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Otache et al., J. Mater. Environ. Sci., 2021, 12(4), pp. 497-510 497
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J. Mater. Environ. Sci., 2021, Volume 12, Issue 4, Page 497-510
http://www.jmaterenvironsci.com!
Journal(of(Materials(and((
Environmental(Science(
ISSN(:(2028;2508(
CODEN(:(JMESCN(
Copyright(©(2021,(
University(of(Mohammed(Premier((((((
(Oujda(Morocco(
Surface Hydrophobicity of Starch Acetate for Enhanced Bioplastic
Properties
Otache Monday Abel1*, Eke George Ifeanyi1, Amagbor Stella Chinelo1, Godwin
Kparobo Agbajor2, Joseph Edeki Imanah3
1. Department of Industrial Chemistry, Michael and Cecilia Ibru University, Delta State, Nigeria.
2. Department of Physics, Delta state University, Abraka, Nigeria.
3. Department of Physical Science Laboratory Technology, Auchi Polytechnic, Edo State, Nigeria.!
1. Introduction
Based on the food sustainability mandate, the need to harness waste into other viable products that is
income driven is key to human development and environmental preservation [1, 2]. Plastic products are
usually described as bioplastic if their source materials are bio-based (i.e derived from renewable
feedstock, e.g. corn, sugarcane and beet, potato, wheat‚ and cellulose) and are biodegradable (i.e
decomposed by microorganisms, under specified conditions) [3, 4]. Cassava peels is one of the
promising waste raw materials with high starch content [5, 6]. Biodegradable plastics have been reported
from various studies involving cassava starch due to it availability all year round, but focus on the peels
has not been fully exploited [7]. The waste management system of plastics was not given much attention
as a future concern with respect to their various applications, including widespread use as disposable
items [8]. Plastics are lightweight materials, resistant to corrosion [9, 10]. Their inexpensive and
electrical insulation properties, makes them a good material that is highly sorted after [11]. Daily human
endeavours, involve the use of plastics, ranging from packaging materials, telecommunications,
footwear etc [12]. Despite these various applications, continuous research into other sustainable
Abstract
Bioplastics describes the beginning of life based on the carbon bonds present in the
polymer molecule, while biodegradability, focuses on the end of life of bioplastics that
will address environmental clean up by microorganisms. Constructing a carbon backbone
in bioplastics is a vital food for taught that will ensure plastic breaks down readily without
affecting its performance. Retrodegradation is one of the challenges of starch bioplastic
involving gelatinized starch undergoing rearrangement of disaggregated amylose and
amylopectin chains into more ordered structures. Therefore surface modification via
esterification by substituting the highly reactive hydrophilic hydroxyl group (–OH) on
the starch polymer with acetic anhydride as a hydrophobic components has shown a
reduction in water absorption, percentage solubility, and stable structure. The FTIR
spectra of acetylated starch, showed new bands spectra at 1450-1350 cm-1 and 1240 cm-1
assigned to CH3 antisymmetry/symmetry deformation vibration, and carbonyl C-O
stretch vibration, respectively. The result further showed no impact in the cyanide
concentration with corresponding increase in acetic anhydride concentration. The Degree
of Substitution (DS) and percentage acetylation (Ac %) of acetylated starches ranged
from 0.062 to 0.116, and 1.62 to 2.98 g/100g respectively. Therefore, blending acetylated
starch with synthetic polymer has future prospect for altering the persistent –C-C- bonds,
resulting to possible controlled degradation with enhanced surface properties.
Received 2 November 2020,
Revised 07 April 2021,
Accepted 08 April 2021
Keywords
!starch,
!esterification,
!carbohydrate,
!biodegradable,
!polymer.
! degree of substitution.
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@gmail.comfillupotache2456
Phone: +2347035987547
Otache et al., J. Mater. Environ. Sci., 2021, 12(4), pp. 497-510 498
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application has been in the rise in recent time in medicine, source of renewable energy and other forms
of light packaging materials [12]. Despite the environmental friendliness of starch biodegradable
plastics, other factors such as colour, bacteria degradation and low mechanical properties have been
major drawback towards its application [13]. Consequently upon the aforementioned, the need for
modification geared towards enhanced properties through the addition of additives, plasticizers and other
chemical components has been the interest of most researchers. According to Vieira et. al., [14],
Glycerol, gelatin and sorbitol are commonly used plasticizer in the production of biodegradable plastics.
