Cement and Concrete Research 157 (2022) 106822

Contents lists available at ScienceDirect

Cement and Concrete Research

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

On the action mechanism of lignosulfonate plasticizer in alkali-activated

slag-based system
Lukáš Kalina *, Vlastimil Bílek Jr. , Petr Hrubý , Valeriia Iliushchenko , Michal Kalina ,
Jiří Smilek
Brno University of Technology, Faculty of Chemistry, Materials Research Centre, Purkyňova 464/118, Brno CZ-612 00, Czech Republic

A R T I C L E I N F O A B S T R A C T

Keywords: Workability improvement of alkali-activated materials by common plasticizers used for ordinary Portland
Alkali activated cement cement is usually an issue, but certain effectiveness is often found for lignosulfonate-based plasticizers (LS),
Granulated blast-furnace slag especially for activation with sodium hydroxide (its silicate modulus considered as zero). Therefore, the action of
Admixture
LS depending on the silicate modulus of the activator (0, 0.10, 0.25, 0.50) was studied in this paper, using non-
Workability
Adsorption
traditional oscillation strain sweep tests. The results showed that LS works for silicate moduli of 0 and 0.10
Stability especially in terms of great reduction in the viscoelastic moduli due to a significant decrease in zeta potential
magnitude. However, LS had a marginal effect for the silicate moduli of 0.25 and 0.50, which was attributed to
the competitive adsorption of LS and silicates from waterglass onto the slag grains. Although splitting of LS
chains in NaOH was proven using X-ray photoelectron spectroscopy, electrostatic repulsion of smaller fragments
is preserved.

1. Introduction offering products with various molecular architecture and possibilities,

Alkali-activated materials (AAMs), including those based on alkali-
activated blast furnace slag (AAS), have the potential to be an impor­
tant part of the toolkit of sustainable building materials [1]. Compared
to other AAMs, AAS is advantageous by means of fast strength gain even
at room temperatures, while it suffers from extensive drying and
autogenous shrinkage and sometimes rapid setting. Another issue of AAS
can be limited availability of blast furnace slag, as it is extensively
consumed to produce blastfurnace cements, and its expected decreased
production in the near future as well. To reduce these disadvantages,
slag is partially replaced by fly ash (FA) [2] and advances have been
made in the mix design of this blended AAM binder (AASFA) very
recently [3].
Despite these advances, wider use of AAMs is still a challenge. To
unlock their wider use, the finding or development of specific organic
admixtures to enhance their properties such as workability, strength,
shrinkage characteristics, or durability are necessary. One key group are
plasticizing admixtures known as superplasticizers (SPs), whose usage in
concretes based on ordinary Portland cement (OPC) is well established,
now making them an inseparable, value-adding component of modern
concretes. Their development continues in an unprecedented way,
including hydrolysable polymers which release working molecules into
the pore solution over time, etc. [4]. It is widely accepted [5] that
incorporation of FA improves workability of AAS, which implies that
increase in workability of AASFA can be mostly achieved by plasticizing
of the slag, and hence this paper is focused on AAS.
Unlike in OPC, the application of SPs in AAS is very limited. Usually,
commonly available SPs designed for OPC are applied in AAS with
contradictory results. Palacios et al. [6,7] did not observe a significant
effect of SPs based on polycarboxylate ethers (PCEs), vinyl copolymer
(V), melamine (M), naphthalene-formaldehyde (NF) on AAS with so­
dium silicate solution nor NaOH, except for NF in NaOH-activated slag,
where long-lasting improvement of fluidity in terms of increase in
spread diameter and decrease in yield stress was found. These results
were associated with the instability of most SPs in a highly alkaline
environment. The same research group [8] showed that if pH was
decreased to the value of 11.7, V and M greatly reduced the yield stress
and slightly reduced the plastic viscosity of NaOH-activated slag.
Recently, some self-synthesized PCEs [9–11] of different molecular ar­
chitecture were tried in AAS. Kashani et al. [9] observed the best
effectivity of very short cationic charged PCE with five long PEG side
chains, while relatively long anionic PCE with short side chains

* Corresponding author.
E-mail address: kalina@fch.vut.cz (L. Kalina).

