Cement and Concrete Research 67 (2015) 5265

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Cement and Concrete Research

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Effect of superabsorbent polymers (SAPs) on rheological properties of

fresh cement-based mortars Development of yield stress and plastic
viscosity over time
Viktor Mechtcherine , Egor Secrieru, Christof Schr
Technische Universitt Dresden, Institute of Construction Materials, Dresden, Germany

a r t i c l e

i n f o

Article history:
Received 7 October 2013
Accepted 9 July 2014
Available online xxxx
Keywords:
Fresh concrete (A)
Rheology (B)
Admixture (D)
Polymer (D)
Mortar (E)

a b s t r a c t
Superabsorbent polymers (SAPs) are a new, promising, multipurpose chemical admixture for concrete. This article
addresses the rheological behaviour of fresh, cement-based mortars modied with SAP. Two types of SAP with differing water absorption and desorption kinetics were used. Additionally, for one the grading was varied. Three reference mortars were investigated. The rheological properties of these fresh mortars were tested for 90 min by
continuous ow rheometry. It was found that the distinct kinetics of water uptake inherent in the SAP samples,
as governed by their particular chemical structures, is the major factor that governs the rheological properties of
fresh mortar. Furthermore, the grading of SAP distinctly affects the development of yield stress and plastic viscosity
over time. The particular effects of specic SAP addition on the rheological characteristics of a mortar depend on the
water-to-binder ratio, the dosage of superplasticizer, and the dosage of silica fume, if present.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
In recent decades great advances in concrete technology have been
made, to a large extent due to the development and use of new chemical
additives. These additives such as, e.g., superplasticizers, although
added to concrete in very small quantities, can dramatically improve
crucial characteristics of concrete in its fresh and/or hardened state
[13].
One of the key considerations in concrete technology is gaining control over the water therein. The introduction of superabsorbent polymers
(SAPs) as a new component for the production of concrete materials
makes available a number of new possibilities with respect to water control. As a result, the rheological properties of fresh concrete are governed
due to the purposeful water absorption and/or water release in either
fresh or hardened concrete [4]. The well controlled uptake and release
of water can be fostered by the specic design of SAP materials adapted
to particular practical needs. As examples of this, the internal curing of
high-performance concrete [5,6] and the inducing of abrupt changes in
rheological behaviour during shotcreting [7] might be named here, but
the potential for innovation is far wider [8].
Another persistent problem in modern concrete technology relates
to the creation in concrete of advantageous pore systems which could
improve concrete durability, especially in terms of freezethaw resistance. Contemporarily, air-entrainment agents are widely used in

Corresponding author.
E-mail address: mechtcherine@tu-dresden.de (V. Mechtcherine).

http://dx.doi.org/10.1016/j.cemconres.2014.07.003
0008-8846/ 2014 Elsevier Ltd. All rights reserved.

achieving high resistance to freezethaw cycles, with and without deicing salts, respectively. However, the entrained air voids are frequently
not sufciently stable to tolerate transport, compacting, or in some instances specic methods of application such as spraying. In contrast,
pore system built-up as a result of SAP addition seems to remain stable
regardless of concrete consistency, presence of superplasticizer or of the
method of placement and compacting. A considerable improvement of
freezethaw resistance due to the addition of SAP has been demonstrated by various researchers [7,9,10]. Also, a number of further applications
have been proposed, some as vague ideas as well as some supported by
recent studies [8].
To use the new additive effectively in concrete technology a profound knowledge of its effect on concrete or mortar rheological properties in fresh state is required since these properties directly inuence
the ease of pumping, placement, and compactibility. Therefore, the rheological properties are decisive for the choice of equipment and techniques for concreting as well as for the place and quality of the
production, the last one affecting properties of concrete in hardened
state like durability and mechanical performance [11,12].
At present only few results are available in the literature regarding
the inuence of SAP on concrete rheology [1315]. It was reported
that addition of a certain type of SAP relative to cement mass is equivalent to removing water from the system [16]. If extra water is not added
to compensate this tendency, an increase in the yield stress and in
the plastic viscosity of the cementitious system will be observed if a rheometer is used to measure the rheological properties [17]. When empirical methods are used, a decrease in the slump ow spreading [15] and
an increase in ow time occur [14,17]. Further, published results also

V. Mechtcherine et al. / Cement and Concrete Research 67 (2015) 5265

indicate that concretes with SAP may have an increased air content [10,
13].
The article at hand presents the results of a systematic study on the effects of SAP on rheological behaviour of cement-based mortars in fresh
state. Two types of SAP having different water absorption and desorption
kinetics were used, while for one of them additionally the neness of
grading was varied. Corresponding three reference mortar mixtures varied in water-to-binder ratio, amount of superplasticizer and presence of
silica fume. The inuence of the parameter variations on the rheological
properties of fresh mortars was studied for 90 min after mixing. The
ow behaviour of mortars was approximated to that of Bingham uids,
characterised by yield stress 0 and plastic viscosity . All mixes were tested by continuous ow rheometry using a universal rheometer with a
measuring cell designed specically for cement paste and mortar. Additionally, the slump ow test was used in order to establish a link to the
common empirical testing procedure. When adding SAP some extra
water was provided to most of the tested mixtures in order to compensate the prominent loss of their owability. The main focus of the present
study was to elucidate the combined effects of SAP and extra water on the
development of individual rheological properties in time.

53

2. Materials and experimental methods

2.1. Superabsorbent polymers
Superabsorbent polymers are synthetic materials which were rst developed in the 1980s. Since then they have been used primarily in sanitary and convenience products [18,19]. However, the number and
volume of applications in technical elds have been steadily increasing
up to date. SAP have a unique ability to absorb, retain and, depending
on changes in their environment, release a signicant amount of water
or aqueous solution [16,20].
From the point of view of the sciences of polymer chemistry and colloidal physics, the SAPs do not dissolve in the classical way. Of course, the
hydrophilic trunk chains of SAPs surround themselves with solvent
(water) molecules and bind them. However, the trunk chains are interconnected by stable chemical bonds oriented in arbitrary directions.
Thus, they cannot move freely in the liquid phase; thin particularey can
only move apart to a restricted extent. The consequence is not dissolution
of the bulk into single polymer chains but an intense swelling (volumetric
expansion) and retention of water molecules inside a so-called hydrogel.

a)

b)

c)

d)
Fig. 1. ESEM images of a) SAP-B, b) SAP-DS, c) SAP-DC and d) SAP-DN.

54

V. Mechtcherine et al. / Cement and Concrete Research 67 (2015) 5265

This is essentially different to the behaviour of water retaining

agents or viscosity modifying agents which are commonly used in
construction materials. These polymers, which are based on,
e.g., modied cellulose or starch ethers or welan gum usually have
no three-dimensional interconnections and can dissolve in the form
of individual (but rather large polymeric) molecules.
That being said, the authors think that microstructural and colloidal
physical/chemical aspects which are of essential importance in describing,
among other phenomena, the working mechanisms of superplasticizers
or organic retarders, are of minor importance when discussing the
efciency and working mechanisms of SAPs on a molecular-scale in
cement-based construction materials. What is most important are the
water migration kinetics into the SAPs and, in the course of time, its
backing out into the cement-based suspension (cement-based matrix).
In the present study two chemically distinctly different SAP samples
were used (as provided by SNF Floerger, Andrzieux Cedex/France).
These materials have already been used in publications [15] and [21]
and their nomenclatures accord to those in the previous studies:
SAP-B;
SAP-D; in the present study in three individual gradings: DS (very
ne), DC (ne) and DN (coarse; this grading corresponds to that
used in [15] and [21]).
SAP-B has acrylic acid as the sole primary monomer in the trunk
chains; it has thus the highest possible density of carboxylic groups
along the backbones. The cross-linking density is qualitatively rather
high. SAP-D was synthesised from two primary monomers acrylic acid
and acrylamide. Thus, the density of free carboxylic groups along the
backbones is diminished by uncharged hydrophilic amide functionalities. The cross-linking density of SAP D is intermediate and, in particular
it is lower than that of SAP-B. Fig. 1 shows ESEM pictures and Fig. 2b represents the particle size distributions of the SAP samples in the dry state.
The main reason for choosing these two kinds of SAP was their distinctly different kinetics of absorption and desorption behaviour in extracted cement pore solution, cf. [15]. Fig. 2a demonstrates on hand
the results of the teabag test (standard test for determining the absorption capacity of SAP [15,19]). The teabag method was conducted
as follows. A cement pore solution was obtained from a suspension of
ordinary Portland cement used for mortar preparation (cf. Section 2.2)
at w/c = 4.3 after 24 h of immersion. It had a pH value of 13 and an electrical conductivity of 880 S/cm. Masses of 0.2 to 0.3 g of SAP (exact
mass m1) were put in a teabag (mass m2) which had been pre-wetted
in the cement pore solution. The teabag containing SAP was then
hung in a beaker lled with the cement pore solution. The beaker was
carefully and tightly covered with a plastic foil to avoid carbonation;
the foil was released only for short time intervals to conduct the necessary weighing. After 30 s, 2, 5, 10, 15, 30, 60 and 180 min, the teabag
with the SAP was weighed (mass m3). It was rst put on a dry cloth
and wiped with another dry cloth for a short time of approximately
30 s to remove surplus and weakly bound liquid. Some liquid held as
capillary water between SAP particles could have left the sample. However, the sample was not squeezed so as not to disturb the storage function of the polymers. Some residual surface or capillary water may have
remained in the teabags, but this was considered to be irrelevant to the
present study. The amount of absorbed liquid in relation to the initial
mass of SAP was calculated according to Eq. (1).
mH2 O

