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5
Ion-Exchange and Gel-Forming Properties of Alginate Fibers
5.1 Introduction
Alginate bers have had a long history. As early as 1944, Speakman and Chamber-
lain [19] reported a detailed process for the production of alginate bers and in the
following years, more studies were carried out for the applications of these bers in
the textile industry [1, 2,4]. In the 1950s, alginatebers were used as draw threads for
sock production and as home decoration materials, utilizing their ability to dissolve
in a dilute aqueous alkali solution and their inammable properties.
Since the 1980s, alginate bers have been widely used in the production of func-
tional wound dressings. In this particular application, alginate bers have unique
ion-exchange and gel-forming characteristics whereby on contact with wound exu-
dates, sodium ions in the exudates exchange with calcium ions in the ber, and as
more and more sodium ions enter the ber structure, the resultant calcium sodium
alginate bers absorb more and more water to become a brous gel [10, 15]. When
used on wound, this in situ formed hydrogel provides an ideal moist healing envi-
ronment that can promote wound healing [11, 12].
This chapter summarizes the ion-exchange properties between alginate bers and
a number of metal ions and describes the gelling characteristics of several types of
alginate bers.
5.2 Characterization Methods for Ion Exchange and Gel
Forming Properties
Since their introduction into the wound management market, many types of com-
mercially availablewound dressings made from dierent typesofalginatebers have
been marketed globally by many producers and distributors. Table 5.1 summarizes
the key structural features of7 types ofcommerciallyavailablealginate wound dress-
ings which are used in the studies described in this chapter [10].
The commercially available alginate wounddressingsin Table 5.1 represent a wide
variety of chemical and physical structures of alginate bers, which were used to
assess the eect of structural parameterson product performances.Among the three
Alginate Fibers and Wound Dressings: Seaweed Derived Natural Therapy, First Edition. Yimin Qin.
© 2024 WILEY-VCH GmbH. Published 2024 by WILEY-VCH GmbH.
84 5 Ion-Exchange and Gel-Forming Properties of Alginate Fibers
Table 5.1 Key structural features of seven types of commercially available alginate wound
dressings.
Brand name of
alginate dressing
Guluronate and
mannuronate content
Calcium and
sodium content
Nonwoven
structure
Sorbsan ∼39/61 ∼96.6/3.4 Un-needled
Tegagel
TM
∼39/61 ∼96.6/3.4 Hydro-entangled
Algosteril ∼68/32 ∼99.6/0.4 Needled
Kaltostat ∼68/32 ∼80/20 Needled
Tegagen HG
TM
∼38/62 ∼65/35 Needled
Curasorb
TM
∼68/32 ∼99.2/0.8 Needled
Urgosorb
TM
(Alginate/CMC blend) ∼68/32 ∼95.2/4.8 Needled
main products, Sorbsan
TM
is made of calcium alginate ber in a loose nonwoven
format, Algosteril
TM
is a needled felt of calcium alginate, and Kaltostat
TM
is made
of calcium/sodium alginate ber in a needled nonwoven format. These products
were made from alginate containing dierent proportions of α-
L-guluronic acid and
β-
D-mannuronic acid. After chemical treatment to the bers, they also contain dif-
ferent amount of calcium and sodium ions.
The calcium and sodium contents are expressed as the percentage of carboxylic
acid groups being as calcium salt or sodium salt. This assumes that all the car-
boxylic acid groups on the alginate molecular chain exist either as calcium salt
or as sodium salt. To measure the calcium and sodium contents, the bers were
rst digested in 98% sulfuric acid solution, and the calcium and sodium contents
were measured with atomic absorption spectrometer. Assuming the wt/wt calcium
content of the ber is C
1
and the sodium content is C
2
,thebercalciumcon-
tent equals to [C
1
/20]/[C
1
/20 + C
2
/23] × 100%, while the ber sodium content is
[C
2
/23]/[C
1
/20 + C
2
/23] × 100% (note: one calcium ion binds with two carboxylic
acid group).
