Polymer International Polym Int 52:11581164 (2003)

DOI: 10.1002/pi.1218

Novel approach to highly porous

superabsorbent hydrogels: synergistic effect
of porogens on porosity and swelling rate
K Kabiri, H Omidian and MJ Zohuriaan-Mehr
Superabsorbent Hydrogel Division, Adhesive & Resin Department, Iran Polymer Institute (IPI), PO Box 14965-115, Tehran, Iran

Abstract: A novel practical strategy for preparing highly porous superabsorbent hydrogels (HPSHs)
was invented. HPSHs were quantitatively prepared through an optimized rapid convenient solution
polymerization of partially neutralized acrylic acid in the presence of a crosslinking agent under normal
atmospheric conditions. Acetone and sodium bicarbonate were used as porosity generators (porogens)
during the polymerization process to create highly porous structures. Time and sequence of addition of
the porogens, as well as the gelation time of the polymerization, were recognized to affect the efficiency
of the porogens. Sodium bicarbonate produced the more porous hydrogels with a higher rate of swelling.
In comparison with a hydrogel prepared under porogen-free conditions (control), acetone and sodium
bicarbonate enhanced the swelling rate as high as 4355% and 111131% of the control, respectively. When
both the porogens were used consecutively in the process, a remarkable synergistic effect was observed
in the swelling rate of the products. Nearly all the two-porogen processes resulted in foamy products
from the polymerization system. With the single-porogen systems, however, the foam formation stage
was observed only in a part of the total process time. The apparent volume of the as-synthesized foamy
products prepared from the two-porogen system was more than that of the single-porogen systems by up to
fourfolds. Morphological studies using scanning electron microscopy (SEM) showed that the two-porogen
systems created highly porous structures. The density of all the HPSHs synthesized was about 1.5 g cm3
and no distinct differences were observed in their equilibrium swelling. These superabsorbent hydrogels
exhibited a very high rate of swelling, so that their swelling time was measured to be less than one minute.
2003 Society of Chemical Industry

Keywords: superabsorbent; hydrogel; acrylic acid; polymerization; porosity; foaming; swelling

INTRODUCTION kind of superabsorbent polymer, named superporous

Superabsorbent hydrogels are loosely crosslinked
hydrophilic polymers that can absorb, swell and
retain aqueous solutions up to hundreds of times
their own weight.1 Because of their superior
properties they have hygienic, agricultural, med-
ical and pharmaceutical applications. They may
be used in controlled release of drugs that are
initially dissolved or trapped within a polymer
matrix.1 3
Desired features of superabsorbents are (a) high
swelling capacity, (b) high swelling rate and (c) good
strength of the swollen gel. Conventional hydro-
gels have very low swelling capacity and swelling
rate. They mainly need several hours to reach max-
imum absorption capacity. The majority of reported
superabsorbents comprise only the first feature men-
tioned, ie high absorbency,4 whereas they must
also have a high rate of swelling especially in
certain applications, eg in the absorbents incor-
porated in baby diapers. Park has developed a
hydrogel, in recent years for controlled delivery of
drugs.5 8 Other researchers have recently extended
the hydrogel for designing other novel drug-delivery
systems.9 So, creation of porosity in hydrogels has
been considered as an important process in many
ways.
In the recent years, we have focused on studying the
synthesis and characterization of acrylic-based super-
absorbents through solution and inverse-suspension
methods.10 15 We mainly attempted to modify prop-
erties by changing and altering the nature and kind of
process and the concentrations of the major reactants.
We are currently working on improving these hydro-
gels to achieve a higher rate of absorption through
creating porosity.
There are few methods for preparing porous
hydrogel structures. The phase-separation technique is
a known method in which the porous hydrogels can be
synthesized at temperature higher than LCST (lower
critical solution temperature) of the base polymer.

