Budownictwo o zoptymalizowanym potencjale energetycznym

Agnieszka KLEMM, Karol SIKORA

Glasgow Caledonian University, Glasgow, UK

SUPERABSORBENT POLYMERS IN CEMENTITIOUS COMPOSITES

Construction industry like any other areas of economic and social life undergoes
a continuous modifications and improvements in order to successfully comply with
the requirements of sustainable development. Consumers demand more durable, less
labour and service intensive materials at a competitive price. To meet these expecta-
tions various types of modifications of concrete has been proposed. One of the pro-
mising solutions is modification of concrete by Superabsorbent Polymers (SAP). This
paper presents the review of the recent developments in the area of SAP modified
cementitious composites.

1. SUPERABSORBENT POLYMERS (SAP)

1.1. Background
Superabsorbent are cross-linked networks of hydrophilic polymers with a high
capacity for water uptake [1]. They have a variety of valuable applications in medi-
cine, agriculture and industry in general.
Early superabsorbents were made from chemically modified starch and cellu-
lose and other polymers like polyvinyl alcohol, polyethylene oxide, all of which are
hydrophilic and have a high affinity for water. When lightly cross-linked, chemi-
cally or physically, these polymers became water-swellable but not water-soluble [2].
Today’s superabsorbent polymers are made from partially neutralised, lightly
cross-linked acrylic acid and acrylamide and their modifications. The polymers are
manufactured at low solids levels for both quality and economic reasons, and are
dried and milled into granular white solids. In water they swell to a rubbery gel that
up to 99 wt.% water [3].

1.2. Mechanism of swelling

Superabsorbent polymers hydrate in contact with liquids leading to formation of
swollen polymer gel. When their three-dimensional networks with chemical cross-
links come into touch with fluid, the water molecules diffuse into the void space
inside the polymer network and hydrate the chains. This process is reversible so the
removal of water results in collapsing of SAP (Fig. 1) [4].
 Superabsorbent polymers in cementitious composites 87

+ Water

- Water

Fig. 1. Schematic representation of SAP network in collapsed and swollen state [4]

The process of swelling is very complex and comprises of several mechanisms.

The hydrophilic properties of SAP result from the presence of hydrophilic carbo-
xylic acid groups in polymer’s backbone. Immediately after mixing SAP with
water the process of hydration is initiated and the electrostatic interactions between
molecules start to form. Hydrogen bonds are created in molecules that have hydro-
gen atoms attached to electronegative atoms. Non-bonding electron pairs on neigh-
bouring electronegative atoms draw the hydrogen atoms. Oxygen, which has elec-
tronegative atom, forms a dipole in the molecule by pulling the hydrogen’s
electrons against each other. Hydrogen’s atoms, which have positive potential, are
attracted to the oxygen lone pairs on other water molecule. Oxygen has two lone
pairs of electrons and each is capable of hydrogen bonding to two other water
molecules [2]. Figure 2 below shows images of two different types of SAP under-
going absorption process (swelling stage).

Fig. 2. Micrographs of SAP swelling process (courtesy of Prof. Kovler)

The ability to absorb water is determined by swelling ratio defined as the weight
of swollen SAP (swollen state) to the dried SAP (collapsed state). The swelling ra-
tio and strength of the network are directly determined by the degree of cross-
linking, the chemical structures of the monomers forming the SAP network, and
external stimuli such as pH and ionic concentration in the surrounding. [4]. The
term centrifuge retention capacity can also be found in literature [3]. It defines the
amount of 0.9 wt.% saline solution, which SAP can retain under free swelling con-
ditions when surface water has been removed in a centrifuge.
In principle the degree of cross-linking corresponds to the number of the chemi-
cal bonds. The higher degree of cross-linking indicates the shorter the distance be-
tween the two cross-links, which results in the lower degree of swelling [4-6].
The degree of swelling also depends on temperature [7]. The polymers with the
ability to respond to temperature belong to a special class referred to as tempera-
88 A. Klemm, K. Sikora

ture sensitive polymers. These polymers demonstrate a transition from hydrophilic

to hydrophobic structures at the temperature known as the Lower Critical Solution
Temperature (LCST). When the temperature is below LCST, the hydrophilic
chains are hydrated, and the hydrogels become swollen. As the temperature in-
creases past LCST, the hydrophobic interaction becomes stronger, thus the balance
between hydrophilic and hydrophobic interactions break down, causing the gel to
collapse.

2. EFFECT OF SAP ON PROPERTIES OF CEMENTITIOUS COMPOSITES

Over the last couple of decades a considerable number of research studies on
application of SAP in cementitious composites have been undertaken worldwide.
They have been predominantly focused on shrinkage behaviour [8-15], mechanical
characteristics [16-22] and freeze/thaw performance [18-20, 23, 24]. Unfortunately,
as it is shown below, no consensus has been reached on the efficiency of SAP
products.

