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Environmental Technology

ISSN: 0959-3330 (Print) 1479-487X (Online) Journal homepage: http://www.tandfonline.com/loi/tent20

Swelling Mechanism of Urea Crosslinked Starch-


Lignin Films in Water

Ariyanti Sarwono, Zakaria Man, M. Azmi Bustam, Duvvuri Subbarao, Alamin


Idris, Nawshad Muhammad, Amir Sada Khan & Zahoor Ullah

To cite this article: Ariyanti Sarwono, Zakaria Man, M. Azmi Bustam, Duvvuri Subbarao,
Alamin Idris, Nawshad Muhammad, Amir Sada Khan & Zahoor Ullah (2017): Swelling
Mechanism of Urea Crosslinked Starch-Lignin Films in Water, Environmental Technology, DOI:
10.1080/09593330.2017.1332108

To link to this article: http://dx.doi.org/10.1080/09593330.2017.1332108

Accepted author version posted online: 19


May 2017.

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Download by: [The UC San Diego Library] Date: 19 May 2017, At: 18:39
Publisher: Taylor & Francis & Informa UK Limited, trading as Taylor & Francis Group
Journal: Environmental Technology
DOI: 10.1080/09593330.2017.1332108

Swelling Mechanism of Urea Crosslinked Starch-Lignin Films


in Water

Ariyanti Sarwono*a, Zakaria Mana, M. Azmi Bustama, Duvvuri Subbaraoa,


Alamin Idrisa, Nawshad Muhammadb, Amir Sada Khana, Zahoor Ullaha

a
Centre of Research in Ionic Liquids (CORIL), Chemical Engineering Department,
Universiti Teknologi PETRONAS (UTP), 32610, Bandar Seri Iskandar, Perak, Malaysia
b
Interdisciplinary Research Centre in Biomedical materials, COMSATS Institute of
Information Technology, Lahore, Pakistan
*Corresponding authors email ID: arisarwono3@gmail.com

Details:

Corresponding Author:

1. Ariyanti Sarwono
Centre of Research in Ionic Liquids (CORIL), Chemical Engineering Department,
Universiti Teknologi PETRONAS (UTP), 32610, Bandar Seri Iskandar, Perak,
Malaysia
Email: arisarwono3@gmail.com

Co-Authors:

2. Zakaria Man
Centre of Research in Ionic Liquids (CORIL), Chemical Engineering Department,

1
Universiti Teknologi PETRONAS (UTP), 32610, Bandar Seri Iskandar, Perak,
Malaysia
Email: zakaman@utp.edu.my

3. Mohamad Azmi Bustam


Centre of Research in Ionic Liquids (CORIL), Chemical Engineering Department,
Universiti Teknologi PETRONAS (UTP), 32610, Bandar Seri Iskandar, Perak,
Malaysia
Email: azmibustam@utp.edu.my

4. Duvvuri Subbarao
Centre of Research in Ionic Liquids (CORIL), Chemical Engineering Department,
Universiti Teknologi PETRONAS (UTP), 32610, Bandar Seri Iskandar, Perak,
Malaysia
Email: subbarao_duvvuri@yahoo.com

5. Alamin Idris
Centre of Research in Ionic Liquids (CORIL), Chemical Engineering Department,
Universiti Teknologi PETRONAS (UTP), 32610, Bandar Seri Iskandar, Perak,
Malaysia
Email: alamino97@yahoo.com

6. Nawshad Muhammad
Interdisciplinary Research Centre in Biomedical materials,
COMSATS Institute of Information Technology, Lahore, Pakistan
Email: nawshadchemist@yahoo.com

7. Amir Sada Khan


Centre of Research in Ionic Liquids (CORIL), Chemical Engineering Department,

2
Universiti Teknologi PETRONAS (UTP), 32610, Bandar Seri Iskandar, Perak,
Malaysia
Email: aamirsada_khan@yahoo.com

8. Zahoor Ullah
Centre of Research in Ionic Liquids (CORIL), Chemical Engineering Department,
Universiti Teknologi PETRONAS (UTP), 32610, Bandar Seri Iskandar, Perak,
Malaysia
Email: zahoor7979@yahoo.com

3
Swelling Mechanism of Urea Crosslinked Starch-Lignin Films in Water

Ariyanti Sarwono, Zakaria Man, M. Azmi Bustam, Duvvuri Subbarao, Alamin Idris,
Nawshad Muhammad, Amir Sada Khan, Zahoor Ullah