Bartz et. al., [15] describes esterification of starch to involve the introduction of functional groups into
the starch molecules via the available hydroxyl (-OH) surfaces with potential to alter certain
physicochemical properties. In another study, Ashogbon & Akintayo, [16]; Huang et al., [17] noted that
the degree of substitution is dependent on the nature of the substituent. This side chain substitution is
commonly expressed as the degree of substitution (DS). Colussi et. al., [18] in a related study, described
the influence of DS on water solubility of starch acetate films, (i.e. DS < 1.1 are soluble in water, DS>1.1
are insoluble in water). Studies has also shown that bioplastics have superior advantage compared to
conventional plastics with respect to change in shape when an external force is applied without altering
their chemical composition, thereby still retaining their basic elemental structure [19]. Most
conventional plastic waste, accumulates in landfills, and can remain undegraded over many years,
thereby posing a serious course of concern in the ecosystem [20]. Bozena Mrowiec, [21] in another
study, stated that the production of 335 million tones of plastics in 2016, has possible projected increase
to double this figure in the next 2 decades. The demands for a new approach towards a new future of
bioplastics targeted at creating a sustainable plastics economy by improving the economics and uptake
of recycling, reuse‚ and controlled biodegradation with enhanced potential towards a drastic reduction
in the leakage of plastics with enhanced surface [22]. Therefore, the use of waste biomaterials opens
new doors towards a more sustainable bioplastics production. However, daily human existence needs
the synergy between organizational and social awareness, which plays a key role in National economy
[23]. Irena et al., [24] in their finding, noted that future economic determinant will leverage on the
bioplastics production from waste biomaterials. Bioplastics have two possible representations that are
independent; as the beginning of life that will be anchored on the carbon in the polymer molecule while
biodegradability addresses the end of life of bioplastics that will address environmental clean up by
indigenous microorganisms [4, 25]. The possibility of altering the carbon back-bone as contained in
polyethylene without affecting performance, but opens up the possibility of a controlled biodegradation
as compost, rather than creating a perceived bioplastics that is non biodegradable, thereby arousing more
environmental concern.
Polyethylene Cellulose Starch
Biodegradable feedstock
Fig 1. Some polymeric carbon backbone found in biomaterial feedstock
The polyethylene biobased carbon source has been reportedly produced from BioSource such as
sugarcane to form biopolethylene [26]. But irrespective of the feedstock obtained from a biomaterial,
their biodegradability potential can suffer setback due to the presence of the persistent -C-C- backbone
Otache et al., J. Mater. Environ. Sci., 2021, 12(4), pp. 497-510 499
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as compared to the other biobased feedstock as shown in Figure 1. This paper unveils the possibilities
of using acetylated starch from cassava waste peels as raw materials for bioplastics production with
enhanced surface properties. The produced plastic film was tested based on water solubility and water
absorption. The focus of this study was, producing starch acetate from esterified waste peels cassava
starch with different degrees of acetylation and used it in the preparation of biodegradable plastic. The
results from the study were analyzed with respect to the FTIR peaks to ascertain its functional group
modification and hydrophobic properties.
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2. Experimental Details
2.1 Materials
Sorbitol 99% was obtained from BDH chemical limited Poole England. Analytical grade chemical
reagents were used in this study.
2.2 Sample Collection and Starch Extraction
The raw materials were obtained from freshly harvested cassava tubers at Agbarha-Otor market which
is located in Ughelli North Local Government Area of Delta State, Nigeria on longitude 6° 2' 54" E /5°
30' 40" N. The tubers were properly peeled and washed. The peels were carefully separated from other
layers (cortex and parenchyma) with a clean knife. The separated cassava peels (100 g) were washed
again with clean water before blending to small pieces with a blender. The blended cassava peels were
then soaked in water (100 ml) for 45 minutes. Subsequently, sediments were separated from the slurry
and the residual white starch were pre-dried under the sun to remove all the moisture with further oven
drying at temperature of 70 oC for removal of any residual water with subsequent blending into
homogenized sizes [27].
