polymers

polymers
Article
Sustainable Bioplastics for Food Packaging Produced from
Renewable Natural Sources
Rajesh Jesudoss Hynes Navasingh 1,2 , Manoj Kumar Gurunathan 1, * , Maria P. Nikolova 3
and Jolanta B. Królczyk 2
1 Department of Mechanical Engineering, Mepco Schlenk Engineering College,

Sivakasi 626005, Tamil Nadu, India; nrajesh@mepcoeng.ac.in
2 Faculty of Mechanical Engineering, Opole University of Technology, Proszkowska 76, 45-758 Opole, Poland;
j.krolczyk@po.edu.pl
3 Department of Material Science and Technology, University of Ruse “Angel Kanchev”, 8 Studentska Street,
7017 Ruse, Bulgaria; mpnikolova@uni-ruse.bg
* Correspondence: manojkumargmmech@gmail.com
Abstract: It is crucial to find an effective, environmentally acceptable solution, such as bioplastics or

biodegradable plastics, to the world’s rising plastics demand and the resulting ecological destruction.
This study has focused on the environmentally friendly production of bioplastic samples derived
from corn starch, rice starch, and tapioca starch, with various calcium carbonate filler concentrations
as binders. Two different plasticizers, glycerol and sorbitol, were employed singly and in a rich
blend. To test the differences in the physical and chemical properties (water content, absorption
of moisture, water solubility, dissolution rate in alcohol, biodegradation in soil, tensile strength,
elastic modulus, and FT-IR) of the produced samples, nine samples from each of the three types
of bioplastics were produced using various ratios and blends of the fillers and plasticizers. The
produced bioplastic samples have a multitude of features that make them appropriate for a variety of
applications. The test results show that the starch-based bioplastics that have been suggested would
be a better alternative material to be used in the packaging sectors.
Keywords: bioplastics; starch; fillers; packaging
Citation: Navasingh, R.J.H.;

Gurunathan, M.K.; Nikolova, M.P.;
Królczyk, J.B. Sustainable Bioplastics
for Food Packaging Produced from
1. Introduction
Renewable Natural Sources. Polymers Plastics and other items made of plastic are created from a variety of organic sub-
2023, 15, 3760. https://doi.org/ stances that are flexible. Most organic polymers with a high molecular weight and other
10.3390/polym15183760 materials are compounds of plastics (fillers, colors, and additives); usually, they are created
synthetically. When referring to unfilled and uncolored plastics rather than compounds, the
Academic Editor: Alfonso Jimenez
phrase “natural plastics” is occasionally used in the industry. Every year, 12 million tonnes
Received: 21 June 2023 of plastic end up in the ocean. Of these, 9.5 million tonnes reach the ocean via land, with
Revised: 31 August 2023 1.75 tonnes coming directly from the fishing and shipping industries [1]. It is estimated that
Accepted: 12 September 2023 there are 51 trillion microscopic fragments of plastic, comprising around 269,000 tonnes. As
Published: 14 September 2023 evidenced by the endurance of natural materials, it is anticipated that since the 1950s, some
1 billion tonnes of plastics have been dumped, some of which may endure for centuries or
perhaps substantially longer [2].
Based on how they respond to heat, all plastics may be categorized into the following
Copyright: © 2023 by the authors.
two basic groups: thermosetting and thermoplastic. Thermoplastics are polymers that
Licensee MDPI, Basel, Switzerland.
