International Journal of Biological Macromolecules 192 (2021) 1013–1020

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International Journal of Biological Macromolecules

journal homepage: www.elsevier.com/locate/ijbiomac

Mechanical and barrier properties of starch blend films enhanced with

kaolin for application in food packaging
Thitirat Rammak a, b, Phetdaphat Boonsuk a, Kaewta Kaewtatip a, b, *
a
Division of Physical Science, Faculty of Science, Prince of Songkla University, Hat Yai, Songkhla 90112, Thailand
b
Center of Excellence for Trace Analysis and Biosensor, Prince of Songkla University, Hat Yai, Songkhla 90112, Thailand

A R T I C L E I N F O A B S T R A C T

Keywords: Starch blend films of native cassava starch and medium distarch phosphate cassava starch (crosslinked cassava
Starch film starch) were prepared by solution casting. The effects of kaolin content on the water resistance and mechanical
Sachet properties of the starch blend films were investigated. The addition of 10 wt% kaolin to the starch blend film
Kaolin
lowered water vapor permeability to 3.51 × 10− 5 g m day− 1 m− 2 Pa− 1, water solubility to 31.60% and raised
tensile strength to 2.99 MPa. At this loading of kaolin, the structural integrity of the starch blend film was
maintained during immersion in water and thermal stability was enhanced. Scanning electron microscopy
revealed kaolin to be well dispersed and embedded within the starch matrix. In summary, the starch blend film
composite with 10 wt% kaolin had interesting properties as a material to replace non-biodegradable synthetic
plastics for packaging, particularly sachets for food products.

1. Introduction
Petroleum-based plastic waste from single-use packaging materials
has become a serious problem worldwide [1,2]. Without good man­
agement, this type of waste can persist in the environment for hundreds
of years. Considering the shortage of fossil fuel resources, the develop­
ment of biodegradable films from renewable resources is becoming a
necessity. Starch is an interesting, renewable agricultural resource. It
has good film-forming ability and is inexpensive. Films developed from
starch have good transparency, are odorless, fully biodegradable and do
not release toxic products [3,4]. Also, starch films can be produced using
common technologies such as solution casting and extrusion [5]. How­
ever, the water resistance of starch films is poor due to their hydrophilic
nature and their mechanical and thermal properties are weak [3,6,7].
Preparing starch film composites with fillers is an effective way to
overcome these disadvantages and improve the performance of starch
film. Fillers commonly used for starch film include cellulose nanofibers
[3,8], starch nanoparticles [6,9,10] and clay [11–14]. The excellent
reinforcing effect of clays such as kaolin, montmorillonite and bentonite
can improve the barrier, mechanical, thermal and physical properties of
starch films. Monteiro et al. [14] reported that bentonite improved the
water vapor permeability (WVP) and dissolution capacity of starch film
in water without spoiling the visual appearance of the film. The addition
of the clay Cloisite Na+ increased the tensile strength of starch film by
150–310% [11]. Mbey et al. [13] reported that DMSO–kaolin acted as a
UV light barrier and also improved the thermal stability of starch film.
Their findings identified kaolin as one of the most promising clays for
use in starch films. It has a high aspect ratio, large surface area, low
price, is environment-friendly and presents reactive surface -OH groups.
A versatile material, kaolin has been used in paints, adhesives, phar­
maceuticals, paper, electronics, ceramics, rubber, plastics and coatings
[15,16]. However, there is no report of the effect of unmodified kaolin
on the properties of starch blend films of native cassava starch and
medium distarch phosphate cassava starch. Therefore, the objectives of
this work are to investigate the influence of unmodified kaolin on the
viscosity of starch blend solutions and on the water vapor permeability,
water solubility and swelling of starch blend films. The neat starch blend
film and its composites are morphologically and chemically character­
ized and the mechanical and thermal properties of the neat starch blend
film and the composites are determined. Finally, the changes in
appearance of the neat starch blend film and the film composites after
burial in soil are reported.