The gel swelling abilities of the alginate bers are measured by placing 0.2 g ber
in 100 ml of either distilled water or 0.9% wt/wt aqueous sodium chloride solution
(normal saline). After one hour, the bers are separated with the contacting solution
and placed in a centrifuge tube with the bottom half lled with knitted viscose
rayon fabric to contain the spin-o solution. The centrifuge is carried out at 1200
rev/min for 15minutes. After that, the ber (W
1
) is dried at 105
∘
Ctoconstant
weight (W
2
). The gel swelling ratio is expressed as the ratio between the weight of
the wet sample and that of the dry sample, i.e. W
1
/W
2
.
In order to measure the gel strength, 2 g of alginate bers was rst cut to about
5 mm length. They were placed in a beaker with 50 ml distilled water. After stirring
for a few minutes, 10 ml of 9% wt/wt aqueous tri-sodium citrate solution is added
into the above mixture. The resultant mixture contains about 3% alginate and 1.5%
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5.2 Characterization Methods for Ion Exchange and Gel Forming Properties 85
tri-sodium citrate. After thorough mixing, the mixture is left for ve minutes before
measuring gel strength on a Stevens gel strength meter.
The ion exchange of alginate bers with the contacting solution is conducted with
solution A as the contacting medium. The British Pharmacopoeia species solution
A as an aqueous solution containing 142 mmol of sodium chloride and 2.5 mmol of
calcium chloride. In total, 1 g ber is placed in 40ml of solutionA and is conditioned
at 37
∘
C for 30 minutes. After separating the ber from the solution, the calcium and
sodium contents in the solution were measured by atomic absorption spectrome-
ter. If the calcium content in the original solution is C
1
ppm, and that after the ion
exchange process is C
2
ppm, then the calcium ions released per gram of ber equal
to 40 × (C
2
− C
1
) × 10
−6
g/g.
The absorption capacitiesof the dressings weremeasured according to themethod
specied in the British Pharmacopoeia monograph for alginate dressings and pack-
ings. A piece of 5 cm × 5 cm dressing (W
1
)isplacedinaat-bottomedPetridish
90 mm in diameter, to the dish added a quantity of solution A 40 times the weight
of the dressing. After conditioning at 37
∘
C for 30 minutes, the sample is lifted from
one corner and held in the air for 30 s before the weight of the sample is measured
(W
2
). The absorption capacity is expressed as (W
2
− W
1
)/W
1
g/g. Figure 5.1 shows
an illustration of the testing procedure
The changes in ber length after wetting were measured under an optical micro-
scope. A piece of ber about 2 mm in length is wetted with either distilled water
or 0.9% saline, and the length change is expressed as (wet length − dry length)/dry
length × 100%.
Contact at 37 °C for 30 min Suspend for 30 s
Figure 5.1 An illustration of the absorption test procedure for alginate wound dressing.
86 5 Ion-Exchange and Gel-Forming Properties of Alginate Fibers
5.3 Ion-Exchange Properties of Alginate Fibers
5.3.1 Ion-Exchange Between Calcium Alginate Fibers and Sodium Ions
Table 5.2 shows the concentrations of calcium ions in the contact solution after algi-
nate bers were in contact with solution A. It is clear that the amount of calcium
ions released was signicantly dierent for Algosteril and Sorbsan. In the solution
containing Algosteril, 321.5 ppm of calcium ions were measured, while for Sorbsan,
the concentration was 557.5 ppm, almost twice that of the Algosteril sample. The
release of calcium ions from the Sorbsan sample is equivalent to 1.86% of the ber
weight.
It is known that the Algosteril bers are made from a grade of alginate rich in
guluronic acid, while the Sorbsan bers are made with alginate containing a high
percentage of mannuronic acid. Literature studies have shown that guluronic acid
has a stronger binding to calcium ions than mannuronic acid [3, 8, 17, 18]. Chem-
ically, when calcium ions form salt bonds with alginic acid, they t into the space
between two neighboring guluronic acid units, creating what is called an egg box
structure, which is highly stable and dicult to be replaced by sodium ions. In this
sense, alginate bers with a high percentage of guluronic acid, or high G alginate,
have stronger binding withcalcium ions and aretherefore more dicult toexchange
with sodium ions when in contact with saline solution.
