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Super absorbent Polymers

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 Superabsorbent Polymers
By
Assist. Prof. Dr. Auda Jabbar Braihi
Polymer and Petrochemical Industries Dep. / College of Materials Engineering / University of
Babylon /Iraq.

Superabsorbent polymers (SAPs) represent a special polymeric

materials which can appear in a gel state as a result of absorbing huge
amounts of water and aqueous solutions [1]. There are some requirements
for polymeric material to quantify as a SAP, such as:
1- Dry polymeric substances must absorb twenty times or more of their
original weights from water, saline, or physiological solutions.
2- The swollen hydrogels must kept their initial shapes.
3- The resulting hydrogel should have enough physical integrity to resist
flow as well as incorporation with the adjoining particles [2].
4- Retain the absorbed solutions under some pressure [3].
SAPs can absorbs deionized water up to 100,000% (1000 g/g) while
absorption capacities for the ordinary hydrogels is not exceeds 100%
(1g/g).This ultrahigh absorption capacity makes SAPs ideal for many
absorbing applications like disposable diapers, holding soil moisture,
adults incontinence pads, medicine for drug delivery systems, bandages
to absorb surgical fluids, and controlled release medium [2]. Also, these
high water contents, give the resultant hydrogels a flexibility level
comparable to that of the natural tissue.
SAPs, consist generally from polymeric chains network which are
cross-linked to overcome the dissolution tendency and to support water
diffusion into the network; there are ionic functional groups available
along the chains [4]. SAPs can hold over the absorbed solutions under
some pressure due to their loosely cross-linked structures as well as their
hydrophilic nature, where the hydrophilic groups are hydrated in an
aqueous environment, thus creating a hydrogel structure [5].
 The desired lineaments of SAPs involve high capacities of swelling,
high rates of swelling, highest durability during storage, as well as good
gel strength. Indeed, SAPs cannot fulfill all the desired features, therefore
the reaction variables must be optimized to obtain a suitable balance
among properties. For instance, hygienic hydrogels should have highest
absorption rate, as well as lowest both residual monomer content and re-
wetting, while an agricultural hydrogel must have higher AUL and lowest
sensitivity to salinity [7].
Some of the resultant hydrogels responds to the external stimuli, like
pH, heat, electric field, as well as chemical environments. Such
responsive hydrogels (called "intelligent" or "smart" hydrogels) attracted
an increased attention in many areas like the pharmacy, biotechnology,
drug delivery systems, separation processes and agriculture [6].
Types of Superabsorbent Polymers
SAPs can be classified with different point of view (Figure 1).
1- According to their morphological structures, SAPs can be classified as
powders, particles, fibers, spherical, emulsions and membranes. These
morphological structures were designed to satisfy the various applications
needs.
For instance, sanitary napkins and diapers can be formed by putting the
powder product in a multi-layers sheet, while for deodorant application,
spherical products and particle can be used. Antistatic electric fibers were
manufactured from fiber forms, while membranes utilized in anti-fost
sheets. For soaking and painting, an emulsion forms can be used.
2- Based on their resources, SAPs can be categorized to:
a- Natural macromolecules such as polysaccharide-based and
polypeptide-based materials.
Polysaccharide-Based SAPs such as cellulose, starch, chitin, chitosan
and natural gums (xanthan, guar, and alginates) can prepared by either
 direct cross-linking of polysaccharide or by graft copolymerization
reaction of vinyl monomer(s) upon the polysaccharide in the existence
of the cross-linker agent [9].

Figure 1:Types of SAPs depended on different point of view [8].