* Corresponding author at: Division of Physical Science, Faculty of Science, Prince of Songkla University, Hat Yai, Songkhla 90112, Thailand.
E-mail address: kaewta.k@psu.ac.th (K. Kaewtatip).

https://doi.org/10.1016/j.ijbiomac.2021.10.081
Received 6 July 2021; Received in revised form 8 October 2021; Accepted 11 October 2021
Available online 16 October 2021
0141-8130/© 2021 Elsevier B.V. All rights reserved.
T. Rammak et al.
2. Materials and methods
2.1. Materials
Native cassava starch (NS) (PD 10369) and medium distarch phos­
phate cassava starch (crosslinked cassava starch; DSP) (PD 10374) were
donated by Siam Modified Starch Co., Ltd. (Pathum Thani, Thailand).
Kaolin (Wizkay TU-90) was from WIZARD Chemical Co., Ltd. (Bangkok,
Thailand). The properties of the kaolin were typical and were described
as follows: the particle size was finer than 1 μm; particles larger than 325
mesh comprised a maximum 0.02% of the bulk; surface area was 20.47
m2/g; brightness was 90–93%; free moisture content was a maximum of
1%; pH was 6–9; bulk density was 40–50 lbs./ft3 and specific gravity
2.58 [17]. The starches and kaolin were dried in an oven before being
stored in a desiccator. Glycerol was purchased from Ajax Finechem
(Auckland, New Zealand).
2.2. Preparation of starch films
Kaolin (5, 10 or 15 wt% of the total weight of the starch blend) was
dispersed in 300 ml of distilled water at room temperature for 5 min
with constant stirring. After that, the mixture was placed in a sonicator
bath at room temperature for 5 min. Glycerol (30 wt% of the total
weight of the starch blend) was added as a plasticizer, followed by the
addition of the mixed starches (15 g = NS (7.5 g) / DSP (7.5 g)). The
mixture was heated at 95 ◦ C for 15 min under magnetic stirring then
allowed to cool to room temperature. When cool, the mixture was cast
onto a plastic plate (0.27 ml/cm2). The plate was placed in an oven and
the film was dried at 50 ◦ C for 24 h. The resultant films had a thickness of
approximately 0.11–0.14 mm and dried films were kept in a desiccator
at 30 ± 3 ◦ C in 65 ± 5% relative humidity (RH) until characterized.
2.3. Characterization of the starch solution
2.3.1. Determination of viscosity
The viscosities of 600 ml solutions of NS/DSP and NS/DSP with 5, 10
and 15 wt% kaolin content were determined using a Brookfield digital
viscometer (Model DV2T, USA). Testing was performed at 25 ± 2 ◦ C in
55 ± 2% RH with a no. 64 spindle at a mixing speed of 100 rpm. The tests
were run in triplicate for each solution, and average values were
calculated.
2.4. Characterization of starch films
2.4.1. Mechanical properties
Tensile tests were performed according to the ASTM D 412 Type C
protocol. Testing was carried out using a universal testing machine
(Instron model 3365, USA) with a 100 N load cell at a crosshead speed of
20 mm/min. Before testing, samples were stored for 5 days in a
controlled humidity container at 30 ± 3 ◦ C in 65 ± 5% RH. The tests
were carried out on ten specimens of every sample and the reported
values were calculated averages.
2.4.2. Thermogravimetric analysis (TGA)
Thermogravimetric analysis of the samples was performed using a
thermogravimetric analyzer (TGA) (TGA 7, Perkin Elmer, USA). Anal­
ysis was carried out in a nitrogen atmosphere, heating from 50 to 800 ◦ C
at a heating rate of 10 ◦ C/min. Sample weights were from about 9–11
mg. Before testing, the samples were stored in a controlled humidity
container at 30 ± 3 ◦ C and 65 ± 5% RH for 5 days.
2.4.3. Morphological properties
The morphology of fracture surfaces of the starch films was observed
using scanning electron microscopy (SEM) (Quanta 400, Netherlands).
Samples were sputter coated with a thin layer of gold before observation
and the starch films were immersed in liquid nitrogen before fracturing.
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International Journal of Biological Macromolecules 192 (2021) 1013–1020
The images were taken at 1000× magnification.
2.4.4. Fourier transform infrared spectroscopy (FTIR) analysis
The Fourier transform infrared (FTIR) spectra of film and powder
samples were measured using a BRUKER® EQUINOX 55 FTIR spec­
trometer (Germany). Film samples were analyzed using the attenuated
total reflection (ATR) method. Film samples were applied directly onto
the diamond and scanned between 4000 and 600 cm− 1. Powder samples
were analyzed using the KBr pellet method and were scanned between
4000 and 500 cm− 1. All samples were scanned at a 4 cm− 1 resolution for
512 consecutive scans.
2.4.5. Water resistance
2.4.5.1. Water solubility. Before testing, film samples (2.5 cm × 2.5 cm)
were stored at room temperature for 5 days. After 5 days, the samples
were placed in an oven at 105 ◦ C for 24 h, allowed to cool to room
temperature and immediately weighed. They were then soaked in
distilled water (10 ml) at room temperature for 60 min. After 60 min,
they were filtered and placed in an oven at 105 ◦ C for 24 h and weighed
immediately after being removed from the oven. The water solubility of
the samples was then calculated using Eq. (1):
