Cement and Concrete Composites 124 (2021) 104224

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Cement and Concrete Composites

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

Rheological properties of cement-based materials using a biopolymer

viscosity modifying admixture (BVMA) under different
dispersion conditions
Nicolás Ortiz-Álvarez a, Juan Lizarazo-Marriaga a, *, Pedro F.B. Brandão b,
Yesmith Santos-Panqueva b, Julian Carrillo c
a
Departamento de Ingeniería Civil y Agrícola, Facultad de Ingeniería, Universidad Nacional de Colombia - Sede Bogotá, Colombia
b
Departamento de Química, Facultad de Ciencias, Universidad Nacional de Colombia - Sede Bogotá, Colombia
c
Departamento de Ingeniería Civil, Universidad Militar Nueva Granada, Colombia

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

Keywords: Nowadays, concrete industry uses viscosity-modifying admixtures (VMA) for the production and placement of
Cement paste special construction applications such as underwater or self-consolidating concrete. VMAs can decrease the
Viscosity-modifying admixture movement of water and fines, and maintain the underwater concrete’s homogeneity. Self-consolidating concrete
Biopolymer
requires high stability since the material shows a high slump-flow, but high viscosity is also required to avoid
Rheological properties
aggregate segregation. Currently, the use of both superplasticizer admixtures (SP) and VMAs is very common, as
Mechanical properties
Rheology they improve the stability of special cement-based materials. The combined influence of a biopolymer admixture
(BVMA) and a commercial SP under different dispersion conditions on the rheological properties of cement
pastes was analyzed. Results showed a delayed hydration of cement compounds when incorporating both SP and
BVMA into the mixture; however, SP contents controlled the hydration rate, the setting times, and the specific
heat. Although mechanical strength tests showed that an increase in SP dosages caused a decrease in this
parameter, higher compressive-strength values were achieved with BVMA incorporation. Results also showed
that BVMA increased cement pastes’ viscosity; however, this effect is adequately compensated by the dispersion
properties of the SP employed. The rheological parameters of the cement pastes analyzed were obtained by using
the Herschel-Bulkley’s model. Hence, it was concluded that the BVMA used in this study has a very interesting
potential to be used as a viscosity modifier when it is properly dispersed using superplasticizers.

1. Introduction the material’s homogeneity. Since greater stability is desirable in

Today, concrete is the most common building material in the world,
and it is composed of four basic ingredients: cement, water, aggregates
and admixtures [1]. Chemical admixtures have been developed to
improve cement properties in the fresh and hardened state by making
the material more fluid using low water to cement (w/c) ratios, and
accelerating or decelerating cement hydration. These admixtures could
increase concrete’s viscosity in terms of both, the amount added and
their interaction with concrete’s raw materials [2]. Nowadays, the
concrete industry uses viscosity-modifying admixtures (VMA’s) for the
production and placement of special construction applications such as
underwater or self-consolidating concrete. In underwater concrete,
VMAs can decrease the movement of water and fines, as well as maintain
self-consolidating concrete (SCC) because the material shows a high
slump-flow (low yield stress), a minimum viscosity is also required to
avoid aggregate segregation [3]. Currently, the combined use of
superplasticizing admixtures (SP) and VMAs is very common, since it
improves the fluidity and stability of cement-based specialty materials.
VMAs generally bear polysaccharides as their active ingredient; how­
ever, synthetic starches or polymers are also suitable for controlling the
SCC’s viscosity [4,5]. Both admixtures trigger complementary effects
and produce positive effects in fresh concrete.
Most of the chemical admixtures used in concrete are industrialized
by chemical synthesis and contain some petroleum-derived products
involving high economic costs and environmental impacts. Therefore, in
recent years, admixtures obtained from natural products such as

* Corresponding author.
E-mail address: jmlizarazom@unal.edu.co (J. Lizarazo-Marriaga).