Abstract
Coating fertilizer particles with thin films is a possibility to control the fertilizer release
rates. It is observed that novel urea crosslinked starch-lignin composite thin films,
prepared by solution casting, swell on coming into contact with water due to increase in
volume by water uptake diffusion. The effect of lignin content, varied from 0% to 20% in
steps of 5% and three different temperatures (25°C, 35°C and 45°C) on swelling of the
film was investigated. By gravimetric analysis, the equilibrium water uptake and
diffusion coefficient decrease with lignin content indicating that the addition of lignin
increases the hydrophobicity of the films. When temperature increases, diffusion
coefficient and the amount of water absorbed tends to increase. Assuming that swelling
of the thin film is by water uptake by diffusion, diffusion coefficient is estimated.
Estimated diffusion coefficient decreases from 4.3 to 2.1 x 10-7 cm2/sec at 25°C, from 5.3
to 2.9 x 10-7 cm2/sec at 35°C and from 6.2 to 3.8 x 10-7 cm2/sec at 45°C depending on the
lignin content. Activation energy for increase of diffusion coefficient with temperature is
observed to be 16.55 kJ/mol. Empirical model of water uptake as a function of percentage
of lignin and temperature was also developed based on the Fick’s law.

Introduction
In recent years, the use of starch, a low cost biodegradable natural hydrophilic polymer,
as controlled release device for agrochemicals such as fertilizers [1], insecticides [2],
pesticides [3], fungicides [4] and herbicides [5], etc has gained interest [6]. However,
water sensitivity in starch leads to substantial swelling causing reduction on physical
stability of the starch matrix therefore provides less effective control over the coated
fertilizer. Therefore, studying the ingress of the water into starch matrix which influences
the profile of agrochemicals release is crucial to obtain an efficient release system.
Chen et al. prepared unmodified corn starch film by solution casting for urea
encapsulation purpose [6]. The film was swollen but quickly broken when immersed in

4
water within less than 12 hours at room temperature. The same observation is reported by
Huang et al.[7]. Film of various native starches (potato, corn, tapioca and amylopectin) is
broken into pieces within 30 minutes once in contact with water.
Ghanbarzadeh et al. [8] cross linked corn starch film with citric acid by casting to reduce
the water sensitivity of starch. Approximately 8.5% and 23% reduction in total water
absorption was achieved by 5% and 10% citric acid respectively. Das et al. [9]
crosslinked starch/polyvinyl alcohol (PVA) film with formaldehyde, borax,
epichlorohydrin, and ZnO and found that moisture absorption (93%RH) at 27°C was
considerably decreased in all crosslinked films. Estimated water diffusion coefficient in
unmodified starch/PVA, ZnO crosslinked starch/PVA, borax crosslinked starch/PVA,
epichlorohydrin crosslinked starch/PVA and formaldehyde crosslinked starch/PVA were
12 x 10-15 m2/s, 6 x 10-15 m2/s, 9 x 10-15 m2/s, 3.9 x 10-15 m2/s and 3.7 x 10-15 m2/s
respectively. Cao et al. [10] developed controlled release granule for insecticide
acetamiprid based on tapioca starch-urea-borate. The increasing urea content, acting as
monomer in urea-starch-borate polymer, prolonged insecticide release. The more urea is
added; the larger the polymer is formed therefore delay the release of entrapped
acetamiprid in modified starch polymer matrix. The similar observation was also reported
by Ramakrishna et al. [11]. They evaluated the potato starch-urea-borate as a release
retarding materials for tablet of diclofenac and gliclazide. The increasing polymer
concentration from 10 – 50%, prolonged the half time release of both drug released from
3.5 – 6 hours for diclofenac and 5.1 – 7.6 hours for gliclazide.
Another approach to reduce the water sensitivity of starch is by blending with more
hydrophobic material such as lignin. As a low cost waste product in the paper industry,
lignin is a material that may be ideal for soil application since it acts as a humic acid
precursor substance according to Martin and Haider [12] and Stevenson [13]. Flaig [14]
also proved that lignin reduces the nitrification rate of urea which enables urea to remain
in the soil longer. Baumberger et al. used kraft lignin as a filler for wheat starch films
[15]. The presence of 15% lignin did not significantly affect the sorption isotherm of
starch film while 30% of lignin addition reduced the equilibrium moisture content at any
water activity due to the hydrophobicity of lignin. Starch-lignin foam prepared by

5
Stevens et al. has lower diffusion coefficient of 0.8 x 10-6 cm2/sec than unmodified corn
starch foam of 2.68 x 10-6 cm2/sec [15].
The present work reports the experimental investigation of swelling characteristics of
lignin modified urea cross linked starch films prepared by the method presented in
Sarwono et al. [16].

