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Abstract
Availing medium water swelling hydrogel would significantly contribute to the production
of soil conditioner and conductive gels. In the present work, hydrogel was prepared based on
corn and potato starches, acrylonitrile (AN) as a grafting monomer and H2O2/Fe2+ redox system
as a source of free radicals. The parameters tested for the preparation were (AN) / starch ratio of
0.3 to 1.6, H2O2 dose of 0.03 to 0.21 of starch weight and liquor to solid ratio of 10 to 30. The
best conditions for grafting efficiency were obtained at :AN/starch ratio of about 1.4 for corn
and potato starches, H2O2 dose of about 12% and 15% of starch weight for corn and potato
starches, respectively and liquor to solid ratio of 1:10.
The prepared hydrogel at optimum attained conditions was tested for water swelling under
different operating conditions. An empirical correlation for hydrogel water retention (WR) was
deduced as a function of pH, temperature (T oC), electric conductivity (C, as mho /cm) and
time (t, hr) as follows:
WR = [21.5C -0.21 - 1.2pH + 0.44T] (t0.3).
Performance indicators revealed significant water holding capacity in the range of 48 to 56
g/g. Scanning Electronic Microscopy investigations depicted the morphological features of the
prepared hydrogel. Electric conductance properties were depicted at different swelling conditions of pH, NaCl concentration and temperature. The process design implications for the proposed hydrogel production are also outlined.
Key words: hydrogel; starch; acrylonitrile; redox system; swelling.
* Corresponding author - Tel. 20123284428; Fax (0202) 33370931
1. Introduction
Hydrogels are insoluble; water swollen networks composed of hydrophilic homo or copolymers [1, 2].Due to their biocompatibility, permeability and physical characteristics, hydrogels
are suitable for use in many agricultural, industrial and medical applications [3-7]. The hydrogel
networks can be formed by conventional crosslinking methods or free radical polymerisation
processes which are initiated by redox initiation or by using free radical initiators activated by
irradiation in the form of
[2,8].
Hydrogels of natural polymers, especially polysaccharides, are in general, non-toxic and
biodegradable [9]. Considerable research and technical work have been reported. The chemical
modification of starch or modified starch via vinyl graft co-polymerisation constitutes the most
important fields for improving the properties of starch and enlarging the range of its utilization
[7, 8, 10]. The starch graft-copolymer such as starch-g-polystyrene [11], starch-g-polyvinyl alcohol [12], starch-g-methacrylonitrile [13] and starch-g-acrylonitrile [14] have been synthesized
by generating free radicals on the surface of the starch granules followed by copolymerization
of these free radicals with the respective vinyl monomers. These copolymers have also limited
biodegradability because of the presence of a non biodegradable part of the polymer [15].
In this work, the preparation and characteristics of a modified hydrolysed grafted starch are
investigated. A redox system (Fe2+/H2O2) is used as a source of [OH] free radicals. The grafted
starch is hydrolysed using sodium hydroxide followed by precipitation in methanol. Further, the
swelling characteristics and electric properties of the prepared hydrogel are
investigated.
2.2. Methods
2.2.1 Hydrogel preparation
Ten grams of starch (ethyl alcohol washed), a weighed quantity of acrylonitrile (AN), and
0.1 ml of non ionic surfactant were added with distilled water (liquor to solid ratio of 1:10 to
1:30) to the reaction vessel. The mixture was mixed by a magnetic stirrer and sparged with a
slow stream of nitrogen. Specific quantities of H2O2 and FeSO4.7 H2O solutions were injected
to the reaction vessel to begin the grafting process.The weight ratio of H2O2/FeSO4.7H2O was 6.
Starch type, AN/starch ratio, initiator ratio (H2O2/ Fe2+) and H2O2 dose were studied. Percent grafting efficiency (GE %) was calculated according to the following equation:
GE % = [(w2 w1) / w1] x 100
(1)
Where, w1 and w2 are the weight of dry starch and polymerized samples in grams. The reaction
time was 30 minutes at room temperature followed by another 60 minutes at temperatures from
30 to 40 C. The product was filtered, washed by distilled water and then dried
at room tem-
perature.
A suspension of poly AN grafted starch in 0.7 N NaOH (liquor ratio 1/9, w/v) was introduced in a reflux system and with mixing in a water bath. Saponification was maintained for an
hour at 95 C till complete saponification (the colour changes from deep red to light brown). The
mixture was cooled, then dispersed in methanol (1/20, w/v). The precipitate was washed with
slightly acidified ethanol (ethanol with few drops of acetic acid to pH= 8), then filtered and
dried at 60 C for 3 hours [9].