2.3 Acetylation of Starch
Synthesis of starch acetates was carried out in an aqueous medium. The starches were acetylated with
some modification in line with proposed method by Phillips et. al., [28]. A suspension of 50 g of cassava
peels starch in distilled water (100 ml) was subjected to shaking at 1500 rpm (ZENGJI 800) for 60 min
at 25 oC. Aqueous 3.0 g/100g NaOH solution was added to the suspension to adjust the pH to 8.0. Slow
addition of acetic anhydride (5, 10 and 15 g/100g) were added into separate reaction flask, while
maintaining the pH between 8.0 and 8.4 with a 3.0 g/100g NaOH solution. The reaction was sustained
for 15 min after the complete addition of the respective acetic anhydride concentrations. Adjusting the
pH to 4.5 with a 0.5 mol equi/L HCl solution was employed to quench the reaction. The final suspension
was centrifuged for 3 min at 1000 x g with subsequent washings with 95 mL/L ethyl alcohol. The
residual starches were dried in an oven at 40 oC.
2.4 Bioplastic Preparation
Method according to Maulida et al., [29] was adopted for this study with some modification as reflected
in Figure 2. The ratio of 10 g mixture of 8:2 acetylated starch and sorbitol was prepared. The various
concentration of acetylated starch and sorbitol was dissolved in distilled water with starch mixture :
distilled water = 1 : 10 (w/v) ratio. The resulting starch solution was heated and stirred on a hotplate
between 65oC to 70oC to ensure gelatinization for 10 minutes. Furthermore, the hot film produced from
the heating was cooled, poured onto a flat surface and dried in an oven at 60o C for 24 hours. The
bioplastic obtained from the process was removed from the surface, placed in a desiccators and ready to
be analyzed.
Otache et al., J. Mater. Environ. Sci., 2021, 12(4), pp. 497-510 500
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Cassava peels
Removal of outer brown cortex!!!!!!!!!!!!!!!!!!
!!!!!!!!!!!!!!!!!!!!!
!!!!!!!!!!!!!!
Peels without the outer Brown layer
Meshing and extraction of starch
Dried starch
Grounding into fine particle size
Modifications
1. Acetic anhydride addition
2. Plasticizer addition(
((((((((((((((((((((((((((((((((((((((((((((((((((((((((
((((((((((((((((((((((((((((((((((((((((((((((((((((((((((Bioplastic film(
(
Fig. 2 Chart of starch extraction for bioplastic film production
2.5 Instrumentation
FT-IR spectra of samples as described by Liang et al., [30] was adopted for this study, using
SHIMADZU FTIR-8400S equipped with deuterated triglycine sulphate (DTGS) as detector, potassium
bromide (KBr) as beam splitter. The measurements were carried out on a HATR surface at room
temperature in the IR region of 4000–450!cm−1, by accumulating 40 scans with a resolution of 4 cm−1.
2.6 Water Absorption
Water uptake of samples was investigated by weighing film samples with an area of approximately 1 x
1 cm2. The samples were then dried at 70 ºC for 3 hours, cooled, and then immediately weighed. The
Otache et al., J. Mater. Environ. Sci., 2021, 12(4), pp. 497-510 501
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film samples were then submerged in distilled water for 3 hours without agitation. After the immersion
period, the samples were then removed from the water and weighed. The percentage water absorption
was calculated thus; (Wittaya, 2009; Mukuze, Magut, & Mkandawire 2019) [31,32].
(%) = [!2 –!1] × 100
!1
Where: !2="#$%&'(#)ℎ+, !1=,$#+#%&'(#)ℎ+
2.7 Solubility in Water
Dried samples with an area of approximately 1 x 1 cm2 were weighed. Each sample was subsequently
immersed in 50 mL of distilled water under constant agitation for 3 hours at room temperature. Insoluble
portion of the film was air dried for 24 hours and reweighed. The water solubility (%) of the films was
calculated thus; [27, 31].