https://doi.org/10.1016/j.cemconcomp.2021.104224
Received 4 October 2020; Received in revised form 4 August 2021; Accepted 17 August 2021
Available online 20 August 2021
0958-9465/© 2021 Elsevier Ltd. All rights reserved.
N. Ortiz-Álvarez et al.
Table 1
Chemical composition of the hydraulic cement used.
Component CaO SiO2 Al2O3
% 67.18 18.84 3.31
alternative biomaterials have been incorporated to a large extent with
the purpose of maintaining the construction industry sustainability.
Biopolymers that have been developed for the concrete industry, in
addition to being economical and environmentally sustainable, can
modify several concrete’s properties. These include polymers from
agricultural resources (polysaccharides, cellulose, starch, chitin, chito­
san, and alginates), from microorganisms by fermentation (poly­
hydroxyalkanoates, such as polyhydroxybutyrate), and from
conventional synthesis biotechnology (polylactides (PLA), poly­
butadiene succinate, biopolyethylene, polytrimethylene terephthalate,
poly-p-phenylene) [6,7].
Some water-soluble polymers have been used to improve stability,
cement-based systems cohesion and the ability to retain suspended
components. These high molecular weight and water-soluble organic
polymers modify viscosity, improving deformability and preventing
mixture segregation when used with superplasticizers [2]. The most
used ones are biopolymers such as microbial polysaccharides (diutan
gum, welan gum, and xanthan gum), microbial polysaccharides pro­
duced by aerobic fermentation, or starch sources, cellulose derivatives
such as hydropropyl methylcellulose and chitosan [8–13].
In 2018, Schmidt et al. [14] assessed the potential of plant-based
chemical admixtures on the performance of cementitious materials.
They studied Acacia gum and cassava starch as stabilizing agents and
plasticizers, and Triumfetta pendrata A.Rich gum as a thixotropic agent.
These authors concluded that these plant-based materials could poten­
tially be used as environmentally friendly chemical admixtures. They
reported a fluidity increase due to an increase in Acacia gum content,
while cassava starch showed limited effect on plastic viscosity, but
modified the yield stress; Triumfetta pendrata A.Rich gum showed an
extremely cohesive consistency. In 2006, Sonebi [15] studied the
rheological behavior of grouts containing diutam gum and welan gum
acting as VMAs. Results showed that increasing the dosage of both VMAs
for a given SP dosage, increases the yield value, the plastic and apparent
viscosity, and reduces fluidity. At low shear rates, both VMAs showed
high apparent viscosity values, which was attributed to the entangle­
ment and intertwining of VMA polymer chains at low shear rates, and
the association of water between adjacent chains.
In 2010, Patural et al. [16] evaluated the water-retention capacity of
different cellulose ethers (CE) (water-soluble polymers derived from
cellulose) in mortars by using the standard DIN method. They reported
that cellulose ethers improved water retention up to 92.3% for
hydroxyethyl cellulose (HEC) H1, and up to 99.5% for hydroxyethyl
methyl cellulose (HEMC) C6 with respect to the water-retention capacity
obtained from unmixed mortars (60.2%). In 2013, Gómez et al. [17]
studied interactions between microcrystalline cellulose particles (MCC),
cement hydration products and water. These authors analyzed how
those interactions modify rheology, hydration reaction and hydration
degree. They also evaluated the possibility of using MCC to develop new
based composites. Results showed that adding MCC causes workability
to decrease due to the water-retention and hydrophilic capacity. MCC
also delayed the hydration reaction and decreased the maximum adia­
batic temperature by interacting with hydration products, cement par­
ticles and water, which in turn promoted the formation of a waterproof
barrier on the anhydrous cement particles.
According to the aforementioned, this paper shows and discusses the
results of a research aimed at assessing the potential effect of a novel
biopolymer used as a viscosity modifying admixture (BVMA) on cement-
based materials under different flow conditions. The BVMA used in this
work is a water-soluble biopolymer developed by the Universidad
Nacional de Colombia’s Biotechnology Institute (IBUN). This
2
Cement and Concrete Composites 124 (2021) 104224
Fe2O3 SO3 MgO K2 O Na2O
3.88 4.10 1.74 0.322 0.147
biopolymer is a natural-origin fiber derived from sucrose obtained
through a biotechnological process [18]. Due to its physicochemical and
rheological properties, it can be used as an emulsifier, stabilizer,
encapsulant, and viscous and gelling agent. These characteristics turn it
into a promising biopolymer for the food, pharmaceutical and chemical
industries, among others.
Several dispersion conditions were controlled in this study to assess
the rheology and strength of paste and mortar mixtures by using a
commercial polycarboxylate SP admixture in combination with the
BVMA. Engineering properties were examined through standardized
testing for assessing the effect produced by the BVMA on the compres­
sive strength, the slump, the initial and final setting times, the specific
heat generated during the first 24 hydration hours and the rheological
parameters such as yield stress, consistency index and flow index, by
means of the Herschel-Bulkley rheological model. The rheological pa­
rameters analyzed through this paper aim at explaining, from a physical
point of view, the molecular agglomerations caused by the BVMA
admixture and how dispersion conditions interfere with those agglom­
erations. The above will define the polymer’s technical feasibility for
future industrial applications in concrete and cement technology.
2. Experimental research
Twenty mixtures bearing different dosages of SP and BVMA were
analyzed to assess the effect of a biotechnological viscosity-modifying
admixture under different dispersion conditions on the rheological
and mechanical properties of mortars and hydraulic-cement pastes. A
standard mixture (MP) containing 0% BVMA and 0% SP was assessed
along with 19 other different mixtures that were varied in terms of
cement weight percentage. Fresh and hardened tests were carried out to
analyze the rheological and mechanical behavior of these combined
admixtures. Cement pastes were used for early fresh properties such as
setting times, calorimetry, mini-slump and rheology, while mortars were
used for compressive strength and flowability. Throughout all tests, the
temperature and RH of the laboratory environment were maintained at
20 ± 3 ◦ C and 60 ± 5%, respectively.
2.1. Materials
The materials used in this study were ASTM C1157 general-purpose
hydraulic cement [19] in both, pastes and mortars, a commercial
superplasticizer (SP) as a dispersing agent, and a biotechnological-origin
polymer with potential properties as a BVMA. The chemical composition
of the cement used is shown in Table 1. A high range water reducer,
chloride-free polycarboxylate-based superplasticizer was used as a
dispersing agent. The biotechnological biopolymer was used to prepare
a BVMA admixture. This is a dextran-type biopolymer obtained from the
bifidobacterium Leuconostoc mesenteroides strain IBUN 91.2.98, a
microorganism categorized as GRAS (generally recognized as safe). In
the biotechnology production, an enzyme complex and bioseparation
processes are used to obtain a quality product [18]. It is formed by
monomeric glucose units linked mainly by α(1 → 6). The average mo­
lecular weight reported by the manufacturer is 850 kDa. The biopolymer
is water soluble, forming homogenous hydrogel-like dispersions and
homogenous solutions in concentrations (weight/volume) up to 20%. Its
water absorption ranges from 6% to 15%, showing a slightly hygro­
scopic behavior. It is stable over a wide range of pH (2–10) and tem­
perature (10–50 ◦ C). It is compatible with and has good stability in the
presence of monovalent and divalent salts at different concentrations,
maintaining its rheological properties, thus favoring different industrial
N. Ortiz-Álvarez et al. Cement and Concrete Composites 124 (2021) 104224