https://doi.org/10.1016/j.cemconres.2022.106822
Received 13 October 2021; Received in revised form 19 April 2022; Accepted 22 April 2022
Available online 30 April 2022
0008-8846/© 2022 Elsevier Ltd. All rights reserved.
L. Kalina et al.
adversely influenced the yield stress due to non-desirable bridging
across slag particles. In contrast, Lei and Chan [10] found PCEs with
high anionicity, high molecular weight and short side chains very
effective in NaOH-activated slag, emphasizing the role of solubility and
stability of PCE in the activating solution as well as its adsorption. Conte
and Planck [11] also achieved fluidity improvement by specifically
synthesized PCEs, especially those based on allyl ether maleic anhydrite
with short side chains, which showed an excellent dispersion effect of
NaOH-activated slag, whereas activation using Na2CO3 resulted in none
of the tested PCEs being effective.
Based on the above, it is possible to synthesize efficient PCEs usable
in AAS, at least for a certain mixture design including the type of acti­
vator. In contrast to these last-generation SPs, lignosulfonate (LS) based
plasticizers, i.e., those of the first generation, whose plasticizing effect
on OPC has been known for almost one hundred years [12] can be a
possible choice. In addition, their use is advantageous due to their
availability and price, as they are industrial by-products [13]. Again, the
results concerning their performance in AAS are diverging in different
studies, but they seem to be efficient in most cases. Douglas & Brandstetr
[14] reported that neither lignosulfonate nor naphthalene sulfonate
improved the workability of pastes based on sodium silicate activated
slag, while reducing their one-day compressive strength. On the other
hand, Bakharev et al. [15] found a very similar effect of LS in OPC
concrete as well as in AAS concrete containing sodium silicate-based
activators (silicate modulus of 0.75 and 1.25) or blended activator of
NaOH and Na2CO3. Recent comparative study of Luukkonen et al. [16]
on the suitability of various superplasticizers in one-part AAS found LS
the most efficient of all tested types, although certain workability and
strength improvement was observed for other superplasticizers. In this
case, LS prolonged setting time and, after the optimization of water
content, doubled the 28d compressive strength. Reduction of water
demand, prolongation of setting time as well as increased strength
performance by LS was also reported by Kovtun et al. [17], again for
one-part AAS. A beneficial effect on rheological properties was also re­
ported for other AAMs, e.g. one-part geopolymer based on red mud [18]
or geopolymer concrete based on fly ash [19]. However, in the latter
work, the beneficial effect of LS was restricted to the concentrations of
NaOH lower than 4 M, while adverse effects were shown at higher
concentrations.
Based on the above, the performance of plasticizing admixtures in
AAS is a highly complex issue, where the composition of both activator
and organic admixture plays a decisive role. As is summarized in [20],
these variables determine the chemical stability and solubility of SPs in
highly alkaline media, as well as their adsorption onto the slag grains,
where competition between the anionic species and anionic SPs is of
high importance, and therefore more in-depth studies in this field are
necessary. Bearing this in mind and putting it in context with the
effectiveness of LS specifically in NaOH-activated slag, this paper looks
closer at the transition from activation with sodium hydroxide to sodium
silicate activator. In other words, the action of LS depending on the
gradually increasing silicate modulus MS (SiO2 to Na2O molar ratio) of
the activator in the narrow interval was our prime interest, starting with
MS = 0 (NaOH) and increasing it to 0.10, 0.25 and finally to 0.50. This
was studied in terms of chemical stability, adsorption extent, surface
chemistry, and rheological properties. Unlike other studies, where SPs
effects are investigated in terms of flow curves, from which (dynamic)
yield stress, viscosity, and/or other parameters can be extracted using a
suitable rheological model, a non-traditional approach based on oscil­
latory rheology was applied.
For AAS pastes (and their blends with fly ash), oscillatory rheology
was recently used to monitor the structural build-up using time sweep
measurements [21–23], while strain sweep tests were used only to
determine the linear viscoelastic region (LVR) in terms of critical strain,
i.e. the strain below which the deformation is non-destructive, to set the
already mentioned time sweep measurements. Nevertheless, in the
present study, the strain sweep measurements were used to observe the
2
Cement and Concrete Research 157 (2022) 106822
evolution of viscoelastic parameters during the structural breakdown of
the pastes with respect to activator composition and LS dose.
2. Experimental part
2.1. Materials
The main material used to produce the alkali-activated paste was
blast furnace slag (BFS) with the Blaine fineness of 400 m2/kg. The
chemical composition of BFS was measured by X-ray fluorescence
analysis (XRF) and is given in Table 1. The XRD analysis of BFS indicates
the presence of approximately 70 wt% of amorphous phase. The method
of internal standard (20 wt% of calcium fluorite) for the amorphous part
determination was applied. The crystal phases identified in BFS were
akermanite and traces of calcite, quartz, and merwinite (Fig. 1). Sodium
hydroxide (Carl Roth GmbH.), and sodium silicate solutions Na-SS
(Vodní sklo, a.s.) with different molar ratios of SiO2/Na2O (Ms = 0.10;
0.25; 0.50) served as the alkaline activators. To unify the labelling of the
samples, sodium hydroxide was considered as the alkali activator with
silicate modulus of zero. The lignosulfonate (LS) dispersant was used as
a plasticizing admixture (Chryso Chemie, s.r.o.). Physical and chemical
characteristics of LS are shown in Table 2. The sodium and calcium
content expressed as oxides were determined using ICP-OES.
2.2. Sample preparation
The alkali-activated pastes were prepared by mixing BFS with an
appropriate amount of alkaline activator to set the Na2O/BFS ratio of 4
wt%. The water-slag ratio was adjusted to 0.40. The lignosulfonate
admixture was added to the mixture together with alkaline activator
from 0 to 1.0 wt% by mass of BFS. The water content in LS was always
calculated into the water-slag ratio. The alkali-activated paste was
prepared in a polypropylene beaker using a hand mixer. The whole
duration of the mixing process took 3.0 min, of which the first minute
the mixture was mixing at the slow rate (260 rpm), for the following 30 s
the speed was increased to the maximum (1250 rpm), while the
following 30 s the mixture was stirred manually using a spatula and the
stick residuals were homogenized with the suspension. In the last min­
ute, the suspension was mixed at maximum rate. Thereafter, the specific
amount of the prepared paste required for the following tests was used.
2.3. Rheological investigations
Rheological measurements were performed using the rotational
rheometer DHR-2 (TA Instruments) equipped with vane-in-cup geome­
try. Both the vane and cup were made of stainless steel. The vane had six
blades, a diameter of 20.3 mm and a height of 19.5 mm, while the
diameter of the cup was 30.4 mm. The cup was Peltier-controlled to the
temperature of 25.0 ◦ C during the whole experimental procedure.
Directly after the end of mixing (3 min), the AAS paste was filled into
the cup, and the vane was moved to the measuring position. Rheological
measuring procedure started at 4.5 min (since the mixing was started)
and consisted of two steps. The first one was a pre-shear at the shear rate
of 100 s− 1 for 30 s followed by 30 s at rest. Then the strain sweep
measuring step started. Strain amplitude was logarithmically increased
from 5 ⋅ 10− 4% to 500%, 20 points per decade, 2 cycles at each strain
value. Constant angular frequency of 10 rad/s (i.e., 1.59 Hz) was used.
This frequency was selected on the basis of our previous experience. The
aim was to simulate rather slow motions close to the rest state and
simultaneously to obtain sufficient signal. The latter is an issue for lower
frequencies, along with long measuring time, which not suitable for the
materials with considerable structural build-up. Similar frequencies (1
Hz) are commonly used for related time sweep measurements [21,22].
Values below strain amplitudes of 10− 3% were not used for further
analysis because of scatter due to the limitation of the device at these
extremely low strains. Analyzed values were gently smoothed using the
L. Kalina et al. Cement and Concrete Research 157 (2022) 106822

Table 1
Chemical composition of blast furnace slag.
Raw material Chemical composition (wt%)

SiO2 Al2O3 CaO MgO SO3 Na2O K2O TiO2 MnO Fe2O3 LOI/others

Blast furnace slag 39.8 8.2 37.4 8.6 1.4 0.4 1.2 0.3 0.9 0.7 1.1

σ (Eq. 3) can be calculated, all of them corresponding to the critical

strain amplitude γ in this case. Actually, the rheometer measures only
two independent variables (torque and phase shift in this case) from
which, by knowing the preset parameters and dimensions of the ge­
ometries, all viscoelastic parameters are calculated roughly in the
opposite direction. In other words, G* is calculated according to the Eq.
3, and is further decomposed to its portions G′ and G′′ .

tanδ = G′′ /G′ (1)

√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
G* = (G′ )2 + (G′′)2 (2)

Fig. 1. XRD pattern of blast furnace slag used.
Table 2
Physical and chemical characteristics of lignosulfonate
plasticizer.
Property
Density (kg⋅dm− 3) 1.215
pH 8.4
Chloride content (%) ≤0.1
Na2O content (wt%) 3.1
CaO content (wt%) 1.2
Solid content (%) 43.4
default smoothing technique in the TRIOS software (least-squares
moving window, 5 windows). First of all, the critical strain value
determining the LVR was evaluated. This is, however, quite a delicate
issue as the critical strain values of concentrated suspensions are very
low, and the evaluation is further complicated by the structural build-up
of the pastes over time. Hence, there is a competition between the
structural evolution manifested by the increase in viscoelastic moduli in
time and breaking this structure down as the strain amplitude gradually
increases. The issues of critical strain determination were already
mentioned by Yuan et al. [24] for cement pastes, where the strain value
corresponded to the largest value of storage modulus G′ followed by its
decrease. In fact, the same approach was adopted in this work, where the
strain corresponding to the maximum of G′ was taken as the critical
strain, but its finding was facilitated by the aforementioned smoothing.
Another option on how to determine the critical strain can be by
decreasing the storage modulus by 5–10% with respect to its maximum
or average value within the LVR [23,25]. This approach was not used as
we expect that it would overestimate the critical strain value.
Once the critical strain is determined, other viscoelastic parameters
corresponding to this value can be found in the measured data and/or
calculated from those that are already known. The key parameter is the
loss factor tanδ (tangent of the phase angle δ), defined as the ratio of the
loss modulus G′′ to the storage modulus G′ (Eq. 1). The value of the loss
modulus as well as the complex modulus G* (Eq. 2) and oscillation stress
σ = G* ⋅γ (3)
Nevertheless, the critical strain is only one interesting point on the
amplitude sweep output. It contains information about the stresses and
other parameters initializing the mechanical breaking of the structure.
If, however, G′ prevails over G′′ at rest, the samples still behave as a
viscoelastic solid just beyond the critical strain. As the strain continues
to increase, the ongoing structural breakdown results in the faster
decrease in G′ than G′′ so at a certain point, a crossover of both moduli
(G′ = G′′ ) can be observed, beyond which G′′ prevails over G′ (i.e. tanδ
>1). This means that the sample starts to behave instead as a viscoelastic
liquid, and starts to flow. According to Mezger [25], the stress corre­
sponding to the LVR limit can be called yield point or yield stress, while
the stress needed to reach the modulus crossover is called flow point or
flow stress. This terminology has already been used to characterize
cement pastes containing viscosity enhancing admixtures [26].
It should be noted that, especially from the terminological point of
view, the terms “yield stress” or “yield point” related to the LVR limit
can be confusing with respect to the “yield stress” obtained from the
classical flow curves fitted by the suitable rheological model (e.g.
Bingham or Herschel-Bulkley). The latter correspond to the “flow point”
in amplitude sweep curves, but they are different due to the different
nature of their test (static vs. dynamic). In addition, Roussel et al. [27]
mentioned another possibility to determine the “static yield stress”
describing the flow onset as the stress peak on the stress-strain curve. In
this paper, both approaches to determine the flow point were tried (see
examples in Fig. 2), but finally, the crossover was selected to assess the
effect of LS. The main reason was that all tested pastes exhibited a
crossover point, while the plateau rather than a clearly visible peak was
recorded in some cases. Once the crossover modulus (G′ = G′′ ) and the
corresponding strain were determined (automatically by the software),
the remaining values of the complex modulus and stress were obtained
using Eqs. (2) and (3), respectively.
2.4. Zeta potential measurement
The effect of both alkaline activators and plasticizing admixture on
the values of zeta potential of BFS suspension was investigated by the
method of electrophoretic light scattering (ELS) using Zetasizer Nano ZS
(Malvern Panalytical Ltd., UK). For this purpose, 1000 g of water sus­
pension obtained by diluting the prepared alkali-activated paste con­
taining 10 g of BFS (according to Section 2.2) was used for analyses. The
pH, controlled during the measurement (Unitrode with Pt1000; Met­
rohm AG), was 12.1 ± 0.06 for all diluted samples regardless of the used
alkaline activator and LS dosage. Simultaneously, the average scattered
light intensity and the zeta potential of the suspension were measured in
three repeated scans of three individually taken samples (results are

