Construction and Building Materials 49 (2013) 134–143

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Construction and Building Materials

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

The effect of Superabsorbent Polymers (SAP) on microstructure

and mechanical properties of fly ash cementitious mortars
Agnieszka J. Klemm ⇑, Karol S. Sikora
Glasgow Caledonian University, School of Engineering and Built Environment, 70 Cowcaddens Road, Glasgow G4 0BA, UK

h i g h l i g h t s

 Majority of pores created by SAP are ‘ink-bottle’ and/or closed.

 SAPs increase ‘polymer pore’ walls’ strengths by densification of microstructure.
 The addition of SAP with high WAC results in an increased compressive strength.
 SAPs increase number of small pores which do not affect compressive strength.

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

Article history: The paper is focused on microstructure and strength development in fly ash cementitious mortars con-
Received 1 February 2013 taining superabsorbent polymers. In order to evaluate the effect of different water absorption/desorption
Received in revised form 17 July 2013 kinetics of SAPs, comprehensive MIP and SEM analysis supplemented by the mechanical properties
Accepted 21 July 2013
assessments have been performed. The vast majority of pores created by SAP are ‘ink-bottle’ and/or
Available online 4 September 2013
closed. Gradual release of water stored by SAP facilitates formation of denser, more homogenous and pre-
dictable cementitious matrix, further enhanced by the pozzolanic reaction of fly ash with portlandite.
Keywords:
Addition of SAP with high water absorption capacity results in an increased compressive strength.
Superabsorbent polymers
Portland fly ash cement
Ó 2013 Elsevier Ltd. All rights reserved.
Microstructural characterisation
Mechanical properties

1. Introduction One of the relatively new developments is based on application

Concrete based on Portland cement is probably the most widely
used material made by man and the global production of cement is
steadily increasing [1]. The motives of its popularity may vary;
nonetheless it is primarily a consequence of economic reasons –
a relatively low price to value ratio. This, in turn results from the
general availability of constituents, commonly accessible cement
production and concrete placement technology, as well as its long
life cycle. Moreover, construction industry undergoes a continuous
modifications and improvements in order to successfully comply
with the requirements of sustainable development. It is expected
to develop more durable, less labour and service intensive materi-
als at a competitive price. To meet these demands various types of
additives, admixtures (EN 206-1) and supplementary cementitious
materials are more commonly incorporated into cement matrices.
This however necessitates thorough analysis of their individual
reactions with clinker and between each other [2,3].
⇑ Corresponding author. Tel.: +44 1413313892; fax: +44 1413313696.
E-mail addresses: a.klemm@gcu.ac.uk (A.J. Klemm), karol.sikora@gcu.ac.uk (K.S.
Sikora).
of Superabsorbent Polymers (SAP) as internal curing agents. SAPs
are cross-linked networks of hydrophilic polymers with a high
capacity for water absorption [4]. In contact with liquids superab-
sorbent polymers hydrate and form a swollen polymer gel. This
process is reversible so the removal of water results in collapsing
of SAPs. In cementitious matrices of fresh/young materials, they
form a system of evenly distributed pores filled with water which
can be gradually released during hydration process, thus prevent-
ing self desiccation. However, the occurrence of SAP pores may
have an impact on mechanical properties, in particular on com-
pressive strength development [5]. It is generally accepted that
SAPs, by diminishing self-desiccation, increase a degree of hydra-
tion [6–11]. Consequently a denser paste phase is formed and
propagation of micro-cracks is generally prevented. On the other
hand, collapsed polymers increase porosity of hcp by creation of
voids and thus negatively influence strength [12]. This view has
been supported by results presented in a number of studies [13–
18].
However, other studies argue contradictory effect of SAPs. Dud-
ziak and Mechtcherine [19] pointed out that, despite an initial neg-
ative influence of extra pores, SAPs reduce autogenous shrinkage

0950-0618/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.conbuildmat.2013.07.039
 A.J. Klemm, K.S. Sikora / Construction and Building Materials 49 (2013) 134–143 135