The ion exchange between calcium ions in the alginate bers and wound dressing
and sodium ions in the wound exudate has a practical signicance in that when part
of the calcium ions in the bers are replaced by sodium ions in the solution, water is
drawn into the ber since sodium alginate is water soluble. As moreand more water
is drawn into the ber, it swells to become a gel that has uid retention ability and
hence helps to keep a moist healing environment on the wound surface. Figure 5.2
Figure 5.2 An illustration of the gelling process when calcium alginate fiber is in contact
with saline solution.
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5.3 Ion-Exchange Properties of Alginate Fibers 87
Table 5.2 Release of calcium ions from alginate fibers when in contact with sodium ions.
Test sample
Test criteria Solution A Algosteril Sorbsan
Ca(II) concentration in the contact solution (ppm) 92.5 321.5 557.5
Calcium release as % of ber weight N/A 0.91% 1.86%
shows the process of gel formation when a piece of calcium alginate ber is placed
in contact with saline solution.
As Table 5.2 clearly shows, it is far more dicult for the high G-type Algosteril
bers to exchangewith sodium ions,giving them poorer gelling ability than the high
M-type Sorbsan bers. One way to improve the gelling ability of high G alginate
bers is to introduce sodium ions into the bers before being applied to the wound
surface. In order to make bers with dierent levels of sodium ions, the original
calcium alginate bers can be treated with aqueous solutions containing dierent
amount of Na
2
SO
4
, which is able to replace part of the calcium ions in the bers
with sodium ions, since the reaction between calcium alginate ber and Na
2
SO
4
results in the formation of CaSO
4
which is only slightly soluble in water.
As previously mentioned inTable 4.5, afterthecalcium alginate bers weretreated
with aqueous solutions containing various levels of Na
2
SO
4
, it was found that as
the Na
2
SO
4
concentration increased, more and more calcium ions were replaced by
sodium ions. Gel swelling results show that while the original sample swelled only
a little in water, with a gel swelling ratio of 1.8, there were signicant increases in
the gel swelling ratio as more and more calcium alginate was converted into sodium
alginate. The ber treated with 0.7% Na
2
SO
4
hasagelswellingratioof21[8].
5.3.2 Ion-Exchange Between Alginate Fibers and Zinc Ions
Zinc is an important microelement in the human body, playing a unique role in the
wound healing process. Similar to calcium ions, zinc ions can be used in the coagu-
lation bath to precipitate sodium alginate, resulting in the formation of zinc alginate
bers. A studyby Mikołajczyk and Wołowska-Czapnik [5] showedthat under appro-
priate conditions, the tenacity of zinc alginate bers can reach 28.65 cN/tex, where
the zinc ion content in the bers is 164.4 mg/g.
In order to prepare zinc alginate bers containing dierent amount of zinc ions,
calcium alginate bers can be treated with zinc salt to load the bers with dier-
ent amount of zinc ions [14, 16]. During the preparation process, calcium alginate
bers were rsttreated with aqueous hydrochloric acid solutionto convert the bers
into alginic acid, before placing them in contact with aqueous zinc sulfate solution.
Table5.3 shows the eect of treatment time on the zinc ion content of alginate bers.
After 0.5 hour, the zinccontent in the ber was 116.0 mg/g, while after 24 hours,zinc
content was 122.6 mg/g, which means that the zinc content at 0.5 hour is 94.6% of
88 5 Ion-Exchange and Gel-Forming Properties of Alginate Fibers
Table 5.3 Effect of treatment time on the zinc ion content of alginate fibers.
Treatment
time (h)
Dry weight of
fiber (g)
Zinc concentration
in the digest
solution (mg/l)
Zinc content in the
fiber (mg/g)
0.5 0.938 5.44 116.0
11.054 6.32 119.9
30.936 5.65 120.7
80.924 5.61 121.4
24 0.687 4.21 122.6
Table 5.4 Effect of ZnSO
4
7H
2
O concentration on the zinc ion content of alginate
fibers.
Amount of
ZnSO
4
7H
2
O(g)
Amount of alginic
acid fiber (g)
Zinc content in the
digest solution (mg/l)
Zinc content in the
fiber (mg/g)
0.5 0.595 1.58 53.1
10.873 3.07 70.3
30.521 2.84 109.0
10 0.839 5.39 128.5
that at 24 hours, showing that the absorption of zinc ions by alginic acid bers is a
fairly fast process [14].