Table 2 diameter of 19.0 mm. This method was used to record the rheological
Experimental design of mortar and cement-paste mixtures. effect of the admixtures on pastes in a ‘quasi-static’ condition.
BVMA Vicat needles were used to determine the hydraulic-cement setting
times under the influence of SP and BVMA following ASTM C191 [25]
0.0% 1.0% 4.0% 8.0% 12.0%
requirements. For this purpose, a total of 10 cement paste samples were
SP 0.0% MP M4 M8 M12 M16 prepared using the following percentage pairs: 0.0% and 0.3% SP, and
0.3% M1 M5 M9 M13 M17
0.6% M2 M6 M10 M14 M18
0.0%, 1.0%, 4.0%, 8.0% and 12.0% BVMA. The initial (fi) and final (ff)
0.8% M3 M7 M11 M15 M19 setting times were obtained according to ASTM C191. Additionally, for
all mixtures in Table 1, the early heat evolution was used to examine the
effect of both admixtures on the hydration reactions of cement pastes.
applications. The evolution of the initial temperature development of the fresh paste
In order to ensure a uniform mixing of the biopolymer throughout samples was monitored to quantify the heat profile during the first 24 h
the cementitious matrix, the BVMA admixture was prepared as a solu­ after mixing. The heat throughout the hydraulic-cement paste hydration
tion using 5 g/L of the biopolymer in distilled water. Then, the ready-to- process was obtained using a semi-adiabatic calorimetric system [26],
use BVMA liquid admixture was added to the paste and mortar mixtures adapted from the British Standard BS EN 196–9:2003 [27].
at different ratios. Table 2 shows the experimental design for the mortar To assess the experimental rheological properties of cement pastes
and cement-paste mixtures used through this research. The BVMA and under the influence of the two admixtures (SP and BVMA), the Herschel-
SP admixtures were varied in 5 and 4 dosages respectively, where the Bulkley rheological model [28] was used to describe their behavior,
mass of each was obtained by cement weight. fitting the experimental data to the functional form of Equation (1).
Mechanical properties were assessed by mortar mixtures, which
were cast using a 0.5 water to cementitious material ratio and a 2.75 τ = τ0 + K × (γ̇n ) Eq. 1
sand to cementitious material ratio. The sand used met ASTM C778 [20]
requirements. The mixing was carried out according to ASTM C305 where, τ is the shear stress in Pa, τ0 is the yield stress or initial shear
[21]. Cement paste mixtures were cast using a 0.35 water to cementi­ stress in Pa, Κ is the consistency index in Pa⋅sn , γ̇ is the rheometer shear
tious material ratio to assess cement paste flow, calorimetry, and speed in 1/s and n is the flow index. This model was adopted in this
rheology properties; whereas for setting times, a 0.28 water to cemen­ study because other researchers [29] have concluded that the
titious material ratio was used. Tap water with a controlled temperature Herschel-Bulkley equation represents well the fresh concrete flow,
of 22 ◦ C ± 2 ◦ C was used. The dosages of the two admixtures (BVMA and avoiding the drawback of the negative yield stress obtained when using
SP) were chosen in order to obtain a wide flow range, where lower and the Bingham model to fit the experimental data [30].
upper limits represent several flow conditions, ranging from agglomer­ A Haake Viscotester-reference viscometer was used to obtain rheo­
ated to highly dispersed mixtures. logical curves in controlled rate (CR) mode. A four-phase rheological
protocol was stablished to obtain representative data, according to the
rheological changes caused by the admixtures used (Fig. 1). A pre-shear
2.2. Testing methods stress was first produced for 60 s at 180 s− 1 (first phase). Then, the
mixture was allowed to stand for 60 s (second phase). Upon completion
The influence of the dosages of both admixtures (BVMA and SP) on of these two phases, the shear rate was increased from 0 s− 1 to 180 s− 1
the compressive strength was examined since it is one of the most over a period of 180 s (third phase), followed by a decrease in the
relevant material properties. Three mortar samples from each of the rotation speed from 180 s− 1 to 0 s− 1 in 180 s (fourth phase). The protocol
mixtures were tested using ASTM C109 [22]. For cube casting, the molds used was designed in this way based on reported experiments [28,31],
were filled with paste in three layers and compacted to remove air. After preliminary tests carried out in the study, and the analysis summarized
demolding, the specimens were stored in containers with lime water. below.
Additionally, the relative flow behavior of mortar mixtures was The data obtained from the fourth phase in Fig. 1 (downward-curve
measured using the flow table per ASTM C1437 standard [23]. of shear rate vs. shear stress), corresponding to the discharge phase,
To measure the hydraulic-cement paste flow, the mini-slump test was were considered for the rheological analysis of each sample. In the third
carried out by the mini-cone [24] on a total of 20 cement paste mixtures, phase, as there is a gradual increase in the shear rate from rest, the
taking into account the admixture combinations shown in Table 2. The materials’ molecules show an irregular rheological behavior, undergo­
mini-cone used was a non-absorbent stainless steel truncated cone with ing a gradual rupture with a tendency to segregation. In contrast, as
a height of 57.2 mm, a bottom diameter of 38.1 mm and an upper there is a gradual decrease in the shear rate during the fourth phase,