and lead to internal stress reduction and increased strength. The resulting from self-desiccation, prevention of this process may
study by Siramanont et al. [20] also concludes that the usage of actually improve tensile properties [7].
SAPs as internal curing agent may increase the strength of cemen- It should be stressed that previously published studies were
titious materials. If SAP swelling properties are adequately predominantly focused on the effect of SAP on composites based
matched the volume of the swollen SAPs can be replaced, at least on CEM I Portland cements. Since medium and high volume addi-
partially, by the hydration products at later ages. These claims tions of supplementary cementitious materials are becoming more
and findings are in accordance with the compressive strength of a standard in general concrete technology practice, the behav-
results of the other researches [3,21–25]. Results published by iour of SAP modified composites requires an appropriate
Reinhardt and Assmann [23] suggest that the differences in sizes verification.
and quantities of SAP pores do not have an effect on strength
development. It can be attributed to the predominant role of air
pores over the polymer pores formed in the collapsed state. In turn, Table 2
Lura et al. [26] argued that interfacial transition zones (ITZ) in Median pore diameter and total porosity.
aggregate vicinity and the pre-cracked aggregates decrease com-
Property Median pore diameter (volume) (nm) Porosity (%)
pressive strength of matrix more than voids created by SAP. There-
fore, ITZ and aggregates determine compressive strength of Sand/cement 1:1 2:1 1:1 2:1

mortars and the effect of SAP is negligible. R 1w 87.1 108.8 21.83 18.33
The effects of SAP on tensile strength development may not be 2w 52.3 65.3 21.02 17.36
3w 48.9 57.3 20.33 17.45
of the same magnitude as that of compressive strength. Since ten-
4w 50.8 92.1 18.75 17.47
sile strength depends specifically on the micro-cracks occurrence 5w 63.4 45.1 20.43 15.14
6w 42.1 61.2 19.92 17.22
A 1w 100.3 166.5 26.31 22.46
2w 61.5 97.8 23.43 20.95
3w 61.9 111.8 21.46 20.61
4w 52.5 338.9 21.31 15.55
5w 74.5 49.2 21.39 17.99
6w 45.0 65.0 20.90 16.66
B 1w 73.6 102.1 20.66 16.15
2w 67.9 64.1 19.73 17.42
3w 59.6 63.9 20.30 17.52
4w 42.1 70.2 17.72 21.29
5w 55.8 49.0 20.00 15.44
6w 58.2 57.0 18.81 16.08
C 1w 74.9 111.6 23.13 20.39
2w 63.8 117.2 19.92 21.21
3w 57.8 119.1 22.31 20.67
4w 59.3 85.0 23.77 19.49
Fig. 1. The SEM micrograph of CEM II/B-V 32.5 cement used in the study. 5w 64.0 186.7 22.86 22.70
6w 53.7 82.1 21.12 19.41

Fig. 2. The SEM micrographs of SAP: (a) dry and (b) wet.

Table 1
Cement mortar compositions and fresh mortar consistencies.

Mix code R1 A1 B1 C1 R2 A2 B2 C2
Sand/cement 1:1 1:1 1:1 1:1 2:1 2:1 2:1 2:1
(Water/cement)tot 0.45 0.45 0.45 0.45 0.45 0.45 0.45 0.45
(Water/cement)eff 0.45 0.425 0.438 0.375–0.388 0.45 0.425 0.438 0.375–0.388
SAP content (% by weight of cement) 0 0.25 0.25 0.25 0 0.25 0.25 0.25
Flow before jolts (mm) 217.5 100 192.5 103.8 105 100 100 100
Flow after 15 jolts (mm) >250 197.5 >250 202.5 185 112.5 165 113.5
136 A.J. Klemm, K.S. Sikora / Construction and Building Materials 49 (2013) 134–143

0.25 0.25
R1-1w R1-4w

Log Differential Intrusion (mL/g)

Log Differential Intrusion (mL/g)
A1-1w 0.2 A1-4w 0.2

B1-1w B1-4w
0.15 C1-4w 0.15
C1-1w

0.1 0.1

0.05 0.05

0 0
1000000 100000 10000 1000 100 10 1 1000000 100000 10000 1000 100 10 1
Pores size Diameter (nm) Pores size Diameter (nm)

0.25 0.25
R1-2w R1-5w

Log Differential Intrusion (mL/g)

Log Differential Intrusion (mL/g)

A1-2w 0.2 A1-5w 0.2

B1-2w B1-5w
0.15 C1-5w 0.15
C1-2w

0.1 0.1

0.05 0.05

0 0
1000000 100000 10000 1000 100 10 1 1000000 100000 10000 1000 100 10 1
Pores size Diameter (nm) Pores size Diameter (nm)

0.25 0.25
R1-3w R1-6w
Log Differential Intrusion (mL/g)

Log Differential Intrusion (mL/g)

A1-3w 0.2 A1-6w 0.2

B1-3w B1-6w
0.15 0.15
C1-3w C1-6w

0.1 0.1

0.05 0.05

0 0
1000000 100000 10000 1000 100 10 1 1000000 100000 10000 1000 100 10 1
Pores size Diameter (nm) Pores size Diameter (nm)

Fig. 3. Pores size distribution curves for samples in age between 1 and 6 weeks.