3
L. Kalina et al.
Fig. 2. Schematic illustration of the evaluation of the oscillation strain sweep curves in terms of their important points on two selected data sets (AAS pastes with two
different silicate moduli and 1.0% of added LS plasticizer).
presented in the form of mean values ± SD, n = 9; i.e. three repeated
measurements of three sample replicates). The obtained data from ELS
analysis were processed using the Zetasizer software (version 7.11;
Malvern Panalytical Ltd., UK).
2.5. Adsorption test
The adsorption isotherms were obtained based on UV spectroscopy
measurements. The fresh pastes containing 150 g of BFS were prepared
according to Section 2.2. This means that the used amounts of LS ranged
nominally from 0 to 1.5 g (0–1% with respect to the slag weight). Since
the LS had to be added dropwise, it was not possible to reach exactly the
target value, and therefore precise amount of added LS was determined
using an analytical balance (readability of 0.1 mg). The fresh paste was
subsequently centrifuged for 5 min at 4800 rpm. The centrifuging
started 5 min after the beginning of mixing. It was assumed that the
equilibrium between the adsorbed and non-adsorbed LS was reached.
This was supported by the measurement of the adsorbed amount of LS in
time ranging from 5 to 15 min, whose deviation was lower than 0.09
mg/g BFS. In addition, it was an effort to keep the same timing as was
used for rheological experiments. The supernatant was then filtered
through a 0.45 μm syringe filter, and diluted (50×) with demineralized
water to ensure linearity of Beer-Lambert law. The non-adsorbed
amount of lignosulfonate admixture was determined by Hitachi U3900
UV spectrometer with a wavelength of 285 nm. Based on the calibration
line, the amount of admixture adsorbed on BFS was taken as the dif­
ference between the initial amount of admixture and the amount present
in the supernatant after adsorption. This similar methodology was used
in a previous study by Palacios et al. [8]. The crucial parameters (namely
saturated plateau Qsat and coefficient of determination R2) were calcu­
lated using empirical Freundlich-Langmuir adsorption model, which
combines the Langmuir-type and Freundlich-type adsorption behaviour.
4
Cement and Concrete Research 157 (2022) 106822
The fitting of Freundlich-Langmuir model (Eq. 4) to the experimental
data was performed using Origin Pro 2018b (OriginLab) software.
a = Qsat ⋅(K⋅c2 )n /(1 + (K⋅c2 )n )) (4)
In this equation, a represents the occupancy of adsorption sites
(adsorption of lignosulfonate in mg related to 1 g of BFS), Qsat is the
maximal adsorption capacity of thy system (in mg of LS to 1 g of BFS), K
represents the equilibrium constant of adsorption (in g of BFS per mg of
LS), n represents the index of heterogeneity of binding sites, and c2 is the
amount of freely accessible lignosulfonate related to 1 g of BFS.
2.6. XPS measurement
The chemical stability of lignosulfonate admixture in alkaline envi­
ronment was determined using X-ray photoelectron spectroscopy (XPS).
The samples for the XPS analyses were prepared in a glove-box under a
nitrogen atmosphere to prevent surface contamination by CO2 as fol­
lows. A thin layer of slag was pressed in a special XPS sample holder. The
grains were then poured (a few drops) with the solution of alkaline
activator and lignosulfonate admixture (in a volume ratio of 1:1)
ensuring the wetting of their whole surface. The purpose of its appli­
cation on slag grains should simulate the invocation of the pore solution
environment; the slag grains on the holder are partially dissolved and
the chemistry of the alkaline solution is changed, which may potentially
change the conformation of LS molecules. Although the conformation
cannot be studied using XPS, it cannot be fully excluded that its changes
may affect the chemical stability of chemical bonds in LS. The XPS
spectra of pure lignosulfonate were measured without the presence of
slag. After the application of the solution, the samples were dried under
a nitrogen atmosphere for 24 h. Then the samples were transferred in a
special box with inert atmosphere into XPS where the vacuum pump-
down sequence was started immediately. Thereafter, the XPS holder
L. Kalina et al.
with species was transferred into the analytical chamber with the
pressure of 2⋅10− 8 Pa where the measurement was launched. XPS ana­
lyses were carried out with Kratos Axis Ultra DLD spectrometer using the
monochromatic Al Kα (hν = 1486.7 eV) X-ray source operating at 75 W
(5 mA, 15 kV). The spectra were obtained using the analysis area of
~300 × 700 μm. The Kratos charge neutralizer system was used for all
analyses. The high resolution spectra were measured with the step size
0.1 eV and 20 eV pass energy. The instrument base pressure during the
measurements was consistently kept at 2⋅10− 8 Pa. The spectra were
analyzed using CasaXPS software (version 2.3.15) and have been
charge-corrected to the main line of the carbon C 1s spectral component
(C–C, C–H) adjusted to 285.0 eV. A standard Shirley background was
used for all sample spectra.
Fig. 3. Evolution of complex modulus of AAS paste with different silicate modulus and lignosulfonate dose with increasing oscillation strain (left) or corresponding
oscillation stress (right).
5
Cement and Concrete Research 157 (2022) 106822
3. Results and discussion
3.1. Effect of activator type and LS dosage on paste rheology
The overall comparison of the effect of LS for the used MS is given in
Fig. 3, where the evolution of the complex modulus, which represents
the overall viscoelastic response, is plotted against the increasing strain
and corresponding stress. All these curves show the same basic shape,
starting with the LVR for sufficiently low strains. In the wide range of
strains (3–4 orders of magnitude) higher than the critical strain, a
gradual decrease in G* can be observed as the structure is destroyed. In
the last stage, the G* tends to flatten or slightly increase, but the
measured data are not reliable in this region as the values of the storage
modulus were negative, which is physically impossible. In addition, the
instrument inertia can severely affect the obtained results at large
strains. If the G* is plotted against the oscillation stress, the shape of the
curves changes to a rapid decrease in G* within the narrow interval of
the oscillation stress. This shows that the stress is roughly constant or
L. Kalina et al.
even slightly decreases over a wide range of strains, as was already
mentioned in Fig. 2, where a stress plateau with a more or less apparent
peak on stress-strain curves can be observed.
Fig. 3 clearly shows the overall action of LS in AAS depending on the
modulus of the activator. Significant plasticizing effect of LS for slag
activation with sodium hydroxide has already been reported in the
literature [16] by means of flow table testing as well as rotational tests.
We confirmed this by oscillatory testing in terms of decreasing complex
modulus with increasing LS dose across the whole range of applied
strains. Based on Eq. 3, this means that the stress arising during this test
is also decreased, so the obtained curves of the complex modulus tend to
move towards the lower values of both axes. However, if the silicates are
present even at very low amounts, the plasticizing effect of LS di­
minishes. For the silicate modulus of 0.10, a certain efficiency of LS can
still be observed, while for higher silicate moduli the obtained curves
instead overlap regardless of the LS dose and hence the stiffness of the
Fig. 4. Effect of LS on the rheological parameters corresponding to the yield point and flow point of AAS pastes with different silicate modulus.
6
Cement and Concrete Research 157 (2022) 106822
paste is almost unaffected by LS.
A closer look on the course of structural breakdown can be made by
the analysis of the most important points during its initiation (yield
point) and flow onset (flow point). These parameters are given in Fig. 4,