-
./&0bility (%) = ['0−'1]×100
-------------------------------------'0
where: '0 = Weight-before-submersion, '1 =-Weight-after-submersion
2.8 Hydrogen Cyanide Determination
The cyanide concentration in acetylated waste peels cassava starch was determined using ninhydrin
based spectrometer of trace cyanide at 485 nm [32, 33]. Concentrations of 0.02, 0.04, 0.08, 0.1 and 0.2
µg/ mL was used to generate a calibration graph within linear range by adding appropriate volumes of
cyanide solutions at concentration of 20 µg CN−/mL to 1 mL of 2% Na2CO3. Ninhydrin solution (0.5
mL) containing 5 mg/mL in 2% NaOH was added to each standard cyanide solution. Homogenization
and incubation of the mixure for 15 minutes for colour development was performed. In the same vein,
the blank containing 1 mL of 2% Na2CO3 without CN− was added. Different concentrations of cyanide
was measured using UV/Vis Spectrophotometer (UV 2100C) at 485 nm. Thereafter, 0.1 g of the ground
sample was added in a standard volumetric flask (5 mL) and made up to mark with 0.1% NaHCO3.
Sonicated of the sample for 20 minutes in a water bath was followed up with centrifugation at 10,000
rpm for 10 minutes. An automatic pipette was used to obtain a clear supernatant. The aliquots (2 mL)
was added to 0.5 mL ninhydrin in NaOH, allowed for 15 min for colour development and absorbance
measured at 485 nm.
2.9 Determination of the acetyl percentage (Ac%) and degree of substitution (DS)
The percentage of acetyl groups (Ac%) and the degree of substitution (DS) of the acetylated starches
were determined using method described by Wurzburg [34]. Ethanol (50 mL) containing 75 mL/L
ethanol in distilled water was used to dissolve the acetylated starch (1 g). An aluminium foil was used
to cover the 250 mL flask containing the slurry and placed in a water bath at 50 oC for 30 min. To the
cool sample, 40 mL of 0.5 mol equi/L KOH were added, and the slurry was kept under constant stirring
at 200 rpm for 72 h. Thereafter, the alkali excess was titrated with 0.05 mol equi/L HCl, using
phenolphthalein as an indicator. The solution was left to stand for 2 h and then any additional alkali,
which may have leached from the sample, was titrated. A blank, using the unmodified starch, was also
used. The Ac % and the DS were calculated according to Equations (1) and (2) respectively.
Ac % = ([Vblank –Vsample] x Molarity of HCl + 0.043 x 100)
Sample weight (1)
Where: Vblank = titration volume used for the blank sample.
Otache et al., J. Mater. Environ. Sci., 2021, 12(4), pp. 497-510 502
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Vsample = titration volume used for each sample.
Both titration volumes were expressed in mL; the sample weight was expressed in g. DS is defined as
the average number of sites per glucose unit that is possessed by a substituent unit
DS = (162 x Acetyl %)
(4300- [42 x Acetyl %]) (2)
3. Results and Discussion
3.1 FTIR Analysis
The changes in the chemical conformation of the treated starch were analyzed using FTIR. The results
from the FTIR spectra in Figure 3, 4, 5 and 6 show two main regions of absorbance within the range of
500-1750 cm-1 at lowwavenumbers and 2000-3500 cm-1 at higher wavelengths. This observation was in
line with the studies done by Nordin et al., [35] on starch films reinforced with microcellulose fibres.
Also in another study by Moràn et al., [36] and Lani et al., [37], showed that their results are in agreement
with the results from this study. The broadband atregions between 3373.61 cm-1to 3414.12 cm-1 for all
plastic is attributed to the hydroxyl group -OH stretching vibrations [38].
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Fig. 3 FTIR chart of raw starch plastic film
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Fig. 4 FTIR chart of 5 % acetylated starch plastic film
The slightly projected peak between 2928.04 cm-1 to 2935.76 cm-1 corresponded to aliphatic saturated -
CH stretching vibrations. Bands at 1732.13 cm-1 is commonly associated with the ester carbonyl group
Otache et al., J. Mater. Environ. Sci., 2021, 12(4), pp. 497-510 503
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C=O, as a result of acetylation reaction [39, 40]. Further confirmatory peak between 1637.62 cm-1 to
1651.10 cm-1is related to C-O bending associated with OH group. Peaks at 1450 cm-1 to 1370 cm-1 are
related to C-C stretch in the various plastics. Also the results showed a C-O stretched peak between 1000
cm-1 to 1250 cm-1, reflecting the possible formation of esters, alcohols and ethers. The absorbance bands
around 894 cm-1 and 1020 cm-1 are associated with the C-H rocking vibrations and C-O stretching
respectively [40].