Experimental Procedure

1. Material
The raw material of starch used in this study was commercially available food grade
tapioca starch from local market (Kapal ABC brand, Malaysia). Disodium tetraborate
(Na2B4O7.10H2O) and urea were obtained from R&M Chemicals and Petronas Fertilizer
Kedah (PFK) respectively. Lignin (Indulin AT) was obtained from Sigma Aldrich (CAS
No 8068-05-1) having the molecular weight distribution as Mn, Mw and PDI are 1700
g/mol, 8000 g/mol and 4.71 Mw/Mn respectively.

2. Lignin characterization
Fourier transform infrared (FTIR)
The functional groups of lignin were analyzed by Perkin Elmer Fourier Transform Infra-
Red spectrometer. The spectra were analyzed by Spectrum One data acquisition. All
powder samples were mixed with solid potassium bromide (KBr) (0.2% -1%) [17], then
ground and pressed to form pellet. Each FTIR spectrum was recorded with a blank KBr
pellet as background. The samples were then run under transmittance mode in the
wavelength range of 400 cm-1 to 4000 cm-1.
Thermal gravimetric analysis (TGA)
The thermal stability of lignin was assessed using TGA Perkin Elmer STA 6000. Samples
of 5-10 mg were weighed and placed in aluminum crucibles. The measurements were
taken in the temperature range of 25 °C to 600 °C (depending on the raw materials) at the
heating rate of 10°C/min. The measurement was carried out under nitrogen gas
atmosphere at flow rate of 20 ml/min. The data were recorded using Pyris Player Data
Analyzer [18].

6
Elemental analysis
Elemental composition of lignin was determined. Dried lignin was placed in a tared small
tin capsule (LECO Corporation) and precisely weighed between 1.5-2 mg. The capsule
was then crimped, folded and run on CHNS-932 (LECO instruments). The values were
obtained by averaging three samples. The equipment settings are as follows: furnace
temperature: 1000°C, analysis time: 3 minutes and helium was used as the carrier gas for
the measurement.

3. Film Preparation
Starch-urea-borate (SUB) film was prepared by casting method. An aqueous solution of
5% wt starch was prepared and gelatinized at 80ºC for 30 minutes. Urea (20% wt), borate
(3.5% wt) and lignin (L%) were then added into gelatinized starch and stirred for another
3 hours at 80ºC. Lignin content (L% wt) was varied from 0% to 20% in steps of 5%. The
solution samples were poured into Petri dishes and dried for 2 hours at 120°C. The
starch-urea-borate-lignin films prepared with 0% to 20% of lignin in steps of 5% are
referred to as SUB and SUB5%L, SUB10%L, SUB15%L, and SUB20% L, respectively
as summarized in Table 1. Small rectangular modified starch films of dimensions 30 x 30
x 0.6 mm were prepared and immersed in water. Each film grew in size due to swelling
by water uptake with time till it reached an equilibrium size. On addition of more than
20% lignin, a good film cannot be formed due to incompatibility between starch and
lignin which will give poor mechanical properties. Therefore, SUB20%L was not studied
for its water absorption behavior.

Table 1. Codes and composition of modified starch film


Film Starch-Urea-Borate content Lignin content, % Starch fraction (Xs)
SUB 100 0 1
SUB5%L 95 5 0.95
SUB10%L 90 10 0.9
SUB15%L 85 15 0.85
SUB20%L 80 20 0.8

7
4. Film Swelling Kinetics

Kinetics of water uptake by the film was gravimetrically measured by noting mass of the
film m t with time at 25°C, 35°C and 45°C [19, 20] The percentage of water absorption
was calculated using Eq. 1
mt − m0
Mt = × 100% (1)
m0

M t is the percentage of water diffused into the film at t time, mt is weight of the wet

films at time t and m 0 is the weight of initial dry film. It was observed that the film swell
isotropically as shown in Fig.1. The swelling is essentially due to increase in volume due
to water uptake by diffusion.

Figure 1. Physical appearance of film before (left) and after (right) swelling

Experimental Observations
The percentage of water uptake plotted against time for the five films at 25ºC, 35ºC and
45ºC are presented in Figure 2, 3 and 4 respectively.