from which it can be seen that the presence of LS significantly changes
the arising structure.
The basic characteristic is the critical strain determining the LVR. Its
values determined for the tested pastes are similar to those already re­
ported for AAMs [22,23] or Portland cement pastes [24,28,29]. It can be
seen that the increasing dose of the LS results in a slight increase of the
critical strain, which was already reported for Portland cement pastes
[24]. Nevertheless, unlike plasticizers in Portland cement paste, LS was
not very efficient for the pastes with the presence of soluble silicates. In
contrast, if the slag was activated by sodium hydroxide, the LS efficiency
was the highest, while a similar or even lower change of the critical
strain compared to other silicate moduli was observed. Similar trend of
L. Kalina et al.
the critical strain evolution with increasing dose of LS was observed for
the yield point.
Due to the relatively low effect of LS on the strain corresponding to
the LVR limit as well as on the flow point of the NaOH-activated slag,
and the simultaneous approximated 10× and 6× decreased complex
modulus at these points, respectively, the stress at which the breaking of
the structure begins decreases in a similar manner as when using the
complex modulus (Eq. 3). At the same time, the loss factor slightly de­
creases in the presence of LS, which means that the behaviour of the
evolving structure is even more solid-like compared to the plain AAS
without LS and thus indicates that the pastes' rheology is still controlled
by the presence of a net of attractive interparticle forces. Nevertheless,
these forces are greatly weakened by LS, which facilitates the flow of
such pastes under its own weight.
For the lowest used non-zero silicate modulus (MS = 0.10), high LS
efficiency can be still observed. Expressed in relative values, the effi­
ciency seems much decreased, e.g., at the yield point the oscillation
stress and complex modulus were reduced 2 and 4 times, respectively.
Nevertheless, it means that there is only slightly lower efficiency
compared to Ms = 0 in terms of absolute values of the complex modulus
and even slightly higher efficiency in terms of the oscillation stress, with
the latter parameter of non-plasticized paste with MS = 0.10 two times
higher compared to that of MS = 0 paste. Although the slight decrease in
the complex modulus with increasing LS dose at the yield point is also
noticeable for the pastes with silicate moduli of 0.25 and 0.50, the
corresponding stresses needed to start the structural breakdown did not
change due to the simultaneous increase in strain, which demonstrates
how LS efficiency diminishes. A similar phenomenon was also observed
for the flow point, where the crossover stress for MS = 0.25 even slightly
increased as the LS dose increased. This was already observable from
Fig. 3 where the curves of the complex modulus for the pastes containing
LS did not bend back to lower stresses the same way that the reference
paste without LS did, which points to a slight toughening effect of LS on
the arising structure.
3.2. Effect of activator type and LS dosage on surface chemistry of slag
The crucial factor in the working mechanism of plasticizers in AAS is
the adsorption on slag particles causing subsequently their dispersion
through electrostatic and/or steric repulsion. The driving force for the
adsorption of plasticizers including LS is controlled by electrostatic in­
teractions [30]. Since the sulfonate groups in LS are negatively charged,
higher adsorption can be expected on a surface with a positive charge,
therefore the surface charge of slag particles plays a very important role.
The surface chemistry of slag is strongly affected both by its chemical
composition and the surrounding environment. When slag makes con­
tact with water, the deprotonization of the silanol groups occurs and the
Fig. 5. Evolution of zeta potential (A) and adsorbed amount (B) with increasing amount of dry matter of added LS; please note that the values of zeta potential are
affected by the dilution (100×) of the original pastes.
7
Cement and Concrete Research 157 (2022) 106822
negative charge on the slag surface is created. At the same time, the
chemical bonds with ionic (Ca–O; Mg–O) as well as covalent (Si–O;
Al–O) character break under the polarization effect of OH− . Because of
a low dissociation energy of ionic bonds, the concentration of Ca2+ and
Mg2+ in solution is much higher in comparison with silicate or alumi­
nate species [31]. These cations tend to adsorb on the negatively
charged surface of slag which affects the electrical potential in the
interfacial double layer known as zeta potential. It has been found that
the zeta potential values strongly depend on the ability of slag to release
the alkali and earth alkali cations into the pore solution. The amount of
released cations, particularly of divalent Ca2+ ions, presenting in the
equilibrium state with the surface of slag affect whether the charge
becomes either less negative or overall positive [32].
The determined zeta potential values of used slag with chemical
composition characterized by Table 1 show the negative charge of
particles (approx. –13 mV) in the water environment. This situation
changes greatly after the addition of an alkaline activator (Fig. 5A). The
activation with the solution of sodium hydroxide exhibits a less negative
charge on the slag surface. The change of zeta potential values in pres­
ence of NaOH is associated with the adsorption of Na+ on the slag sur­
face. On the other hand, the activators based on sodium silicate solution
(Na-SS) show a higher magnitude of zeta potential due to the negatively
charged silicate species which can adsorb on the slag surface. One can
see that the more negative values of zeta potential are observed in the
case of Na-SS with a higher silicate modulus because the molar quantity
of silicate species is growing. Similar results were also obtained in
Kashani et al. study [33]. It should be kept in mind that the obtained
values are distorted by the dilution of the original paste with deminer­
alized water (100×). There are two aspects, why dilution was necessary.
The first one is that only device working on electrophoretic light scat­
tering principle was available, which needs relatively low volume
fraction of solids in the sample. The solution of this issue could be
diluting the paste with original activating solution and not with pure
water, but this rises another issue of high pH and particularly extremely
high conductivity of activators, exceeding 300 mS/cm.
As mentioned above, the adsorption of LS is directly related to the
surface charge of slag in suspension. It can be expected that the
adsorption of LS with negatively charged sulfonate functional groups on
slag particles is higher with the usage of NaOH as an alkaline activator.
The adsorbed negatively charged LS forms an additional slipping layer
on the slag which leads to the measurement of more negative values of
zeta potential with its higher content in a sample. Similar behaviour is
also observed with the Na-SS activation. However, the rate of zeta po­
tential reduction dramatically decreases with a higher silicate modulus.
Whereas the difference in zeta potential between the samples without
the plasticizer addition and with 1 wt% of LS is more than 38 mV in case
of NaOH activation, the samples activated by Na-SS with silicate module
L. Kalina et al.
higher than 0.25 exhibit only small changes (reduction of approx. 6 mV).
Based on DLVO theory [34], to obtain a better electrostatic repulsion
force for the dispersion of the slag particles, one can say, that the highest
efficiency of LS is achieved with NaOH activation. Higher change of the
zeta potential to more negative values would also indicate higher
adsorption of LS onto the slag surface, which was further confirmed by
the measurement of adsorbed amount (Fig. 5B).
Due to the unavoidable dilution of the pastes as mentioned above,