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Fig. 5 FTIR chart of 10 % acetylated starch plastic film
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Fig. 6 FTIR chart of 15 % acetylated starch plastic film
3.2 Surface Modification
Subsequently via acetylation reaction upon the addition of acetic anhydride in various proportion as
depicted in Figure 7, the FTIR analysis of the acetylated plastic film in Figure 4, 5 & 6, indicate acetyl
groups addition to the starch molecule was only reflected in the 10 % and 15 % acetylated bioplastic
film. This incorporation of acetyl group in the starch molecule may be visualized by an increase in the
peak intensity with 5 % acetic anhydride at a wave number of 1651.12 cm-1 for carbonyl C=O
corresponding to possible amide, but bands commonly associated with ester carbonyl group C=O, was
not detected. Reaction with 10 % and 15 % acetic anhydride, shows new peaks commonly associated
with ester carbonyl group C=O at 1732.13 cm-1 and 1737.92 cm-1 respectively. Other spectra of the
acetylated starch, showed some new absorption bands that increases in peak intensity with increase
acetic anhydride concentration between 1450 cm-1 to 1350 cm-1 and 1240 cm-1 assigned to CH3 anti-
symmetry/symmetry deformation vibration, and carbonyl C-O stretch vibration, respectively [41]. The
Otache et al., J. Mater. Environ. Sci., 2021, 12(4), pp. 497-510 504
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result from this study is in agreement with assertion by Chi et al., [40], describing these new absorptions
as possible acetylated starch products formed during the esterification process. The absence of
absorption peak in the region 1950 cm-1 to 1750 cm-1 implied that the product was free of unreacted
acetic anhydride, and the absence of absorption in the area of 1700 cm-1 for the carboxylic group
indicated that the product was also free of acetic acid byproduct. This claim was also made by Diop, Li,
Xie, and Shi [42]. Salaberria et al., [43], noted that variation in the bands as observed in all spectra, is
possible even if a pure sample is used.
Fig. 7 Proposed surface modification of bioplastic film from cassava peels
Table 1 Acetyl percentage (Ac %) and degree of substitution (DS) of the acetylated starch
The DS and Ac % of acetylated starches ranged from 0.042 to 0.116, and 1.11 to 2.98 g/100g,
respectively. The acetylated starches with the highest concentrations of acetic anhydride (10 g/100g)
presented higher DS and Ac% as compared with other concentration of acetylated starch (Table 1).
According to the United State Food and Drug Administration (FDA), 2.5 g/100g, is the safe limit for
acetyl group maximum for foods uses [44]. Therefore, results from this study revealed that acetylated
starches (5, 10 and 15 g/100g) showed lower Ac %, but slightly above the safe limit at 10g/100g. Results
from this study were within range for 5 and 10 g/100g acetic anhydride as reported by Rosana et al.,
[45]; Vasanthan, Sosulski, & Hoover [46]. In another study involving acetylated maize starch (10g/100g
of acetic anhydride in starch slurry of 31 g/100g), Liu, Ramsden, and Corke [47] reported a higher Ac%
between 2.71 and 4.22 g/100g and a DS of 0.105-0.165. Similarly in another finding using Corn starch,
Luis, Silvia,Antonio & Octavio [48] reported values are in agreement with results from this study.
Therefore it could be stated that this variations in DS and Ac% could be as a result of some key factors
such as concentration, presence of catalyst, reaction time, type of reagent, structure of starch granules as
well as other growth conditions.