m3 m2 m1
m1

All SAP samples intensely absorb a large quantity of the ionic solution at rst instance. Starting approximately 10 min after immerging
SAP in the solution, SAP-B releases continuously the majority of the
stored liquid by itself. On the other hand, none of the SAP-D desorbs
any substantial portion within the rst 90 min. Corresponding absorptiondesorption behaviours of the four SAP samples were expected

also in fresh mortar. It should be assumed that the fundamentally differing kinetics of SAB-B and the SAP-Ds will distinctly affect the rheological
characteristics of the mortars.
Fig. 2a shows the particle size distributions of the SAP samples
in the dry state. SAP-DN has the largest particle sizes, followed by
SAP-B, SAP-DC and SAP-DS. It should be highlighted here that the
cement pore solution is taken in by ne particles more rapidly, see
Fig. 2b,c. This is in agreement with [14,20,22] and can be traced back
to larger absorption surface and consequently a faster achievement of
the volumetric equilibrium.
The reasons underlying the SAPs' individual sorption characteristics
and, specically, their ability to absorb water are as follows: The absorption kinetics of SAPs, the absorbable amount of liquid and the stability of
the swollen product, the so-called hydrogel, depend on the molecular
composition and grading of SAPs as well as on the ions dissolved in
water. SAPs bind water molecules intensely to their polymer chains
due to their hydrophilicity. However, chemically stable cross-links
built among the primary trunk chains prevent these primary chains
from dissolving by forming a three-dimensional network. Eq. (2) describes the thermodynamic equilibrium state with respect to liquid intake and swelling of the SAP to form a hydrogel [23]:
mix elastic ion bath 0:

Polymer/solvent interactions raise the osmotic pressure (mix)

which acts expansively because solvent (water) molecules surround
each solvophilic (hydrophilic) polymer chain. The chains cannot move
freely because they are interconnected by chemical bonds. As a result,
the counteracting elastic force (elastic) rises and limits the expansion.
Anionic groups situated along the chains (here: carboxylic groups from
the acrylic acid monomer) deprotonate in an alkaline solution such as
cement pore solution. The likewise charged groups repel each other,
and the expansive pressure (ion) builds up. Counter ions then become mobile, but since the hydrogel has to remain electronically neutral
they cannot leave without replacement. If exterior cations are present
and the overall ionic strength is high, which is the case in cement pore
solution, they will penetrate the hydrogel and set free its initial cations.
This results in polyelectrolyte shielding (bath) which reduces the osmotic pressure and can be so intense as to cause contraction [23].
In the cement pore solution not only monovalent cations (e.g., Na+,
K+) but also bivalent Ca2+ ions are present. Ca2+ can bind with the carboxylic groups of the SAP chains and form stable complexes [24]. In SAP
B, which has the highest portion of carboxylic groups incorporated into
its backbone chains, this activity increases (bath) greatly. When the cement pore solution intrudes into the SAP from outside, Ca2+ enters the
SAP particles as well. Over time the extent of complex formation increases
and causes a breakdown in liquid storage capacity. In SAP D, which has
signicantly fewer carboxylic groups than SAP B, (bath) is considerably
weaker. Thus, SAP D is much more retentive than SAP B. However, some
complexation still occurs over the longer term and a minor release of liquid can be detected.
The effect of Ca2+ intrusion reects itself in the different gradings of
SAP D. The small particles of DS and DC are much more quickly infused
with Ca2+ than the clearly larger particles of DN. Thus, the desorption
process initiates and progresses much more rapidly in DS and DC than
in DN. The particles of DN are so large that they require much longer
time for complete swelling than those of DS and DC. And not only
does water take longer time to enter DN in a quantity which can produce equilibrium, but also the extent of partial desorption is clearly
lower in DN than in DS and DC. Most probably, this is the consequence
of a chromatography effect, i.e., the outer regions of the hydrogel bind so
tightly to Ca2+ that the above-mentioned complex formation does not
affect the core region. This effect will be studied in much more depth
in a subsequent, independent manuscript.

V. Mechtcherine et al. / Cement and Concrete Research 67 (2015) 5265

55

10
Differential Volume [%]

B
DS

DC
DN

6
4
2
0
0

500
1000
1500
Particle Diameter [m]

2000

50

50

40

40
Absorption [g/g]

Absorption [g/g]

a)

30
20

30
B

20

DS

10

10

DC
DN

30

60 90 120 150 180

Time [min]

b)

10 15 20
Time [min]

25

30

c)

Fig. 2. a) Particle size distributions of the SAP samples under investigation. b, c) Kinetics of absorption and desorption of the SAP samples in cement pore uid as obtained from the teabag
test during 180 min (b) and in the rst 30 min (c).

Table 1
Compositions and slump ow results of the mortars under investigation (bwoc = by weight of cement).
Gr.

No.

Mortar designation

w/c,
w/b

Aggregates
[kg/m3]

Silica fume
[% bwoc]

Superplasticizer
[% bwoc]

SAP type

SAP dosage
[% bwoc]

Slump
ow 10 mm
[mm]

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18

A_Ref_0.30
A_0.40B_0.35
A_0.20DS_0.35
A_0.20DC_0.35
A_0.20DN_0.35
B_Ref_0.30
B_0.40B_0.35
B_0.40B_0.38
B_0.20DS_0.35
B_0.20DC_0.35
B_0.20DN_0.35
C_Ref_0.45
C_0.40B_0.45
C_0.40B_0.50
C_0.40B_0.53
C_0.20DS_0.50
C_0.20DC_0.50
C_0.20DN_0.50

0.30
0.35
0.35
0.35
0.35
0.30
0.35
0.38
0.35
0.35
0.35
0.45
0.45
0.50
0.53
0.50
0.50
0.50

1300
1300
1300
1300
1300
1300
1300
1300
1300
1300
1300
1300
1300
1300
1300
1300
1300
1300

10
10
10
10
10
10

1.40
1.40
1.40
1.40
1.40
2.00
2.00
2.00
2.00
2.00
2.00
0.50
0.50
0.50
0.50
0.50
0.50
0.50

B
DS
DC
DN

B
B
DS
DC
DN

B
B
B
DS
DC
DN

0.40
0.20
0.20
0.20

0.40
0.40
0.20
0.20
0.20

0.40
0.40
0.40
0.20
0.20
0.20

200
280
190
240
280
200
270
290
190
250
280
200
110
165
280
120
150
170

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V. Mechtcherine et al. / Cement and Concrete Research 67 (2015) 5265