can be heated, melted, and molded into the desired shape before cooling. The produced
This article is an open access article
distributed under the terms and
thermoplastic softens and remelts when heated. Polyacrylates, polyesters, polyolefin,
conditions of the Creative Commons
polyamides, etc., are examples of well-known thermoplastics. In addition to other products,
Attribution (CC BY) license (https:// these polymer materials are used to make packaging, disposable utensils, carpets, lab
creativecommons.org/licenses/by/ equipment, apparel, and other items [3]. Unlike thermoplastics, thermosetting polymers
4.0/). are permanently stiffened by the curing of soft solid or liquid resins. Curing is brought
Polymers 2023, 15, 3760. https://doi.org/10.3390/polym15183760 https://www.mdpi.com/journal/polymers

Polymers 2023, 15, 3760 2 of 25
on by heat or radiation, and it can be accelerated by adding catalysts. Considerable

research has been performed on bioplastics, which are currently the subject of significant
research among scientists all over the world due to their susceptibility to water exposure,
lack of compatibility, and lower melting point than polymers derived from petroleum [4].
Bioplastics are made from biological or biodegradable components, such as corn starch, food
scraps, or even agricultural byproducts. Bio-based plastics are simple to break down in a
natural environment, as compared to petroleum-based plastic. They are made from fossil
fuels and petrochemical polymers. These results are less negative environmental impacts and
global sustainability. The durability of plastics, which is one of their greatest benefits, is also
one of their greatest drawbacks as follows: the rate of disintegration (biodegradation) does
not correspond to their intended service life, leading to environmental accumulation [5,6].
Compared to commercial plastics used to make polyethylene bags and containers,
bioplastics are typically produced at a faster rate [7]. These bioplastics aid in lowering
greenhouse gas emissions to reduce environmental pollution [8]. Nevertheless, bioplastics
deteriorate gradually depending on the environment’s soil quality [9,10]. Starch, plasti-
cizers, and fillers are the main components of bioplastics in general [11]. Starch-based
polysaccharides are thought to be a cost-effective material since they contain a mixture
of amylose and amylopectin [12–14]. Starch is commonly available and can be found in
foods including rice, corn, wheat, potatoes, tapioca, and others; therefore, thermoplastic
starch is their primary usage (TPS). Amylopectin and amylose of glucose molecules make
up starch, and several types of starches have variable amounts of amylose and amylopectin.
Additionally, tensile strength and elongation both increase as the amylose level rises. Plas-
ticized starch will replace synthetic polymers as a material. Tensile strength will rise as
molecular interactions and hydrogen bonding intensify. The rigid films’ flexibility will
suffer if the tensile strength is too great. Due to package degradation brought on by the
environment or product moisture, bioplastic solubility for food packaging applications
must be minimal [15–18]. Mechanical qualities are significant for applications involving
food packaging. A sample’s tensile strength varies depending on the type of polymer
used, the processing environment, the additives, and the blends. Depending on how it
is processed and stored, this will alter. When creating bioplastic samples, several agents,
such as additives, catalysts, antioxidants, fillers, and so forth, are added to improve the
qualities of the bioplastics [19,20]. According to the tensile and mechanical properties,
the main purpose of the fillers is to increase the strength of the bioplastic compound.
Starch content is combined to create composite bioplastics, which are formed of the fol-
lowing two major materials: matrix and reinforcement [21,22]. Due to their hydrophilic
characteristics, glycerol and sorbitol are used as plasticizers because they have excellent
mechanical qualities.
Starches that are compatible with plasticizers, like sorbitol and glycerol, which are
inexpensive and abundantly available, are used in the blends of bioplastics. The recycla-
bility of the material is another important factor, and the created bioplastic samples have
better mechanical qualities that are comparable to conventional plastics [23,24]. Compared
to bioplastics based on individual starch content, the mechanical qualities of composite
bioplastics have higher mechanical strength [25,26]. The water solubility and mechanical
qualities should be compared to the standard plastic material to replace it for applications
such as food packaging [27–29]. The composite bioplastics have different starch contents,
including rice, corn, and tapioca. The cassava plant, which is readily available, inexpensive,
and has qualities like being odorless and colorless, is typically used to extract tapioca
starch [30,31]. The amylose and amylopectin content for tapioca starch is 21.2% and 78.8%,
respectively. The sample of cassava-based bioplastic is translucent and white in color, and
it has a better level of biodegradability. The tensile strength increases with an increase in
tapioca starch. The bioplastic sample made of maize starch is transparent. Composite-based
bioplastic degrades much more slowly than corn-based bioplastic, and the material’s capac-
ity to degrade is also impacted by humidity. The degradation of composite bioplastics made
of cassava and corn starch and cassava-based bioplastics is best at 15% relative humidity.