Correspondence to: MJ Zohuriaan-Mehr, Superabsorbent Hydrogel Division, Adhesive & Resin Department, Iran Polymer Institute (IPI),
PO Box 14965-115, Tehran, Iran
E-mail: m.zohuriaan@proxy.ipi.ac.ir
(Received 16 June 2002; revised version received 28 October 2002; accepted 7 January 2003)

2003 Society of Chemical Industry. Polym Int 09598103/2003/$30.00 1158

 Novel approach to highly porous superabsorbent hydrogels

Hydrogels based on N-isopropylacrylamide are usually Table 1. Amounts of the porogens used in the optimized experiments
synthesized by this method.16 18 In the second method
Porogen
a pore generator is added in the polymerization
mixture and then extracted with a suitable solvent. Sodium
Water-soluble materials (such as sodium chloride, Sample Acetone (ml) bicarbonate (g)
polyethylene glycol, and sucrose) may be used as the
Exp 1 0 0
porogens.19,20 Poly(vinyl chloride) is also used as a
(no porogen)
porogen.21 These materials should not react with the Exp 2 1 0
other reactants and they have to be easily extractable Exp 3 3 0
after polymerization. When a hydrogel is placed in the Exp 4 5 0
extracting medium, the incorporated porogen comes Exp 5 0 0.5
out from the hydrogel network and pores remain. Exp 6 0 2
The third method is the foaming technique in Exp 7 0 4
which a porous structure is formed by using foaming Exp 8 0 6
agents. Two kinds of foaming agents can usually be Exp 9 3 2
used, ie carbonate compounds (such as magnesium Exp 10 3 4
Exp 11 3 6
carbonate, calcium carbonate, sodium bicarbonate,
Exp 12 1 4
potassium bicarbonate,6 8,22 24 and organic solvents,
Exp 13 3 4
such as n-pentane, 2-methylbutane, hexane, heptane, Exp 14 5 4
dichloromethane, acetone and methanol.25
This paper deals with a novel practical approach
to the synthesis of highly porous superabsorbent the bubbles were trapped within the highly viscous
hydrogels (HPSHs). We used the foaming technique mixture. The time elapsed to reach to the gelation
by applying acetone and sodium bicarbonate as point is referred as the gelation time. After this point,
porosity generators. a couple of visible phenomena, including evaporation
and foaming, were observed within less than 7 min.
The products were removed from the beaker, dried in
EXPERIMENTAL a forced-draft oven for 18 h at 70 C to reach constant
Materials weight. Quantitative yields were generally obtained.
Acrylic acid (AAc) monomer and N, N  - Dry products were ground with a hammer-type min-
methylenebisacrylamide (MBA) crosslinker supplied igrinder and screened. The particles were stored in
by Fluka were used as received. Ammonium well-sealed bottles away from moisture and light.
persulfate (APS), sodium metabisulfite (SMBS),
sodium bicarbonate (SBC), acetone and potassium
hydroxide (KOH) supplied by Merck were used Swelling measurements
without further purification. A 0.500-g sample of dried polymer (mesh 5060) was
dispersed in 250 ml of distilled water and allowed to
swell for half an hour. Each dispersion was filtered
Synthesis
through a 100-mesh wire gauze and the excess water
HPSH was synthesized by using two different foaming
was removed carefully from the retained gel using
agents. An optimized two-porogen procedure is given
a piece of a soft, open-cell polyurethane foam. The
here. In the case of the single-porogen system, one
blotting process was completed when the gel particles
foaming agent is omitted.
no longer slipped from the gauze when it was held
Acrylic acid monomer (30.00 g) was partially neu-
vertically. The degree of swelling was determined as
tralized with potassium hydroxide solution (18.15 g
the weight gains on the gauze after immersion in
KOH + 15.0 g H2 O). Then the crosslinker solution
water.13
(0.02 g MBA + 4.0 g H2 O) was gently added to the
To measure the swelling rate, a 0.500-g sample of
monomer mixture. The monomer and the crosslinker
dried polymer (mesh 5060) was dispersed in 250 ml
solutions were poured into a 600-ml beaker equipped
of distilled water under mild magnetically stirring. The
with a magnetic stirrer and a thermometer to monitor
swelling capacity was measured as above at definite
temperature changes during the exothermic reac-
intervals to draw a profile of swelling against time
tion. Then other components were added to mixture
for individual samples. The detailed procedure can be
in the following sequence: the persulfate solution
found elsewhere.13
(0.075 g APS + 2.0 g H2 O), SBC, metabisulfite solu-
tion (0.063 g SMBS + 2.0 g H2 O) and acetone. The
amounts of foaming agents in each experiment are Density measurement
listed in Table 1. After addition of SMBS solution, The density of superabsorbent powder was measured
the temperature as well as the viscosity of the reaction using a picnometric method according to ASTM
mixture were rapidly increased in a 2060-s period to D792. One gram of sample was placed in a pre-
reach the gelation point. This point may be detected weighed 10-ml picnometer and then the latter was
practically when the magnetic stirrer was stopped and filled with acetone, an inert solvent with known