2.2. Mortars
Three different reference mortars were chosen for this study. Mortars designated as A and B had a water-to-binder ratio (w/b) of 0.30
which is typical for high-performance mortars and concretes. In such
mortars SAP are primarily supposed to serve as an internal curing
agent. The particular difference between mortars A and B was the use
of silica fume as a partial replacement cement in group B (10% by weight
of cement, bwoc). Mortar C had a water-to-cement ratio (w/c) of 0.45
and a lower content of superplasticizer than A and B. Its composition
is representative for ordinary concretes and mortars to which SAP is
added to increase their resistance against frostthaw cycles. Based on
the three reference mortars a total of eighteen different mortars, classied in three groups A, B and C according to the corresponding references, were investigated (Table 1). Except SAP the raw materials were
not varied. The following components were used:
Cement CEM I 42.5 R according to EN 197-1, obtained from Schwenk
Zement, production plant Bernburg/Germany;
Quartz sand 0/2 mm, obtained from Kieswerk Ottendorf/Germany;
Silica fume (SF) Elkem 971, obtained from Elkem Refractories, Kristiansand/Norway;
Polycarboxylate-based superplasticizer (SP) Glenium 51, aqueous solution, provided by BASF, Trostberg/Germany.
Each mortar was given a specic name indicating its composition,
e.g.:
A_Ref_0.30: Reference mix for the group A, w/b of 0.30;
C_0.40B_0.45: The mortar belongs to group C and contains 0.40% of
SAP-B by weight of cement, w/b of 0.45, no extra (curing) water in
comparison to the reference mixture C;
C_0.20DN_0.50: The mortar belongs to group C and contains 0.20% of
SAP-DN, w/b of 0.50 includes 0.05 units of extra water in comparison
to the reference C.
To have a common starting point for all compositions, the same
slump ow value of 200 mm 10 mm for testing with a small cone according to DIN EN 1015-3:2007-05 was attained for all reference mixtures. The spread diameter on the even glass plate was measured
10 min after water addition to the mortar dry components. This was
achieved by adjusting the dosage of superplasticizer.
The next step was to establish an adequate dosage of SAP for the
assigned amount of extra water. The amount of extra water was chosen
on the basis of earlier investigations on both high-performance concrete
(in this case extra water is associated with internal curing water) [13]
and ordinary concrete [25] and corresponded to an increase of w/b by
0.05. To estimate the adequate dosage of SAP a preliminary rheometer
test series on the basis of reference A_Ref_0.30 was performed by varying the amount of SAP. The parameters plastic viscosity and yield stress
of mortars modied by adding extra water and SAP were compared to
the corresponding values of the reference. It was found that it is not possible to adjust the SAP dosage in a way that both parameters were close
enough to those of the reference mortar at the same time. Therefore, it
was decided to make the choice of the SAP dosage based on the comparison of the values for the plastic viscosity only, see Section 3.2 for details.
According to the results of the preliminary tests which are presented in
detail in Section 3.2, the amount of SAP was established as follows:
0.40% bwoc of SAP-B and 0.20% bwoc for SAP-DN. The later percentage
was also used for SAP-DS and SAP-DC. Thus, the effect of the grain size
on the rheological properties of mixtures could be analysed.
Two and a half litres of mortar was produced per batch using a laboratory mixer HSM 20 Hobart (Offenburg, Germany) and following
the mixing sequence according to Table 2. Mixing and testing of mortars
were performed in laboratory conditions at room temperature of 20 C
and a relative humidity of 65%.

Table 2
Mixing regime for all mortars used in the present study [15].
Time [min]

Action

Duration [min]

03:0000:00
00:0001:00

Mixing of mortar dry components

Addition of water including pre-dissolved
Superplasticizer
Mixing, intensity 1 (170 rpm)
Mixing, intensity 2 (198 rpm)
Manual scraping of agglomerates
from the mixing drum walls
Mixing, intensity 3 (361 rpm)

3
1

01:0002:00
02:0003:00
03:0003:30
03:3005:00

1
1
0.5
1.5

2.3. Rheometry
The fresh mortars were tested with a HAAKE MARS II rheometer
(Thermo Electron GmbH, Karlsruhe/Germany) 10, 20, 30, 45, 60 and
90 min after the water addition to the dryly pre-blended components
of the mortars. A unit cell designed for building materials with a volume
of approximately 550 ml and 74 mm diameter was used together with a
specially conceived vane rotor having a radius of 26 mm, Fig. 3. The
mortar was kept in the unit cell for the entire testing period. Before beginning each rheological measurement, the mortar was agitated using a
spoon in order to reduce the effect of possible sedimentation.
The unit cell was equipped with protruding lamellas 2 mm thick to
reduce slippage or formation of lubrication layer. The lateral gap between the vane rotor and the lamellas was 9 mm. Therefore, the maximum aggregate size dmax = 2 mm was in accordance with the required
minimum gap size of 4dmax [26,27].
In order to calibrate the measuring equipment and so to consider the
specic geometry of the vane, rheological tests were performed using silicon oil (Newtonian uid). The calibration factors were determined by
comparing the results obtained from the unit cell with vane rotor, i.e. relative measurement system, and a coneplate sensor system, i.e. absolute
measurement system [28]. In the same manner, the calibration factors
were additionally validated by performing rheological tests on
Carbopol gels of various polymer concentrations. The applied shear
rate was between 0 and 15 1/s, thus covering the shear rate range
from 0.96 to 9.6 1/s used for testing the mortars in this study, see Table 3.
A combined testing regime was applied including the two main tests:
Segments 12: Oscillatory test to determine the visco-elastic behaviour of the mortar;
Segments 46: Continuous shear rate controlled test to measure
changes in shear stress as a function of shear rate and subsequent derivation of yield stress and plastic viscosity values according to the
Bingham model.
The article at hand focuses on the continuous shear rate controlled
tests. The results obtained from the oscillatory and recovery tests will
be published elsewhere. The entire measuring prole is provided just
to give an impression of the entire shear history of the mortars.
To measure the ow curves a predened sequence of shear rates was
applied to each fresh mortar. The rheological behaviour of concrete is
usually analysed for shear rates ranging between 0 and 10 1/s [29,30];
this range was adapted also in the study at hand. First, i.e. in Segment
4, shear rate was increased from 0.96 to 9.6 1/s in 20 steps within
40 s. The segment was followed for 30 s by Segment 5 with a constant
shear rate of 9.6 1/s. This measure was needed to achieve a structure
breakdown which represents an important prerequisite to derive the
rheological parameters of cement-based materials according to Bingham model [3,26,31]. In Segment 6 the shear rate was decreased from
9.6 to 0.96 1/s in another 20 steps which took 40 s. From the data obtained from Segment 6 the resulting shear stress transient values were computed (one shear stress value per each shear rate step).
To elucidate the Bingham parameters the descending branch of the
shear stressshear strain curve was approximated by using linear

V. Mechtcherine et al. / Cement and Concrete Research 67 (2015) 5265

H-shaped frame

Measuring head with engine

and measuring unit

Temperature sensor
Rotor

Unit cell holder

Fixed lower mount
Unit cell
Manual control panel

a)

b)
Fig. 3. a) HAAKE MARS II rheometer with rotor and unit cell and b) dimensions of the used geometry.

57

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V. Mechtcherine et al. / Cement and Concrete Research 67 (2015) 5265

Table 3
Measuring prole used in the rheometer measurements.
Segment

Type

Time [s]

Further settings

0
1
2
3
4
5
6

Lift
OscTime
OscAs
CSRT
CRRS
CRTime
CRRS

5
30
150
30
40
30
40

Lift control: moving rotor to measurement position

Oscillationtime test, = 0 Pa, f = 1.0 Hz
Oscillationamplitude test, = 1 400 Pa, f = 1.0 Hz, 40 steps
Controlled shear stress recovery test, = 0 Pa, 30 steps
Controlled shear rate test, = 0.96 9.6 1/s, 20 steps
Controlled shear rate test, = 9.6 1/s, 30 steps
Controlled shear rate test, = 9.6 0.96 1/s, 20 steps

regression analysis [3234]. The intersection of the linear regression

line with the vertical axis gave the value of the yield stress 0 and the
slope of the line provided the value of the plastic viscosity (Fig. 4).
3. Experimental results and discussion
Every mortar was produced in three batches and each batch was
tested with the rheometer according to the procedure described in
Section 2.3. The results for yield stress and plastic viscosity as presented
in the following diagrams (Figs. 5 to 13), except the preliminary tests,
are the outcomes of statistical evaluations. They show average value
and scatter of the values (from the lowest one to the highest one) for
each parameter combination and time point of measurement.
3.1. Reference mortars
In the rst step three SAP-free reference mortars were investigated.
As mentioned in Section 2.2 all of them met the requirement of (200
10) mm slump ow when tested 10 min after addition of water to the
pre-blended solid components. However, the results of rheometry considerably differed for these mortars.
Fig. 5a shows the development of the plastic viscosity in time for all
three reference mortars. A_Ref_0.30 with w/b of 0.30 (without silica
fume) exhibited the highest plastic viscosity right from the beginning
of the measurements, i.e. 10 min after addition of water during mortar
mixing, followed by B_Ref_0.30 (w/b 0.30, presence of silica fume)
and C_Ref_0.45 (w/b 0.45, no silica fume), respectively. Furthermore,
for A_Ref_0.30 the most prominent increase in the plastic viscosity in