Fig. 1. Shear protocol for rheological measurement.

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N. Ortiz-Álvarez et al. Cement and Concrete Composites 124 (2021) 104224

approaching rest.

3. Experimental results and discussion

3.1. Fluidity and heat testing

The flow values shown in Table 3 were obtained prior to casting the
mortar strength cubes, using the flow table set forth in ASTM C1437. It is
noted from the table that no flow could be obtained for samples M1, M2,
M3, M6, M7, M10 and M11, since the mixtures exceeded the table
diameter: 255.0 mm ± 2.5 mm according to the ASTM C230 [32]. In the
case of mixtures with lower BVMA content, their higher flowability was
attributed to the high molecular dispersion related to the steric and
electrostatic repulsion among cement particles that reacted with the SP,
which led to particle deflocculation [10]. Flowability was decreased
with BVMA incorporation due to a viscosity increase resulting from the
BVMA high water-retention capacity [10].
By measuring the diameter of the final extension of the mini-slump
according to the methodology described above, a clear direct
Fig. 2. Rheogram fitted to the Herschel-Bulkley rheological model for the
reference cement paste mixture.

Table 3
Cement paste mixtures flow, in mm.
BVMA

0.0% 1.0% 4.0% 8.0% 12.0%

SP 0.0% 180.0 174.8 171.0 167.2 165.0

0.3% – 250.1 231.8 214.3 209.5
0.6% – – – 241.1 235.0
0.8% – – – 249.2 238.6

starting from the rupture of the material with a tendency to agglomer­

ation at rest, the experimentally described rheological behavior is uni­
form [31]. Fig. 2 shows the standard reference mixture’s rheogram for
the third and fourth steps, being the upward curve much more dispersed
than the downward curve (step 4), which shows more uniform and
stable data. This is in accordance with the CR mode used for the mea­
surement, where the rheological properties are determined from a
condition in which the flow is dispersed due to a pre-shear given by steps
1, 2 and 3, and which tends to agglomerate during the fourth stage, Fig. 4. Variation of Vicat needle penetration.

