and 302 m2/mg, setting times increased
with cement fineness. Lauten et al. [40], Nicolás et al. [29], and
type cement was finer, which leads to higher viscosity. Secondly,
the effect of plasticizers diminished because of the higher C3A/Ca
(SO4)2H2O ratio of the B-type cement; the low alkali (Na2O +
K2O) and (C3A + C4AF) contents of the A-type cement, as described
in the literature, was effective in this situation. Similar to the point
emphasized by Chandra and Björnstörm [41], the (C3A + C4AF) con-
tent also contributed significantly to decreasing the plasticizer
effect. The B-type cement had a greater (C3A + C4AF) content, so
the admixture adhered to these components, thereby decreasing
10 min 15 min the relative amount adhering to the C3S and C2S components,
which resulted in a decrease in pulp viscosity. Thirdly, the B-type
cement had a higher C3A/C4AF ratio, which caused an increment
in viscosity. Similar findings were reported by Simard et al. [42].
As mentioned above, LS causes air entrainment, which is attrib-
uted to a reduction in surface tension. The effects of LS on the air
contents of concrete are shown in Fig. 7.
LS molecules have both hydrophilic and hydrophobic ends. This
configuration stabilizes air bubbles and caused an increment in air
content, compared with the reference mixture, as seen in Fig. 7.
The highest values were 3.55% and 3.60% for the A- and B-type
mixtures, respectively, which were lower than the specification
of 4–6% of TS EN 934–2 [43].
The effect of cement type on air content was negligible when
compared with that of cement fineness; however, air contents
were slightly higher in mixtures containing B-type cement. B-LSc
mixtures had 3.6% higher air content than A-LSc mixtures; this
value dropped to 1.4% when comparing B-LSm and A-LSm
mixtures.
 H.Sßahan Arel, E. Aydin / Construction and Building Materials 157 (2017) 1084–1091
4,0
3,5
Air content (%)
3,0
2,5
2,0
1,5
1,0
Fig. 7. Air contents of concretes produced with A- and B-type cements and different
lignosulfonate salts.
The air contents of A-type mixtures were 75%, 121.8%, 84.3%
and 40.6% higher when incorporating LSc, LSm, LSn, and LSk,
respectively, when compared with the reference mixture. This
may be due to the changes in the respective molecular masses.
The highest molecular mass was found in mixtures prepared with
LSm (58,000 g/mole); the highest air contents were also found in
those mixtures, measured as 3.55% and 3.60% for A- and B-type
cements, respectively. Similar findings were reported in literature,
where it is frequently reported that increasing molecular mass
increased air content of a mixture [44]. To minimize this problem,
it is advised to add 1% tributylphosphate and silicon-derived chem-
icals to the mixing water; however, more research is still required
in this area [36].
To determine the LS with the most effective water-reduction
properties, water-reduction testing was applied to the two cement
types with differing C3A/CaSO4 ratios and concretes prepared with
different LS while maintaining constant cement dosages, contribu-
tion rates, and slump values.
Water reduction was greater in A-type mixtures. Considering
the LSc, LSm, LSn, and LSk plasticizer mixtures with A-type cement,
the water reductions were, respectively, 25.1%, 16.1%, 13.2%, and
13.4% greater than those of analogous mixtures prepared with B-
type cement. When the amount of plasticizer increased, adsorption
on the surface of the cement particles increased and caused an
increase in cohesion of the mixture for better dispersibility. Similar
observations were reported by Ouyang et al. [44]. The data are
shown in Fig. 8.
The highest and lowest water reductions, of 11.1% and 6.5%,
were found for LSc and LSn mixtures, respectively. Increasing the
molecular mass was expected to cause an increase in surface fric-
tion and thus increase water reduction. Interestingly, this was not
12
Cement B Cement A
11
Water reduction (%)
10
9
8
7 60
6
5
LSc LSm LSn LSk
Fig. 8. Water-reduction effect of different lignosulfonate salts in A- and B-type
cement mixtures.
1089
observed in the highest molecular mass mixtures that contained
LSm.
An 11.1% water reduction was found when considering A-type
cement mixtures; this value reduced to 8.8% for B-type mixtures.
These values were 9.2% and 7.9% for A- and B- type mixtures con-
taining LSm, respectively. This might be due to both the physical
(fineness) and chemical (C3A and C4AF contents and ratio) charac-
teristics of the cements. A comparison between cement types, in
accordance with the literature, revealed that water reduction in
A-type cements with lower C3A and alkali contents, greater fine-
ness, and higher SO3 ratios was higher than that in B-type cements.
All of the LS tested produced water-reduction effects proportional
to the amounts of sugar in their chemical structures.
The slump loss and setting-time experiments were closely
related and complementary. The data acquired for the A- and B-
type mixtures are shown in Figs. 9 and 10, respectively.
Super- and hyper-plasticizer mixtures were added to the LS
because of their abilities to prevent slump loss. Experiments were
conducted to determine which type of LS effectively prevented
slump loss. The lowest slump losses for each cement type occurred
for their respective reference samples, while the highest were
observed for mixtures containing LSk. Of the A-type mixtures,
the lowest slump loss for the reference sample was 30 mm at 60
min, whereas that of the highest-slump-loss-producing LSk sample
was 65.5 mm. That for the B-type cement produced using LSk was
70 mm at 60 min. Slump losses for mixtures produced using the
LSc admixture were closest to those of the reference samples: a
50-mm slump was observed for the A-type mixture with LSc,
whereas the corresponding LSc-B-type cement exhibited a slump
of 59.5 mm. Nicolás et al. [29] reported slump losses of 20 mm
and 50 mm at 30 min and 120 min, respectively, for a mixture pro-
duced using LSc.
3.2. Compressive strength test results
Air bubbles that are stable and form as a result of air entrain-
ment caused by LS, which have surface-tension-reducing charac-
teristics, also lead to strength reduction. Compressive tests were
used to determine the effects of LS in terms of strength losses of
the different structures. The results are shown in Figs. 11 and 12
for A- and B-type cements, respectively.
Samples with LS admixtures attained higher compressive
strengths than the references. The effects of LS on compressive
strength increased in direct proportion to their water-reduction
ratio, but varied according to the cement type, which affected dif-
140
130
120
Slump (mm)
110
100
90
80
70
0 30 60
Time (min)
Ref. A-LSc A-LSm A-LSn A-LSk
Fig. 9. Slump loss in mixtures produced with A-type cement and different
lignosulfonate salts.
1090 H.Sßahan Arel, E. Aydin / Construction and Building Materials 157 (2017) 1084–1091