Polymers 2023, 15, 3760 3 of 25
A cassava-based bioplastic degrades substantially more effectively than a corn-based bio-

plastic when the relative humidity is below 15% [32–34]. Understanding the structure and
characteristics of the bioplastic compound is made easier by the morphology of the starch
content [35,36]. The quick degradation of bioplastic materials will happen as a result of
their weak integrity [37]. Above this point, the tensile strength will drop, with an increase
in starch content of around 5%, producing an increase. The glycerol level of about 1.5% will
be effective up to a point where the plasticizing capability starts to decline. The glycerol
will have limited solubility and swell in water if it is kept at 5–10%. Furthermore, strong
mechanical properties and resistance were also attained [38–40]. The innate nature of
protein-based (β-glucans) bioplastics has increased their performance and improved their
tensile strength, water vapor permeability, water retainability, and thermal stability under
atmospheric conditions. These grains of protein are strongly bonded together through
hydrogen bonds that exhibit the enhanced properties of the bioplastics [41,42].
High starch concentrations resulted in a loss of the tensile and mechanical characteris-
tics of albumen/starch-based bioplastic blends. Also, it was observed that the transparency
of the film reduced significantly when the starch concentration increased [43]. The bio-
plastic film made from the potato and rice protein compositions has shown an acceptable
range of viscoelastic and water absorption properties that would be utilized in the food
packaging industry. The glycerol concentration and thermo molding temperature treatment
seem to have an impact on the viscoelastic characteristics of rice protein-based bioplastics.
Bioplastics made from potato protein, however, did not appear to be affected [44,45]. As
per the researcher, a microbial enzyme, on which use of an aqueous solution with a level
exceeding 10%, is required for the bioplastic to prevent microbial growth; therefore, it
appears to be the most resilient microbe as a result. Protein-based bioplastics have been
studied; however, they are unable to stop formic acid from migrating to water. Gradually
moving away from the WG-based matrix, this material is ideal for long-term applications;
moreover, essential oil-infused bioplastics may even prevent the growth of germs. These
enzymes assist in the creation of an antimicrobial environment inside the container if they
are not in direct contact with them [46–48]. Recent research has been established on bioplas-
tics to develop the current trend in the bioplastics market. The major contributing factors,
such as starch, PLA, and PHA on bioplastic production, provide future implementing ideas
onto the market. Bioplastics are favored more in the food packaging industry [49,50]. From
research and studies of lateral years on plastics, it is proven that for the next ten years, the
bioplastics industry is anticipated to be dominated by non-biodegradable bioplastics, such
as bio-based PE, PP, and PET that can be recycled in current systems [51,52].
Whey protein bioplastics of biopolymers: natural latex and egg white albumin on
combining these and fabricated by compression molding. Water is added as a plasticizer in
that mixture. It is found that the addition of about 10% latex and albumin to the whey-based
bioplastics would increase its toughness properties and also enhance the characteristics
of whey-based materials without compromising their strength and stiffness [27]. This
article contemplates that current trends in bioplastics are focused on bio-based technology
production rather than conventional methods. Such resource technologies were genetically
modified organism cell lines and biomass refinery methods. All these modern bio-based
aspects were meant to drive sustainable industry development and regulate the ability of
bioplastics to degrade at a certain rate [53,54]. Incorporating glycerol with larger-sized
plasticizers, such as xylitol or sorbitol, in the bioplastic film results in the stickiness of
the film, promoting separation onto double wall areas and indicating improved tensile
strength, stiffness, and oxygen-regulating properties. Thermoplastic starch-blown films
having high quantity of plasticizers would not be recommended due to their high wa-
ter/moisture sensitivity and surface stickiness [55]. In biochemical and soil conditions,
PLA breaks down quickly for about a few weeks [56]; however, because of its high price
and excessive brittleness relative to typical synthetic materials, it is not extensively utilized.