b- Semi-synthesized polymer
c-Synthesized polymers such as petrochemical-based.
As compared with their artificial counterparts, natural-based SAPs
possess some advantages like biodegradability(thus escaping the
environment from pollution), biocompatibility, their natural source, non-
toxic materials, as well as low cost [1].Furthermore, petrochemical-based
SAPs have faced some problems such as increasing of global oil price
and pollution concerns. The disadvantage of the natural polymers is the
low solubility in water, thus, they are modified chemically to soluble
derivatives, such as carboxymethyl starch (CMS) and carboxymethyl
cellulose (CMC) [10].
3- Based on preparation method types, SAPs can be divided to cross-
linking polymerization, radiation cross-linking, graft polymerization, and
networks formation of water-soluble polymer [11].
4- Based on the probability of existence of electrical charges upon the
cross-linked chains and types of this charge, SAPs may be grouped into:
a- Non-ionic polymers: They absorb water and aqueous fluids via a
mixing effect due to the hydrophilic groups. Water molecules are
solvated through hydrogen bonds results in a swollen, soft gel [12].
b-Ionic polymers: They contain anionic and cationic polymers. The
presence of charges along the backbone greatly increases swelling due to
the strong backbone ion-dipole interaction and due to the enhancement of
the osmotic pressure in the gel because of the solvation of the counter-
ions.
c- Ampholytic (amphoteric) includes both basic and acidic groups.
d- Polybetaines(zwitterionic) contain both cationic and anionic groups in
every repeating unit [4].Photo-chromic hydrogels, recently were prepared
with 2800 g/g WAC.
Design Considerations
A SAP material involves two processes; swelling and cross-linking.
1. Swelling Process
Swelling behavior is affected by several factors, such as:
1-Interaction nature: There are four prime forces affect the swelling
capacities for the ionic hydrogels: interactions between polymer and
solvent, ionic interaction, elastic interaction, as well as electrostatic
repulsion. The most important one of these forces is the ionic interaction
because of the presence of the mobile ions like K+ and Na+ within the
SAP structure.
2-Polarity: Generally, for natural polymers there is a one-to-one
correlation between the number of polar groups and the number of water
molecules adsorbed [14].
3-Elastic retroactive force: Swelling tendency will stop at an
equilibrium point when the swelling force is balanced by the retroactive
force, which is developed as the chains between the cross-links become
increasingly elongated [15].
4-Type and degree of cross-linking: The cross-linker varies the
polymeric chain length. Smaller chains have more polymer ends,
therefore do not contribute to water absorption, while longer chains have
more network space and thus increase swelling.
According to Flory equation ( Equation 1), for a given polymer-
solvent system the equilibrium swelling (S e ) is a function of the cross-
link density
S e 5/3 = B M c / (1-2M c /M w ).(1)
Where: B represents a constant for a given polymer-solvent system,
M w is the weight average molecular weight of the similar uncross-linked
polymer, M c is the average molecular weight per cross-link.
5- Solvent properties: Since the swelling involves diffusion of the solvent
molecules within the gel network structure, the concentration of the
solvent has announced effect according to the Fick's diffusion equation
[15]:
c/t = (D c) ...(2)
Where D is the diffusion coefficient and c is the solvent concentration.
6-Morphological properties (porosity, particle size): the smaller the
average grain sizes, the larger the swelling.
7- Conditions of the swelling environment such as pH, temperature, ionic
strength as well as the counter ion and its valance [16].
 The mechanism of the swelling process contains the following actions:
solvent molecules penetrate the polymeric networks structures.
Simultaneously, the molecular chains among the cross-linked points
expanding, therefore reducing their enthalpy values. This new molecular
network structure has an elastic contractive forces which increases the
contraction tendencies of the networks (Figure 2).
Unless these two opposed forces get their balance state, expansion and
contraction tendencies cannot reach their equilibrium also. So, the
osmotic pressure will be the driving force behind the swelling expansion,
while the elastic force within the network is responsible of the gel
contraction [11].

Figure 2:Mechanism of swelling in SAPs[14]

If water is added to the SAP particles, a water /polymer interaction will
arises due to the (Mixing Effects), which consists of effects of both
hydration(solvation) and the formation of hydrogen bonds.
The hydrationis the interaction between solute ions and solvent
+ -
molecules, i.e. Na and COO ions attract the polar water molecules
(Figure 3).
 Figure 3: The hydration (solvation) effect [2]
Hydrogen bond (H-bond) which is an electrostatic interaction among
molecules, arises in molecules which possess hydrogen atoms connected
to atoms with low electronegative like N, F, and O (Figure 4).

Figure 4:Hydrogen Bonds [2]

These effects creates a cellular structure within the SAP network which
can store water molecules.
2. Cross-linking process
Cross-links between polymer chains result in a 3D network; makes
SAPs insoluble in water by preventing the polymer to swells to infinity;
preventing dissolving. Such behavior arises the elastic retraction forces of
the polymeric network. These forces are associated by a reduction of
entropy of the chains, since these chains become stiffer from their initial
coiled state as shown in Figure 5.

Figure 5: Elastic retraction effect of the network in SAPs [2]

Now, there is an equilibrium between the retraction forces and the chains
tendency to swell to infinite dilution. Cross-linking level possess a direct
influence on both the swelling capacity range and the gel strength [2].
Several parameters affected the cross-linking efficiency such as, the steric
hindrance in the position of the pendant double bonds, solubility level of
the cross-linker in the reactants mixture and ability of the cross-linker to
exhibit intermolecular addition reactions [7].Cross-links formed either by
covalent, ionic, or H-bonds.
Covalent cross-links are formed either when the major monomers (e.g.,
acrylic acid) is copolymerized with a di-, tri-, or tetra vinyl monomer or
by reacting the polymer chains with a di- or tri - functional reagents that
reacts with the carboxylic acid groups[17].
The reaction between charged polymer chains and polyvalent ion with
opposite charge leads to the ionic cross-linking as shown in Figure 6.

Figure 6: Ionic cross-linking [12]

The creation of H- bonds between segment of one chain with the
segment of another chain resulted in the weak chemical cross-linking
(Figure 7).

Figure 7: Hydrogen bonds cross-linking [12]

 Cross-linking in SAPs, can be classified also into bulk (core) and
surface cross-linking. Core cross-linking is usually occurs during the
polymerization reaction stage of SAP production [2].
Surface cross-linking of SAP particles can improves both the flow and
the absorption against pressure greatly [18]. Particles with surface-cross-
linking protected their shapes during the swelling process. This leads to a
less densely packed gel bed with air pockets, therefore the fluid can easily
flow in high permeability pattern (Figure 8 b).

Figure 8: Effect of surface cross-linking on the solution flow [18]

In contrast, SAP with no surface treatment tends to show high swelling

capacity but possess poor absorption versus pressure. Unfortunately, this
way to improve the swelling capacity by reducing the cross-linking
density, usually restricted by the increasing in extractable content of the
hydrogel.
Furthermore, the pressure on these untreated particles can cause a "gel
blocking" which prevents further liquid penetrating the gel bed.
To obtain cross-linking density in the surface higher than in the bulk
(Figure 9),particles subjected to the cross-linking solution, then cured
by heating [2].
 Figure 9: A surface cross-linked superabsorbent particle [2]
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