One of the most popular supplementary materials blended with
Portland cement is fly ash. A partial replacement of OPC by pozzo-
lanic material such as fly ash may have significant consequences on
material performance even without any SAPs additions [27]. High
volume fly ash composites produce a stronger body, indicating that
cement matrix and residual unreacted fly ash particles form a solid
bonding [28]. Cementitious matrix containing fly ash is generally
more homogeneous due to the reduction of Ca(OH)2 at the aggre-
gate–paste interface and in the bulk paste [29–31]. Fly ash reactiv-
ity level can be attributed to its particle size distribution. Reactivity
was found to be directly proportional to the amount of particles
below 10 lm, and inversely proportional to particles bigger than
45 lm [32]. Furthermore, the average pore size diameter is
decreased by fly ash [33], even though the total porosity is higher.
This phenomenon is associated with significant increase in per-
centage of very small pores, below 10 nm.
Although fly ash cement mortars have been widely researched
and published and the concept of superabsorbent polymers has
been known for a couple of decades the application of SAPs in
blended cements is not very well documented. This paper
endeavours to evaluate the effect of superabsorbent polymers with
different water absorption/desorption characteristics on the micro-
structure and strength development in fly ash cementitious mor-
tars. The main purpose of this study is to assess correlations
between microstructural alterations, resulting from SAP effect, of
clinker-fly ash based matrix on mechanical properties. Further-
more, in order to assess the effectiveness of SAP the relationship
between the compressive and flexural strength of mortars is ana-
lysed, as well as the influence of aggregate content.
2. Experiment
All samples have been prepared using Portland cement with minimum 30% of
fly ash by weight CEM II/B-V 32.5 (BS EN 197-1). Sizes of fly ash particles belonged
predominantly to the range between 5 and 15 lm. Fig. 1 shows the SEM micrograph
of cement used in the study.
Three types of cross-linked Superabsorbent polymers (later called SAP A, SAP B
and SAP C) have been used in this study. SAP A is a copolymer of acrylamide and
acrylic acid, SAP B is a polymer based on acrylic acid and SAP C is a modified
polyacrylamide. All polymers have absorption capacity of 200–250 ml/g in demi-
neralised water measured by the ‘tea bag’ method [34]. However, their absorption
characteristics in cement paste solution differ significantly; approximately 10 g/g
 A.J. Klemm, K.S. Sikora / Construction and Building Materials 49 (2013) 134–143 137

0.25 0.25
R2-1w R2-4w

Log Differential Intrusion (mL/g)

Log Differential Intrusion (mL/g)

A2-1w 0.2 A2-4w 0.2
B2-1w B2-4w

C2-1w 0.15 C2-4w 0.15

0.1 0.1

0.05 0.05

0 0
1000000 100000 10000 1000 100 10 1 1000000 100000 10000 1000 100 10 1
Pores size Diameter (nm) Pores size Diameter (nm)

0.25 0.25
R2-2w R2-5w

Log Differential Intrusion (mL/g)

Log Differential Intrusion (mL/g)

A2-2w 0.2 A2-5w 0.2
B2-2w B2-5w

C2-2w 0.15 C2-5w 0.15

0.1 0.1

0.05 0.05

0 0
1000000 100000 10000 1000 100 10 1 1000000 100000 10000 1000 100 10 1
Pores size Diameter (nm) Pores size Diameter (nm)

0.25 0.25
R2-3w R2-6w
Log Differential Intrusion (mL/g)

Log Differential Intrusion (mL/g)

A2-3w 0.2 A2-6w 0.2
B2-3w B2-6w

C2-3w 0.15 C2-6w 0.15

0.1 0.1

0.05 0.05

0 0
1000000 100000 10000 1000 100 10 1 1000000 100000 10000 1000 100 10 1
Pores size Diameter (nm) Pores size Diameter (nm)

Fig. 4. Pores size distribution curves for samples of 2:1 sand/cement in age between 1 and 6 weeks.