Polym Int 52:11581164 (2003) 1159

K Kabiri, H Omidian, MJ Zohuriaan-Mehr

density. It was re-weighed and the sample density the exothermic polymerization proceeded very fast (C
was calculated based on the standard method. to D) and the temperature rose to 90 C in less than
5 min. The increased temperature caused the acetone
Morphology to evaporate. Evaporation of acetone caused, in turn,
The morphology of porous structures was studied progressive foam formation (E to F). The foam height
with a scanning electron microscope (SEM). Dried (F) did not change very much with an increase in
superabsorbent powder was coated with a thin layer the amount of acetone. The blown foam subsided in
of palladium gold alloy, and imaged in a Cambridge a few moments (F to G). The final shape of the as-
S-360 SEM instrument. synthesized hydrogel is shown in Fig 2 (the first sample
from the left). It was elastic and relatively transparent
with large voids in its apparent structure.
RESULTS AND DISCUSSION
Polymerization and foaming processes Sodium bicarbonate as porogen
The time of foam formation and the polymerization To obtain a homogenous porous structure, we
process were both of significant importance for making added sodium bicarbonate (SBC) before adding the
porous superabsorbent hydrogels. Description of these reductant (SMBS) solution. When SBC was added
processes in the case of individual foaming agents is as after the SMBS solution, gelation occurred in few
follows. seconds due to the fast increase of viscosity, and

Acetone as porogen Table 2. Observation during polymerization, rate parameter, and

Figure 1 represents typical profiles of the polymer- density of synthesized HPSHs
ization and foam-formation processes involved in the
Temperature
preparation of porous hydrogel using of acetone as
increase
porogen (Exp 2Exp 4 ). At point A, SMBS reduc-
Gelation up to gelation Rate Density
tant solution was added to the mixture. At this point Sample time (s) point C parameter, r (s) (g cm3 )
the mixture contained all the ingredients except ace-
tone. Acetone was added to the mixture at point B. It Exp 1 60 20 171 1.59
was important to pour in the acetone after adding the (no porogen)
SMBS solution, otherwise it prevented initiation of Exp 2 55 15 120 1.57
Exp 3 50 15 110 1.56
polymerization, especially with larger amounts of ace-
Exp 4 51 12 116 1.56
tone. The polymerization proceeded slowly (A to C)
Exp 5 56 10 81 1.54
until the gelation point, C. Observation during poly- Exp 6 39 5 79 1.54
merization and properties of the synthesized HPSHs Exp 7 35 10 81 1.54
are listed in Table 2. Gelation point was observed Exp 8 45 8 74 1.54
5055 s after starting the polymerization (addition of Exp 9 19 7 42 1.49
SMBS solution) at 3235 C. After the gelation point, Exp 10 23 5 38 1.48
Exp 11 17 4 29 1.47
Exp 12 19 7 43 1.49
100 24 Exp 13 17 6 42 1.49
90 Exp 14 15 5 30 1.48
D 20
80
Foam height (cm)

70
Temperature (C)

16
60

50 C 12
A B
40
8
30 F

20
4
E G
10

0 0
0 50 100 150 200 250 300
Time (s)

Figure 1. Typical profiles of the simultaneous polymerization and

foam-formation processes for the single-porogen (acetone) system
(Exp 2Exp 4). A: SMBS addition, B: acetone addition, C: gelation
point, CD: fast polymerization, EF: progressive foam formation, Figure 2. Apparent shapes of the as-synthesized HPSH samples
FG: foam subsidence. (from left to right: Exp 3, Exp 7 and Exp 10).