the observed differences in the zeta potential should be treated only as
comparative by trend instead of their absolute values, because the
adsorption of plasticizing admixtures is very sensitive to the pH, the
electrolyte concentration, and the content of surfactant [35]. Previous
research proved that a high concentration of OH− in the case of NaOH-
activated slag increases the ionic strength in the pore solution resulting
in a reduction of the plasticizer adsorption in comparison with a sus­
pension based on slag dispersed in a water environment [36]. From this
perspective, the dilution could somewhat favour the adsorption due to
the decrease in the ionic strength. However, greatly decreased amount
of plasticizer in the solution leads to its desorption to establish a new
equilibrium between adsorbed LS and its concentration in the solution.
It can be expected that this will prevail over the effect of dilution of
activating solution itself, and consequently that the dilution will lead to
the underestimation of the presented values of zeta potential. Especially
in the case of non-zero silicate moduli, the dilution could possibly affect
the adsorbed amounts of silicates and thus their competition with LS to
adsorb on free sites on the slag surface. This could explain, why still less
negative zeta potential was determined for MS = 0.10 compared to MS =
0.25 and 0.50 at higher doses of LS, although the rheological properties
(Fig. 4) were generally lower for plasticized paste with MS = 0.10, along
with much higher adsorbed amount of LS (Fig. 5B). Unlike zeta poten­
tial, both rheological and adsorption measurements were carried out on
the real, non-diluted pastes, and are therefore more representative.
The adsorption of LS followed the Freundlich-Langmuir adsorption
model isotherm and revealed the effective dosages of LS characterized
by saturated plateau. The higher value of saturated plateau Qsat indicates
that a stronger electrostatic attractive force exists between LS and slag
particles [37]. Therefore, the results in Fig. 5B suggest that the efficiency
of LS with a higher silicate modulus of used Na-SS obviously decreases.
The values of saturated plateau are summarized in Table 3. Saturated
plateau Qsat (represent the maximal amount of lignosulfonate-based
plasticizer adsorbed per 1 g BFS) is strongly dependent on different
molar ratios of SiO2/Na2O (MS = 0.10; 0.25; 0.50). For the two highest
silicate moduli (0.25 and 0.50), very low Pearson coefficient was ob­
tained, indicating that the data were not reasonably fit by the used
model. They are highly scattered due to too low adsorbed amount of LS
plasticizer, whose detection is below the sensitivity of the used meth­
odology. Consequently, the obtained Qsat values for 0.25 and 0.50 pastes
were not meaningful and are not given in Table 3. These findings could
be beneficial in future applicability of these innovative materials and
tailoring of final properties. Generally, if the molar ratio of SiO2/Na2O is
increasing, the saturated plateau rapidly decreases, especially beyond
the silicate modulus of 0.10 [38].
3.3. Effect of activator type on LS chemical stability
In general, the behaviour of plasticizers depends strongly on their
molecular structure. During their action in a high alkaline environment,
Table 3
Parameters calculated from Langmuir-Freundlich adsorption isotherms.
Alkaline activator R2 Qsat (mg⋅g− 1)
NaOH (Ms = 0) 0.995 0.956 ± 0.024
Na-SS (Ms = 0.10) 0.993 0.863 ± 0.016
Na-SS (Ms = 0.25) 0.393 – of zeta potential [33], hence the zeta potential is an important factor
Na-SS (Ms = 0.50) 0.588
–
8
Cement and Concrete Research 157 (2022) 106822
the influence on their polymeric chains may occur. X-ray photoelectron
spectroscopy (XPS) seems to be a very suitable method for this purpose
mainly due to the evaluation of chemical bonding states of elements. The
high-resolution C 1s spectrum (Fig. 6) of pure admixture represents
various chemical states of carbon in the LS structure. The peak at 285.0
eV is associated with the bonds between C–C and C–H in aliphatic
chains while the binding energy at 284.6 eV indicates the presence of
aromatic rings confirmed by the shakeup satellites at 291.3 eV. The
peaks at 286.1 and 286.3 eV belong to hydroxyl and ether units,
respectively. The bond between carbon and sulfonate functional group is
typical for the binding energy at 286.6 eV. Finally, the peak at 288.1 eV
corresponds to the carboxyl groups which also occur in the LS structure.
After the alkaline activation process, the high-resolution spectrum of C
1s has undergone significant changes. The amount of ether linkages
decreases at the expense of alcohol bonds (Table 4 – grey filled area).
Due to the high alkaline environment, the alkaline hydrolysis takes
place, resulting in the breakage of aryl-alkyl ether bonds, which can be
cleaved much more easily in comparison with very stable aryl-aryl ether
bonds [39]. Subsequently, the molecules of LS are subjected to the
depolymerization process proposed in Fig. 7 where deprotonated hy­
droxyl groups in position to the aryl-alkyl ether bond serve as nucleo­
philes, and the sodium cations catalyze the reaction by forming cation
adducts. This leads to an increased negative partial charge on the oxygen
atom and reduces the energy required for heterolytic fission of covalent
bonds [40,41]. The formed sodium alkoxides hydrolyze in a water
environment, thus the amount of C–OH bonds characterized by the
binding energy at 285.9 eV grow in the XPS spectra. The depolymer­
ization process of LS is also closely related to the selection of alkaline
activator. It was found that sodium silicate solution (Ms = 0.50) with pH
at 12.6 initiates a small fraction of ether bond cleavage. Conversely, at a
very high pH (sodium hydroxide solution; pH = 13.3) almost complete
depolymerization of lignosulfonate chains occurs. This is associated
with an increase in pH value and subsequent higher concentration of
OH− in solution supporting the alkaline hydrolysis process. These
findings lead to the conclusion that the stability of LS in extremely high
alkaline environment is very low. A similar situation has already been
studied in the case of polycarboxylate (PC) admixtures [6], where the
decomposition of PC polymeric chains takes place based on alkaline
hydrolysis of ester groups. Due to the cleavage of this functional group,
the long hydrocarbon side chain is separated from the backbone struc­
ture and the steric hindrance among the BFS particles ceases to exist.
This may lead to the side interactions that negatively influence the
deflocculation of slag particles resulting in the loss of workability [9].
However, in the case of LS admixtures the positive effect on workability
of AAM was previously confirmed even though the alkaline activation
process was initiated by sodium hydroxide solution. It follows that
although the LS structure is disintegrated to smaller units, the electro­
static repulsion of plasticizer realized by untouched sulfonate anions is
still maintained.
3.4. Rheology vs. surface chemistry
Rheological properties of fine inorganic suspensions are strongly
related to the balance of attractive and repulsive interparticle forces of
several kinds, [42]. Two basic types are strongly attractive short-range
van der Waals forces originating from instantaneous dipoles of atoms
in the particle, and repulsive electrical double layer (EDL) forces
depending on the particle nature as well as on the properties and
composition of the disperse media. Van der Waals forces are considered
to be the main reason why cementitious particles tend to agglomerate,
[43], however, the electrostatic attraction of oppositely charged sur­
faces can also be a reason [44]. On the other hand, EDL forces can be
affected by the dissolved species in the solution via their adsorption onto
oppositely charged surfaces. They are directly proportional to the square
affecting the resulting yield stress and other rheological parameters.
L. Kalina et al. Cement and Concrete Research 157 (2022) 106822