time was observed while for B_Ref_0.30 the increase was less evident
and for C_Ref_0.45 nearly no changes were recorded. These results
were not unexpected. The higher water content of C_Ref_0.45 explains
the low and stable values of . The decreased of B_Ref_0.30 in comparison to A_Ref_0.30 can be traced back to the presence of silica fume. According to [1,3,35] silica fume exerts, when added in a moderate
quantity, a so-called ball-bearing effect resulting in low internal friction at elevated shear rates and therefore in a decrease in the plastic viscosity if dispersed properly.
With respect to the yield stress the sequence of reference mortars
was opposite to that observed for plastic viscosity. C_Ref_0.45 showed
the highest yield stress and a pronounced increase of this parameter
in time; the yield stress of B_Ref_0.30 was approximately three times
lower at the initiation of the measurements and remained nearly unchanged for further 80 min. Finally, the A_Ref_0.30 exhibited the lowest
values of the yield stress and in the time period between 10 and 30 min
even a decrease in values of this rheological parameter. The low yield
stresses recorded for A_Ref_0.30 and B_Ref_0.30 result from their relatively high superplasticizer content, an effect very well-known and numerous times described in the literature, e.g. [3638]. Since B_Ref_0.30
had a slightly higher content of superplasticizer in comparison to
A_Ref_0.30, one might expect that the later one would have a higher
0. However, the yield stress reducing effect of the superplasticizer
was partly diminished by the presence of silica fume since addition of
silica fume is known to cause an increase in 0 [3,35,39,40].
The fact that A_Ref_0.30 (to a higher extent) and B_Ref_0.30 (to a
lower extent) showed a decrease in the yield stress within the time interval 10 to 30 min was most likely caused by continuous or delayed absorption of superplasticizer on the cement particles, silica fume spheres
(B_Ref_0.30) and surfaces of early hydration products during the
rheometric tests [24,40]. This effect is also well known in the practice
of construction when the slump ow of concretes containing
polycarboxylates increases, e.g. due to the transport of mixtures in
the concrete trucks with continuous rotation of the drum. Thus, in
this particular test series the entire shear history must be considered
including the intermediate oscillation tests which brought supplemental shear [41]. For the mixture C_Ref_0.45 this phenomenon was
not observed due to its low superplasticizer content. Moreover
Goaszewski et al. [36] reported the effectiveness of SP based on
polycarboxylate decreases with increasing w/b.
Finally, it should be noted that although all reference mortars exhibited the same slump ow of 200 mm, the initial values of 0 coincided
only for A_Ref_0.30 and B_Ref_0.30 but not for C_Ref_0.45. This conrms once again that empirical tests have serious drawbacks and are
suitable only for the quality control of similar mortars or concretes
[37,42] but not for estimations of rheological properties of mixtures
with various compositions.
3.2. Preliminary tests: establishing dosages of SAP for a given amount of extra water in the mortar series A

Fig. 4. Typical curve obtained from a continuous shear rate controlled test showing the ascending and descending branches and a linear approximation of the descending branch to
determine the yield stress 0 and plastic viscosity .

As explained in Section 2.2, the preliminary tests served for establishing adequate dosage of SAP. The results provided in Figs. 6 and 7
show no scatter indicators because only one measurement per parameter combination was used (except for the reference).

V. Mechtcherine et al. / Cement and Concrete Research 67 (2015) 5265

100

40

80

30
Yield Stress [Pa]

Plastic Viscosity [Pas]

59

20

10

60

A_Ref_0.30
B_Ref_0.30
C_Ref_0.45

40
20

0
0

20

40
60
Time [min]

80

100

a)

20

40
60
Time [min]

80

100

b)
Fig. 5. Development of a) plastic viscosity and b) yield stress 0 of reference mortars over time.

The values of the plastic viscosity of the mixtures enriched with SAPB are shown in Fig. 6a. The SAP amount varied between 0.30 and 0.50%
bwoc. The pattern of plastic viscosity change in time was similar for all
three mixtures enriched with SAP-B, i.e. at rst an increase followed
by a decrease or stagnation of the values, none of these curves resembled the behaviour of the reference mortar, which showed a steady increase in plastic viscosity. The decrease in was observed for
A_0.40B_0.35 and A_0.50B_0.35 and stagnation of these values for
A_0.30B_0.35 starting at 20 min after addition of mixing water. This effect should be interpreted as a direct consequence of early release of
stored aqueous solution from SAP-B which occurs in correspondence
to the teabag tests, see Fig. 2a. This effect was most pronounced for
the mixture A_0.50B_0.35 which contained a higher SAP amount and
therefore could absorb and desorb more liquid. Accordingly, the least effect was noted for A_0.30B_0.35 which had the lowest SAP content. Further, it is evident that the dosage of SAP-B of 0.50% bwoc was too high
for the given amount of extra water (w/c = 0.05) because the intense
water absorption caused a pronounced increase in plastic viscosity at
the early stage of measurements. It is also clear that the dosage of
SAP-B of 0.30% bwoc was too low. Only the mixture A_0.40B_0.35, having 0.40% bwoc SAP-B incorporated, exhibited plastic viscosity values
close to those of the reference mortar during the rst 40 min.
The effect of the addition of SAP-B on the yield stress of the fresh
mortars was more intense than that on the plastic viscosity, see
Fig. 6b. The dosage of 0.50% bwoc caused an increase in yield stress
nearly by an order of magnitude while the too low dosage of 0.30% in
the combination with the same amount of extra water led to a dramatic

120

40

100
30

Yield Stress [Pa]

Plastic Viscosity [Pas]

decrease of the yield stress. For the mortar with 0.40% the values of yield
stress were two and more times higher than the corresponding values
of the reference. Furthermore, similar to the results for plastic viscosity,
a clear decrease in the yield stress in time was observed for the mortars
containing SAP-B. Here again this phenomenon can be explained by a
premature release of absorbed aqueous solution by this type of SAP.
Summarising the results obtained for the mortars with SAP-B it can
be concluded that owing to the specic kinetics of water absorption
and desorption inherent to this kind of SAP, a comparable plastic viscosity or yield stress to the reference mortar can be achieved only for some
distinct moment of time. Beforehand and afterwards, liquid released
from the SAP causes both reduced plastic viscosity and yield stress. It
can also be stated that the specic sorption kinetics of this SAP sample
(free releasing, see Fig. 2a) make it impossible to attain the same values
of plastic viscosity and yield stress than for the SAP-free reference mortar
simultaneously. Thus, one has to decide which of these two rheological
parameters should be used as a basis for the choice of the SAP dosage.
Fig. 7a depicts the evolution of plastic viscosity in time for the mortars containing SAP-DN in different dosages. The values of plastic viscosity of A_0.15DN_0.35 and A_0.20DN_0.35, i.e. mortars containing 0.15
and 0.20% SAP-DN bwoc, respectively, are close to those of the reference. This indicates that the amount of SAP-DN was quite adequate to
provide comparable results. A dosage of 0.30% bwoc was too high
since it caused quite an excessive increase in the plastic viscosity.
The results for yield stress are presented in Fig. 7b. All mortars doped
with SAP-DN exhibited relatively stable values with some minor increase in time. An abrupt decrease of yield stress as registered for the

20
A_Ref_0.30
A_0.30B_0.35
A_0.40B_0.35
A_0.50B_0.35

10

a)

20

40
60
Time [min]

80

A_Ref_0.30
A_0.30B_0.35
A_0.40B_0.35
A_0.50B_0.35

60
40
20
0

0
0

80

100

20

40
60
Time [min]

80

100

b)

Fig. 6. Development of a) plastic viscosity and b) yield stress 0 over time for mortar series A with and without SAP-B in various dosages and extra water (w/c = 0.05).