8
3000

2500 SUB
SUB5%L
SUB10%L
2000 SUB15%L
Water uptake (%)

1500

1000

500

0
0 100 200 300 400 500 600 700

Time (min)

Figure 2. Water uptake profile of modified starch film at 25ºC


3000

2500 SUB
SUB5%L
SUB10%L
SUB15%L
2000
Water uptake (%)

1500

1000

500

0
0 100 200 300 400 500 600 700

Time (min)

Figure 3. Water uptake profile of modified starch film at 35ºC

9
3000

2500 SUB
SUB5%L
SUB10%L
Water uptake (%)

2000 SUB15%L

1500

1000

500

0
0 100 200 300 400 500 600 700

Time (min)

Figure 4. Water uptake profile of modified starch film at 45ºC

It can be seen from these observations in Figs. 2, 3 and 4 that the samples absorb water
and approach an equilibrium value. These observations are analyzed in the following
section.

Results and Discussion

1. Characterization of lignin
The properties of Indulin AT especially solubility in water greatly affected by its
molecular weight distribution. The Indulin AT used in this study was obtained from
Sigma Aldrich having higher molecular weight distribution as Mn, Mw and PDI are 1700
g/mol, 8000 g/mol and 4.71 Mw/Mn respectively which causes its insolubility in water.
The lignin was used to reduce the hydrophilicity of starch.

To understand the behaviour of the lignin, it is necessary to study the characteristics of


lignin. The FTIR spectrum of lignin was given in Figure 5.

10
50

Transmittance (%) 45

40

35

30

25

20
4000 3500 3000 2500 2000 1500 1000 500

-1
Wavenumber (cm )

Figure 5. Infrared spectrum of Indulin AT

The spectrum was analyzed for the presence of hydroxyl, carbonyl, methoxyl and
carboxyl functional groups that reportedly have been used for identification of lignin.

Table 2. Interpretation of absorption bands for Indulin AT


Wavenumber (cm-1) Functional group
3362 O-H stretching
2930 C-H stretching
1600-1510 Aromatic skeletal vibration
1449, 1419 C-H deformation
1264 Guaiacyl ring breathing with C-O stretch
1211, 1121 Syringyl ring and C-O stretch
1029 C-O stretch
825 C-H deformation in syringyl unit

A broad band of hydroxyl and methoxyl groups were observed around 3400 cm-1 and
2960-2930 cm-1 respectively. Strong intensity peaks from 1600-1507 cm-1 could be

11
assigned to the aromatic skeleton of lignin. The detail interpretation of the spectrum is
presented in Table 2.

As shown in Figure 6, a single step degradation process was observed for lignin. The
onset of degradation was at around 200°C. From the Figure 6, it is obvious that the
decomposition of lignin occurred over a broad range of temperature (175-500°C). This is
due to the variety of chemical bonds of the branches attached to the aromatic rings of
lignin [21]. The final lignin char residue at 550°C is around 49%. The higher char yield
from lignin is due to higher thermal stability of lignin, which is attributed to the more
complex carbon-carbon bonds that exist in lignin as compared to starch [22]. Similar
observations are reported by Yang et al. [21] and Chen et al. [23].
120

100

80
Weight (%)

60

40

20

0
0 100 200 300 400 500 600

o
Temperature ( C)

Figure 6. TGA thermogram of lignin

The elemental analysis of Indulin AT was assessed by CHNS analyzer and is given in
Table 3. The high carbon content in lignin is expected since lignin is structurally rich in
phenyl propane groups that are rich in carbon. The obtained result is in the range of
reported composition in the literature [24]. From Table 3, it can be seen that kraft lignin

12
still contains a small amount of sulfur which originates from kraft process [24] while the
nitrogen is assumed to be related to protein residue [25].
Table 3. Elemental composition of Indulin AT
Element wt (%)
C 58.56
H 5.17
N 1.51
S 1.59

2. Equilibrium water uptake


In this study, lignin modified starch film was prepared and studied for its water
absorption behavior at three different temperatures. Lignin content was varied from 0%
to 20% in steps of 5%.
Equilibrium water uptake of modified films (Meq) performed at three different
temperatures is shown in Fig 7.
3000
25°C
35°C
2500 45°C

2000
M (%)

1500
eq

1000

500

0
0.85 0.9 0.95 1

X
s

Figure 7. Equilibrium water uptake of modified starch films at


three different temperatures

13
It can be seen from Figure 7 that equilibrium water uptake decreases with decrease in
starch fraction in the film and can be empirically correlated by
ΔS ΔH
ln M = − (2)
Teq R RT

as shown in Figure 8 and Table 4 with Meq is equilibrium water uptake; MTeq is
equilibrium water uptake at different temperature and Xs is starch fraction.
100
15.13 2
25°C y = 29.37 x R = 0.98
14.60 2
35°C y = 29.49 x R = 0.98
45°C 13.95 2
y = 29.53 x R = 0.98
eq