Fig. 3. Variation of the mini-slump diameter.

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N. Ortiz-Álvarez et al. Cement and Concrete Composites 124 (2021) 104224

Table 4 thus providing greater fluidity to the cement paste [36]. These com­
Vicat initial and final setting times. plementary behaviors could be used to avoid segregation at specific
BVMA dosages, thus ensuring fluidity and stability.
Fig. 4 and Table 4 show the behavior of the initial and final setting
0.0% 1.0% 4.0% 8.0% 12.0%
times, which indicate the loss of workability and the beginning of the
fi (min) SP 0.0% 138 138 150 142 133 stiffening of a paste sample. They were measured through Vicat needles
0.3% 220 235 240 227 238
ff (min) SP 0.0% 175 300 330 340 440
using the established dosages for both admixtures together, showing
0.3% 445 480 500 550 670 that needle penetration is mainly controlled by the SP. Comparing the
setting times of the reference mixture with respect to the SP and VBMA
mixtures, it is shown that both admixtures retarded cement hydration;
relationship with the addition of both admixtures is evident as is shown however, the intensity of delay was mainly a function of the SP dosage.
in Fig. 3. Although the BVMA causes a decrease in the fluidity of the Although the viscosity modifying admixture could delay the hydration
mixtures, a stability increase is also achieved. This is believed to occur of tricalcium silicate (C₃S) and tricalcium aluminate (C₃A) [37], an in­
because the water-soluble polymeric chains of this admixture absorb crease in the VBMA content resulted in a slight effect on the initial
part of the free water from the hydraulic cement paste, increasing its setting time and a moderate effect on the final setting time. In contrast, a
plastic viscosity [33]. The opposite occurs with the incorporation of SP higher polycarboxylate SP content resulted in much longer setting times.
dosages, where fluidity increased due to a stability reduction and the As reported by Zhang et al. [38], this situation could be attributed to the
elimination of the flocculating structure of the cement particles [34, 35],

Fig. 5. Semi-adiabatic calorimetry curves.

Fig. 6. Variation of peak Temperature.

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Fig. 7. Evolution of accumulated specific heat (a) and variation of accumulated specific heat at 24 h (b).

interaction between Ca2+ ions and the admixture compounds which

Table 5
lower the Ca2+ concentration in the system, hindering the nucleation of
Rheological parameters of cement pastes by applying the Herschel-Bulkley
the solid phase and the growth of hydration products, delaying cement
rheological model.
hydration.
In Fig. 5, the semi-adiabatic calorimetry curves show the represen­ SP BVMA τo (Pa) K(Pa ⋅sn ) n r

tative specific temperature profile of all paste mixtures during the first (a) MP 0.0% 0.0% 27.9 1.8119 0.8642 0.9949
24 h. To make them comparable, it was necessary to normalize the M4 0.0% 1.0% 42.4 1.4798 0.9481 0.9884
temperature increments with respect to the amount of cementitious M8 0.0% 4.0% 73.1 0.7656 1.0266 0.9809
M12 0.0% 8.0% 18.0 13.0569 0.4902 0.9924
material used in each mixture. According to the Portland Cement As­
M16 0.0% 12.0% 41.1 4.5767 0.6916 0.9811
sociation, PCA [39], the amount of heat produced by a cementitious (b) M1 0.3% 0.0% 7.4 0.0634 1.4136 0.9940
material depends mainly on the cement chemical composition, with C₃S M5 0.3% 1.0% 5.2 0.1209 1.3490 0.9957
and C₃A being the most reactive compounds for heat evolution. As stated M9 0.3% 4.0% 14.7 0.1849 1.2477 0.9952
before, although the BVMA produced a slight delay in cement hydration, M13 0.3% 8.0% 29.9 0.2552 1.1699 0.9911
M17 0.3% 12.0% 27.8 0.2109 1.1679 0.9907
the SP controlled the level of delay and the peak temperature reached. (c) M2 0.6% 0.0% 2.3 0.0095 1.6892 0.9934
Usually, some stages are reported during cement hydration [38]: an M6 0.6% 1.0% 3.9 0.0328 1.5031 0.9919
initial wetting peak followed by the induction or dormant period which M10 0.6% 4.0% 6.8 0.0946 1.4170 0.9950
in turn is followed by the acceleration period in which C3S begins to M14 0.6% 8.0% 30.3 0.1671 1.3079 0.9967
M18 0.6% 12.0% 53.8 0.5172 1.0908 0.9956
hydrate and a maximum peak is reached. Initial setting occurs at the
(d) M3 0.8% 0.0% 2.0 0.0055 1.7310 0.9923
beginning of the acceleration period, and the final setting occurs before M7 0.8% 1.0% 1.5 0.0350 1.4828 0.9887
the end of this period. After reaching the maximum peak there is a M11 0.8% 4.0% 6.6 0.0544 1.5211 0.9878
slowdown period controlled by the C3A hydration. Since a M15 0.8% 8.0% 11.5 0.1894 1.3257 0.9966
semi-adiabatic calorimeter was used in this research, the data obtained M19 0.8% 12.0% 20.3 0.6193 1.1843 0.9901