Table 5.4 shows the eect of ZnSO
4
7H
2
O concentration on the absorption of zinc
ions by alginic acid ber. When excess amount of ZnSO
4
7H
2
O was used, the ber
zinc content reached 128.5 mg/g, which compares to zinc content of 164.4 mg/g for
zinc alginate bers obtained through the wet spinning process using aqueous zinc
chloride as the coagulation bath. These two sets of results show that when alginic
acid bers were treated with ZnSO
4
7H
2
O, the majority of the carboxylic acid groups
were able to combine with zinc ions to form zinc alginate. As illustrated in Table 5.4,
by controlling the ratio between the ber and ZnSO
4
7H
2
O, it was possible to control
the zinc content of the alginate bers [14].
Table 5.5 shows the eect of temperature on the zinc ion content of alginate bers
when alginic acid bers were treated with ZnSO
4
. When the temperature was 30,
40, 50, 60, and 80
∘
C, the zinc content in the ber was 103.0, 109.5, 110.8, 119.8,
and 127.9 mg/g, respectively, indicating that higher treatment temperature benets
the absorption of zinc ions. When comparing the absorption of zinc ions by high M
and high G alginic acid bers, results showed that the zinc contents were 127.9 and
132.5 mg/g, respectively, in the high M ber and high G ber, indicating that high G
alginic acid ber is better at absorbing zinc ions [14].
Figure 5.3 shows the zinc ion concentration in the contact solution when zinc
alginate bers were placed in contact with solution A at dierent temperatures.
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5.3 Ion-Exchange Properties of Alginate Fibers 89
Table 5.5 Effect of treatment temperature on the zinc ion content of alginate
fibers.
Treatment
temperature (
o
C)
Dry weight
of fiber (g)
Zinc content in the
digest solution (mg/l)
Zinc content in the
fiber (mg/g)
30 0.829 4.27 103.0
40 0.869 4.76 109.5
50 0.819 4.54 110.8
60 1.135 6.8 119.8
80 0.483 3.09 127.9
20 °C
37 °C
50 °C
65 °C
0
100
200
300
400
500
600
700
800
900
Zinc concentration (mg/l)
0 5 10 15 20 25
Time (h)
Figure 5.3 Zinc ion concentration in the contacting solution when zinc alginate fibers
were placed in contact with solution A at different temperatures. Source: Adapted with
permission from Qin and Chen [14].
It can be seen that the release of zinc ions from zinc alginate ber is a fairly fast pro-
cess, with the zinc ion concentration in the contact solution reaching equilibrium
in three hours. It is worth noting that the bers release more zinc ions at lower tem-
peratures. After being in contact for 0.5 hour, the zinc concentration was 708 mg/l at
20
∘
C, while at 65
∘
C, the zinc concentration was324mg/lover the same period.After
24 hours, the zinc concentrations in the contact solutions were 818 and 457mg/l at
20 and 65
∘
C, respectively.
Figure 5.4 shows the zinc ion concentration in the contact solution when zinc
alginate bers were placed in contact with aqueous solutions containing dierent
amount of protein at 37
∘
C. After 0.5 hours, the zinc ion concentrations were 92,
347, and 626 mg/l in the contact solutions containing 1.0%, 2.9%, and 5.0% protein,
respectively, showing the chelating eect of protein in promoting the release of
zinc ions.
The ion exchange between alginate bers and zinc ions can be used to prepare
bers with dierent zinc contents [16]. As shown in Table 5.6, in three separate
90 5 Ion-Exchange and Gel-Forming Properties of Alginate Fibers
0
200
400
600
800
1000
1200
1400
1600
1800
2000
024681012141618202224
Zinc concentration (mg/l)
Time (h)
1%
2.90%
5%
Figure 5.4 Zinc ion concentration in the contact solution when zinc alginate fibers were
placed in contact with aqueous solutions containing different amount of protein at 37
∘
C.
Source: Adapted with permission from Qin and Chen [14].
Table 5.6 Calcium and zinc ion contents in Zn
2
SO
4
7H
2
O treated calcium alginate fibers.
Sample no.