60

V. Mechtcherine et al. / Cement and Concrete Research 67 (2015) 5265

30

75

A_Ref_0.30
A_0.15DN_0.35
A_0.20DN_0.35
A_0.30DN_0.35

60
45
30

25
Yield Stress [Pa]

Plastic Viscosity [Pas]

90

A_Ref_0.30
A_0.15DN_0.35
A_0.20DN_0.35
A_0.30DN_0.35

20
15
10
5

15

0
0

20

40
60
Time [min]

80

100

a)

20

40
60
Time [min]

80

100

b)

Fig. 7. Development of a) plastic viscosity and b) yield stress 0 over time for mortar A with and without addition of SAP-DN in various dosages and extra water (w/c = 0.05).

reference in the rst 30 min did not occur. Between 30 and 90 min the
yield stresses of A_0.20DN_0.35 well matched those of the reference,
followed by A_0.15DN_0.35. The quantity of SAP in A_0.30DN_0.35
was clearly too high for the pre-selected amount of extra water.
Hence, not only the additional water but most likely also a part of ordinary mixing water was sucked up by this amount of SAP-DN, which led
to a dramatic increase in 0.
Comparing the principal curve shapes obtained for mortar containing SAP-DN (Fig. 7) to those with SAP-B (Fig. 6) reveals that no relevant
amount of aqueous liquid was released from SAP-DN within the time of
measurement. This indicates that the fundamental sorption kinetics
read from the teabag test in cement pore solution (Fig. 2a) well picture
those in the mortars, at least with respect to a qualitative distinction in a
free releasing and a retaining type of SAP, cf. [21].
The preliminary tests further showed that quite a similar rheological
behaviour of the mortars with and without SAP and extra water could
be achieved either for plastic viscosity or yield stress but not for both parameters at the same time. Since the determination of the yield stress
very much depends on the experimental procedure and the shear history [12,43,44], plastic viscosity was considered as the more reliable parameter to compare the rheological behaviour of the reference
mortars and the mortars enriched with SAP and extra water. Furthermore, it is a common knowledge that the plastic viscosity has a more
pronounced effect on many technological processes such as pumping
of concrete, than the yield stress has [4548].
According to the obtained results the dosage of 0.40% SAP-B bwoc
was adopted for the subsequent investigations since A_0.40B_0.35 exhibited close to those of the reference during the rst 40 min of testing.

For SAP-DN a dosage of 0.20% bwoc was chosen since A_0.20DN_0.35

delivered values for both and 0 closest to those of the reference mixture. To elucidate the effect of grading of SAP-D on the rheological properties the same dosage was used in mortars with SAP-DS and SAP-DC.
3.3. Results of group A mortars (based on Portland cement, w/c = 0.30)
This group of mortars is characterised by a w/c of 0.30 for the reference (no SAP or extra water) and w/c = 0.35 for the mortars with SAP as
well as by a relatively high amount of superplasticizer. Fig. 8 shows the
results for the plastic viscosity of the mortar series A. For the sake of
clarity of graphical presentation, here and in the following gures two
diagrams are provided for each test series and each rheological parameter. The rst diagram gives average values obtained for individual parameter combinations and herewith provides a good overview of the
main results. For the second diagram the scaling of the ordinate axis is
enlarged and the scatter of the results is shown for the curves which
are close to each other.
The particle size distribution of SAP-D exhibits a considerable effect
on the values of the plastic viscosity: A_0.20DN_0.35 containing the
largest SAP-D particles has the lowest value of plastic viscosity of all
mortars and A_0.20DS_0.35 containing the smallest SAP particles exhibits the highest values at the rst point of time measured. Thus,
the smaller particles absorb at this stage a larger amount of pore solution than the larger particles. This results in a higher plastic viscosity
due to the diminished quantity of freely available water for the intergranular spaces. This trend corresponds to the sorption kinetics in the
teabag tests (Fig. 2a). Furthermore, A_0.20DN_0.35 shows the most

45
Plastic Viscosity [Pas]

Plastic Viscosity [Pas]

50
40
30
20

A_Ref_0.30
A_0.40B_0.35
A_0.20DS_0.35
A_0.20DC_0.35
A_0.20DN_0.35

10
0
0

20

40
60
Time [min]

80

40
35
30
25
20

100

20

40
60
Time [min]

80

100

Fig. 8. Development of plastic viscosity for mortar group A over time, average values and scatter of the results obtained.

V. Mechtcherine et al. / Cement and Concrete Research 67 (2015) 5265

15

50

30

Yield Stress [Pa]

A_Ref_0.30
A_0.40B_0.35
A_0.20DS_0.35
A_0.20DC_0.35
A_0.20DN_0.35

40
Yield Stress [Pa]

61

20
10

10

0
0

20

40
60
Time [min]

80

100

20

40
60
Time [min]

80

100

Fig. 9. Development of yield stress. 0 in the mortar group A over time, average values and scatter of the results obtained.

pronounced increase in plastic viscosity so that starting with the measurement 20 min after adding mixing water it has the highest values.
In contrast to this, for A_0.20DC_0.35 and to a lesser extent also for
A_0.20DS_0.35, containing smaller particles of SAP D, only a slightly
stronger increase in values in time can be observed at the initial
stage (rst 20 min), in comparison to the reference mixture, but the
values from the very rst measurement are higher than those of the
SAP-free reference. Under assumption that SAP particles as such, due
to a low percentage of this additive, have no signicant effect on the viscosity, it can be concluded that for the same dosage of SAP D, smaller
SAP particles absorb in the rst 10 min not only the entire extra water
for the internal curing, but also some part of mixing water. At later
stages no or only very moderate additional water absorption takes
place. In contrast to this, the larger particles of SAP-DN seem to not
have nalized their absorption in the rst 10 min and continue to absorb approximately 45 min after mixing.
The mortar A_0.40B_0.35 containing SAP-B shows a similar trend
only for the rst 20 min, i.e. for the rst two measurements. Afterwards
the development of changes fundamentally. First, increases clearly
slower in comparison to all other mortar compositions and secondly,
starting at 30 min after mixing, a clear decrease in the plastic viscosity
is registered. This trend indicates that primary absorbed aqueous solution is voluntarily released from SAP-B in the course of time, the phenomenon which was observed in the teabag tests already, see Fig. 2a,
and cf. neutron imaging in [21]. From comparison of the trends in
Figs. 2a and 8 it can be suggested that the water absorption and release
in teabag tests, in which SAP is surrounded by a pore uid, are considerably faster than the corresponding processes occurring when SAP acts in
fresh mortar. This seems to be a logical case, since when placed in a

hydraulically active suspension, SAP must compete for water with cement and other ne solid particles, which decrease the absorption rate.
The yield stress values of the mortars of group A are presented in
Fig. 9. By comparing the initial yield stress results of the mortars obtained from the rheometer tests at 10 min with their slump ow spreading
(Table 1) measured at the same time one can notice a good matching
between the sequences of the mortars. A_0.20DS_0.35 has the highest
yield stress value and the lowest slump ow while A_0.20DN_0.35
and A_0.40B_0.35 have both the lowest yield stress and the largest
slump ow. In the same manner, the matching is valid for the other
two mortars (A_Ref_0.30, A_0.20DC_0.35) as well. Starting at 10 min
and continuing up to 30 or 45 min after addition of water the yield stress
values considerably decreased for all the mortars except
A_0.20DN_0.35, which showed a steady increase in 0 until 90 min.
While 0 of A_0.20DS_0.35 and A_0.20DC_0.35 increased again after
45 min, the reference A_Ref_0.30 showed an increase in yield stress
after 30 min already. The 0 for A_0.40B_0.35 showed a decrease over
the entire period of the measurements.
The observed decreases in yield stress for all mortars (except
A_0.20DN_0.35) for the rst 30 to 45 min resulted most probably
from the continuous absorption of superplasticizer molecules to the surfaces of cement particles and early products of hydration such as,
e.g., ettringite [24]. This effect has been well known for mortars with
high dosages of polycarboxylate-based superplasticizers [40] (also cf.
Section 3.1). SAP-B, SAP-DS and SAP-DC either supported this effect or
did not inuence it to a signicant extent. On the contrary SAP-DN
strongly counteracted and overruled this effect. An increase in the
yield stress was caused due to the continuous water absorption by
SAP-DN (largest SAP-D particles), see also the previous comments

19
Plastic Viscosity [Pas]

Plastic Viscosity [Pas]

20

15

10
B_Ref_0.30
B_0.40B_0.35
B_0.40B_0.38
B_0.20DS_0.35
B_0.20DC_0.35
B_0.20DN_0.35

0
0

20

40
60
Time [min]

80

17
15
13
11
9

100

20

40
60
Time [min]

80

100

Fig. 10. Development of plastic viscosity of mortar group B over time, average values and scatter of the results obtained.

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V. Mechtcherine et al. / Cement and Concrete Research 67 (2015) 5265

30
20
25
Yield Stress [Pa]

Yield Stress [Pa]

17
20
15
B_Ref_0.30
B_0.40B_0.35
B_0.40B_0.38
B_0.20DS_0.35
B_0.20DC_0.35
B_0.20DN_0.35

10
5
0
0

20

40
60
Time [min]

80

14
11
8
5

100

20

40
60
Time [min]

80

100

Fig. 11. Development of yield stress 0 of mortar group B over time, average values and scatter of the results obtained.

with regard to the development of the plastic viscosity. The decrease in

yield stress observed for A_0.20DS_0.35 at the early stage (10 to 20 min)
is less pronounced than for the reference mortar which again indicates
that some water was taken in by SAP particles from the fresh mortar. Finally, the continuous decrease of 0 values in time as observed for
A_0.40B_0.35 can easily be explained by the desorption behaviour of
SAP-B present in this mixture, see also Fig. 2a.