Plastics that have poor mechanical characteristics are typical of PLA composites made with
other natural polymers. The natural polymer and the PLA matrix were not bound well
Polymers 2023, 15, x FOR PEER REVIEW 4 of 24
Polymers 2023, 15, 3760 and excessive brittleness relative to typical synthetic materials, it is not extensively4 of uti-
25
lized. Plastics that have poor mechanical characteristics are typical of PLA composites
made with other natural polymers. The natural polymer and the PLA matrix were not
bound well together. Recently, polyethylene glycol, polyethylene, glucose, monoesters,
together. Recently, polyethylene glycol, polyethylene, glucose, monoesters, and partial
and partial fatty acid esters have been utilized to enhance the flexibility and impact re-
fatty acid esters have been utilized to enhance the flexibility and impact resistance of PLA.
sistance of PLA. Many
Many compounds, compounds,
including citrateincluding
esters, have citrate
been esters,
tested have been tested as
as plasticizers. Asplasticiz-
a result,
PLA polymers’ properties and possible uses have been identified and they areand
ers. As a result, PLA polymers’ properties and possible uses have been identified they
greatly
are greatly improved [57,58]. The starch is promoting a pathway
improved [57,58]. The starch is promoting a pathway for the manufacturing of bioplastics,for the manufacturing of
bioplastics, which could result in the creation of materials with exponentially
which could result in the creation of materials with exponentially better performance in the better per-
formance
food in the industries.
packaging food packaging industries.
It follows that theItproperties
follows that the properties
of various materials of various mate-
are connected
rials are connected to how well starch materials cling to them
to how well starch materials cling to them and how they are compounded. As thermoplas- and how they are com-
pounded. As thermoplastics are processed using extrusion technology,
tics are processed using extrusion technology, which is one of the basic techniques that has which is one of the
basic techniques that has been investigated and developed to treat
been investigated and developed to treat starch-rich products [59]. The solubility of the sub- starch-rich products
[59]. The
stance andsolubility
the valuesof of
thethe
substance
intrinsicand the values
viscosity of theofsynthetic
the intrinsic viscosity
component bothof the synthetic
demonstrate
component
the remarkable bothtransformation
demonstrate the ofremarkable
the structure transformation of the structure
of the unstabilized sample duringof the photo-
unsta-
bilized sample
oxidation. during photo-oxidation.
The positive The positive
effect of the stabilizers effect of the
on the durability stabilizersbiodegradable
of produced on the dura-
bility of produced
polymer would have biodegradable
been interpretedpolymer by would have been
the amount interpretedproportionate
of absorbance by the amount toofa
absorbance proportionate to a lower wavelength region of these
lower wavelength region of these compounds [60]. Biopolymers are polymers derived compounds [60]. Biopol-
ymersrenewable
from are polymers derived
biological from renewable
sources, biological
such as plants, sources,
animals, andsuch as plants, animals,
microorganisms. They
and microorganisms.
offer several advantages They offer
over several advantages
traditional over traditional
petroleum-based polymers petroleum-based
(plastics) and have pol-
ymers (plastics)
gained increasingand havein
interest gained
various increasing
applicationsinterest
due toin their
various applications
eco-friendly anddue to their
sustainable
eco-friendly
nature. and sustainable
Biodegradability, nature. Biodegradability,
compostability, compostability,
energy-efficient processing, reducedenergy-efficient
dependence
processing,
on fossil fuels,reduced dependence
non-toxic, and safety on are
fossil
somefuels, non-toxic,
of the and safety
key advantages ofare some
using of the key
biopolymers.