1160 Polym Int 52:11581164 (2003)

 Novel approach to highly porous superabsorbent hydrogels

105 24 100 H 24

90 20
20 80 K

Foam height (cm)

Temperature (C)
75

Foam height (cm)

Temperature (C)

16 16
60
60
F 12
12 G
C E F
45 B 40 D
B 8
8
30
20
4
G 4
A 15
A C
O D 0 0
0 0 0 50 100 150 200 250 300
0 50 100 150 200 250 300
E Time (s)
Time (s)
Figure 4. Typical profiles of the simultaneous polymerization and
Figure 3. Typical profiles of the simultaneous polymerization and
foam-formation processes for the two-porogen system (Exp 9Exp
foam-formation processes for the single-porogen (SBC) system (Exp
14). A: SBC addition, B: SMBS addition, C: acetone addition, D:
5Exp 8). A: SBC addition, B: SMBS addition, C: gelation point, OD:
gelation point, EF: foam formation due to SBC, GH: foam
CO2 emission without foam formation, DEF: foam formation, FG:
formation due to acetone, HK: foam subsidence.
foam subsidence.

SBC powder, SMBS solution and acetone were

no acceptable dispersion of SBC particles and no consecutively added at points A, B and C, respectively.
homogenous foams were obtained. Before the gelation point (point D) carbon dioxide
Figure 3 shows representative profiles of the bubbles produced by SBC reacting with acidic
polymerization and foam-formation processes for the groups were emitted without any foaming effect.
SBC series of experiments (Exp 5Exp 8). The SBC After the gelation point, the gas bubbles could not
porogen was added to the mixture at point A. It escape easily from the highly viscous mixture and,
reacted with the non-neutralized acidic groups of the therefore, they caused foaming. The blowing foam
acrylic acid monomer and carbon dioxide gas bubbles rose homogeneously (E to F) while the exothermic
were evolved. The gelation point was observed at polymerization proceeded. In contrast to the SBC
point C. Carbon dioxide bubbles were easily emitted series, the blown foam did not subside; instead, after a
from the mixture before the gelation point (O to D) steady period (F to G), the foam height increased,
with no major effect on starting foam formation. After again more intensively (G to H). This additional
the gelation point, however, the gas bubbles could blowing of the foam was related to evaporation of
not escape from the very viscous mixture and thus acetone due to the increasing reaction temperature.
they were trapped and consequently created a foamy The foam height was approximately twofold the height
structure. The foam came up continually, slowly and of the 600-ml beaker (reactor) and its volume was
homogeneously (D to E). It remained constant during nearly fourfold that of the corresponding volume of the
the E- to- F period. Then the foam started to subside previous single-porogen series. The appearance and
intensively (F to G) with increasing the temperature. shape of the as-synthesized foam was white, hollow,
Finally a white sticky material was obtained. elastic and non stick, as shown in Fig 2 (the right-hand
It should be pointed out that, although the height of image).
the initial foam (D to E) was enhanced with increasing
amount of SBC, the foam vigorously subsided later Morphologyfoaming process relationship
as the temperature increased, so that the final foam Scanning electron microscopy SEM studies showed
volume in the case of all amounts of SBC did not differ that each foaming system had a different effect on
very much. The visual final form of a sample of this the morphology. An SEM micrograph of the superab-
series of experiments is illustrated in Fig 2 (the middle sorbent prepared under porogen-free conditions (Exp
sample). 1) is presented in Fig 5. No porosity is observed in
the figure and the surface of the particle is completely
smooth. In contrast, particle surfaces of the sam-
Two-porogen system (acetone/SBC) ples prepared from the porogen-associated systems are
In a third series of experiments, we consecutively clearly porous, as illustrated in the Fig 6, 7 and 8. Ace-
used both foaming agents in each synthetic process. tone, as a porogen, generates spherical pores. These
These two-progen systems exhibited the foaming phe- pores make an increased surface area as can also be
nomenon during the entire time of the polymerization observed in the course of the synthesis.
process. The polymerization and foam formation pro- An SEM micrograph of the SBC series is shown
cesses for this series are typically illustrated in Fig 4. in Fig 7. A porous structure is clearly seen in the