Fig. 6. High-resolution of C 1s XPS spectra of dried original lignosulfonate plasticizer and after exposure to highly alkaline conditions.

affect it significantly. A higher rate of structural build-up for silicate

Table 4
modulus of 0.40 compared to 0 during the first minutes of measurement
The binding energies and atomic concentration of functional groups within the
was observed for alkali-activated slag/fly ash pastes [22]. This is also
pure lignosulfonate (LS) admixture influenced by the alkaline activators.
likely the reason for a higher loss factor of NaOH-activated pastes than
Binding energy (eV)/atomic concentration (%)
those with content of silicate species, although one could expect the
Functional Pure LS LS + Na-SS (Ms = LS + NaOH (Ms opposite trend due to the generally observed plasticizing effect of sili­
groups 0.50) = 0) cates [33]. In addition, for the very low silicate moduli that was used,
284.6/ the vast majority of silicate species is in the monomeric form [45], their
C 1s Aromatic C 284.6/36.0 284.5/37.8
35.4 adsorption onto the slag grains significantly reduces zeta potential with
285.0/
C–C; C–H 285.0/23.7 285.0/23.4 an already apparent effect on rheology, but their plasticizing potential is
21.6
C–OH 286.1/2.3 286.0/8.0 285.9/19.4 likely higher at higher silicate moduli due to larger silicate species and
286.3/ thus there is a wider electric double layer around slag particles.
C–O– 286.4/15.2 286.4/5.8
23.9 If polymeric species are present in the suspension, other types of
C–SO−3 286.6/3.6 286.5/3.1 286.5/3.0 forces come into play. Repulsive electrostatic, steric or combined elec­
COO– 288.1/6.5 288.0/5.7 288.0/4.1
trosteric forces on which the action of water-reducing admixtures is
carbonate 289.1/6.6 289.2/8.1 289.1/6.7
satellite 291.3/– 291.5/– 291.5/– based are well-known [44], but the surfactant molecules can also induce
S 2p3/ 167.6/ attractive forces, such as bridging and depletion forces. A very important
C–SO−3 167.6/100 167.6/100
2 100 phenomenon affecting these interactions and thus the action of super­
plasticizers is their adsorption onto slag particles, as bridging arises from
adsorption of one polyelectrolyte onto more surfaces, while depleting
Before we discuss the effects of LS, let us recall the rheological results forces from non-adsorbing polymers [42]. Competitive adsorption of
from Fig. 4 as well as the determined values of the zeta potential anionic superplasticizers with anions from activator or possibly other
(Fig. 5A) for the different silicate modulus of the tested samples. Based anionic species have already been found as one of the reasons for low
on the significant changes in the zeta potential to more negative values efficiency of superplasticizers in AAMs [10,46] and our results clearly
with increasing silicate modulus, one could expect increasing flowability demonstrate that the competitive adsorption of silicates and LS is one of
of the corresponding pastes. This is roughly fulfilled for the complex the reasons why the LS plasticizer loses most of its effectiveness in
modulus which decreases in an expected manner, except of its value for silicate-activated slag pastes. Nevertheless, the limited adsorption of LS
MS = 0.50. The reason is the different rate of structural build-up of the is still able to soften the arising structure as expressed in terms of
samples before the start of the test and its initial part taking place on the reduction in its complex modulus (Fig. 4), and this trend gradually
LVR, as is given in Fig. 8. In the beginning of the measurement (30 s after continues with increasing the LS dose in the tested range, which be­
the preshear), the complex modulus decreases with increasing content of comes observable on the evolution of the zeta potential towards the
silicates as expected, but the structural build-up is accelerated by the more negative values (Fig. 5A). Such evolution supports the idea of
increased silicate modulus. Depending on its value, critical strain was competitive adsorption, showing that increased concentration of LS in
reached after 70–100 s from the end of the preshear, which explains why the pore solution allows its further adsorption and hence reduction in a
a higher complex modulus was determined for Ms = 0.50 than for Ms = complex modulus. Similar trends in the complex modulus evolution
0.25 at the yield point as well as the flow point. In the case of the paste were recorded for LS doses higher than 0.4 wt% in pastes with MS =
with Ms = 0, the determined structural build-up could be slightly 0 and MS = 0.10, i.e., at the doses, where more than 90% of the saturated
reduced by the relatively high value of preset strain (0.005% for all plateau of LS adsorption was reached, so only a small fraction of further
samples), which roughly corresponds to the critical strain of these added plasticizer is adsorbed and thus a lower effect on complex
pastes. Unfortunately, it was not possible to use lower strain amplitude modulus compared to its lower doses is observed.
for the time sweep measurements due to limits of the rheometer and thus Although the structure of most AAS pastes was softened in the
scattered data. presence of LS (decreased complex modulus), a slight decrease in the
It is worth noting that during the 5 min of measurement (after 30 s of loss factor with increasing LS dose suggests a certain degree of relatively
rest), the complex modulus is increased 3, 9, 8 and 18 times for silicate weak bridging interactions. The most apparent is the effect for MS = 0 up
modulus of 0, 0.10, 0.25 and 0.50 respectively, and that LS does not to 0.4–0.6 wt% of LS, where the highest loss factor decrease as well as

9
L. Kalina et al. Cement and Concrete Research 157 (2022) 106822

Fig. 7. Proposed chemical changes in lignosulfonate molecule when mixed with alkaline activator (e.g., NaOH solution).

Fig. 8. Initial stages of structural build-up of AAS paste depending on the silicate modulus of activator and presence of LS plasticizer (absolute values on the left,
values relative to the start of the measurement on the right).

the greatest adsorption extent was observed, i.e., the slag surface was
not fully covered by LS. In contrast, for LS doses higher than 0.6 wt%,
where the saturated plateau is almost fully reached (Fig. 5B), the loss
factor (Fig. 4) seems to slightly increase which could be related to the
complexation of Ca2+ in the pore solution by the non-adsorbed LS
molecules. This may result in a shielding of Ca2+ in the solution, which
can otherwise also contribute to bridging via attraction with two
different LS molecules and thus explains the increase in the loss factor.
Complexation of Ca2+ by lignosulfonate was already related to a
retarding effect on setting and even increased the 28 day strengths of
AAS mortar [16], so its effect of workability can also be expected. Af­
finity of LS to Ca2+ both adsorbed onto the slag particles and “free” in a
pore solution is, however, lower when compared to the affinity of sili­
cates to Ca2+, as shown already by the mentioned competitive
adsorption issues, especially with increasing concentration of silicates.
Hence, the overall rheological properties depend on the mutual con­
centrations of Ca2+, silicates and LS. The obtained results showed that
the critical silicate modulus of the activator is between 0.10 and 0.25. In
the former case, adsorption of LS observed for MS = 0 was still preserved
and LS weakened the evolving structure at its yield point as well as flow
point, while for MS = 0.25 adsorption extent was greatly reduced and
interactions between Ca2+, silicates and LS increased strain necessary to
force the paste to flow. For silicate moduli around 0.50 and possibly
higher, the rheology was controlled mainly by the silicates present in
high amounts, both of which were adsorbed onto the slag grain and
present in the pore solution.