3.3 Water Absorption
Decrease in the water absorption was observed with subsequent increase in acetic anhydride
concentration as reflected in Figure 8. This trend is in line with the assertion that describes the
hydrophilic property starch and cellulose, thereby influencing their water reactivity according to
Sample
% Ac
DS
5
Ac
1.62±1.023
0.062
7.5
Ac
2.37±0.001
0.091
10
Ac
2.98±0.010
0.116
Otache et al., J. Mater. Environ. Sci., 2021, 12(4), pp. 497-510 505
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Dufresne & Vignon, [49]. In another study, Maulida, Siagian, & Tarigan, [29], stated that starch has a
low hydrogen bonding capacity as compared to cellulose, thereby making it more easily prone to
hydrolysis. This trend was accounted for by Abdullah, Putri, Fikriyyah, Nissa & Intadiana, [50], based
on the high hydrophilic property of the solid sugar alcohol. Therefore, it can be concluded that the higher
the acetic anhydride concentration, the more the degree of substitution, evident in lower water absorption
potential.
Fig. 8 Percentage Water Absorptivity of Acetylated Starch and Sorbitol Bioplastic film
3.4 Solubility in Water
Hydrogen bonding has been reported to play a vital role in limiting the effective bonding of starch with
water [51]. Therefore, the results as captured in Figure 9 revealed a decreasing solubility with increase
acetic anhydride concentration. This observed reduction could be caused by the substitution of the OH-
groups in the starch molecule by acetyl groups. This assertion is in agreement with report from other
studies [52, 53, 54]. Thus, the result from this study has further strengthen the claim by Schmidt, Blanco-
PascuaL, Tribuzi, & Laurindo, [54], that acetylation of starch is an interesting method for the
development of starch films with improved properties.
Fig. 9 Percentage Water Solubility of Acetylated Starchand Sorbitol Bioplastic film
Acetylation, shows no impact on the residual cyanide potential of the bioplastic film as reflected in
Figure 10. The reduced cyanide concentration could be attributed to other starch processing techniques
such as mashing, filtering, drying and subsequent heating above the reported boiling temperature of 26
oC [55, 56]. The average cyanide concentration of 2.19 mg/kg as reported in this study is below the
acceptable values by WHO and hence suitable for use as bioplastic for industrial application [19, 57].
Considering the importance of evaluating the cyanide content, water absorption and solubility of the
14,67
8,34
6,06
4,98
0
2
4
6
8
10
12
14
16
0 2 4 6 8 10 12 14 16
Water&Absorption&(%)
Acetic&anhydride&concentration&(%)
36,23
27,59
22,76
17,21
0
5
10
15
20
25
30
35
40
0246810 12 14 16
Solubility&(%)
Acetic&anhydride&concentration&(%)
Otache et al., J. Mater. Environ. Sci., 2021, 12(4), pp. 497-510 506
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bioplastic film, a correlation study of these parameters was analyzed on a 3-D plot as shown in Figure
11. The highlight from the graph shows a clear trend of increase in concentration of acetylation as it
impacts on these surface parameters with exception to the cyanide content.
Fig. 11 A 3-D chart on the effect of acetylation on cyanide content, solubility and water absorption of cassava
starch bioplastic film
4. Conclusions
Replacing synthetic polymers in packaging application is very essential, but for customer the cost of
packaging material weighs over environmental concerns. Therefore, in other to balance the need for
environmental sustainability and the demand to turn waste into wealth, the use of cassava waste peels
has shown prospect as a potential source for bioplastic production that can address the major limitation
in the various applications of bioplastics based on its sensitivity to moisture and retrogradation processes.
The result from this finding has shown that surface modification of starch via esterification using acetic
anhydride has shown a reduction in water absorption, solubility and no impact on the cyanide
concentration. Sequel to the aforementioned, more research is required on possible nanoparticles with a
focus on further enhancing its surface against possible hydrolysis resulting to retrogradation, thereby
sustaining its mechanical strength during storage that can further be implemented and commercialized
as an eco-friendly packaging materials.
2,178
2,18
2,182
2,184
2,186
2,188
2,19
2,192
0 2 4 6 8 10 12
Cyanide Conc (mgkg)
Acetic anhydride concentration (%)
Fig. 10 Residual Cyanide Content in Acetylated Starch
Otache et al., J. Mater. Environ. Sci., 2021, 12(4), pp. 497-510 507
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