Polym Int 52:11581164 (2003) 1161

K Kabiri, H Omidian, MJ Zohuriaan-Mehr
Figure 5. SEM micrograph of the sample prepared from the
porogen-free process (Exp 1).
Figure 6. SEM micrograph of the sample prepared from the
single-porogen (acetone) process (Exp 3).
Figure 7. SEM micrograph of the sample prepared from the
single-porogen (SBC) process (Exp 7).
picture, but its shape was not similar to that of
the acetone series samples. Here there are some
layers connected to each other and some holes
and pores remain. This morphology is related
to the foam-formation stage of the synthesis, in
which the foam slowly and homogeneously rose.
1162
Figure 8. SEM micrograph of the sample prepared from the
two-porogen process (Exp 10).
This foam was not stable and rapidly subsided as
the exothermic polymerization proceeded. During
the blowing process, some interconnected pores
were probably created in the hydrogel, but, when
the temperature increased due to the exothermic
polymerization, most of these pores closed or became
partially blocked.
The SEM micrograph given in Fig 8 shows that the
two-porogen foaming system acts more efficiently than
the single-porogen systems. Here, SBC and acetone
porogens were consecutively used (see Experimental
section) and a more porous structure was obtained.
According to the figure, this morphology, which is
a result of an intensive synergistic effect of the
two porogens, has greater similarity to the SBC
system (Fig 7) than the acetone system (Fig 6). More
layers with more connections are observed. Here, the
significant importance of the sequence of addition
of the components as APSSBCSMBSacetone is
understood (see Experimental section). SBC starts
carbon dioxide gas generation just before initiating
the polymerization by adding the reductant, SMBS.
The evolved gas starts pore-forming associated with
the acetone vapours. The latter porogen somehow acts
as a foam stabilizer as well, ie even after the end of
the exothermic reaction, an internal force of acetone
vapour prevents the pore walls from adhering to each
other. These more stable pores cause an increase in the
empty spaces in the hydrogel. This morphology as well
as its very high swelling rate (swelling Kinetics section)
confirms the superiority of the two-porogen system.
In an aqueous medium, the fluid easily diffuses into
the hydrogel mass through these semi-interconnected
pores thus leading to a substantially increased rate of
absorption.
Density
Density values, listed in Table 2, were around
1.50 g cm3 . According to Fig 2 and also the above
discussions, the samples from the two-porogen system
were expected to exhibit a lower density than the
single-porogen systems. In fact, the density differences
are small but noticeable. While the density of the
Polym Int 52:11581164 (2003)