3.4. Results of group B mortars (based on blend of Portland cement and

silica fume, w/b = 0.30)
The particular features of the group B mortars are the presence of silica fume as a part of the binder and the highest superplasticizer content
compared to group A and C mortars.
The plastic viscosity evolution of the group B mortars in time is illustrated in Fig. 10. Similar to the results presented in Section 3.3 for group
A, the particle size of SAP-D clearly affected the plastic viscosity: Mortar
B_0.20DN_0.35 containing the largest SAP particles (SAP-DN) had the
lowest value of plastic viscosity at the rst measurement and
B_0.20DS_0.35 containing the smallest SAP particles (SAP-DS) exhibited
the highest value. Furthermore, again similar to the observations for
group A, the increase of plastic viscosity in time was more pronounced
for B_0.20DN_0.35 (larger particles) than for the reference or for
B_0.20DS_0.35 and B_0.20DC_0.35 (smaller particles). It is worth to
note that B_0.20DS_0.35 shows a less signicant increase in plastic viscosity when compared to B_Ref_0.30. This let us suggest that SAP-DS
may release some aqueous solution kept inside to the matrix; this effect
was not observed for the mixtures of the group A (without silica fume).

12

C_Ref_0.45
C_0.40B_0.45
C_0.40B_0.50
C_0.40B_0.53
C_0.20DS_0.50
C_0.20DC_0.50
C_0.20DN_0.50

Plastic Viscosity [Pas]

Plastic Viscosity [Pas]

The plastic viscositytime curve of B_0.40B_0.35 containing SAP-B is

shallower than the curve of the reference B_Ref_0.30. However, in contrast to the results obtained for group A, the curve of B_0.40B_0.35
showed no descending trend at any time. Though, the plastic viscosity
after 10 min was lower for B_0.40B_0.35 in comparison to the reference.
Considering the fact that the corresponding mortars of group A exhibited no difference in values let us suggest that the action of SAP-B in
mortars containing silica fume varied from that in mortars without silica
fume. Possible explanations are that SAP-B either absorbed less water in
the mortar with silica fume than in that without silica fume or it released some of the absorbed water in rst minutes after mixing already.
Desorption kinetics published in [21], which were recorded in a
paste of Portland cement, 10% silica fume bwoc and a w/c of 0.42,
may give a hint that the latter explanation is quite probable, while
for the rst one no experimental data has been published to the
best knowledge of the authors up to date. The latter suggestion is
also supported by the difference in the course of the plastic viscositytime curves for A_0.40B_0.35 (higher initial water absorption
and/or later, but signicant water release) and B_0.40B_0.35
(lower initial water absorption and/or earlier water release). Such
differences can be traced back to a more intense competiveness
of the silica fume/cement blend for water against SAP in comparison
to cement only. It is not a surprising effect considering a very high
neness of silica fume particles. Finally, an increased amount of
extra water corresponding to a nominal increase of the w/b from
0.35 to 0.38 (w/b = 0.08 instead of w/b = 0.05) had not exhibited much effect on plastic viscosity of the mortar containing SAP-B:
B_0.40B_0.38 showed only moderately lower values in comparison
to B_0.40B_0.35.

5
4
3
2
1
0

20

40
60
Time [min]

80

100

20

40
60
Time [min]

80

100

Fig. 12. Development of plastic viscosity of mortar group C over time, average values and scatter of the results obtained.

V. Mechtcherine et al. / Cement and Concrete Research 67 (2015) 5265

175

400
C_Ref_0.45
C_0.40B_0.45
C_0.40B_0.50
C_0.40B_0.53
C_0.20DS_0.50
C_0.20DC_0.50
C_0.20DN_0.50

300

200

Yield Stress [Pa]

Yield Stress [Pa]

63

100

125

75

25
0

20

40
60
Time [min]

80

100

20

40
60
Time [min]

80

100

Fig. 13. Development of yield stress 0 in mortar group C over time, average values and scatter of the results obtained.

Fig. 11 presents the yield stress values for the group B mortars. The
results have some similarities and some differences in comparison to
the corresponding results of group A and are described in Sections 3.2
and 3.3. For the mortar age of 10 min the same sequence in both series
was observed starting with the mortar containing SAP-DS (smallest particles) and showing the highest 0 values and ending with the mortars
containing SAP-B providing the lowest 0 values. Also, as in the group
A experiments, this sequence is in agreement with the results of the
slump ow tests. Another similarity is the presence of some decrease
in yield stress between 10 and 30 min. However, in group B this phenomenon was less noticeable than in group A and it was observed for
the reference and for B_0.20DS_0.35 only. Furthermore, in contrast to
the results of group A, the reference B_Ref_0.30 had a less pronounced
decrease than the mortar containing the small SAP-DS particles. This observation supports the suggestion drawn on the basis of the evaluation
of the data of plastic viscosity. Particles of SAP-DS, after having initially
absorbed a relatively high amount of water, may desorb a small but decisive part of it back to the mortar containing silica fume starting at the
earliest stage after mixing, i.e. clearly before the rst recording of yield
stress. Mortars B_0.20DN_0.35 and B_0.20DC_0.35 had lower yield
stresses than the reference B_Ref_0.30 at the time of the rst measurement, but they ended up with the same yield stress or even higher
values at the end of measurement time. This indicates that the larger
SAP particles indeed exhibited some long-lasting absorption. Finally,
mortars B_0.40B_0.35 and B_0.40B_0.38 showed lower values of yield
stress in comparison to the others and the lowest increase of these
values in time, but, in contrast to A_0.40B_0.35, no decrease of this rheological parameter at any point of time. The reason for this trend may be
according to that explained in the discussion of Fig. 10 (see above).
In general, higher yield stress values were observed for the mortars
of group B (containing silica fume) in comparison to those of group A
(without silica fume). The counteracting effect of silica fume leading
to increased yield stress was stronger than the reducing effect of somewhat higher effect of superplasticizer.
3.5. Results of group C mortars (based on Portland cement only, w/
c = 0.45)
The mortars of group C are characterised by the highest w/b of 0.45
for the reference and higher when internal curing water is considered
and the lowest superplasticizer content in comparison to groups A
and B. Fig. 12 shows the evolution of plastic viscosity of the group C
mortars in time.
Two evident differences in comparison to groups A and B can be stated: a) any values of plastic viscosity are considerably lower and
b) plastic viscosity remains nearly unchanged over the entire period of
measurements (other than the high increase in time as observed for
the mixtures of groups A and B).

Some effect of the different gradings of SAP-D was detected but it

was less pronounced than in the series with lower w/b, Figs. 8, 10, 12.
The measurement at 10 min revealed slightly higher values of plastic
viscosity of C_0.20DS_0.50 and C_0.20DC_0.50 containing ner SAP-D
particles than C_0.20DN_0.50 with the coarser SAP-DN. By 40 min this
discrepancy had vanished. In the time period between 10 and 40 min
a very slight decrease in values for the mortars containing the ner
SAP-D was registered, whereas the mortar with the coarser SAP-DN exhibited a slight increase. These specic behaviours can be explained by
the differences of the absorption kinetics of SAP particles with various
sizes as was discussed in the previous sections. All mortars containing
SAP-D were close to the reference curve, actually within the scatter of
the results. Thus, the effect of SAP-D dosage of 0.20% bwoc and the
predened amount of extra water, which corresponded to a w/c of
0.05, was very moderate.
For SAP-B in the dosage of 0.40% bwoc the effect of the quantity of extra
water was investigated in three levels: a) no extra water (w/c = 0.45,
C_0.40B_0.45), b) the common amount of the study of w/c = 0.05
(C_0.40B_0.50) and c) an evident oversupply of internal curing water corresponding to w/c = 0.08 (C_0.40B_0.53). The plastic viscosity of
C_0.40B_0.45 was highest at the time of the rst measurements which is directly related to the absorption activity of the SAP. In this case, nominally a
part of the mixing water was taken in by the SAP and should thus be
regarded as internal curing water. However, values of this mortar
composition decreased in time, meeting the plastic viscosity of the reference C_Ref_0.45 at 40 min. Eventually, values of C_0.40B_0.45 became
even slightly lower than those of C_Ref_0.45. Obviously, SAP-B released
the vast majority of the absorbed water which was efcient enough to decrease the plastic viscosity of the mortar to that of the SAP-free reference
(within the range of scatter, but potentially even some further decrease to
below the reference may occur). The other two mortars with SAP-B,
C_0.40B_0.50 and C_0.40B_0.53 behaved similarly in principal. However,
the extra water caused a considerably decreased plastic viscosity already
at the start of the rheological measurements at 10 min after mortar preparation. This may result from either insufcient absorption by the 0.40% SAPB bwoc right from the beginning (most likely in C_0.40B_0.53) or premature release of stored liquid (most likely in C_0.40B_0.50) in accordance
to the reasoning at the other two mortar groups.
The intense releasing action of SAP-B came to an end after approximately 30 to 40 min. This indicates that by that time the SAP particles
were exhausted to the largest extent. As a consequence, internal curing
will be improbable at later ages. However, this should not be regarded as
troublesome for this mortar composition. At w/c of 0.45 and higher the
Portland cement is expected to hydrate completely anyway [16].
The results for the yield stress are presented in Fig. 13. The initial
yield stress results at 10 min matched well the order of the results
from the slump ow tests as depicted in Table 1. C_0.40B_0.45 had the
highest yield stress value and the lowest slump ow, whereas