2.1. Shrinkage
Relatively high number of reports confirmed shrinkage reduction resulting from
SAP addition to mixes. The common view is that water captured by SAP, which is
distributed evenly in whole volume leads to reduction of self-desiccation and con-
sequently leads to decrease in autogenous shrinkage. However, the recent results
presented by Kovler et al. [15] indicate that the internal curing by SAPs application
have a minor effect on the cracking prevention. As it was pointed out by Ribeiro et
al. [11] the reason for shrinkage in cementitious materials may not only be a self-
desiccation, but also creep. Although lower self-desiccation during the first week
was observed in SAP mortars the higher strain increase associated with creep was
simultaneously recorded.
Other phenomena may also contribute to the increase of shrinkage in mixtures
with higher water content. The accessibility of water to continue the hydration is
higher not only due to the amount of water present in the mixtures but also due to
the higher mobility of this water within the pore structure.

2.2. Strength
Due to the potential practical applications of SAP containing cementitious mate-
rials its influence on strength development is of a paramount importance. The ef-
fects of SAP may be twofold - increase or decrease of compressive strength [16].
It is generally accepted that SAPs increase a degree of hydration and can prevent
concrete from self-desiccation. Consequently a denser paste phase is obtained and
propagation of microcracks is prevented. However, on the other hand, SAP in-
 Superabsorbent polymers in cementitious composites 89

creases porosity of hcp by creation of voids in its collapsed state. These pores may
have a negative influence on strength. Therefore, the higher moisture content in
concrete the lower resulting compressive strength.
The changes in the ion concentration in the pore solution may influence the
swelling behaviour of SAP [17]. Different types of SAP and their preparation
methods result in different internal curing potential due to variation in swelling
abilities. SAPs with higher swelling ratios have a strong affinity for water and al-
low water release into the concrete when it begins to desiccate. Hence, the negative
impact on long term strength development may occur. In addition, any changes in
the concentration of the pore solution during water curing results in further swell-
ing and formation of microcracks, which may impede the strength gain [15].
On the other hand, SAP with a lower affinity for water easily releases water
back into the hydrating cement paste matrix, allowing internal curing to occur more
efficiently. SAP of lower affinity for water results in a good control of the rate of
absorption and desorption of pore solution in the SAP during internal curing and
lead to the improvement of strength development. The study by Siramanont et al.
[17] shows contradicting results with SAPs voids not decreasing strength of cement
paste, mortar and concrete. Authors have concluded that the usage of SAPs as in-
ternal curing agent in concrete actually increase the strength of cementitious mate-
rials. If SAPs swelling properties are adequately matched the volume of the swol-
len SAPs would be replaced (at least partially) by the hydration products at later
ages. These claims and findings are in accordance with the results of the other re-
searches [18, 19]. Results published by Reinhard et al. [20] also support the above
statement. The study suggests that the differences in pores sizes and their numbers
do not have an effect on strength development. It can be attributed to the predomi-
nant role of air pores over the polymer pores formed in the collapsed state.
Contrary views have been however presented in other studies [21, 22]. The
strength test of concretes mixed with SAP showed rather low results. The loss of
strength was explained by the low cement paste content and increased porosity.

2.3. Freeze/Thaw performance

Degradation of concrete by frost action is another issue, which can be potential-
ly counteracted by SAP addition. This view is based on an assumption that SAP
forms a system of fine, evenly distributed pores, which are filled with swollen
polymers in fresh or young concrete. At the later ages these pores become empty
(collapsed state) and can act similarly to air-entrained pores. The main advantage
of SAP in comparison to the use of air entraining agents is the high robustness of
SAP-pore system and the resulting high predictability of its properties. Air bubbles
formed by the AEA may be relatively easily destroyed during concrete transport or
processing (pumping, compaction, spraying) [8].
Studies presented by Brudern et al. [8], Monning et al. [19] and Reinhardt et al.
[23] confirmed the positive effect of SAP on freeze/thaw performance of concrete.
However the type of SAP and its absorption/desorption characteristics may have
90 A. Klemm, K. Sikora

stronger effect than originally anticipated [24]. Different polymers may therefore
offer different degree of protection. It should be noted that there are no published
reports indicating the negative effect of SAP on F/T performance of cementitious
composites.

FINAL COMMENT
Due to its excellent ability to absorb/release water superabsorbent polymers
may become a valuable modifying agent in cementitious materials development.
However due to the complicated nature of swelling processes and stability of varie-
ty of SAP products more comprehensive studies are required to verify experimental
results and to develop the performance prediction model.

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