10
M

1
0.1 1
X
s

Figure 8. Equilibrium water uptake versus lignin fraction at 25°C,


35°C and 45°C

It can be seen in Table 4 that the exponent is around 14. The high exponent value
indicates that starch fraction drastically influences the equilibrium water uptake. Due to
the inherent hydrophilic nature of starch, starch tends to absorb large quantities of water
therefore contributes to the high equilibrium water uptake. Lignin decreases the
equilibrium water content due to its hydrophobic aromatic fragments.
This observation is in agreement with Baumberger et. al. [15]. They reported the
influence of kraft lignin on moisture adsorption of wheat starch in different relative
humidity (RH) ranging from 33-84%. The presence of 15% lignin is reported to
insignificantly affect the sorption isotherm while addition of 30% lignin has lower

14
equilibrium moisture content in all RH. Another work by Baumberger et al. [26]
established that reduced water content in wheat starch-kraft lignin (80/20) blends from
11.6% to 10.2% at room temperature over a saturated sodium bromide solution (water
activity, aw = 0.57) was due to the amount of water soluble phenolics present in lignin as
these hydrophilic compounds are likely to interact with the starch matrix, through
hydrogen bonding and lead to increased bonding to lignin.

Table 4. Correlation between equilibrium water uptake and starch fraction


Temperature correlation
25°C ln Meq = 15.13 ln Xs + 3.380
35°C ln Meq = 14.60 ln Xs + 3.384
45°C ln Meq = 13.95 ln Xs + 3.385

The amount of water absorbed tends to increase when temperature increases as shown in
Fig. 8. Higher temperature increases free volume available therefore allowing more
penetration of water. Russo et al. [27] studied diffusion of water in high amylose maize
starch blend using magnetic resonance imaging (MRI) and reported that higher intensity
of water protons was available across the starch film at 45°C than at 25°C. Yu et al. [28]
reported an increasing of moisture absorbed of dent corn starch from 6-8 (g water/100 g
sample) as temperature increases from 15 -35°C at 50% RH. Aubin et al. [29] as well
observed the increasing of mass uptake at equilibrium of high amylose starch tablets as
temperature increases from 25 - 60°C.
Utilizing Arrhenius relationship to explain effect of temperature and power law to explain
the effect of lignin content, the data are analyzed in terms of the following equation
ΔS ΔH
ln M Teq = − (3)
R RT
as shown in Figure 9.

15
3.388

2
y = 3.47 - 25.4x R = 0.97
3.386

3.384
Teq
ln M

3.382

3.38

3.378
0.003 0.0031 0.0032 0.0033 0.0034 0.0035

1/T

Figure 9. Arrhenius plot of ln MTeq versus 1/T

Together, equilibrium water uptake can be summarized as


−( 25.387 T ) 14 −( 25.387 T ) 14
M = 31.99e X = 31.99e (1 − X ) (4)
eq s l

For validation, the model equation of water uptake equilibrium as a function of lignin
fraction and temperature is compared with all the experimental data as presented in
Figure 10.

16
30

25

20
eq
Predicted M

15
25°C

10 35°C

45°C
5
Parity

0
0 5 10 15 20 25 30

Experimental M
eq

Figure 10. Comparison of experimental Meq with model based on


equation 4

3. Rate of water uptake


Swelling is essentially due to diffusion of water into the film and it can be described by
Fick’s second law. For one dimensional diffusion, it can be written as
∂C ∂ 2C
=D 2 (5)
∂t ∂x
l l
t=0 − <x< C = C1
2 2
l
t =0 x=± C = C0
2
The solution of Eq. 5 is given in the form of an error function series:
1
Mt  Dt  2  ∞
nl 
= 4 2  1 + 2π 0.5  (−1) nierfc  (6)
M eq  πl   n =1 2 Dt 

For short time, Eq. 6 can be approximated by

17
1
Mt  Dt  2
= 4 2  (7)
M eq  πL 
Water uptake data in the initial period (Mt/Meq ≤ 0.6) are utilized to estimate diffusion
coefficient of water into the various films, containing various levels of lignin content, by
using this equation at three different temperature. Figs 11 to 13 present the data in terms
of Mt/Meq as a function of square root of time for the three temperatures.