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V. Mechtcherine et al. / Cement and Concrete Research 67 (2015) 5265

C_0.40B_0.53 had both the lowest yield stress and the largest slump
ow. The results of the other mortars are as well in a good agreement.
Compared to groups A and B, considerably higher yield stress values
were recorded for all mortars of group C.
Considering the values of 0 measured at 10 min, the addition of SAP
resulted in an increase in this rheological parameter in comparison to
the reference C_Ref_0.45 with the prominent exception of mortar
C_0.40B_0.53, which is the logical consequence of the purposeful overdose of extra water. Such distinctly increased yield stress values were
not observed in groups A and B, both having lower w/b and higher contents of superplasticizer.
Thus, it seems as though SAP absorbed more water from fresh pastes
with a higher overall water content, i.e. higher w/b. This would result in
the observed increase in yield stress values of group C mortars in comparison to those with a lower w/b while providing the same amount of
extra water. Note that the so-called adequate amount of extra water
(w/c = 0.05) was the outcome of the preliminary tests with group A
which features a lower w/c than group C.
The effect of the particle sizes of SAP-D is well traceable in this mortar group as well. Similar to the tendencies observed in groups A and B,
group C mortars with ner SAP-D particles show higher 0 values at
10 min. However, in contrast to the ndings for groups A and B, the differences in the slopes of the ascending curves of mixtures with various
gradings of SAP-D and also in comparison to the reference mortar, here:
C_Ref_0.45, were much less pronounced and in part not evident. This indicates that continuous water absorption or some potential minor desorption by SAP-D in mortars with this high w/c occurred either to a
lesser extent or has a less prominent effect on the yield stress in comparison to mortars with lower w/c.
The various water additions to the mortars containing SAP-B clearly
affected the yield stress of the mortars. The 0 values of C_0.40B_0.45
were highest at 10 min and considerably higher than those of the reference C_Ref_0.45 over the entire measurement period, even though a signicant drop was recorded for C_0.40B_0.45 between 10 and 20 min,
most probably due to partial desorption of water by SAP-B; see the reasoning above. The mortar C_0.40B_0.50 containing the regular amount
of extra water had a considerably higher yield stress at the beginning
and lower 0 values at the end of the recordings than the reference. Actually, 0 values of C_0.40B_0.50 hardly changed over time at all, indicating a
continuous and steady release of water by the SAP-B particles. Finally,
mortar C_0.40B_0.53, containing an overdose of water, revealed the lowest values of yield stress of all the others at any point in time. The yieldstress/time curve showed a slight ascent over the entire time under consideration, which was, however, shallower in comparison to the reference
mixture. This smaller inclination over time indicates that some minor
amount of stored liquid in SAP-B kept on releasing over the long term
and had not became evident in the plastic viscosity recordings; cf.
Fig. 12. There seems to be some portion of liquid retained until later stages
than was the case with lower w/c or w/b values. This trend may support
the assumption that this SAP absorbed more liquid in the mortar with
higher w/c than with lower; cf. discussion for SAP-D.
4. Summary and conclusions
In this study the effects of superabsorbent polymers (SAP) on the
rheological properties of fresh Portland cement-based mortars were investigated. The main ndings can be summarized as follows:
Two types of SAP with various molecular structures could be clearly
distinguished based on their sorption behaviour: SAP-B, which freely released solution in the so-called teabag test showed a very early
release of liquid when mixed in mortar as well, whereas retentive
SAP-D kept the absorbed liquid to a great extent over the entire
90 min of rheometrical assessment. In this connection, the sorption
processes in the teabag test seem to be considerably faster than
those in fresh mortar.

The distinct sorptivity of SAP specically affects yield stress and plastic viscosity of fresh mortars. The release of a part of initially
absorbed liquid by SAP-B caused a slower increase in plastic viscosity over time, as compared with the reference mixture, or even a
slight decrease, while mortars containing retentive SAP-D showed
a steady increase in this parameter either because of negligible desorption of liquid from the SAP or because of some additional absorption by the SAP. The effect of SAP addition on the yield stress
was less straightforward since it counteracted the effect of
superplacticizer on the development of this rheological parameter
over time.
The particle size of SAP inuences their absorption and desorption
kinetics. For the same amount of internal curing water, mortars containing the nest SAP-D particles provided the highest values of
yield stress and plastic viscosity due to the greater total absorption
surface of the particles and, consequently, more rapid achievement
of equilibrium. However, the larger particles of SAP-D, while slow
at the beginning, continued to absorb water over the entire time of
the experiments, leading to a steady and most pronounced increase
in the values of the Bingham parameters.
The absorption and desorption of water by SAP in fresh mortar, and
subsequently the effect of SAP addition on its rheological behaviour,
depend on the availability of free water in the mix. Increasing the
water-to-binder ratio results in higher water absorption by SAP
and, accordingly, in higher relative changes in the Bingham parameters for such mixtures in comparison to the reference mixture.
The use of silica fume leads to changes in water absorption and desorption kinetics of SAP in fresh mortar. It seems that the competition for absorbing and attaining water becomes more difcult for
SAP in the presence of silica fume.
The investigations showed that similar to other chemical additives
SAP affects the plastic viscosity and yield stress of fresh mortar or concrete in different manners. Particular effects, especially on the development of these two parameters over time, depend on the type and
particle size of SAP on the one hand, and on mortar composition on
the other hand. More research efforts are needed in order to develop a
comprehensive approach to deal with these effects from the prospective
of application of SAP in concrete construction.
Acknowledgement
The authors acknowledge with gratitude the nancial support of the
European Social Fund (Europischer Sozialfonds) in German Federal Free
State of Saxony (Freistaat Sachsen) as part of the programme Europe
supports Saxony (Europa frdert Sachsen) with the grant number
100119059. The assistance of Dr. Dmitry Borin (TU Dresden) in helping
with carrying out the calibration of the rheology equipment is greatly
acknowledged. For generously providing the SAP samples and for permission to publish the data scientically, the authors are cordially grateful to SNF Floerger (Andrzieux Cedex/France).
References
[1] P.-C. Atcin, High-Performance Concrete, E&F SPON, London, 1998.
[2] J.E. Wallewik, Rheology of Particle Suspensions Rheology of Particle Suspensions,
The Norwegian University of Science and Technology (NTNU), 2003.
[3] .H. Wallevik, Introduction to rheology of fresh concrete, Course Compendium, ICI
Rheocenter, Reykjavik, 2009.
[4] P. Lura, F. Durand, A. Loukili, K. Kovler, Compressive strength of cement pastes and
mortars with superabsorbent polymers, Int. RILEM Conf. Vol. Chang. Hardening
Concr. Test. Mitig. 2023 August, Lyngby, 2006, pp. 117125.
[5] V. Mechtcherine, M. Gorges, C. Schroe, A. Assmann, W. Brameshuber, et al., Effect of
internal curing by using superabsorbent polymers (SAP) on autogenous shrinkage
and other properties of a high-performance ne-grained concrete: results of a
RILEM round-robin test, Mater. Struct. 47 (3) (2014) 541562.
[6] J. Pirard, V. Pollet, N. Cauberg, Mitigating autogenous shrinkage in HPC by internal
curing using superabsorbent polymers, Int. RILEM Conf. Vol. Chang. Hardening
Concr. Test. Mitigation, 2023 August, 2006, pp. 97106.