Water solubility (%) = [(S1 − S2 )/S1 ] × 100 (1)
where S1 was initial weight and S2 was final weight after drying in the
oven.
2.4.5.2. Swelling. Swelling was tested using the method described by
Soni et al. [18] with slight modification. Dried starch films (2.5 cm ×
2.5 cm) were soaked in 10 ml of distilled water at room temperature for
60 min. After 60 min, the swollen samples were immediately removed
and excess water was removed with tissue paper before being weighed.
The percent swelling of the samples was then calculated using Eq. (2):
Swelling (%) = [(Sw1 − Sw2 )/Sw2 ] × 100 (2)
where Sw1 was the weight of the swollen sample and Sw2 was the weight
of the dried sample.
2.4.5.3. Water vapor permeability (WVP). The water vapor permeability
of the starch films was determined using the ASTM method E96/E96M-
10 with some modifications. Square samples (5.0 cm × 5.0 cm) were
sealed on the top of the test cups and covered with paraffin. The cups
were prefilled with silica gel, leaving 2 in 3 of the test cup. The assembly
was then weighed and placed in a container and kept at 30 ± 3 ◦ C in
100% RH. The WVP was calculated from Eq. (3) [6,19,20]:
( ) /
WVP g m day− 1 m− 2 Pa− 1 = (W × L) (A × T × ΔP) (3)
where is W is weight gain (g), L is film thickness (m), A is the permeation
area (m2), T is the time of permeation (days), and ΔP is the water vapor
pressure difference between the two sides of the film (Pa).
2.4.6. Soil burial degradation test
Film samples measuring 2.5 cm × 5.0 cm were buried in natural soil
at a depth of 9 cm. The environmental RH was about 59% and the
temperature and pH of the soil were about 30 ◦ C and 5.5, respectively.
2.5. Statistical analysis
Data were subjected to analysis of variance (ANOVA) using the SPSS
statistical software package (SPSS Thailand Co., Ltd., Bangkok,
Thailand). Tukey's multiple comparison test at P value ≤0.05 was per­
formed to determine significant differences.
T. Rammak et al.
3. Results and discussion
3.1. Starch solution properties
The viscosity of the starch solution plays an important role in the film
casting process [21,22]. If the starch solution is highly viscous, the
elimination of air bubbles is hindered and the casting of thin layers can
become difficult. The effect of kaolin content on the viscosity of the NS/
DSP solution was investigated using a Brookfield digital viscometer. The
viscosity of the neat NS/DSP solution was 417 cP whereas the NS/DSP
solutions with 5, 10 and 15 wt% kaolin had viscosities of 435 cP, 432 cP
and 1392 cP, respectively. The viscosity of the NS/DSP solution
increased with increments of kaolin content because the interaction
between starch chains and kaolin particles led to increasingly high flow
resistance [23]. The addition of 5 wt% kaolin caused only a slight in­
crease in the viscosity of the starch solution, and increasing the kaolin
content to 10 wt% did not significantly increase the viscosity of the
solution, although the kaolin was still well dispersed. In contrast, the
viscosity of the NS/DSP solution rose sharply with the addition of 15 wt
% kaolin and the increased viscosity had a negative effect on the film
casting process [21,22].
3.2. Starch film properties
3.2.1. Appearance of starch films
Since the viscosities of the respective film forming solutions were
suitable for casting thin film, the neat NS/DSP film and NS/DSP com­
posite films with 5 and 10 wt% kaolin presented smooth and homoge­
nous surfaces (Fig. 1) [21,22]. However, the NS/DSP composite with 15
wt% kaolin presented a rougher surface caused by agglomerations of
kaolin and trapped air bubbles in the casting solution (Fig. 1). These
defects occurred because kaolin content above the optimum value (over
10 wt% kaolin content) promoted kaolin-kaolin interactions, and the
high viscosity of the NS/DSP solution with 15 wt% kaolin hindered the
escape of air bubbles.
Therefore, the effects of kaolin content on the mechanical and barrier
properties of starch films were evaluated using the kaolin contents of 5
and 10 wt% and the results obtained with these formulations were
compared with the results of neat starch film.
3.2.2. Water resistance
The main factor that determines the shelf life and quality of film-
wrapped foods is the water resistance of the film. In this work, water
resistance was investigated by testing WVP, water solubility and
swelling. The neat NS/DSP film exhibited the highest WVP and water
solubility. These values were 4.38 × 10− 5 g m day− 1 m− 2 Pa− 1 and
44.87%, respectively (Table 1). These results were due to the hydro­
philic property of starch film. The availability of OH groups within the
starch matrix enabled water molecules to diffuse easily though the
starch film. The addition of 5 wt% kaolin had no statistically significant
effect on the WVP of the NS/DSP film but the WVP of the NS/DSP film
composite with 10 wt% kaolin was 3.51 × 10− 5 g m day− 1 m− 2 Pa− 1,
about 20% lower than the neat NS/DSP film. These results were corre­
lated with the water solubility of the NS/DSP film composites, which