for SAP A, 5 g/g for SAP B and 25–30 g/g for SAP C. All materials were prepared by
grinding and screening to size of 63–125 lm with less than 10% of finer particles.
Fig. 2 presents the SEM micrographs of used SAPs in dry condition (a) and 5 min
after their contact with water (b).
Fine sand used in the study contained 99% of particles distributed below
0.6 mm. Mix compositions are presented in Table 1. Total water to cement ratio
of 0.45 was maintained for all mixes. However, due to additional water absorption
by SAPs the effective water to cement ratios for mixes containing polymers were
lower than the total water to cement ratios. The resulting changes in fresh mortar
consistencies are presented in Table 1. Since SAP B has significantly lower absorp-
tion capacity than SAP A and SAP C, a little effect on fresh mortar flow has been re-
corded. Strong effect of SAP A on flow values can be attributed to its higher
absorption rate at the time of flow test.
Specimens were cast into prismatic moulds (160 mm  40 mm  40 mm) and
after 24 h of curing under polyethylene cover were demoulded. Prior to testing they
were then cured in polythene bags in laboratory conditions of 40 ± 5 RH% and tem-
perature of 24 ± 2 °C.
3. Experimental results
3.1. Microstructural characteristics
In order to evaluate the effects of different SAPs on the micro-
structure development comprehensive analyses of mortars by the
Mercury Intrusion Porosimetry (MIP) technique were performed
at the predetermined time intervals. The established features were
subsequently verified by the extensive examination under the
Scanning Electron Microscope (SEM).
Table 2 presents Median Pore Diameter and Total Porosities
measured by MIP for all analysed samples. Small decrease in poros-
ity with time was recorded for all laboratory cured samples con-
firming the progress of hydration. The influence of SAPs
manifests itself in an increase of total porosities for lab cured A1
and C1 samples and in a decrease for B1 samples in comparison
with the corresponding reference samples. Similar trends were ob-
served for mortars with s/c 2:1 but due to the reduced percentage
of cement paste, porosities were lower than for specimens with s/c
1:1. Despite the lower porosities samples had generally higher
median pore diameters.
Pore size distribution curves for samples (R1, A1, B1, C1) in lab
conditions up to 6 weeks are shown in Fig. 3. In general two
distinctive pore size ranges can be indentified for specimens cured
in laboratory conditions: 50–80 nm and 200–700 nm.
Although some similarities to the reference sample have been
observed for all specimens modified by superabsorbent polymers,
138 A.J. Klemm, K.S. Sikora / Construction and Building Materials 49 (2013) 134–143

(a) 60

2
Compressive Strength N/mm
50

40

30

20

10

0
A1
A2
B1
B2

A1
A2
B1
B2

A1
A2
B1
B2

A1
A2
B1
B2

A1
A2
B1
B2

A1
A2
B1
B2
R1
R2

C1
C2
R1
R2

C1
C2
R1
R2

C1
C2
R1
R2

C1
C2
R1
R2

C1
C2
R1
R2

C1
C2
1 week 2 weeks 3 weeks 4 weeks 5 weeks 6 weeks

(b) 10
9
2
Flexural Strength N/mm

8
7
6
5
4
3
2
1
0
R1
R2

C1
C2
R1
R2

C1
C2
R1
R2

C1
C2
R1
R2

C1
C2
R1
R2

C1
C2
R1
R2

C1
C2
A1
A2
B1
B2

A1
A2
B1
B2

A1
A2
B1
B2

A1
A2
B1
B2

A1
A2
B1
B2

A1
A2
B1
B2
1 week 2 weeks 3 weeks 4 weeks 5 weeks 6 weeks

Fig. 5. Compressive (a) and flexural (b) strength development of samples cured in lab conditions with sand to cement ratio 1:1 in comparison with samples of sand to cement
ratio 2:1.

Fig. 6. SEM micrographs presenting example of pores of very irregular shapes (samples A1 and C1).

0.16
crease of peak representing smaller pores has been recorded.
R1-1w-Intrusion
Cumulative Intrusion (mL/g)

Specimens C1 have shown some similarities to samples R1. How-

0.14 R1-1w-Extrusion
ever, the evident peak for pores in diameters of 300 nm has de-
0.12 A1-1w-Intrusion
creased with the formation of hydration products. On the other
0.1 A1-1w-Extrusion hand, the effect of SAP B is very limited. Pores size distribution
0.08
curves for samples B1 have shown distinct similarities to the refer-
0.06 ence specimens at all ages.
0.04 Alterations in the pore size distributions for samples with 2:1
0.02 sand to cement ration are shown in Fig. 4. On all pore size distribu-
0 tion charts two clearly defined peaks have been observed
1 10 100 1000 10000 corresponding to the increased volume of pores with sizes
Pressure (psia) 300–900 nm and 10-200 nm.
The most significant changes in pore size distributions have
Fig. 7. Mercury intrusion–extrusion hysteresis for 1 week samples: R1 and A1.
been observed for samples A2. Initial high percentage of larger
pores decreased relatively soon (by week 2) and a higher per-
centage of smaller pores by the week 5 become a characteristic
the most significant changes in pore size distributions have been feature. Reduction in cement content has resulted in the notice-
recorded for sample A1. In the first week the share of bigger pores able change of pore size distribution. The total porosities for all
has been higher and the share of pores of small size has been lower samples were lower and the peaks of PSD curves were much
by comparison with the reference sample. This feature disappeared flatter. The changes in the microstructure were less pronounced
by week 2 and a decrease in contribution of larger pores in the ex- and have been observed later. The effect of SAP B was
pense of small ones has been noted. In later weeks a gradual in- negligible.
 A.J. Klemm, K.S. Sikora / Construction and Building Materials 49 (2013) 134–143 139