did not include the initial period; however, from a qualitative point of
view, the other three stages can be identified in Fig. 5.
From the semi-adiabatic temperature data shown in Fig. 5, the peak
reached for each sample was extracted and plotted in Fig. 6. For each SP
content, there is a well-defined decreasing trend in which lower tem­
peratures and longer times are obtained as the BVMA increases. For the
highest BVMA dosage used, the peak temperature decreased by
approximately 16% and the time increased by approximately 19% when
compared to mixtures using 0.0% BVMA. For the remaining BVMA
dosages (≤8.0%), these decreases were less noticeable. As mentioned
before, the SP controlled the hydration rate. For example, in samples
using high superplasticizer levels (≥0.6%), the peak temperature was
reduced by approximately 24%, and the time increased by approxi­
mately 100% relative to samples without SP. Small SP dosages (≤3%)
did not significantly affect the peak temperature; however, they delay
the Portland cement hydration process.
The accumulated specific heat reached by each sample during the
first 24 h can be observed in Fig. 7, which shows a decreasing trend for
the total specific heat as the BVMA dosages increased. This is more
noticeable for the 0.6% and 0.8% SP dosages. The heat developed by
high SP content samples (≥0.6%) decreased by about half compared to
samples bearing 0.0% SP, confirming that the effect by superplasticizers
on the hydration heat and setting times is much more intense than that
resulting from BVMAs. This situation is considered positive because
when both admixtures are used simultaneously, there is not a significant
reduction of the cement hydration, different from that produced by the
superplasticizer.
3.2. Rheology
The experimental rheological data were mathematically adjusted
using a statistical commercial software [40], in which non-linear re­
gressions were performed to fit Equation (1). Results obtained are shown
in Table 5 for each of the rheological parameters. The correlation co­
efficient (r) was calculated to evaluate the goodness of fit of the equation
to the experimental data. In all cases, values higher than 0.98 were
obtained, showing an adequate fit to the proposed equation. The
adjusted rheograms obtained are shown in Fig. 8.
Table 5 shows the yield stress (τ₀), which is the intersection of the
flow curve with the consistency index (K) and the flow index (n). When n
takes values lower than 1 (n < 1), the flow behavior is dilatant, and for
values greater than 1 (n > 1), the behavior is thickening. Fig. 8 shows
that, except for the curves obtained for 0.0%, 1.0%, 8.0% and 12.0%

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Fig. 8. Cement paste flow curves: (a) 0.0% SP, (b) 0.3% SP, (c) 0.6% SP and (d) 0.8% SP.

Fig. 9. Yield stress (τ₀): (a) 0.0% SP, (b) 0.3% SP, (c) 0.6% SP and (d) 0.8% SP.

BVMA at 0.0% SP dosage, all the curves show a thickening behavior of
the mixture, in which microstructural changes occur to the point that the
flow resistance increases with the shear rate. This can be verified by the
n values shown in Table 5, where this parameter reached values greater
than 1. This occurs because the particles are subjected to a molecular
breakdown when applying a small disturbance to the mixture structure,
inducing a disordered structure when a shear deformation is applied
[40]. According to Moreno [41], this may also be related to BVMA
polymer chains, where shear stress causes long-chain polymer solutions
to promote molecular crosslinking.
The opposite occurs when incorporating the highest BVMA dosages
(8.0% and 12.0%) to the hydraulic-cement paste mixtures with no
dispersion conditions (0.0% SP), where a dilating behavior can be
noticed (values n < 1). When the BVMA comes into contact with water,
it begins an adsorption process, adhering to the periphery of the water
molecules, imbibing and fixing part of the water in the mixture, thus
increasing the viscosity of the material. In this process, adjacent poly­
meric chains become entangled and intertwined due to attractive forces,
limiting the movement of water molecules thus causing the formation of
a highly viscous gel-like structure. This is because long chains increase

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Fig. 10. Consistency index (k) (a) 0.0% SP, (b) 0.3% SP, (c) 0.6% SP and (d) 0.8% SP.