samples from the porogen-free system (Exp 1) is
1.59 g cm3 , average density of the acetone and
SBC systems are reduced to 1.56 and 1.54 g cm3 ,
respectively. In the case of the two-porogen system, a
much lower density is observed (1.47 g cm3 ). This
is attributed to the synergistic effect of the two
porogens that are consecutively used in the synthesis.
In such a foaming system, the foam-formation occurs
during the whole period of the polymerization process.
Consequently, the resulting foam has an increased
volume with more and bigger pores and it has a lower
density.
Swelling kinetics
The swelling kinetics was studied by means of a
previously reported Voigt-based viscoelastic model:14
St = p(1 et/r )
where St = amount of swelling at any moment (g g1 ),
p = power parameter (g g1 ), t = time (s), and r = rate
parameter (time required to reach 0.63 of equilibrium
swelling) (s).
The data obtained from the equilibrium swelling
and the swelling rate of the individual samples were
fitted into the above equation to find the values of the
rate parameters. The rate parameter, r, is a measure
of swelling rate of a superabsorbent sample so that
a lower r-value means a higher rate of swelling. The
power parameter, p, shows the water-holding capacity
of an individual superabsorbent.
The rate parameter of the sample obtained from
the porogen-free process (Exp 1, Table 2) was
171.3 s. When acetone was used as porogen, the
r-value decreased to 110119 s. A 4355% rate
enhancement of the swelling rate (Fig 9) was achieved
350
300
250
Swelling (g g-1)
200
150
Porogen-free
Acetone
SBC
100 SBC-Acetone
50
0
0 100 200 300 400 500
Time (s)
Figure 9. Water-swelling kinetics for the HPSHs synthesized via
various foaming systems.
Polym Int 52:11581164 (2003)
Novel approach to highly porous superabsorbent hydrogels
by using acetone. With SBC as the only porogen,
the rate parameter decreased to 7381 s (swelling rate
enhancement of 111131% in comparison with the r-
value of Exp 1). When both foaming agents were used
in the polymerization process, the two-porogen system
had a strong effect in increasing the swelling rate, so
that rate parameter decreased to 2842 s. In other
words, the swelling rate increased up to 600%. This
synergism phenomenon is clearly illustrated in Fig 9.
According to the figure, no appreciable difference was
observed in the power parameter (300 g g1 ).
CONCLUSION
Rapid convenient synthesis of highly porous superab-
sorbent hydrogels is possible by using foaming agents
in aqueous media at room temperature under normal
(1) atmospheric conditions. The main conclusions may
be summarized as follows:
(1) The timing and sequence of adding porogen(s), as
well as the gelation time of the solution polymer-
ization process, are very important for synthesis
of HPSHs, especially in the case of bicarbonate
foaming agent (SBC). These procedural param-
eters should be precisely optimized. If the time
interval between addition of SBC and the gela-
tion point is very short, the porogen will not
completely disperse in the viscous solution and
a non-homogenous porous hydrogel is obtained.
Conversely, a long time between addition of the
bicarbonate and the gelation point results in non-
efficient porosity generation due to the CO2 gas
freely escaping from the polymerization mixture.
(2) In the case of acetone or other organic solvents
that can be used as foaming agents, the maximum
temperature of the polymerization mixture should
not be lower than evaporation point of the porogen
used.
(3) Since each individual porogen used in this
study acts in its own way during a specific
part of the polymerization process, the final
result of their process is totally different in
terms of the type of porous structure and the
extent of porosity generation. While acetone
acts via evaporation only after increasing the
polymerization temperature (Fig 1), SBC starts
its foaming action (via CO2 gas evolving from
a COOHHCO3 in situ reaction) soon as it
is added to the polymerization mixture (Fig 2).
Therefore, either the mechanism or the duration
of action of these two porogens differ, so that
acetone and SBC improve the swelling rate of the
products 54% and 115%, respectively, more than
that of the sample prepared from the porogen-
free system. When both the porogens are used
600
in one system, they not only compensate the
deficiencies of each other, but also exhibit a
distinctive synergism (Fig 2, Fig 4, and Table 2).
In our newly optimized two-porogen system, the
1163
K Kabiri, H Omidian, MJ Zohuriaan-Mehr
porosity generation process effectively acts during
the whole polymerization time, and leads to a
superabsorbent hydrogel having a high porosity.
(4) Overall, our novel optimized synthetic route to
highly porous superabsorbent hydrogels (HPSHs)
comprises several advantages: simplicity, rapidity,
quantitative yield, processing at room temperature
under normal atmospheric conditions, cheapness
and availability of all the reactants and foaming
agents, as well as very low toxicity of the
porogens. Because of these clear advantages,
the synthetic strategy may be considered an
excellent candidate for producing fast swelling
superabsorbent polymers on larger scales and also
for designing novel systems for controlled delivery
of bio-active agents.
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