70% 4. Analysis
65%
60% 4.1. Microstructural characteristics
55%
50% Extensive analysis of pore size distributions were conducted by
45% a commonly accepted method of the Mercury Intrusion Porosime-
40% try. However, the method is based on a number of assumptions
A1-1w
B1-1w

A1-2w
B1-2w

A1-3w
B1-3w

A1-4w
B1-4w

A1-5w
B1-5w

A1-6w
B1-6w
R1-1w

C1-1w
R1-2w

C1-2w
R1-3w

C1-3w
R1-4w

C1-4w
R1-5w

C1-5w
R1-6w

C1-6w
Fig. 8. Mercury retention as a percentage of total porosity for lab cured samples.
3.2. Compressive and flexural strength
Microstructural characterizations of all studied samples were
accompanied by the mechanical properties testing. Compressive
and flexural strengths have been determined according to BS EN
1015-11:1999. Fig. 5 shows clear similarities in strength develop-
ments. As anticipated, samples with sand to cement ratio 2:1 have
showed slightly lower compressive strength than samples with 1:1
ratio. The similar pattern have been observed for the reference
samples and modified by SAPs, however the smallest differences
have been recorded for samples containing SAP B.
Flexural strength values for all samples have shown some
increase during the first 2 weeks, then stabilised for next 2 weeks
and then increased further. No significant changes have been
observed after 4 weeks of curing for samples with 2:1 s/c ratio,
in contrary to the compressive strength results. Increase in
strength values for specimens with 1:1 s/c have been recorded
after the fourth week with the most pronounced ones for the refer-
ence sample.
A1-1w A1-6w
and simplifications which may result in a slightly distorted picture
of the actual microstructure. Firstly, the method is based on the
Washburn’s model assuming the pores of cylindrical shape with
open ends and circular in cross-section. In reality this ‘idealised’
structure does not exist and pores and capillaries are far from
being of regular shape as seen on SEM images, shown in Fig. 6.
Some pores may be closed, some connected by very narrow
openings (ink-bottle pores). In consequence, the recorded high
porosity in a range of small pores (below 100 nm) may be incor-
rect. In order to analyse pore size distribution plots from MIP, a
close examination of intrusion–extrusion hysteresis was under-
taken. The examples of such hysteresis are shown in Fig. 7.
The fact that intrusion and extrusion curves has not lined up
indicates a substantial proportion of mercury retained in the pore
systems. Fig. 8 presents the mercury retention after complete test-
ing cycle test of intrusion and extrusion, which may be calculated
from the following formula:
um ¼ V extr: =V intr:  100 ð%Þ
where um is the mercury retention after intrusion–extrusion cycle,
Vextr. the volume of remaining mercury inside the pores after intru-
sion-extrusion cycle for the lowest test applicable pressure (approx
18 psia) and Vintr. is the volume of mercury inside the specimen
after intrusion cycle for the highest test applicable pressure (approx
60,000 psia).
The mercury retention values were very similar for the particu-
0.25
lar mixes at different ages. Significantly higher percentage of the
Log Differential Intrusion (mL/g)

R1-1w R1-6w
mercury retention (by approximately 10% points) was recorded
0.2
for samples A1 and C1 than for the reference samples. In turn, all
samples B1 had a similar or slightly higher retention values (less
0.15
than 5% points) in comparison to the reference samples.
It is very likely that higher mercury retention resulted from the
0.1
presence of ‘ink-bottle’ pores with narrow openings. These pores
could have been created by the collapsing superabsorbent poly-
0.05 mers. Water from SAPs promoted creation of hydration products
in a collapsed state, which consequently led to the pores closures.
0 The phenomenon was much more pronounced for samples A1 and
1000000 100000 10000 1000 100 10 1
Pore size Diameter (nm)
C1, both polymers with higher water absorption capacity than SAP
B. Due to the high mercury retention in samples A1 and C1, per-
Fig. 9. Pores size distribution curves for samples containing SAP A in comparison to centage of small pores in these samples might be questionable.
the corresponding reference samples for 1 week and 6 weeks. When ‘ink-bottle’ pores were intruded the high pressure had to
be applied (higher than for equivalent of this size of pore according