advantages
While of usingoffer
biopolymers biopolymers. While biopolymers
many advantages, it is importantoffertomany advantages,
note that it is im-
their adoption is
not without
portant to notechallenges. Issues such
that their adoption as cost,
is not without scalability,
challenges.performance,
Issues suchand competition
as cost, scalabil-
with well-established
ity, performance, and petroleum-based
competition withpolymers remain considerations
well-established petroleum-based forpolymers
widespread re-
implementation.
main considerations Nonetheless,
for widespreadongoing research and technological
implementation. Nonetheless, advancements
ongoing research continue
and
to address these
technological challenges and
advancements further to
continue expand
address thethese
use ofchallenges
biopolymers andinfurther
variousexpand
industries.
the
Figure 1 illustrates the
use of biopolymers lifecycle
in various of the bioplastics.
industries. Figure 1 illustrates the lifecycle of the bioplastics.
Figure 1. Lifecycle of the bioplastics.
This investigation focuses on the use of renewable waste from organic agricultural
sources, such as corn starch, rice starch, and tapioca starch, to make bioplastics. Using
widely available, plentiful, biodegradable, and renewable natural waste as reinforcing
sources,
Thissuch as corn starch,
investigation focusesrice
onstarch,
the useand tapioca starch,
of renewable wastetofrom
make bioplastic
organic agr
widely
sources,available, plentiful,
such as corn biodegradable,
starch, and tapioca
rice starch, and renewable natural
starch, waste bioplastic
to make as reinfor
ers, canavailable,
widely help reduce the risks
plentiful, and problemsand
biodegradable, associated
renewablewith conventional
natural waste as plastic
reinfor
as the degradation of mechanical properties.
ers, can help reduce the risks and problems associated with conventional plastic
Polymers 2023, 15, 3760 5 of 25
as the degradation of mechanical properties.
2. Materials and Their Properties
2.1. Starch
2. Materials
fillers, and Their
can help reduce Properties
the risks and problems associated with conventional plastics as well
as the degradation of mechanical
The two polysaccharides properties.
amylose and amylopectin make up the granular
s
2.1. Starch
2.ofMaterials
starch,
The twowhich is Properties
and Their very cheap amylose
polysaccharides and abundant in nature. These
and amylopectin makestarch-based mates
up the granular
biodegradable
2.1. Starch which
of starch, and thermoplastic.
is very cheap and abundant in nature. These starch-based mate
The two polysaccharides
biodegradable amylose and amylopectin make up the granular structure
and thermoplastic.
2.1.1.
of Corn
starch, Starch
which is very cheap and abundant in nature. These starch-based materials are
biodegradable and thermoplastic.
2.1.1.One
Corn ofStarch
the cereal starches obtained from maize is corn starch, which is ment
Figure
2.1.1. 2. Starch
Corn
One Commonly
of the cerealrecognized for its white
starches obtained from color
maizeand widestarch,
is corn rangewhich
of uses,
is inclu
ment
food sector
One of theand adhesive
cereal starches preparations;
obtained from moreover,
maize is corn it serves
starch, as
which
Figure 2. Commonly recognized for its white color and wide range of uses, inclu a
is component
mentioned in co
in Figure
These 2. Commonly
starches are recognized
made up of for
a itsratio
1:3 whiteofcolor
two and wide polymers,
distinct range of uses, includ- and am
amylose,
food
ing thesector and and
food sector adhesive preparations;
adhesive preparations;moreover,
moreover, ititserves
servesas as a component
a component in in co
tin.
These starches are made up of a 1:3 ratio of two distinct polymers, amylose, and am
cosmetics. These starches are made up of a 1:3 ratio of two distinct polymers, amylose,
tin.amylopectin.
and
Figure 2. Corn starch.

Figure
Figure 2. 2. Corn
Corn starch.
starch.