0.7
SUB
SUB5%L
0.6
SUB10%L
SUB15%L
0.5

0.4
Mt/Meq

0.3

2
0.2 SUB y = 0.227x R = 0.99
2
SUB5%L y = 0.188x R = 0.98
2
0.1 SUB10%L y = 0.169x R = 0.98
2
SUB15%L y = 0.135x R = 0.97
0
0 1 2 3 4 5

Time (minute)^0.5

Figure 11. Mt/Meq ≤ 0.6 versus square root of time at 25°C

18
0.7
SUB
SUB5%L
0.6
SUB10%L
SUB15%L
0.5

0.4
Mt/Meq

0.3

0.2 2
SUB y = 0.174x R = 0.99
2
SUB5%L y = 0.157x R = 0.98
0.1 2
SUB10%L y = 0.138x R = 0.98
2
SUB15%L y = 0.123x R = 0.97
0
0 1 2 3 4 5

Time (minute)^0.5

Figure 12. Mt/Meq ≤ 0.6 versus square root of time at 35°C


0.7
SUB
SUB5%L
0.6
SUB10%L
SUB15%L
0.5

0.4
Mt/Meq

0.3

2
0.2 SUB y = 0.194x R = 0.99
2
SUB5%L y = 0.173x R = 0.98
2
0.1 SUB10%L y = 0.154x R = 0.98
2
SUB15%L y = 0.131x R = 0.97
0
0 1 2 3 4 5

Time (minute)^0.5

Figure 13. Mt/Meq ≤ 0.6 versus square root of time at 45°C

19
As can be seen in Figure 11-13, the addition of lignin decreases the slope at all
temperatures which indirectly indicates that the rate of water uptake decreases with lignin
content. From the slopes, diffusion coefficients are estimated as a function of lignin
content and temperature. To correlate the effect of lignin fraction on diffusion coefficient
at each temperature, the data are presented on a log-log plot in Fig. 14.

-6
10

4.276 2
25°C y = 3.95e-7x R = 0.92
3.683 2
35°C y = 4.94e-7x R = 0.93
Diffusion coefficient (cm /s)

2.986 2
45°C y = 5.86e-7x R = 0.92
2

-7
10
0.1 1

X
s

Figure 14. Plot of log D versus log starch fraction at 25°C, 35°C
and 45°C

Estimated diffusion coefficient decreases from 4.3 to 2.1 x 10-7 cm2/sec at 25°C, from 5.3
to 2.9 x 10-7 cm2/sec at 35°C and from 6.2 to 3.8 x 10-7 cm2/sec at 45°C depending on the
lignin content. For comparison, the values of water diffusion coefficient from previous
works are presented in Table 5.

20
Table 5. Comparison of water diffusion coefficient in different systems
System T (°C) D (10-7 cm2/s) Ea Remarks
(kJ/mol)
This study 25 4.3 -2.1 15.971 D decrease
35 5.3 – 2.9 with lignin
45 6.2 -3.8 addition
Self-diffusion of water 2.4 x 102 - Measurement
[30] by means of
capillaries
Rice starch [31] 25 1.2-1.7x10-2 - RH
depending on gradendient =
plasticizer content 2 -75%
Corn starch [32] 25 5 x10-2 - Water activity
0.75
-3
Citric acid (CA) 23 17.6 x10 (0% CA) - 50%RH
-3
crosslinked 8.91 x10 (5% CA)
hydroxypropylated and 7.01 x10-3 (10% CA)
oxidized potato starch 1.65 x10-3 (15% CA)
[33] 1.18 x10-3 (20% CA)
Modified high amylose 23 3.9x10-11m/s (25°C) 46 kJ/mol Studied by
starch tablets (70% 37 7x10-11 m/s (37°C) (radial nuclear
amylose) [29] direction) magnetic
40 kJ/mol resonance
(axial (NMR)
direction)
Soluble starch 27 (S/PVA)12 x 10-4 93%RH
(S)/polyvinyl alcohol (Z-S/PVA) 6 x 10-4
(PVA) (B-S/PVA)9 x 10-4
Crosslinked with ZnO (E-S/PVA) 3.9 x 10-4
(F-S/PVA) 3.7 x 10-4
(Z),Borax (B),
Epichlorohydrin (E),
Formaldehyde (F) [9]