Fig. 10. SEM micrographs for lab cured samples containing SAP A for 1 week (a), 6 weeks (b).
140 A.J. Klemm, K.S. Sikora / Construction and Building Materials 49 (2013) 134–143

A2-1w A2-6w 0.25 time, it may give an indication of increasing strength of ‘polymer

Log Differential Intrusion (mL/g)

R2-1w R2-6w
0.2
0.15
0.1
0.05
0 indentified in SEM images suggesting that they were consumed
1000000 100000 10000 1000 100 10 1 in reaction with fly ash.
Pore size Diameter (nm)
Fig. 11. Pores size distribution curves for samples containing SAP A in comparison
to the reference samples with sand to cement ratio 2:1 for 1 week and 6 weeks.
to Washburn’s model) and gave an indication of higher percentage
of smaller pores than really existed.
The most distinct differences have been recorded for samples
A1. Fig. 9 presents pore size distribution curves for these samples
after one and 6 weeks of laboratory curing. The noticeable differ-
ences in the height of peaks for SAP and reference samples may
be attributed to the collapse of polymer’s networks. This may lead
to the conclusion that these peaks have represented ‘SAP pores’ i.e.
pores that were directly created by collapsing polymers. In addi-
tion, it could be pointed out from the pores size distribution graphs
that diameters of ‘SAP pores’ were decreasing over time. After
1 week of lab curing the peak was for approximately 500–
600 nm, but in 5 weeks time it moved to about 50–80 nm, Accord-
ing to the Washburn’s model all sizes refer to diameters of a
cylinder.
Due to inherent simplifications of the model it appears that val-
ues of pore diameters corresponding to the peaks do not ade-
quately describe real pore sizes. It is likely that ‘SAP pores’ are of
bigger sizes than cylinders of such diameter for which peaks have
been recorded. Most probably the majority of pores created by
SAPs are poorly connected by narrow ‘throats’ or they are closed.
It follows that peaks in MIP graphs represent a pressure equivalent
for which mercury was able to intrude, and not the actual pore
sizes. The peaks were precipitous (indicating narrow range of pore
sizes), which resulted from relatively high mercury intrusion for
narrow range of pressures. It could be associated with sudden pore
walls damage by intruding mercury. According to this hypothesis,
peaks in pore size distribution graphs might be attributed to a
pore’ walls’ resulting from microstructure densification.
Most likely water released by polymer has promoted creation of
new products, mainly CSH gel and led to the increased ‘breaking
pressure’ resistance. Continuing growth of new hydration products
explains a steady decrease of pore volumes and a reduction of pore
openings – ‘throats’, making them accessible for mercury intrusion
only at higher pressures. The reduction of total porosities over time
indicates a significant contribution of pozzolanic reaction. This
may explain the fact that only very few portlandite crystals were
The analysis of the MIP results for high pressure range cannot
lead to a conclusion on which pore feature was predominant. Both,
‘ink-bottle’ and closed pores could influence the results.
Another explanation of a possible MIP inaccuracy may be asso-
ciated with inappropriate selection of contact angle between mer-
cury and mortar surfaces. Different energies of the mercury and
mortar surfaces lead to assumption that contact angle relates to
a specific solid surface [35]. Due to the fact that it is impossible
to precisely determine contact angle, the constant value for contact
angle was used for the purpose of this study. It seems that contact
angle of 130° used in MIP measurements might be different for the
examined specific composites. Furthermore, contact angle could
vary within a single sample. The specific surfaces of ‘SAP pores’
may be different from surfaces of other pores in cementitious mor-
tar, created during ‘normal’ curing process.
Voids created by polymer A and its remnants are clearly visible
in the Scanning Electron Microscopy images. Pores of irregular and
oblong shapes can be observed in all samples. These pores do not
fully meet the Washburn’s model assumption of cylindrical shapes,
and in consequence may influence the pore size distribution
results. Fig. 10 shows SEM images of ‘SAP pores’ in A1 mortars
cured for one and 6 weeks.
The SEM micrographs do not present any significant differences
between ‘SAP pores’ for different ages. Due to their irregularities,
70%
65%
60%
55%
50%
45%
40%
R2-1w