V. Mechtcherine et al. / Cement and Concrete Research 67 (2015) 5265

[7] O.M. Jensen, Use of superabsorbent polymers in construction materials, 1st Int. Conf.
Microstruct. Relat. Durab. Cem. Compos. 1315 Oct., Nanjing, 2008, pp. 757764.
[8] V. Mechtcherine, H. Reinhardt, Application of super absorbent polymers (SAP) in
concrete construction, State-of-the-Art Report, Springer, 2012.
[9] A.-E. Brdern, V. Mechtcherine, Multifunctional use of SAP in strain-hardening
cement-based composites, Int. RILEM Conf. Use Superabsorbent Polym. Other New
Addit. Concr. 1518 August, Lyngby, 2010, pp. 1122.
[10] H.W. Reinhardt, A. Assmann, S. Mnnig, Superabsorbent polymers (SAP) an admixture to increase the durability of concrete, 1st Int. Conf. Microstruct. Relat.
Durab. Cem. Compos. 13 15 Oct., Nanjing, 2008, pp. 313322.
[11] C.F. Ferraris, Measurement of the rheological properties of high performance concrete: State-of-the-Art Report, J. Res. Natl. Inst. Stand. Technol. 104 (1999) 461478.
[12] P. Banll, Rheology of fresh cement and concrete, Rheol. Rev. 2006 (2006) 61130.
[13] R.D.T. Filho, E.F. Silva, A.N.M. Lopes, V. Mechtcherine, L. Dudziak, Effect of superabsorbent polymers on the workability of concrete and mortar, in: V. Mechtcherine,
H.-W. Reinhardt (Eds.), Appl. Super Absorbent Polym. Concr. Constr. State-of-theArt Rep. Springer, 2012, pp. 3950.
[14] H. Paiva, L.P. Esteves, P.B. Cachim, V.M. Ferreira, Rheology and hardened properties
of single-coat render mortars with different types of water retaining agents, Constr.
Build. Mater. 23 (2009) 11411146.
[15] C. Schroe, V. Mechtcherine, M. Gorges, Relation between the molecular structure
and the efciency of superabsorbent polymers (SAP) as concrete admixture to mitigate autogenous shrinkage, Cem. Concr. Res. 42 (2012) 865873.
[16] O.M. Jensen, P.F. Hansen, Water-entrained cement-based materials. II. Experimental
observations, Cem. Concr. Res. 32 (2002) 973978.
[17] E. Secrieru, Rheometric Characterisation of Fresh Mortars Modied With Different
Superabsorbent Polymers (SAP), Technische Universitt Dresden, 2012.
[18] F.L. Buchholz, A.T. Graham (Eds.), Modern Superabsorbent Polymer Technology,
WILEY-VCH, New York, 1998.
[19] S. Friedrich, Superabsorbent polymers (SAP), in: V. Mechtcherine, H.-W. Reinhardt
(Eds.), Appl. Super Absorbent Polym. Concr. Constr. State-of-the-Art Rep. Springer,
2012, pp. 1319.
[20] P. Esteves, On the absorption kinetics of superabsorbent polymers, Int. RILEM Conf.
Use Superabsorbent Polym. Other New Addit. Concr. 1518 August, Lyngby, 2010,
pp. 7784.
[21] C. Schroe, V. Mechtcherine, Superabsorbent polymers to mitigate autogenous
shrinkage of cement mortar, ACI Spec. Publ. (2012) 265278.
[22] S. Mnnig, Superabsorbing Additions in Concrete Applications, Modelling and
Comparison of Different Internal Water Sources, University of Stuttgart, 2009.
[23] A. Richter, G. Paschew, S. Klatt, J. Lienig, K. Arndt, H.P. Adler, Review on hydrogel
based pH sensors and microsensors, Sensor 8 (2008) 561581.
[24] J. Plank, C. Hirsch, Impact of zeta potential of early cement hydration phases on
superplasticizer adsorption, Cem. Concr. Res. 37 (2007) 537542.
[25] H.-W. Reinhardt, A. Assmann, Effect of superabsorbent polymers on durability of
concrete, in: V. Mechtcherine, H.-W. Reinhardt (Eds.), Appl. Super Absorbent
Polym. Concr. Constr. State-of-the-Art Rep. Springer, 2012, pp. 115135.
[26] G. Schramm, A Practical Approach to Rheology and Rheometry, 1st ed. Gebrueder
Haake, Karlsruhe, 2004.
[27] C.F. Ferraris, N.S. Martys, Concrete rheometers, in: N. Roussel (Ed.), Underst. Rheol.
Concr, 1st ed.Woodhead Publishing Limited, 2012, pp. 6382.
[28] M. Haist, Zur Rheologie und den physikalischen Wechselwirkungen bei
Zementsuspensionen, KIT Scientic Publishing, 2010.

65

[29] N. Roussel, A thixotropy model for fresh uid concretes: theory, validation and applications, Cem. Concr. Res. 36 (2006) 17971806.
[30] H.J. Yim, J.H. Kim, S.P. Shah, Cement particle occulation and breakage monitoring
under Couette ow, Cem. Concr. Res. 53 (2013) 3643.
[31] T.G. Mezger, Das Rheologie Handbuch, 2nd ed. Vincentz Network GmbH & Co. KG,
Hannover, 2006.
[32] O.H. Wallevik, J.E. Wallevik, Rheology as a tool in concrete science: the use of
rheographs and workability boxes, Cem. Concr. Res. 41 (2011) 12791288.
[33] K. Vance, A. Kumar, G. Sant, N. Neithalath, The rheological properties of ternary
binders containing Portland cement, limestone, and metakaolin or y ash, Cem.
Concr. Res. 52 (2013) 196207.
[34] L. Ferrari, J. Kaufmann, F. Winnefeld, J. Plank, Multi-method approach to study inuence of superplasticizers on cement suspensions, Cem. Concr. Res. 41 (2011)
10581066.
[35] H. Vikan, H. Justnes, Inuence of silica fume on rheology of cement paste, in: .H.
Wallevik, I. Nielsson (Eds.), 3rd Int. Symp. Self-Compacting Concr, RILEM Publications S.A.R.L., Reykjavik, 2003, pp. 190201.
[36] J. Goaszewski, J. Szwabowski, Inuence of superplasticizers on rheological behaviour of fresh cement mortars, Cem. Concr. Res. 34 (2004) 235248.
[37] L.N. Thrane, C. Pade, T. Svensson, Estimation of Bingham rheological parameters of
SCC from slump ow measurement, 5th Int. RILEM Symp. Self-Compacting Concr.
35 Sept., Ghent, 2007, pp. 353358.
[38] H. Vikan, H. Justnes, F. Winnefeld, R. Figi, Correlating cement characteristics with
rheology of paste, Cem. Concr. Res. 37 (2007) 15021511.
[39] L.P. Esteves, P.B. Cachim, V.M. Ferreira, Effect of ne aggregate on the rheology properties of high performance cementsilica systems, Constr. Build. Mater. 24 (2010)
640649.
[40] C.G.P. Schiel, O. Mazanec, D. Lowke, J. Plank, C. Schr, M. Gruber, M. Schmidt, D.
Stephan, Investigations on the workability and microstructure development of
UHPC; part 1: effect of superplasticizer and silica fume on mixing and workability
of UHPC, Cem. Int. 8 (2010) 6071.
[41] N. Roussel, A. Lematre, R.J. Flatt, P. Coussot, Steady state ow of cement suspensions: a micromechanical state of the art, Cem. Concr. Res. 40 (2010) 7784.
[42] E.P. Koehler, D.W. Fowler, Aggregates in Self-Consolidating Concrete, Austin, 2007.
[43] H.A. Barnes, Q.D. Nguyen, Rotating vane rheometry a review, J. Non-Newtonian
Fluid Mech. 98 (2001) 114.
[44] P.C.F. Mller, J. Mewis, D. Bonn, Yield stress and thixotropy: on the difculty of measuring yield stresses in practice, Soft Matter 2 (2006) 274283.
[45] S. Jacobsen, J.H. Mork, S.F. Lee, L. Haugan, Pumping of concrete and mortar state of
the art report, COIN Project Rep, Oslo, 2008.
[46] D. Feys, R. Verhoeven, G. De Schutter, Pumping of self compacting concrete: an insight into a daily application, in: J. Walraven, D. Stoelhorst (Eds.), Proc. Int. FIB
Symp. 2008, 19 21 May, Taylor & Francis Group, London, UK, Amsterdam, 2008,
pp. 385390.
[47] M. Jolin, D. Burns, B. Bissonnette, F. Gagnon, L. Bolduc, Understanding the
pumpability of concrete, Shotcrete Undergr. Support XI Enginnering Conf. Int.,
2009.
[48] V. Mechtcherine, V.N. Nerella, K. Kasten, Testing pumpability of concrete using Sliding Pipe Rheometer, Constr. Build. Mater. 53 (2014) 312323.