Fig. 11. Flow index (n): (a) 0.0% SP, (b) 0.3% SP, (c) 0.6% SP and (d) 0.8% SP.

viscosity and promote a shear fluidization process at low shear rates and
at high BVMA dosages (8.0% and 12.0%). However, the increase in
shear rates shows a clearly plastic behavior, in which chains get diluted
and aligned along the flow direction, thus decreasing the viscosity [10,
13,15,42,43].
Figs. 9–11 show the trends of the rheological parameters τ0 , K and n
as a function of both admixtures. Fig. 9 shows that the yield stress was
adjusted using a non-linear quadratic equation for each SP dosage (0.0%
(a), 0.3% (b), 0.6% (c) and 0.8% (d)) as a function of the BVMA content.
In this figure is observed that the yield stress did not show a defined
trend when the material had a limited dispersion (0.0% SP (a)) in which
the correlation coefficient was weak (r = 0.28). However, a very strong
correlation was shown for dispersed mixtures (r > 0.95), in which the
BVMA’s polymer chains absorb some of the free water in the mixture,
thus producing an increase in the stress needed to start flowing. For SP
contents higher than 0.3%, the behavior of the mixtures conforms very
well to the defined function, which allows establishing two facts: (i) the
necessity to disperse the biotechnological viscosity by means of an SP,
and (ii) a very good correlation between the yield stress and the BVMA
content, thus showing a good compatibility between both admixtures
and the cement used.
The consistency index (k) showed a similar behavior (Fig. 10) to that
of the yield stress. It was also adjusted using a no-linear quadratic
equation for each SP dosage. As the BVMA increases, so does the con­
sistency index. The trend is upward and highly correlated (r > 0.98) as
BVMA dosages for dispersed mixtures are increased. According to Li
et al. [33], some of the free water is absorbed by the water-soluble
polymer chains, thus resulting in a further increase in the consistency
index. However, there is an optimum viscosity value around 8.0% BVMA
under medium dispersion conditions (0.3% SP). In the presence of these