decreased from 33.20% at 5 wt% kaolin to 31.60% at 10 wt% kaolin.
These findings indicated that the NS/DSP film composite with 10 wt%
kaolin had much better water resistance than the other two films. The
improvement was due to the tortuous pathway that obstructed the
diffusion of free water through the starch matrix [24]. The water
resistance of the NS/DSP film composite with 10 wt% kaolin was su­
perior to the reported water resistance of starch-gelatin edible films
[25], corn starch and gelatin-based film composites with guabiroba pulp
[18] and starch composite films reinforced with synthetic zeolite and
beidellite [26].
The physical appearances of the neat NS/DSP film and NS/DSP film
composites with kaolin were evaluated after immersion in distilled
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International Journal of Biological Macromolecules 192 (2021) 1013–1020
water for 60 min (Fig. 2). The behavior of a starch film during immersion
in water is a very important consideration for its possible use with water-
rich foods. The neat NS/DSP film exhibited significant shrinking (Fig. 2).
This implied that the hygroscopic properties of the neat starch blend film
allowed water molecules to permeate easily into the starch matrix,
where they disrupted the interaction between starch molecules [25,27].
The NS/DSP film composite with 5 wt% kaolin showed slight shrinking
whereas the NS/DSP film composite with 10 wt% kaolin mostly retained
its shape after immersion. These results indicated that the addition of 10
wt% kaolin not only improved water resistance but also reinforced the
structural integrity of the NS/DSP film when exposed to moisture. These
behaviors were correlated with the results of the swelling test, which
revealed that the addition of kaolin reduced the swelling of the starch
film (Table 1).
3.2.3. Mechanical properties
The tensile strength and elongation at break of the neat NS/DSP film
and the NS/DSP film composites were investigated. The tensile strength
and elongation at break of neat NS/DSP film were 0.64 MPa and
146.63%, respectively. Tensile strength was significantly greater after
the incorporation of kaolin. The tensile strength of NS/DSP film with 5
wt% kaolin was 1.37 MPa and the tensile strength of NS/DSP film with
10 wt% kaolin was 2.99 MPa(Fig. 3(a)). The addition of 10 wt% kaolin
was the optimum loading, dispersing well in the starch matrix and
resulting in superior stress transfer from the starch matrix to the filler.
The high specific surface area of nanoparticles caused stronger filler-
polymer matrix interfacial interactions, bringing about more effective
transfer of stress from the starch matrix to nanoparticles through the
shear mechanism. The load was more efficiently carried and the com­
posite's strength enhanced [27,28].
In contrast, the elongation at break of the NS/DSP composite film
was 129.76% at a 5 wt% kaolin loading and 96.57% at a 10 wt% kaolin
loading (Fig. 3(b)). The reinforcing effect of kaolin decreased the
mobility of starch chains. The reduction in mobility increased rigidity
and brittleness. Similar results were reported by Kampeerapappun et al.
[29], who found that increasing montmorillonite loading from 5 wt% to
10 wt% led to a significant reduction in the elongation at break of starch
films.
3.2.4. Morphology
SEM micrographs of the fracture surfaces of neat NS/DSP film and
NS/DSP film composite with 10 wt% kaolin are presented in Fig. 4. The
fracture surface of neat NS/DSP film (Fig. 4(a)) was homogenous and
smooth. Cracks, pores and residual starch granules were not visible in
the matrix. The morphology of the film clearly indicated that the pro­
cessing conditions of the starch blend film completely destroyed both
the intermolecular and intramolecular hydrogen bonds in the structure
of the NS and DSP granules. The two starches became compatible. In the
fracture surface of NS/DSP film with 10 wt% kaolin (Fig. 4(b)), the
absence of voids or cracks showed that kaolin was well dispersed and
embedded within the starch matrix. Starch biocomposite with sodium
montmorillonite (NaMMT) containing 30% glycerol exhibited similar
morphologies [30].
It is important to clarify that the addition of 10 wt% kaolin greatly
improved the water resistance and mechanical properties of NS/DSP
film due to the strong adhesion and good dispersion of kaolin in the
starch matrix. The exerted internal forces prevented damage to the film.
According to Dai et al. [6] films reinforced with nanoparticles had
greater tensile strength because the large specific surface area provided
by nanoparticles caused stronger filler-matrix interfacial interactions.
Furthermore, Mbey et al. [13] reported that polymer–filler interactions
are enhanced because the surface reactivity of clay can proceed through
hydrogen bonds, complexation, or electrostatic interactions. Mbey et al.
[31] also reported that glycerol present at the starch-kaolin interface
contributes to the interactions within the film network.
T. Rammak et al. International Journal of Biological Macromolecules 192 (2021) 1013–1020