2.2.2 Analytical methods
-The morphology of corn starch, grafted starch, dry hydrogel and swelled hydrogel were characterized by scanning electronic microscopy technique (Electron prop
(2)
Where, w0 and w3 are the weights in grams of the dry and the water swollen hydrogels, respectively. The swelling of the prepared hydrogel was tested at different pH values (from 3.5 to 11)
by adjusting the pH using 0.1 N sulphuric acid and 0.1N NaOH with pH meter (Jennway model 3051). The swelling characteristics were measured in solutions of sodium chloride with
different concentrations (500, 1000, 1500 and 2000 mg/l). The effect of temperature on swelling
capacity of the prepared hydrogel was also tested. The hydrogel was allowed to swell in distilled
water for 3 hours at each predetermined temperature (30, 40 and 50 C).
2.2.4 Electric conductivity studies
A glass cell, with dimensions of 3 x 1.8 x 5 cm, immersed in a water bath was used for
studying the electric conductivity of the swollen hydrogel prepared from corn starch. A defined
weight of the swollen hydrogel (15 g) was immersed in distilled water inside the cell. Two electrodes of Aluminium (anode) and lead (cathode) with dimensions of 5 cm x 2.5 cm were used
with 1.5 cm distance between the two electrodes. The cell was connected to an electric circuit
involving a DC power supply (JW -GPR-3030) to apply the required potential range from 0.1 to
1 volt. The electric current response and the resistance across the cell were measured by a portable digital multimeter (Tenmars model YF-3220).
R2=98%
(3)
(t, hr)] affecting the swelling behaviour for the prepared hydrogel. The developed correlation
is shown below with a correlation coefficient of 0.97. The predicted values are well fitted with
the experimental values as shown in figure (7) according to the following equation:
WR = [21.5C -0.21 - 1.2 pH + 0.44T] (t0.3)
(4)
This correlation is valid for: pH = 3.5 to 11, NaCl concentration up to 2000 mg/l, temperature up to 50 C and time up to 24 hours.
3.3 Surface morphology of the prepared hydrogel
The surface characteristics of corn and grafted starches, dry hydrogel and swelled hydrogel
were investigated by scanning electronic microscopy (SEM). Figure (8) shows the conventional
SEM for corn starch (8a), the impact of grafting and the development of large entities (8 b), the
uniform nature of the hydrogel with limited cracks on its surface (8 c), and the limited swelling
nature of the modified hydrogel (8 d).
3.4 Electric characteristics of the swollen hydrogel
3.4.1 Effect of swelling pH
The effect of swelling pH on hydrogel specific conductance is depicted in table (1). In general, the specific conductance increases as cell potential increases. A maximum specific conductance is attained at pH = 8.5 (for all cell potential values studied). This could be attributed to
the high water content in the swollen hydrogel which reflects the ease of ions to diffuse inside
the gel. The higher the water content, the higher the ionic diffusion rate [20]. The response of
the hydrogel is also attributed to the carboxylic acid groups present in the hydrogel, which results in an increase of the ionic distribution inside the network. Also, the swelling of hydrogel
involves ionization of carboxylic groups which are more ionized in alkaline solution than acidic
solution [21].
3.4.2 Effect of swelling under varying NaCl concentration
Figure (9) shows that the hydrogel specific conductance increases generally with increasing
cell potentials at constant NaCl concentration. By increasing the salt content of the swelling solution, the effective distance, over which the repulsion acts, collapses the gel. The deformation
of the hydrogels under an electric field is possibly caused by the change in the ion distributions
inside and outside the hydrogels [22].
3.4.3 Effect of swelling temperature
Figure (10) depicts the effect of swelling temperature on the hydrogel specific conductance
at different cell potentials. For lower range of cell potentials (0.2 V, 0.4 V), the specific conductance exhibits a peak at a temperature of 30 C. For the higher studied values of cell potential
(0.8 V & 1 V), the peak specific conductance is attained at 40 C. For 0.6 V cell potential,
the specific conductance decreases almost linearly with temperature.