2.1.2. Rice Starch
2.1.2. Rice Starch
2.1.2.The
Ricemilled
Starchrice has a significant amount of rice starch. Using the dry techniq
The milled rice has a significant amount of rice starch. Using the dry techniques, this
ricestarch
rice starch comprises
Thecomprises
milled rice glucans,
has
glucans, as in
shown
aassignificant
shown amount
Figure in
3. Figure
of rice
These 3.starch.
These
starches starches
areUsing
known forare
the theirknown
dry techniq
color
color and
and gel-like
gel-like properties.
properties. As As
with with
any any bioplastic,
bioplastic, the the
environmentalenvironmental
rice starch comprises glucans, as shown in Figure 3. These starches are known benefits of benefits
using
rice
rice
color starch
starch
and in bioplastic
in bioplastic
gel-like production
production
properties. aretied
are closely
As with closely
any tieddisposal
to proper
bioplastic, to the
proper disposal practices.
practices.
environmental benefits
rice starch in bioplastic production are closely tied to proper disposal practices.
Figure
Figure 3. 3. Rice
Rice starch.
starch.
Figure 3. Rice starch.

Polymers 2023, 15, x FOR PEER REVIEW

2.1.3. Tapioca Starch
Polymers 2023, 15, 3760 6 of 25
The cassava plant is used to obtain tapioca starch, a relatively accessible su
These starchesStarch
2.1.3. Tapioca typically have hydrophilic properties. These starches are indige
Brazil’s
2.1.3. northeast,
Tapioca as depicted in Figure 4. The thickening agent for food applic
Starch plant
The cassava is used to obtain tapioca starch, a relatively accessible su
frequently
The tapioca
cassava plant starch.
is used Amylopectin
to obtain tapioca (85%)
starch, and amylose
a relatively (15%)substance.
accessible are both presen
These starches typically have hydrophilic properties. These starches are indige
tapioca
These starch.
starches typically have hydrophilic properties. These starches are indigenous to
Brazil’s
Brazil’s northeast,
northeast, as depicted
as depicted in 4.
in Figure Figure 4. The thickening
The thickening agent
agent for food for food
applications is applic
frequently tapioca starch. Amylopectin (85%) and amylose (15%) are
frequently tapioca starch. Amylopectin (85%) and amylose (15%) are both present in this presen
both
tapioca
tapioca starch.
starch.
Figure 4. Tapioca starch.
2.2. Plasticizers
Figure
Figure 4. 4. Tapioca
Tapioca starch.
starch.
Plasticizers are essential additives used in bioplastics and conventional pl
2.2. Plasticizers
enhance
2.2. their flexibility, durability, and processability. They are incorporated int
Plasticizers
Plasticizers are essential additives used in bioplastics and conventional plastics to
formulations to improve the material’s performance and make it more suitable for
enhance Plasticizers aredurability,
their flexibility, essentialand
additives used They
processability. in bioplastics and into
are incorporated conventional
plastic pl
applications.
formulations to improve the material’s performance and make it more suitable for various
enhance their flexibility, durability, and processability. They are incorporated int
applications.
formulations to improve the material’s performance and make it more suitable for
2.2.1. Glycerol
applications.
2.2.1. Glycerol
Glycerol is a viscous liquid that is odorless, non-toxic, and used in numerou
Glycerol is a viscous liquid that is odorless, non-toxic, and used in numerous appli-
cations
2.2.1.
cations as as a solvent
Glycerol
a solvent and lubricant
and lubricant according
according toAFigure
to Figure 5. 5. A stablebiopolymer
stable hydrophilic hydrophilic bio
chainis is
chain provided
provided by glycerol.
by glycerol.
Glycerol is a viscous liquid that is odorless, non-toxic, and used in numerou
cations as a solvent and lubricant according to Figure 5. A stable hydrophilic bio
chain is provided by glycerol.
Figure
Figure 5. 5. Glycerol.