Fig. 1. The appearance of the neat NS/DSP film (a) and NS/DSP film composites with 5 (b), 10 (c) and 15 (d) wt% kaolin. Defects in the NS/DSP film with 15 wt%
kaolin are indicated with red circles.

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Table 1 weight loss was 15% (Fig. S1). The TGA curves of NS powder and DSP
The water vapor permeability (WVP), water solubility and swelling at 25 ± 2 ◦ C powder revealed two steps of weight loss. The first step appeared at
of neat NS/DSP film and NS/DSP film composites with kaolin. (n = 3, data are around 100 ◦ C and was due to the evaporation of water. The second step
averages ± standard deviation). occurred between 250 and 400 ◦ C and involved the decomposition of
Sample WVP Water solubility Swelling starch. The maximum weight loss (Tmax) of NS powder and DSP powder
(10− 5 g m day− 1
m− 2
Pa− 1) (%) (%) took place at 316 ◦ C and 314 ◦ C, respectively (Fig. S1).
NS/DSP 4.38 ± 0.07a 44.87 ± 1.72a 527.57 ± 7.85a Both film samples also showed two steps of weight loss (Fig. 5(a)).
The first step of weight loss appeared between 100 and 230 ◦ C. This
NS/DSP composites with kaolin (wt%)
5.0 4.35 ± 0.34a 33.20 ± 0.67b 455.00 ± 5.99b weight loss was due to the evaporation of water and glycerol [5]. In this
10.0 3.51 ± 0.15b 31.60 ± 0.96b 456.53 ± 3.90b step, which is marked with a circle in Fig. 5(a), the NS/DSP film com­
posite with 10 wt% kaolin lost less weight (5%) than the neat NS/DSP
Note: The letters a-b indicate significant differences between treatments (p ≤
0.05). film (9%). This result correlated with the water barrier properties of the
two films (Table 1). The addition of 10 wt% kaolin increased the tor­

Fig. 2. Photographs of neat NS/DSP film (a) and NS/DSP film composites with 5 wt% (b) and 10 wt% (c) kaolin after immersion in water for 60 min.