140 15% greater compressive strength than that of the reference. Fur-
130 thermore, better fluidity of the mixtures required less water and
caused an increase in compressive strength. A significant propor-
120
tion of unhydrated cement particles also provides extra cohesion
Slump (mm)

110 to a mixture and, hence, better strength properties. Similar obser-

100
vations were reported by Pereira et al. [30]. Other factors, such as
hydration of LS-enriched composites, microstructure, and porosity,
90
may also affect compressive strength. Small amounts of air at the
80 interface of the matrix reduce compressive strength. Dispersion
70
of cement particles and the process of continuous hydration
change the pore structure, thereby enhancing compressive
60 strength. These findings are compatible with those of Zhang et al.
0 30 60
[7]. Similarly, Topcu and Atesßin [28] reported that the 28-day com-
Time (min)
pressive strength of a concrete containing 1% LS was higher than
Ref. B-LSc B-LSm B-LSn B-LSk that of the control sample, whereas Nagrockiene et al. [3] reported
that the 28-day compressive strength of a concrete containing 0.6%
Fig. 10. Slump loss in mixtures produced with B-type cement and different
lignosulfonate salts.
LS was approximately 25% higher than that of their control sample.

4. Conclusions and recommendation

50 15

The conclusions of this study are summarized as follows:

Compressive strength (MPa)

40 12
Water reduction (%)

When considering mixtures prepared using A-type cement and

30 9 LSc as plasticizer, initial setting times were extended by 8.6%,
34%, and 21.5%, when compared with those of LSm, LSn, and
LSk plasticizers, respectively. The analogous values were
20 6
3.56%, 28%, and 17.6% for B-type cement.