Amount of
Zn
2
SO
4
7H
2
O(g)
Amount of calcium
alginate fiber (g)
Calcium content
in the fiber (mg/g)
Zinc content
inthefiber(mg/g)
1 0.774 5.192 166.446.5
2 2.331 5.216 127.484.9
3 7.885 5.292 98.9 124.6
4
a)
N/A N/A 23.3 164.4
a) Zinc alginate ber made in the wet spinning process with zinc chloride as the coagulant.
samples, 0.774, 2.331, and 7.885 g of Zn
2
SO
4
7H
2
O were dissolved in 1 l de-ionized
water before being placed in contact with 5.192, 5.216, and 5.292g calcium alginate
bers, respectively. After 24 hours, the bers were washed and dried before being
tested for zinc and calcium contents. These three samples have zinc contents of
46.5, 84.9, and 124.6 mg/g, respectively, which means that by controlling the ratio
between calcium alginate bers and Zn
2
SO
4
7H
2
O in the aqueous solution, it is pos-
sible to obtain bers with dierent levels of zinc contents. In comparison to the
zinc-containing alginate bers obtained through the indirect ion-exchange method,
zinc alginate ber made in the wet-spinning process with zinc chloride as the coag-
ulant contained 23.3 and 164.4 mg/g calcium and zinc ions, respectively.
Table 5.7 shows the antimicrobial eect against Bacillus subtilis var. nier of zinc
alginate bers with dierent zinc ion contents. Pure zinc alginate bers made from
the wet-spinning process showed a reduction rate of 99.77% against B. subtilis var.
nier, while the bers with zinc contents of 124.6 and 84.9 mg/g had reduction rates
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5.3 Ion-Exchange Properties of Alginate Fibers 91
Table 5.7 The antimicrobial effect against Bacillus subtilis var. nier of zinc alginate fibers
with different zinc ion contents.
Fiber zinc
content (mg/g)
Bioburden at the
beginning Bioburden after 24h
Reduction of bacteria
count (%)
46.5 1.1 × 10
5
1.1 × 10
5
0
84.9 1.3 × 10
5
1.2 × 10
5
7.69
124.6 1.1 × 10
5
7.9 × 10
4
28.18
164.4 5.3 × 10
4
1.2 × 10
2
99.77
(1) Against Staphylococcus aureus (2) Against Escherichia coli
Figure 5.5 Zone of inhibition for zinc alginate fibers. Source: Adapted with permission
from Qin et al. [16].
of 28.18% and 7.69%, respectively, with the bers containing 46.5 mg/g zinc showing
no antimicrobial eect [16].
Figure 5.5 shows the zone of inhibitionfor zinc alginate bers against Staphylococ-
cus aureus and Escherichia coli. It is clear that with the release of zinc ions, zinc algi-
nate bers have zones of inhibition against the two bacteria commonly encountered
during wound healing. The antimicrobialpropertyis further illustrated in Figure5.6,
which demonstrated that under the same test conditions, calcium alginate bers
were unable to stop the spreading of bacteria, while zinc alginate bers were able to
inhibit the migration of bacteria through the nonwoven structure.
5.3.3 Ion-Exchange Between Alginate Fibers and Copper Ions
As a polymeric acid, alginate can be in the form of alginic acid, sodium alginate, cal-
cium alginate, and many other salts. Alginic acid bers are produced when calcium
ions are removed by treating calcium alginate bers with aqueous acid solutions.
Calcium/sodium alginate bers can be obtained by replacing part of the calcium
92 5 Ion-Exchange and Gel-Forming Properties of Alginate Fibers
(a) (b)
Figure 5.6 Antimicrobial effect of alginate fibers, (a) calcium alginate fibers; (b) zinc
alginate fibers. S ource: Adapted with permission from Qin et al. [16].
4.27
2.62
15
0
2
4
6
8
10
12
14
16
Alginic acid
fiber
Calcium alginate
fiber
Calcium sodium alginate
fiber
Gel swelling (g/g)
Figure 5.7 The swelling ratio of three types of alginate fibers when wet in water.
Source: Adapted with permission from Mo et al. [6].
ions in the bers with sodium ions. When alginic acid ber, calcium alginate ber,
and calcium/sodium alginate ber were placed in water, they showed signicantly
dierent water absorption behavior, with alginic acid ber absorbing more water
than calcium alginate ber, and calcium/sodium alginate ber showing the highest
absorption capacity. Figure 5.7 shows the swelling ratio of the three types of bers
when wet in water.
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