21
Corn starch (CS) - 25 0.2 x 102 (CS/PVA= -
polyvinyl alcohol 0/100)
(PVA) crosslinked with 1.4 x 102 (30/70)
hexamethylenetetramine 1.9 x 102 (40/60)
[20] 6.2 x 102 (50/50)
14.1 x 102 (70/30)
Corn starch- 23 No lignin: - Foam
Kraft lignin [34] 2.68 x 10-6 cm2/sec 7.6x2.5x0.2
With lignin: cm
0.8 x 10-6 cm2/sec %L is 16% of
total dry
weight

The fastest possible aqueous diffusion expected would be 2.4 x 10-9 m2/s, the self-
diffusion of water with itself as mentioned by Doll [30]. The water diffusion coefficient
obtained in this work is reasonable since the obtained diffusion coefficient is lower as
compared to diffusion coefficient of water itself. Diffusion coefficient of moisture in
unmodified rice starch [31] and corn starch [32] is 1.2-1.7 x10-2 and 5 x10-2 x 10-7 cm2/s
respectively. The higher diffusion coefficient obtained as compared to the unmodified
rice and corn starch is probably due to the different condition applied. Instead of
immersed in distilled water, the films were conditioned in desiccators to ensure certain
relative humidity. The same reason goes to the citric acid crosslinked starch [33],
modified high amylose starch tablets [29] and starch/PVA [9] as summarized in Table 3.
Diffusion coefficient of water in hexamethylenetetramine crosslinked starch-polyvinyl
alcohol is ranging from 0.2 -14.1 x 10-5 cm2/s depending on starch/PVA ratio [20]. The
reported result is somehow higher than our data but still comparable with. The presence
of hydrophobic material in this case lignin might be responsible for the lower water
diffusion coefficient obtained.
The estimated diffusion coefficient of 17% (w/w) lignin modified starch foam reported
by Steven et al. [34] decreased around three times as compared to unmodified starch
foam (2.68 x 10-6 cm2/s to 0.8 x 10-6 cm2/s). The result seems comparable with our data
since the addition of 15% and 20% lignin, the diffusion coefficient decreases around two

22
times. The higher diffusion coefficient in starch foam as compared to our data is probably
due to the presence of large void in foam (ranging 100μm -1 mm). The higher density of
starch foam system (around 2.3 g/cm3) than in our system (1-2 g/cm3, data not shown)
may also contribute to the faster water diffusion in starch foam matrix.

As temperature increases, diffusion coefficient is increased. The water mobility increases


due to more available energy resulting in an increase of diffusion coefficient. The faster
diffusion coefficient as temperature is increased in starch system is also reported by
Russo et al. [27], Aubin et al. [29] and Yu et al. [28].

It can be seen that diffusion coefficient increased with starch fraction (decreased with
increase in lignin fraction) and temperature indicating a relationship of the form
D = D0T X sa (8)
Estimated values of D0T and a as a function of temperature are presented in Table 6.

Table 6. Estimated values of D0T as a function of temperature


Temperature, oC a (exponent value) DoT (diffusion constant)
25 (298 K) 4.276 3.95 x 10-7
35 (308 K) 3.676 4.94 x 10-7
45 (318 K) 2.979 5.86 x 10-7

It can be seen that the dependence of diffusion coefficient on starch fraction is not linear
and the exponent is decreasing with temperature as shown in Figure 15.

23
5

3
a

1
y = 23.617-0.0649x
2
R = 0.99
0
295 300 305 310 315 320

T(K)

Figure 15. Estimated values of the exponent (a) as a function of


temperature

The exponent is correlated as


a = 23.617 − 0.0647T (9)
with T is temperature (K).
The effect of temperature on D0T may be accounted through Arrhenius law as
D0T = D0 exp ( − Ed RT ) (10)

Where D0 is a temperature independent pre-exponential (cm2/min), E d is the activation

energy for diffusion (kJ/mol), R is the gas constant 8.31 J/mol K and T is absolute
temperature (K) [35]. The plot of ln D0T versus 1/T is shown in Figure 16.

24
-14.2

-14.3

-14.4

-14.5
ln D 0T

-14.6

-14.7

y = -1991.3x-8.057
-14.8 2
R = 0.99

-14.9
0.0031 0.0032 0.0033 0.0034

1/T(1/K)

Figure 16. Arrhenius plot of ln (D0T) vs 1/T

The estimated activation energy determined from the slope in Figure 16 was 16.55
kJ/mol. The low activation energy obtained is consistent with characteristic of diffusion-
controlled process [36]. Aubin et al. [29] studying diffusion in modified high amylose
starch tablet (70% amylose) using nuclear magnetic resonance (NMR) imaging, reported
the activation energy of around 40 kJ/mol. The higher activation energy compares to our
data is probably due to the high amylose content (70%) used in their work as compared to
normal tapioca starch (<25%). Higher amylose content contributes to the higher
crystallinity therefore increasing in activation energy. The activation energy in the range
of 20-40 kJ/mol is consistent with the potential energy of the hydrogen bonds implicated
in the adhesion forces between the compressed tablets [29] therefore the estimated
activation energy of 16.55 kJ/mol in the films instead of the compressed tablets is
considered reasonable.