tuosity of the permeation pathway, which reduced the penetration of

Fig. 3. Tensile strength and elongation at break of neat NS/DSP film and NS/
DSP film composites with 5 wt% and 10 wt% kaolin.
water into the starch matrix. The main decomposition occurred in the
second step of weight loss, from 250 ◦ C to around 350 ◦ C, which
involved the decomposition of the starch matrix [1,12]. In this step, both
film samples showed the Tmax at nearly the same temperature; 320 ◦ C
for neat NS/DSP film and 322 ◦ C for NS/DSP film composite with 10 wt
% kaolin. The Tmax of neat starch film and starch film composite with
10 wt% kaolin were higher than the Tmax of NS powder and DSP
powder. This synergic effect suggests the existence of interactions be­
tween NS and DSP molecules in the starch film and the heat barrier
properties of kaolin in the starch film composite increased the thermal
stability of the starch film.
At 400 ◦ C, the percentage weight remaining of the NS/DSP film
composite with 10 wt% kaolin was 22% compared to 13% for the neat

Fig. 4. SEM micrographs of fracture surfaces of neat NS/DSP film (a) and NS/DSP film composite with 10 wt% kaolin (b).

3.2.5. Thermal stability
The thermal stability and thermal decomposition temperatures of
kaolin, NS powder, DSP powder, neat NS/DSP film and NS/DSP film
composite with 10 wt% kaolin were evaluated by TGA. The TGA curve of
kaolin revealed only the main decomposition at 517 ◦ C. At 800 ◦ C
NS/DSP film. The difference in weight remaining of both samples was
due to the good dispersion of kaolin in the NS/DSP film composite which
acted as a barrier material that hindered heat transfer through the starch
matrix [13,17,27]. The NS/DSP film composite with 10 wt% kaolin also
had a higher Tmax and percentage weight remaining than potato starch

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T. Rammak et al. International Journal of Biological Macromolecules 192 (2021) 1013–1020

stretching at the glycosidic bonds between monosaccharide units

[34,35]. The broad peak around 3280 cm− 1, which was a characteristic
of the stretching of OH groups in the spectrum of neat NS/DSP film, was
shifted to higher wavenumbers in the spectra of the two film composites.
This is good evidence of the formation of interactions between kaolin
and starch molecules [13,35,36]. Moreover, the ATR-FTIR spectra of
both film composites showed a small peak at 3697 cm− 1 associated with
the structural OH groups of kaolin. However, because the major starch
characteristics overlapped in the spectra of the film composites, it was
difficult to observe the peaks of kaolin which appear at 1110 cm− 1 and
918 cm− 1 in the FTIR spectrum of kaolin (Fig. S2), and which are
respectively assigned to Si–O–Si and Al–OH bending vibrations
[16,27,37]. It was similarly difficult to observe the characteristic peak of
P–– O stretching vibrations of the phosphate group in the structure of
medium distarch phosphate cassava starch which appeared at about
1172 cm− 1 in the FTIR spectrum of DSP powder (Fig. S2) [38].

3.2.7. Biodegradation in soil

The physical appearance of neat NS/DSP film and the two NS/DSP
film composites was assessed after burial in soil for 0, 7 and 14 days. The
neat NS/DSP film exhibited more erosion and a more irregular
morphology than both film composites (Fig. 6). The appearance of the
NS/DSP film indicated that the degradation process had advanced more
rapidly in this film. The kaolin content of the two film composites
increased the hydrophobicity of the starch matrix. Generally, starch
films in soil are degraded by moisture and microorganisms in the soil.
The addition of kaolin hinders the penetration of water and microor­
ganisms into the starch matrix and the rate of degradation is reduced
[39]. This behavior was also found in starch composites with inorganic
fillers such as talcum powder, CaCO3 eggshell powder [40].