C2-1w
R2-2w

C2-2w
R2-3w

C2-3w
R2-4w

C2-4w
R2-5w

C2-5w
R2-6w

C2-6w
A2-1w
B2-1w

A2-2w
B2-2w

A2-3w
B2-3w

A2-4w
B2-4w

A2-5w
B2-5w

A2-6w
B2-6w

‘breaking pressure’, defined as a value of intruded mercury pres-

sure, which has broken pore walls and penetrated it. Since peaks
in PDS have been associated with decreasing diameters over the Fig. 13. Mercury retention as a percentage of total porosity for samples with sand
to cement ratio 2:1.

Fig. 12. SEM micrographs for samples containing SAP A with sand to cement ratio 2:1 for 4 weeks (a) and 6 weeks (b).
 A.J. Klemm, K.S. Sikora / Construction and Building Materials 49 (2013) 134–143 141

20% tribution curves for laboratory cured samples for one and 6 weeks
18%
can be compared in Fig. 11.
16%
14% Higher sand/cement ratio results only in minor differences in
12% pore size distributions. The SEM analyses have confirmed shapes
10% and size similarities of ‘SAP pores’. Fig. 12 shows micrographs for
8%
6% samples A2.
4% Fig. 13 represents mercury retention as a percentage of total
2% porosity for laboratory cured samples with s/c ratio 2:1. The higher
0%
values for mercury retention were obtained for samples A2 and C2
C1-1w

R2-4w
R1-1w

R2-2w

C2-2w
R1-3w

C1-3w

C2-4w
R1-5w

C1-5w

R2-6w

B2-6w
C2-6w
A1-1w
B1-1w

A2-2w
B2-2w

A1-3w
B1-3w

A2-4w
B2-4w

A1-5w
B1-5w

A2-6w
Fig. 14. Mercury retention as a percentage of bulk volume of samples with sand to
cement ratios 1:1 and 2:1.
precise descriptions of their dimensions are very problematic. Nev-
ertheless, it is very likely that the majority of ‘SAP pores’ have
dimensions between outermost edges in the range of 50–250 lm.
The Mercury Intrusion Porosimetry results for samples A2 have
been consistent with the results for samples A1. The pore size dis-
than R2 and B2. The pattern was similar to mercury retention
results for samples with sand to cement ratio 1:1. Only results
for s/c ratio 2:1 were in general higher that might be associated
with a smaller contribution of cement paste than for samples with
sand to cement ratio 1:1.
In order to compare mercury retention for samples with differ-
ent s/c ratios, mercury retentions as a percentage of sample bulk
volume have been calculated. They have been obtained by multi-
plication of mercury trapped inside the pores volume after extru-
sion cycle in mL/g and bulk density at 0.56 psia in g/ml as
follows:

Fig. 15. SEM micrographs for samples containing SAP A (left) and SAP C (right) for 1 week (top) and 6 weeks (bottom).

Fig. 16. SEM micrographs for samples containing SAP B for 3 weeks (a) and 6 weeks (b).
142 A.J. Klemm, K.S. Sikora / Construction and Building Materials 49 (2013) 134–143