The empirical equation of diffusion coefficient as a function temperature is given in


equation 11.

25
By utilizing Arrhenius relationship, the empirical equation of diffusion coefficient as a
function temperature is given in Equation 11.

D0T = 3.1×10−4 e−(16547 RT ) (11)


Together, the model equation of diffusion coefficient as a function of percentage of lignin
and temperature can be summarized as

D = 3.1 × 10
−4
Xs
( 23.617−0.0649T ) e−(16547 RT ) (12)

This is compared with all the experimental data as presented in Figure 17. It can be seen
that experimental result of diffusion coefficient reasonably fit with the model equation.

D
6 Parity
Predicted Dx10 (cm /s)

5
2
-7

0
0 1 2 3 4 5 6 7

Experimental Dx10-7 (cm2/s)

Figure 17. Parity plot for diffusion coefficient

26
4. Model equation for Water uptake into the film
Together, by substituting equation 4 and 12 into equation 7, the water uptake
model can be developed as a function of lignin percentage and temperature as given in
Eq. 13

1/2
 3.1 × 10 −4 X ( 23.617 −0.0649T ) e −(16547 RT ) 
 0.5 ∞ nl 
= 4 
Mt s 1/2 n
−( 25.387 T )
t  1 + 2π n=1 ( −1) ierfc 
(1 − X l )
14
 2
l π   2 Dt 
31.99 e
 

(13)
For Mt/Meq ≤ 0.6, Eq. 13 can be approximated by

 3.1 × 10 −4 X ( 23.617 −0.0649T ) e −(16547 RT )


1/2

= 4 
Mt s 1/2
t (14)
− ( 25.387 T )
(1 − X l )
14
 2
l π 
31.99 e
 
The model equation of water uptake as a function of percentage of lignin and temperature
at Mt/Meq ≤ 0.6 is compared with all the experimental data as presented in Figure 18.
It can be seen that experimental result of water uptake reasonably fit with the model
equation 14.

27
SUB_25°C
16 SUB_35°C
SUB_45°C
SUB5%L_25°C
SUB5%L_35°C
SUB5%L_45°C
SUB10%L_25°C
12
SUB10%L_35°C
t

SUB10%L_45°C
Predicted M

SUB15%L_25°C
SUB15%L_35°C
SUB15%L_45°C
8 Parity

0
0 4 8 12 16

Experimental M
t

Figure 18. Parity plot for water uptake of modified starch film at three different
temperature

Conclusion
Swelling characteristic in starch film was investigated. Water diffuses into starch and
causes the starch film to swell. The addition of lignin varied from 0% to 15% decreases
the swelling characteristic shown by reduction in equilibrium water uptake and diffusion
coefficient. Temperature tends to increase the equilibrium water uptake and diffusion
coefficient. Activation energy for increase of diffusion coefficient with temperature is
observed to be 16.55 kJ/mol which is consistent with characteristic of diffusion-
controlled process. Empirical model of swelling was developed based on the Fick’s law.
The model developed can be used to predict the swelling as function of lignin fraction
and temperature.

Acknowledgements
The authors gratefully acknowledge Ministry of Higher Education (MOHE) for funding
the project under Long Term Research Grant Scheme (LRGS).

28
Nomenclature
Meq equilibrium water uptake
MTeq equilibrium water uptake at different temperature
Xs starch fraction
m the exponent (for water uptake equilibrium)
Meq0 temperature independent pre-exponential
Easw activation energy of swelling (kJ/mol)
XL lignin fraction
D water diffusion coefficient (cm2/sec)
Mt water uptake at t time
L film thickness (cm)
t diffusion time (sec)
D0T diffusion coefficient at different temperature (cm2/sec)
D0 temperature independent pre-exponential (cm2/sec)
a the exponent (for diffusion coefficient)
Tmpw temperature of melting point of water (K)
Ed activation energy for diffusion (kJ/mol)
R gas constant (J/mol K)

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