3.3. Application for packaged biscuits

Sachets were fabricated from neat NS/DSP film and NS/DSP film
composite with 10 wt% kaolin. Rectangular film samples were sealed at
the bottom and along the sides and used to package biscuits [2] (Fig. 7).
Both neat NS/DSP film and the NS/DSP film composite produced sachets
that were sufficiently flexible, easy to handle and would not shrink or
crack. The sachets made from neat NS/DSP film were transparent (Fig. 7
(a)) due to the complete melting of both native and medium distarch
phosphate granules. The absence of residual starch granules allowed
light to pass through the film. The sachets made from NS/DSP film
composite with 10 wt% kaolin (Fig. 7(b)) were translucent because the
dispersed kaolin embedded in the starch matrix prevented the trans­
mittance of some light. Li et al. [41] reported that the opacity of starch
films increased when the content of nanocrystals was increased,

Fig. 5. TGA curves of neat NS/DSP film and NS/DSP film composite with
kaolin 10 wt% (a) and ATR-FTIR spectra of neat NS/DSP film and NS/DSP film
composites with 5 wt% and 10 wt% kaolin (b).

nanocomposite films with montmorillonite, hectorite, and kaolin [32].

In contrast, Kwasniewska et al. [33] reported that the thermal degra­
dation of neat starch film decreased from 240 ◦ C to 221 ◦ C with a kaolin
content of 15 wt%.

3.2.6. FTIR
The chemical structures of neat NS/DSP film and both NS/DSP film
composites with kaolin and the interactions between kaolin and starch
molecules were investigated by ATR-FTIR analysis. The main charac­
teristic peaks of starch appeared at nearly the same positions in the ATR-
FTIR spectra of all three films (Fig. 5(b)). The peak around 2900 cm− 1
was assigned to C–H stretching (CH2 and/or CH3) [34,35]. The peak at
1644 cm− 1 and the strong peak from around 1190–950 cm− 1 were
respectively assigned to water adsorbed by starch molecules and C–O Fig. 6. Photographs of neat NS/DSP film and NS/DSP film composites after
burial in soil for 0, 7 and 14 days.

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T. Rammak et al.
Fig. 7. Sachets made from neat NS/DSP film (a) and NS/DSP film composite with 10 wt% kaolin (b) used to package biscuits.
producing packages that protected contents from light and better
maintained the quality of the packaged food. This earlier finding sup­
ported the potential application of the sachets produced from the NS/
DSP film composite with 10 wt% kaolin. Translucent film packaging not
only leaves the food product visible but also protects it from light and UV
radiation. Moreover, the tortuous permeation pathway produced by
kaolin in the starch matrix could regulate humidity inside the sachet.
4. Conclusion
The barrier and mechanical properties of starch blend film from
native and medium distarch phosphate cassava starches were improved
by the addition of kaolin. A starch blend film with 10 wt% kaolin
showed the best water resistance and lower aqueous solubility. WVP was
3.51 × 10− 5 g m day− 1 m− 2 Pa− 1 and water solubility was 31.60%. The
same film composite showed the highest tensile strength (2.99 MPa).
The addition of 10 wt% kaolin to the native and medium distarch
phosphate cassava starch blend film also preserved the structural
integrity of the film during immersion in water and enhanced the
thermal stability of the starch film. The kaolin not only created a
tortuous permeation pathway that hindered the diffusion of water
molecules into the starch matrix but also dispersed well. As a result,
stress transfer from the starch matrix to the filler was more effective and
the degradation process of the starch film was delayed. Scanning elec­
tron microscopy confirmed the good dispersion and embedding of kaolin
particles in the starch matrix. Food sachets made from the native and
medium distarch phosphate cassava starch blend film composite with
10 wt% kaolin show promise because the translucence of the film pre­
serves the quality and shelf life of the packaged food by hindering the
absorption of light and ultra-violet radiation.
CRediT authorship contribution statement
Thitirat Rammak: Conceptualization, Methodology, Validation,
Formal analysis, Investigation.
Phetdaphat Boonsuk: Methodology, Investigation, Validation,
Formal analysis.
Kaewta Kaewtatip: Conceptualization, Methodology, Validation,
Formal analysis, Resources, Writing - Review & Editing, Visualization,
Supervision.
Acknowledgments
The authors would like to thank Prince of Songkla University and the
Faculty of Science for financial support (Faculty of Science Research
Fund; No. 163004). We thank Siam Modified Starch Co., Ltd. and
1019
International Journal of Biological Macromolecules 192 (2021) 1013–1020
WIZARD Chemical Co., Ltd. for the donation of cassava starch and
kaolin. We also thank Mr. Thomas Duncan Coyne for assistance with the
English text.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.ijbiomac.2021.10.081.
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