For both cement types, the highest viscosity values were mea-
10 3 sured in mixtures prepared using LSm, whereas the lowest vis-
cosity values were measured in mixtures prepared using LSc.
0 0
The effect of cement type on air content was negligible when
Ref. A A-LSc A-LSm A-LSn A-LSk compared with that of cement fineness. Air contents were
3d 7d 14 d 28 d Water Reduction slightly higher in B-type mixtures.

Considering LSc, LSm, LSn, and LSk plasticizer mixtures with
Fig. 11. Compressive strengths of samples produced with A-type cement and A-type cement, the water reductions were 25.1%, 16.1%, 13.2%,
different lignosulfonate salts for curing times of 3, 7, 14, and 28 days. and 13.4% greater, respectively, than those of the analogous
B-type cements.
50 15
The 28-day compressive strengths for mixtures prepared using
A-type cement with LSc, LSm, LSns, and LSk were 6.2%, 8.5%,
Compressive strength (MPa)

40 12 5.6%, and 5% greater, respectively, than those of the analogous

B-type mixtures.
Water reduction (%)

30 9
Scanning electron microscopy would be beneficial to analyze
the pore structures of concretes containing various amounts of
20 6 LS. Other factors, such as hydration of the LS-enriched composites,
microstructure, and porosity may also affect compressive strength.
Rheological studies may also improve understanding of the fresh
10 3
state of such concretes.