8
N. Ortiz-Álvarez et al.
Fig. 12. Compressive strength after a 28-day curing.
dosages, a consistency index peak is reached, followed by a decrease at
higher dosages. This may occur because the BVMA water-soluble poly­
mer chains absorb high rates of water in the mixture, and a high cohe­
sion occurs between the particles, thus generating a molecular
breakdown of the matrix as the shear rates increase. For zero SP dosages,
the viscosity behavior fails to show a defined trend. The behavior of the
mixtures conforms very well to the defined function, which shows the
necessity to use both admixtures to have stable behavior mixtures.
The flow index (n) behavior is shown in Fig. 11. It is contrary to that
of the consistency index, i.e., as the BVMA dosage increases, the flow
index decreases. The figure shows that the flow index tends to decrease
linearly for highly dispersed SP doses (r > 0.92) for 0.6% (c) and 0.8%
(d) SP. At low dispersion conditions, i.e., 0.3% SP, the flow index con­
formed well using a quadratic equation (r > 0.99). It was attributed to
the low dispersion and high agglomeration conditions of the mixture.
This can also be observed in the results obtained with the mini-slump
test in section 3.1, where the dosages of the mixtures M12 (0.0% SP
and 8.0% BVMA) and M16 (0.0% SP and 12.0% BVMA) showed a similar
flow value (38.1 for both cases), that is, a constant flow was maintained
for the highest BVMA dosages. This does not occur for the 0.6% SP (c)
and 0.8% SP (d) dosages. The mixtures showed a maximum flow when
higher dispersion conditions were observed. Experimental data showed
that the low dispersion reference mixture has a moderate correlation
coefficient (r < 0.65) between the flow index and the BVMA content.
Like previous parameters (yield stress and consistency index), the
incorporation of a dispersing agent (SP) along with a binding agent
(VMA) is necessary to achieve a stable molecular interaction. This is
observed in the mixtures bearing SP and BVMA dosages, in which a clear
correlation and interaction was obtained between the cementing mate­
rial and both admixtures used.
3.3. Compressive strength
The compressive strength of each sample was measured and calcu­
lated following the requirements of the ASTM C109 standard. The ob­
tained compressive strength values are shown in Fig. 12. The figure
shows that the lowest compressive strength values are associated to high
9
Cement and Concrete Composites 124 (2021) 104224
SP doses; however, higher compressive strength values are observed
when BVMA dosages are increased. When low SP and BVMA dosages are
used, there is a clear trend to increase the compressive strength of the
mortar samples. As expected, by increasing SP dosages, there is an in­
crease in the molecular dispersion condition, leading to possible
compaction problems, increasing porosity and decreasing compressive
strength. This dispersing effect of the SP is contrasted with the increase
of a binding condition through the addition of BVMA that results in more
stable mixtures, avoiding possible compaction or problems.
4. Conclusions
From the experimental data and the discussion of the results, con­
clusions are summarized below:
• An increase in the BVMA dosages increases the final setting times,
which were obtained by the Vicat needle testing. Similarly, as the SP
dosages were increased, these times were also prolonged, but to a
greater extent. By increasing the BVMA dosages, the maximum
specific heat generated decreases, which results in a lengthening of
reaction times, since hydration of C3 S and C3 A is delayed. The same
occurs with the SP, if the dosage is increased, the maximum specific
heat values are decreased, and the reaction times are longer. The SP
controlled setting times and heat development.
• Considering that the effect by BVMA on the hydration rate is much
lower than that produced by SP, the use of the examined biopolymer
is a promising condition for industrial applications.
• All rheological data were analyzed in a shear rate decrease phase
(fourth phase), in which a previous disturbance (third phase) was
applied. It was conducted using this way because the data distribu­
tion resulted more regular, which allowed obtaining more repre­
sentative rheological data. The Herschel-Bulkley rheological model
used to fit the data describes the rheological behavior of hydraulic-
cement pastes under the influence of a commercial SP and a
biotechnological-origin BVMA, offering this way the possibility to
describe mixtures with dilating or fluidizing behaviors. As for the
0.3%, 0.6% and 0.8% SP dosages, the yield stress behavior (τ0 )
N. Ortiz-Álvarez et al.
increases with BVMA dosages with a well-defined trend, due to an
increase in viscosity that requires a greater stress to start producing
flow in the mixtures.
• The consistency index (k) trend is upward as BVMA dosages increase
for the 0.6% and 0.8% SP dosages, because some of the free water in
the mixture is absorbed by the water-soluble polymer chains,
resulting in a further increase in the consistency index. However, at
low SP dosages (0.3%), the consistency index behavior peaks for a
0.8% BVMA dosage, but decreases for higher BVMA dosages because
of the water-soluble polymeric chains that absorb large amounts of
water in the mixture. BVMAs increases the cohesion among cement
particles.
• The flow index behavior (n) is downward for the highest SP dosages
(0.6% and 0.8%) as the BVMA increases. At low SP dosages (0.3%),
the behavior decreases when increasing BVMA, but it remains con­
stant beyond 8.0% BVMA dosages. This is due to the high agglom­
eration condition present, which also needs a high dispersion
condition by adding a superplasticizer that causes molecular repul­
sion and flow in the mixture.
• The behavior of the rheological parameters for all SP-free BVMA
mixtures is not fully understood. A no defined trend is a condition
attributed to the fact that SP is required to disperse the biotechno­
logical viscosity-modifying agent. This shows the necessity to
combine the effects of both admixtures to obtain a flowable and
stable mix. The biopolymer-based viscosity-modifying admixture
demonstrated the potential to provide stable mixtures, improving the
cohesion of the cement-based system and contributing to ensure the
high performance of highly flowable, yet cohesive, cement pastes.
• A decreasing trend in the compressive strength was observed for high
SP doses. However, with BVMA incorporation, higher compressive
strength values were achieved giving way to stable mixtures. This is
believed to be due to the BVMA binding effect, which could improve
compaction, avoid segregation problems, and decrease the mixture
porosity.
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
• We thank Professor Gustavo Buitrago from the Instituto de Bio­
tecnología, Universidad Nacional de Colombia (IBUN), for giving us
access to the biopolymer.
• We thank Dirección de Investigación y Extensión de la sede Bogotá
(DIEB), Universidad Nacional de Colombia, for financial support
through grant No. 41833.
• We thank Ministerio de Ciencia, Tecnología e Innovación (Min­
ciencias) for financial support through grant No. 120480863795, CT-
190-2019.
• Julian Carrillo thanks Vicerrectoría de Investigaciones, Uni­
versidad Militar Nueva Granada, for providing research grants.
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