up ¼ V extr:  qb  100 ð%Þ by multinomial of the second degree. The effect of superabsorbent
polymers on correlation between compressive and flexural strength
where up is the mercury retention after intrusion–extrusion cycle is noticeable for samples with s/c 1:1. For the reference samples the
as a percentage of sample bulk volume, Vextr. the volume of reaming relationship is nearly linear. In turn, samples containing superabsor-
mercury inside the pores after intrusion–extrusion cycle for the bent polymers have shown that an increase in compressive strength
lowest test applicable pressure (approx 18 psia) and qb is the spec- is not associated with simultaneous raise of flexural strength. A high
imen bulk density at 0.56 psia. scatter of individual results, particularly for higher strengths can be
Fig. 14 shows mercury retention as a percentage of sample bulk related to an increase of small pores which do not affect compressive
volume for analysed samples. strength but influence flexural strength. The difference in behaviour
As anticipated the results for samples with s/c ratio 1:1 and 2:1 between SAP samples and the reference samples suggests rather sig-
have showed a very similar trend suggesting the higher percentage nificant proportion of small pores resulting from the formation of
of ‘ink-bottle’ and closed pores for samples modified by SAP A and CSH gel within larger SAP pores. These observations are in line with
SAP C. the MIP results (Fig. 3).
A systematic studies of mechanical properties revealed that Unlike for samples with s/c 1:1, the effect of SAPs on the perfor-
compressive strength for samples A has been higher than for the ref- mance of mortars with s/c 2:1 is rather negligible. Small but steady
erence samples while its flexural strength was hardly affected increase can be observed for both compressive and flexural
(Fig. 5). These phenomena may be associated with progressive den- strength for all tested samples. It can be associated with the signif-
sification of CSH gel facilitated by SAP A introduction to the mix. The icant role of higher aggregate content. Due to the lower cement
comparison of SAP A and SAP C mortars is presented in Fig. 15. paste content formation of SAP pores has only a limited effect on
Although SAP C reveals a similar behaviour to SAP A, it creates smal- strength development.
ler pores, These pores seems to be filled with water for longer than
in pores for SAP A. The different kinetics of water absorption/ 5. Conclusions
desorption for different polymers plays the key role in microstruc-
ture development and hence in macro scale performance. Based on the presented analyses the following conclusion can
In contrast to SAP A and SAP C findings, rather insignificant ef- be formulated:
fects on mortar microstructure and mechanical properties were ob-
served for SAP B. It is consistent with the expectations since SAP B – The vast majority of pores created by SAP are ‘ink-bottle’ and/or
has relatively low water absorption capacity in pore solution and closed and have at least a few thousands nanometres diameters.
only a minor effect of SAP B on pore size distribution was recorded. – Superabsorbent polymers in fly ash Portland cement mortars
Small pores created by SAP B may not be accessible to the intruded promote creation of a dense network of CSH in a collapsed state
mercury resulting in very similar behaviour to the reference sam- consequently leading to pores closures. The phenomenon is
ple. Fig. 16 shows SEM micrographs of mortar with SAP B content. much more pronounced in samples containing superabsorbent
The characteristic feature here is rather low number of ‘SAP pores’ polymers with a high water absorption capacity.
with diameters generally not exceeding twenty micrometers. – The effects of superabsorbent polymers on mechanical proper-
ties strongly depend on SAP type and water absorption/desorp-
4.2. Mechanical properties tion kinetics. The pace of water release is of much higher
importance than previously anticipated.
Microstructural examinations were accompanied by the analysis – Gradual release of additional water, stored by SAP, facilitates
of mechanical properties. Flexural strength as a function of compres- formation of denser and more homogenous cementitious
sive strength is presented in Fig. 17. The trend has been represented matrix, further enhanced by the pozzolanic reaction of fly ash
10
with portlandite. Since the sizes of fly ash particles are mostly
Flexural strength [N/mm ]

R1 A1 B1 C1
2

9 below 15 lm, they act as effective fillers for voids in the vicinity
R1: y = -0.0008x2 + 0.1817x
8 of aggregate and ensure dense packing of cement particles
7 A1: y = -0.0022x2 + 0.2453x
6
B1: y = -0.0022x2 + 0.2214x (‘wall effect’).
5 C1: y = -0.0033x2 + 0.2804x – SAP with high water absorption capacity (SAP A and SAP C)
4
results in an increased compressive strength. However, there
3
2 is no similar effect on flexural strength. SAP with the low water
1 absorption capacity (SAP B) has a very limited effect on flexural
0
0 10 20 30 40 50 60 and compressive strength.
Compressive strength [N/mm2]
(a) Despite the complexity of interactions between various types of
SAPs and supplementary cementitious materials, superabsorbent
10
polymers may prove to be very effective in internal curing. Careful
R2 A2 B2 C2
Flexural strength [N/mm2]

9 selection of the SAP with a desorption characteristics compatible

R: y = -0.0023x2 + 0.2477x
8 with hydration process is a critical issue. Diversity in types of com-
A: y = -0.0021x2 + 0.2408x
7
B: y = -0.0021x2 + 0.2452x mercially available cements leads to differences in kinetics of
6
C: y = -0.0032x2 + 0.2882x
5 hydration process and hence different requirements of water. Since
4
3
water absorption capacity and the rate of both water uptake and
2 release depend on the SAP type, the adjustment to certain cements
1 may be very complex but possible to achieve.
0
0 10 20 30 40 50 60
Compressive strength [N/mm2] Acknowledgments
(b)
Provision of superabsorbent polymers by the BASF Construction
Fig. 17. Correlation between flexural strength and compressive strength for Chemicals GmbH for the purpose of this study is gratefully
samples with sand to cement ratio 1:1 (a) and 2:1 (b). acknowledged.
 A.J. Klemm, K.S. Sikora / Construction and Building Materials 49 (2013) 134–143 143

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