0 0
Ref. B B-LSc B-LSm B-LSn B-LSk Acknowledgements

3d
Fig. 12. Compressive strengths of samples produced with B-type cement and
different lignosulfonate salts for curing times of 3, 7, 14, and 28 days.
ferences between the water-reduction capabilities of the various LS
for the different cement types. Compressive strengths of samples
produced using the A-type cement, which had greater fineness, a
higher SO3 ratio, and lower C3A and alkali contents, were higher
by approximately 5% than those of the B-type cement.
The 28-day compressive strengths of mixtures prepared with A-
type cement with LSc, LSm, LSn, and LSk were 6.2%, 8.5%, 5.6%, and
5% higher, respectively, than the analogous B-type mixtures. The
highest compressive strength of 41 MPa was obtained on Day 28
for the A-type cement with the LSc admixture. This sample yielded
7d 14 d 28 d Water Reduction
The authors would like to thank Mr. Mert Genç, General Man-
ager, Genoser Engineering, for providing test materials and techni-
cal support; Mr. Recep Göztepe (Construction Technician) for his
contributions in all phases of the construction work; and Mr. Rafet
Özgün, General Manager, Manavgat Building Materials Laboratory
(Denizli, Turkey), for providing the test equipment and allowing us
to conduct the tests in his company’s laboratory. This research did
not receive any specific grant from funding agencies in the public,
commercial, or not-for-profit sectors.
References
[1] Q.-F. Lü, Z.-W. He, J.-Y. Zhang, Q. Lin, Preparation and properties of nitrogen-
containing hollow carbon nanospheres by pyrolysis of polyaniline-
lignosulphonate composites, J. Anal. Appl. Pyrol. 92 (2011) 152–157.
 H.Sßahan Arel, E. Aydin / Construction and Building Materials 157 (2017) 1084–1091
[2] K. Othmer, Kirk-Othmer Encyclopedia of Chemical Technology, Fifth ed., John
Wiley & Sons, Inc, 2005.
[3] D. Nagrockiene, I. Pundienė, A. Kicaite, The effect of cement type and
plasticizer addition on concrete properties, Constr. Build. Mater. 45 (2013)
324–331.
[4] H.Sß. Arel, The effect of lignosulfonates on concretes produced with cements of
variable fineness and calcium aluminate content, Constr. Build. Mater. 131
(2017) 347–360.
[5] N.R. Lummer, J. Plank, Combination of lignosulphonate and AMPSÒ-co-NNDMA
water retention agent – an example for dual synergistic interaction between
admixtures in cement, Cem. Concr. Res. 42 (2012) 728–735.
[6] C. Ma, Y. Bu, B. Chen, Preparation and performance of a lignosulphonate-AMPS-
itaconic acid graft copolymer as retarder for modified phosphoaluminate
cement, Constr. Build. Mater. 60 (2014) 25–32.
[7] R. Zhang, X. Xiao, Q. Tai, H. Huang, Y. Hu, Modification of lignin and its
application as char agent in intumescent flame-retardant poly (lactic acid),
Poly. Eng. Sci. 52 (2012) 2620–2626.
[8] V.S. Ramachandran, Concrete Admixtures Handbook: Properties, Science and
Technology, Noyes Publications, Park Ridge, New Jersey, USA, 1996.
[9] B. Bozsódi, V. Romhányi, P. Pataki, D. Kun, K. Renner, B. Pukánszky,
Modification of interactions in polypropylene/lignosulfonate blends, Mater.
Des. 103 (2016) 32–39.
[10] T. Danner, H. Justnes, M. Geiker, R.A. Lauten, Early hydration of C3A-gypsum
pastes with Ca- and Na-lignosulfonate, Cem. Concr. Res. 79 (2016) 333–343.
[11] S. Ng, H. Justnes, Influence of plasticizers on the rheology and early heat of
hydration of blended cements with high content of fly ash, Cem. Concr.
Compos. 65 (2016) 41–54.
[12] M.C.F. Toledo, P.M. Kuznesof, Calcium lignosulfonate: Chemical and technical
assessment, http://www.fao.org/fileadmin/templates/agns/pdf/jecfa/cta/69/
Calcium_Lignosulfonate__40_65.pdf.
[13] https://pubchem.ncbi.nlm.nih.gov/compound/24711#section=Top.
[14] T.Y. Erdogan, Admixtures for Concrete ISBN 975-429-113-6, Middle East
Technical University Press, 1997.
[15] L.H. Tuthill, R.F. Adams, J.M. Hemme, Observation in testing and use of water-
reducing retarders, in: Symposium on Admixtures Concrete, 1960, pp. 97–117.
[16] X. Wang, Y. Pang, H. Lou, Y. Deng, X. Qiu, Effect of calcium lignosulphonate on
the hydration of the tricalcium aluminate–anhydrite system, Cem. Concr. Res.
42 (2012) 1549–1554.
[17] Y. Elakneswaran, E. Owaki, S. Miyahara, M. Ogino, T. Maruya, T. Nawa,
Hydration study of slag-blended cement based on thermodynamic
considerations, Constr. Build. Mater. 124 (2016) 615–625.
[18] H. Maghsoodloorad, A. Allahverdi, Efflorescence formation and control in