10
L. Kalina et al.
4. Conclusions
In this paper, the action of LS plasticizer in AAS pastes with different
silicate moduli of activator was investigated in terms of oscillatory
rheology, surface chemistry of the slag in pastes and chemical stability of
LS in highly alkaline media. Based on the obtained results, the essential
conclusions may be summarized as follows:
• All investigated AAS pastes at rest behaved like viscoelastic solids
and showed fast structural build-up in time. Its rate increased with
increasing content of silicates. The breaking of such structure was
characterized by the yield point beyond which the amplitude of
deformation becomes destructive, and the flow point where the
solid-like behaviour changes to liquid-like, i.e., loss modulus prevails
over storage modulus.
• Although the LS affects various viscoelastic parameters, the most
pronounced is its effect on the viscoelastic moduli, here represented
by the complex modulus, which is reduced by LS at both yield point
and flow point. Depending on the corresponding oscillatory strain,
the related stress is also decreased. Simultaneously, LS does not
significantly change the viscoelastic nature of the AAS paste as the
loss factor remains roughly the same or is even slightly reduced.
• Plasticizing ability of LS strongly depends on the silicate modulus of
the activator due to the competitive adsorption of anionic LS mole­
cules and silicate species from the activator. Great decrease in LS
efficiency correlates well with greatly reduced adsorption extent for
silicate moduli higher than 0.10.
• Working mechanism of the LS in AAS pastes lies in the electrostatic
effect observable as the change of zeta potential to more negative
values, which in turn increases the repulsive forces and reduces the
complex modulus and consequently static-like yield stress.
• Although alteration of the LS chemical structure in highly alkaline
environment can occur, effectiveness of LS is preserved due to the
presence of smaller species still able to induce electrostatic repulsion.
Further related research will be focused on the observed effects in
longer time perspective, timing of LS addition, different concentrations
of activator and especially LS effectiveness in other AAMs (fly ash,
metakaolin).
CRediT authorship contribution statement
Lukáš Kalina: Conceptualization, Methodology, Writing – original
draft, Writing – review & editing, Investigation. Vlastimil Bílek: Project
administration, Funding acquisition, Conceptualization, Methodology,
Writing – original draft, Writing – review & editing, Investigation. Petr
Hrubý: Investigation. Valeriia Iliushchenko: Investigation. Michal
Kalina: Formal analysis, Investigation. Jiří Smilek: Formal analysis.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This work was financially supported by the project: GA20-26896S
“Towards the organic admixtures tailoring for alkali-activated slag-
based systems” with financial support from the Czech science
foundation.
References
[1] J.L. Provis, Alkali-activated materials, Cem. Concr. Res. 114 (2018) 40–48, https://
doi.org/10.1016/j.cemconres.2017.02.009.
11
Cement and Concrete Research 157 (2022) 106822
[2] N. Marjanovic, M. Komljenovic, Z. Bascarevic, V. Nikolic, R. Petrovic, Physical-
mechanical and microstructural properties of alkali-activated fly ash-blast furnace
slag blends, Ceram. Int. 41 (2015) 1421–1435, https://doi.org/10.1016/j.
ceramint.2014.09.075.
[3] B.B. Sun, Y.B. Sun, G. Ye, G. De Schutter, A mix design methodology of slag and fly
ash-based alkali-activated paste, Cem. Concr. Comp. 126 (2022), https://doi.org/
10.1016/j.cemconcomp.2021.104368.
[4] N. Roussel, Understanding the Rheology of Concrete, 2012.
[5] A.M. Rashad, A comprehensive overview about the influence of different
admixtures and additives on the properties of alkali-activated fly ash, Mater. Des.
53 (2014) 1005–1025, https://doi.org/10.1016/j.matdes.2013.07.074.
[6] M. Palacios, F. Puertas, Effect of superplasticizer and shrinkage-reducing
admixtures on alkali-activated slag pastes and mortars, Cem. Concr. Res. 35 (2005)
1358–1367, https://doi.org/10.1016/j.cemconres.2004.10.014.
[7] M. Palacios, P.F.G. Banfill, F. Puertas, Rheology and setting of alkali-activated slag
pastes and mortars: effect of organic admixture, ACI Mater. J. 105 (2008).
[8] M. Palacios, Y.F. Houst, P. Bowen, F. Puertas, Adsorption of superplasticizer
admixtures on alkali-activated slag pastes, Cem. Concr. Res. 39 (2009) 670–677,
https://doi.org/10.1016/j.cemconres.2009.05.005.
[9] A. Kashani, J.L. Provis, J. Xu, A.R. Kilcullen, G.G. Qiao, J.S.J. van Deventer, Effect
of molecular architecture of polycarboxylate ethers on plasticizing performance in
alkali-activated slag paste, J. Mater. Sci. 49 (2014) 2761–2772, https://doi.org/
10.1007/s10853-013-7979-0.
[10] L. Lei, H.-K. Chan, Investigation into the molecular design and plasticizing
effectiveness of HPEG-based polycarboxylate superplasticizers in alkali-activated
slag, Cem. Concr. Res. 136 (2020), https://doi.org/10.1016/j.
cemconres.2020.106150.
[11] T. Conte, J. Plank, Impact of molecular structure and composition of
polycarboxylate comb polymers on the flow properties of alkali-activated slag,
Cem. Concr. Res. 116 (2019) 95–101, https://doi.org/10.1016/j.
cemconres.2018.11.014.
[12] P.-C. Aïtcin, R.J. Flatt, Science and Technology of Concrete Admixtures, 1st ed.,
2016.
[13] J. Ruwoldt, A critical review of the physicochemical properties of lignosulfonates:
chemical structure and behavior in aqueous solution, at surfaces and interfaces,
Surfaces 3 (2020) 622–648, https://doi.org/10.3390/surfaces3040042.
[14] E. Douglas, J. Brandstetr, A preliminary-study on the alkali activation of ground
granulated blast-furnace slag, Cem. Concr. Res. 20 (1990) 746–756, https://doi.
org/10.1016/0008-8846(90)90008-L.
[15] T. Bakharev, J.G. Sanjayan, Y.B. Cheng, Effect of admixtures on properties of
alkali-activated slag concrete, Cem. Concr. Res. 30 (2000) 1367–1374, https://doi.
org/10.1016/S0008-8846(00)00349-5.
[16] T. Luukkonen, Z. Abdollahnejad, K. Ohenoja, P. Kinnunen, M. Illikainen,
Suitability of commercial superplasticizers for one-part alkali-activated blast-
furnace slag mortar, J. Sustain. Cem.Based Mater. 8 (2019) 244–257, https://doi.
org/10.1080/21650373.2019.1625827.
[17] M. Kovtun, E.P. Kearsley, J. Shekhovtsova, Dry powder alkali-activated slag
cements, Adv. Cem. Res. 27 (2015) 447–456, https://doi.org/10.1680/
adcr.14.00078.
[18] N. Ye, J. Yang, S. Liang, Y. Hu, J. Hu, B. Xiao, Q. Huang, Synthesis and strength
optimization of one-part geopolymer based on red mud, Constr. Build. Mater. 111