3.5 Process Design Implications
Classical hydrogel with medium water swelling characteristics involve high monomer to carbohydrate ratio, adoption of expensive initiators such as citric salts and prolonged saponification time up
to three hours. The immediate environmental consequences comprise significant sensitive polymer
loading to the soils, slow biodegradation of the starch polymer compound, probabilities of monomer
release and high energy requirements to manufacture the very high swelling hydro gel. Further, economic implications caused by high synthetic polymer content, reliance on expensive initiators and
high energy consumption are related to the high production cost and poor market penetration. Thus,
the concept of developing high swelling hydrogel should be re-engineered to permit trade-off
between degree of water retention and other environmental, economic and process design considerations. The adopted concept in this work involves manufacture of moderate swelling hydrogels based
on relatively low monomer to starch ratio, and adoption of safe initiators. The main process parameters concluded in this study may be outlined as follows: AN/starch, 1.4; H2O2 dose, 1.2 & 1.5 g/g
corn and potato starches, respectively
H2O2 / FeSO4.7H2O=6 (w/w); Liquor to solid ratio, 10 : 1; grafting temperature, 30 C; grafting
time 90 min.; saponification time, 90 min.; 9 ml NaOH (0.7N) /g of grafted starch; saponification
temperature, 95 C; methanol used in precipitation & washing (20ml / g grafted starch); Water;
Drying temperature, 60 C and drying time, 3hr. Further work, for scaling up of the process
is essential to verify and rationalize the concluded prementioned parameters. The selection of starch
substrate type is largely implied by cost consideration. In that respect, corn starch seems to be
a favourable raw material for the proposed hydrogel. Other starch sources could be also considered.
4. Conclusion
1- Acrylonitrile (AN) grafted starch was prepared using both corn and potato starches. The best
polymer loading (GE %) was obtained at AN/starch ratio around 1.4 (w/w) for corn and potato staches. A correlation was empirically deduced correlating polymer loading percent
with AN/Starch ratio. Maximum GE % was obtained for H2O2 dose about 1.2 and 1.5 g/10g
for potato starch and corn starch respectively. It is also concluded that GE % decreases as
liquor to solid ratio increases.
2- The swelling characteristics of the prepared hydrogel showed an increase with time
to 24 hours. The maximum water retention of about 55.8 g/g is obtained after 24 hours
and pH = 8.5. The water retention of the prepared hydrogel decreases with increasing NaCl
salt content. The water retention increases as swelling temperature increases to 40 0C. An
empirical formula correlating water retention (WR) with solution conductivity (C), pH, temperature (T) and time (t) was deduced.
3 - The electric conductance of the prepared hydrogel is significantly affected by the swelling
conditions as indicated by the change of specific conductance with pH, salt concentration
and swelling temperature.
5. References
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(V)
pH = 3.5
pH = 7
pH = 8.5
pH = 11
0.2
0.160
0.067
0.167
0.107
0.4
0.187
0.117
0.400
0.117
0.6
0.510
0.644
0.744
0.144
0.8
1.099
0.850
1.358
0.467
1.0
1.080
0.900
1.620
0.627
160
160
140
140
120
120
100
100
80
80
60
60
40
Potato starch"
40
20
Corn starch
20
0
0
0.2
0.4
0.6
0.8
1.2
1.4
1.6
AN/starch ratio
Figure (1): Effect of AN/starch ratio on grafting efficiency
of corn and potato starches-g-AN.
H2 O2 /FeSO4 .7H2 O = 6, H2 O2 dose 0.15 g/g starch
1.8
Cell potential
170
Potato starch
Corn starch
150
130
110
90
70
50
0
0.05
0.1
0.15
0.2
0.25
140
120
100
80
60
5
10
15
20
25
Liquor to solid ratio
30
35
60
24 hr
9 hr
3 hr
50
40
30
20
10
0
0
10
12
pH
Figure (4): Effect of pH on water retention for
the prepared hydrogel
60
50
40
30
20
10
0
0
500
1000
1500
2000
2500
50
40
35
30
25
20
0
10
20
30
40
50
60
Temperature ( C)
Figure (6): Effect of swelling temperature on wate retention
for the prepared hydrogel (after 3 hours)
60
WR = (21.5 C
-0.21
0.3
- 1.2 pH + 0.44 T) ( t )
2
R = 0.97
50
Predicted values
45
40
30
20
10
0
0
10
20
30
40
50
Experimental values
60
Figure (8): SEM for (a) corn starch, (b) grafted starch,
(c) dry hydrogel and (d) swollen hydrogel
6
Cell potential
Specific conductance
(m mho/cm)
0.2 V
0.4 V
0.6 V
0.8 V
1.0 V
4
0
0
200
400
600
800
1000
1200
1400
1600
1.8
Cell potential
1.6
0.2 V
0.6 V
1.0 V
1.4
0.4 V
0.8 V
Specific conductance
(m mho/cm)
1.2
1
0.8
0.6
0.4
0.2
0
15
20
25
30
35
40
45
50
Swelling temperature ( C)
55