alkali-activated phosphorus slag cement, Int. J. Civil Eng. 14 (2016) 425–438.
[19] J.F. Young, Hydration of tricalcium aluminate with lignosulphonate additives,
Mag. Concr. Res. 14 (1962) 137–142.
[20] S. Akman, Role of Admixtures on the Properties of Fresh High Performance
Concrete, RILEM Symposium, Mexico, 1999.
[21] T. Danner, H. Justnes, M. Geiker, R.A. Lauten, Effect of lignosulphonate
plasticizers on the hydration of C3A, 14th International Congress on the
Chemistry of Cement, Beijing, China, 2015.
[22] A. Allahvedi, H. Hashemi, Investigating the resistance of alkali-activated slag
mortar exposed to magnesium sulfate attack, Int. J. Civil Eng. 13 (2015) 379–
387.
[23] M.M. Alonso, F. Puertas, Adsorption of PCE and PNS superplasticisers on cubic
and orthorhombic C3A: effect of sulfate, Constr. Build. Mater. 78 (2015) 324–
332.
View publication stats
1091
[24] F. Dalas, S. Pourchet, D. Rinaldi, A. Nonat, S. Sabio, M. Mosquet, Modification of
the rate of formation and surface area of ettringite by polycarboxylate ether
superplasticizers during early C3A-CaSO4 hydration, Cem. Concr. Res. 69
(2015) 105–113.
[25] W. Prince, M. Espagne, P.C. Aïtcin, Ettringite formation: a crucial step in
cement superplasticizer compatibility, Cem. Concr. Res. 33 (2003) 635–641.
[26] T. Nawa, H. Eguchi, Effect of cement characteristics on the fluidityof cement
pastes containing an organic admixture, 9th Int. Congress on the Chemistry of
Cement, New Delhi, 4, 1992, pp. 597-603. Avaliable from PRO 7: 1st
International RILEM Symposium on Self-Compacting Concrete.
[27] S.L. Sarkar, Effect of Blaine fineness reversal on strength and hydration of
cement, Cem. Concr. Res. 20 (1990) 398–406.
_
[28] I.B. Topçu, Ö. Atesßin, Effect of high dosage lignosulphonate and naphthalene
sulphonate based plasticizer usage on micro concrete properties, Constr. Build.
Mater. 120 (2016) 189–197.
[29] M.P. Nicolás, A. Duran, I.N. Blasco, J.M. Fernández, R. Sirera, J.I. Alvarez, Study
on the effectiveness of PNS and LS superplasticizers in air lime-based mortars,
Cem. Concr. Res. 82 (2016) 11–22.
[30] P. Pereira, L. Evangelista, J. de Brito, The effect of superplasticers on the
workability and compressive strength of concrete made with fine recycled
concrete aggregates, Constr. Build. Mater. 28 (2012) 722–729.
[31] K. Reknes, The Chemistry of Lignosulphonate and the Effect on Performance of
Lignosulphonate Base Plasticizers and Superplasticizers, 29th CONFERENCE on
our World in Concrete and Structures, 25–26 August 2004, Singapore.
[32] TS 706 EN 12620+A1, Aggregates for Concrete, Ankara, Turkey, 2009.
[33] TS EN 1097-6, Tests for Mechanical and Physical Properties of Aggregates –
Part 6: Determination of Particle Density and Water Absorption, Ankara,
Turkey, 2013.
[34] TS EN 12390-2, Testing Hardened Concrete – Part 2: Making and Curing
Specimens for Strength Tests, Ankara, Turkey, 2010.
[35] TS 2987, Determination of the Concrete Setting Time by Measurement of
Penetration Resistance, Ankara, Turkey, 2011.
[36] TS EN 12350-7, Testing Fresh Concrete – Part 7: Air Content of fresh Concrete –
Pressure Methods, Ankara, Turkey, 2010.
[37] TS EN 12350-2, Testing Fresh Concrete – Part 2: Slump Test, Ankara, Turkey,
2010.
[38] TS EN 12390-3, Concrete – testing Hardened Concrete – Part 3: Compressive
Strength of Test Specimens, Ankara, Turkey, 2010.
[39] J. Hu, Z. Ge, K. Wang, Influence of cement fineness and water-to-cement ratio
on mortar early-age heat of hydration and set times, Constr. Build. Mater. 50
(2014) 657–663.
[40] R.A. Lauten, B.O. Myrvold, S.A. Gundersen, New developments in the
commercial utilization of lignosulphonates Chapter 14, in: Surfactants from
Renewable Resources, 2010, pp. 269–283.
[41] S. Chandra, J. Björnström, Influence of cement and superplasticizer type and
dosage on the fluidity of cement mortars – part I, Cem. Concr. Res. 32 (2002)
1605–1611.
[42] M.A. Simard, P.C. Nkinamubanzi, C. Jolicoeur, D. Perraton, P.C. Aïtcin,
Calorimetry, rheology and compressive strength of superplasticized cement
paste, Cem. Concr. Res. 23 (1993) 939–950.
[43] TS EN 934-2, Admixtures for Concrete, Mortar and Grout – Part 2: Concrete
Admixtures: Definitions and Requirements, Ankara, Turkey, 2010.
[44] X. Ouyang, X. Qiua, P. Chen, Physicochemical characterization of calcium
lignosulfonate: a potentially useful water reducer, Colloid Surface A 282–283
(2006) 489–497.