(2016) 317–325, https://doi.org/10.1016/j.conbuildmat.2016.02.099.
[19] A.I. Laskar, R. Bhattacharjee, Effect of plasticizer and superplasticizer on rheology
of fly-ash-based geopolyrner concrete, ACI Mater. J. 110 (2013) 513–518. http
s://doi.org/10.14359/51685902.
[20] C. Lu, Z. Zhang, C. Shi, N. Li, D. Jiao, Q. Yuan, Rheology of alkali-activated
materials: a review, Cem. Concr. Compos. 121 (2021), https://doi.org/10.1016/j.
cemconcomp.2021.104061.
[21] X. Dai, S. Aydin, M.Y. Yardimci, K. Lesage, G. de Schutter, Influence of water to
binder ratio on the rheology and structural build-up of alkali-activated Slag/Fly ash
mixtures, Constr. Build. Mater. 264 (2020), https://doi.org/10.1016/j.
conbuildmat.2020.120253.
[22] X. Dai, S. Aydın, M.Y. Yardımcı, K. Lesage, G. De Schutter, Effects of activator
properties and GGBFS/FA ratio on the structural build-up and rheology of AAC,
Cem. Concr. Res. 138 (2020), https://doi.org/10.1016/j.cemconres.2020.106253.
[23] M.F. Alnahhal, T. Kim, A. Hajimohammadi, Distinctive rheological and temporal
viscoelastic behaviour of alkali-activated fly ash/slag pastes: a comparative study
with cement paste, Cem. Concr. Res. 144 (2021), https://doi.org/10.1016/j.
cemconres.2021.106441.
[24] Q. Yuan, X. Lu, K.H. Khayat, D. Feys, C. Shi, Small amplitude oscillatory shear
technique to evaluate structural build-up of cement paste, Mater. Struct. 50 (2016),
https://doi.org/10.1617/s11527-016-0978-2.
[25] T.G. Mezger, Applied rheology: with Joe flow on rheology road, Anton Paar GmbH,
2014.
[26] F.M. León-Martínez, P.F.D.J. Cano-Barrita, L. Lagunez-Rivera, L. Medina-Torres,
Study of nopal mucilage and marine brown algae extract as viscosity-enhancing
admixtures for cement based materials, Constr. Build. Mater. 53 (2014) 190–202,
https://doi.org/10.1016/j.conbuildmat.2013.11.068.
[27] N. Roussel, G. Ovarlez, S. Garrault, C. Brumaud, The origins of thixotropy of fresh
cement pastes, Cem. Concr. Res. 42 (2012) 148–157, https://doi.org/10.1016/j.
cemconres.2011.09.004.
[28] Q. Yuan, D. Zhou, K.H. Khayat, D. Feys, C. Shi, On the measurement of evolution of
structural build-up of cement paste with time by static yield stress test vs. Small
amplitude oscillatory shear test, Cem. Concr. Res. 99 (2017) 183–189, https://doi.
org/10.1016/j.cemconres.2017.05.014.
L. Kalina et al.
[29] A.M. Mostafa, A. Yahia, New approach to assess build-up of cement-based
suspensions, Cem. Concr. Res. 85 (2016) 174–182, https://doi.org/10.1016/j.
cemconres.2016.03.005.
[30] J. Plank, A. Brandl, N.R. Lurnmer, Effect of different anchor groups on adsorption
behavior and effectiveness of poly (N, N-dimethylacrylamide-co-ca 2-acrylamido-
2.7 methylpropanesulfonate) as cement fluid loss additive in presence of acetone-
formaldehyde-sulfite dispersant, J. Appl. Polym. Sci. 106 (2007) 3889–3894,
https://doi.org/10.1002/app.26897.
[31] C. Shi, P.V. Krivenko, D.M. Roy, Alkali-activated Cements and Concretes, Taylor &
Francis, London; New York, 2006.
[32] A. Habbaba, J. Plank, Interaction between polycarboxylate superplasticizers and
amorphous ground granulated blast furnace slag, J. Am. Ceram. Soc. 93 (2010)
2857–2863, https://doi.org/10.1111/j.1551-2916.2010.03755.x.
[33] A. Kashani, J.L. Provis, G.G. Qiao, J.S.J. van Deventer, The interrelationship
between surface chemistry and rheology in alkali activated slag paste, Constr.
Build. Mater. 65 (2014) 583–591, https://doi.org/10.1016/j.
conbuildmat.2014.04.127.
[34] B. Derjaguin, L. Landau, Theory of the stability of strongly charged lyophobic sols
and of the adhesion of strongly charged-particles in solutions of electrolytes, Prog.
Surf. Sci. 43 (1993) 30–59, https://doi.org/10.1016/0079-6816(93)90013-L.
[35] L.H. Torn, A. de Keizer, L.K. Koopal, J. Lyklema, Mixed adsorption of poly
(vinylpyrrolidone) and sodium dodecylbenzenesulfonate on kaolinite, J. Colloid
Interface Sci. 260 (2003) 1–8, https://doi.org/10.1016/S0021-9797(03)00046-8.
[36] X.F. Liu, J.H. Peng, G.F. Wei, C.H. Yang, L.Q. Huang, Adsorption characteristics of
surfactant on slag in alkali activated slag cement system, Adv. Build. Mater.
Sustain. Archit. 174-177 (Pts 1-4) (2012) 1072, https://doi.org/10.4028/www.
scientific.net/AMM.174-177.1072.
[37] Q.P. Ran, P. Somasundaran, C.W. Miao, J.P. Liu, S.S. Wu, J. Shen, Adsorption
mechanism of comb polymer dispersants at the cement/water interface, J. Disper.
Sci. Technol. 31 (2010) 790–798, https://doi.org/10.1080/01932690903333580.
12
Cement and Concrete Research 157 (2022) 106822
[38] J. Plank, B. Sachsenhauser, J. de Reese, Experimental determination of the
thermodynamic parameters affecting the adsorption behaviour and dispersion
effectiveness of PCE superplasticizers, Cem. Concr. Res. 40 (2010) 699–709,
https://doi.org/10.1016/j.cemconres.2009.12.002.
[39] V.M. Roberts, R.T. Knapp, X.B. Li, J.A. Lercher, Selective hydrolysis of diphenyl
ether in supercritical water catalyzed by alkaline carbonates, ChemCatChem 2
(2010) 1407–1410, https://doi.org/10.1002/cctc.201000181.
[40] V.M. Roberts, V. Stein, T. Reiner, A. Lemonidou, X.B. Li, J.A. Lercher, Towards
quantitative catalytic lignin depolymerization, Chem. Eur. J. 17 (2011)
5939–5948, https://doi.org/10.1002/chem.201002438.
[41] J.J. Li, J.Z. Zhang, S.F. Zhang, Q. Gao, J.Z. Li, W. Zhang, Alkali lignin
depolymerization under eco-friendly and cost-effective NaOH/urea aqueous
solution for fast curing bio-based phenolic resin, Ind. Crop. Prod. 120 (2018)
25–33, https://doi.org/10.1016/j.indcrop.2018.04.027.
[42] S.B. Johnson, G.V. Franks, P.J. Scales, D. Boger, T.W. Healy, Surface
chemistry–rheology relationships in concentrated mineral suspensions, Int. J.
Miner. Process. 58 (2000) 267–304, https://doi.org/10.1016/S0301-7516(99)
00041-1.
[43] R.J. Flatt, Dispersion forces in cement suspensions, Cem. Concr. Res. 34 (2004)
399–408, https://doi.org/10.1016/j.cemconres.2003.08.019.
[44] L. Ferrari, J. Kaufmann, F. Winnefeld, J. Plank, Interaction of cement model
systems with superplasticizers investigated by atomic force microscopy, zeta
potential, and adsorption measurements, J. Colloid Interface Sci. 347 (2010)
15–24, https://doi.org/10.1016/j.jcis.2010.03.005.
[45] J.L. Provis, P. Duxson, G.C. Lukey, F. Separovic, W.M. Kriven, J.S.J. van Deventer,
Modeling speciation in highly concentrated alkaline silicate solutions, Ind. Eng.
Chem. Res. 44 (2005) 8899–8908, https://doi.org/10.1021/ie050700i.
[46] D. Marchon, U. Sulser, A. Eberhardt, R.J. Flatt, Molecular design of comb-shaped
polycarboxylate dispersants for environmentally friendly concrete, Soft Matter 9
(2013), https://doi.org/10.1039/c3sm51030a.