Glycerol.
2.2.2. Sorbitol
2.2.2. Sorbitol
Sugar
Figure alcohol is the common name for sorbitol. They are produced when glucose is
5. Glycerol.
Sugar
reduced. alcoholapplications,
In numerous is the common name is
this substance for sorbitol.utilized
frequently Theyasare produced
g
a sweetener andwhen
reduced.
2.2.2. In numerous applications, this substance is frequently utilized as a sw
Sorbitol
and texturizing agent as shown in Figure 6. It serves as a renewable feedstock, he
Sugar alcohol is the common name for sorbitol. They are produced when g
create a more sustainable and eco-friendlier bioplastic alternative to conventional
reduced. In numerous applications, this substance is frequently utilized as a sw
and texturizing agent as shown in Figure 6. It serves as a renewable feedstock, he
Polymers 2023, 15, 3760 7 of 25

texturizing agent as shown in Figure 6. It serves as a renewable feedstock, helping to create
a more sustainable and eco-friendlier bioplastic alternative to conventional plastics.
Figure 6. Sorbitol.
2.3. Fillers
Figure
Figure Fillers
6. 6. are additives
Sorbitol.
Sorbitol. used in bioplastics to improve certain properties or red
duction
2.3. Fillers costs. These fillers are typically inert, non-toxic materials that are mixed
2.3. Fillers matrix to achieve specific performance enhancements.
biopolymer
Fillers are additives used in bioplastics to improve certain properties or reduce pro-
ductionFillers are additives
costs. These used in inert,
fillers are typically bioplastics tomaterials
non-toxic improve certain
that properties
are mixed with the or red
Calciumcosts.
biopolymer
duction Carbonate
matrixThese
to achieve specific
fillers performance
are typically enhancements.
inert, non-toxic materials that are mixed
Calcium Carbonate
biopolymer
Calciummatrix to achieve
carbonate (CaCOspecific performance
3) is frequently used as enhancements.
filler to lower costs and enh
Calcium carbonate (CaCO3 ) is frequently used as filler to lower costs and enhance
materials’
the materials’mechanical qualities.
mechanical qualities. Calcium
Calcium carbonates
carbonates (Figure(Figure 7) are employed
7) are employed in many in m
Calcium
different Carbonate
ferent applications,
applications, such
such as the
as the production
production of polyesters,
of polyesters, in additionintoaddition to thermopl
thermoplastics.
Calcium carbonate (CaCO3) is frequently used as filler to lower costs and enh
materials’ mechanical qualities. Calcium carbonates (Figure 7) are employed in m
ferent applications, such as the production of polyesters, in addition to thermopl
Figure
Figure 7. 7. Calcium
Calcium carbonate.
carbonate.
3. Methodology
3. Methodology
The bioplastic sample preparation was performed using a variety of techniques. The
Figure
best The bioplastic
7. Calcium
practices sample
binding preparation
carbonate.
for efficient was
of the sample on the performed usingmaterials
process compound a variety of techniq
would
be accomplished
best practicesbyfor theefficient
following: binding
weighing out materials
of the at suitable
sample on thestandard
process levels, such
compound m
as
3. the starch
Methodology content of the corn, rice, and tapioca that are essentially required for making
would be accomplished by the following: weighing out materials at suitable stand
the sample. The first stage in the procedure is to calculate the appropriate ratio of each
els, such
starch, The as the starch
suchbioplastic
as rice, corn, content
sample
and of the
preparation
tapioca. The corn,
wasrice,
measured and
performed
starch tapioca
powder using that
is thena addedare to
variety essentially
thetechniqr
of
for making
best
beaker, practices
followed the sample.
byfor
the efficientThe binding
preparationfirst stage
of the ofinthe
the sample
plasticizers, procedure on isthe
5 mL of glycerol,toandcalculate
process the appropri
sorbitol,compound
which m
are
wouldrequired
of eachbe as
starch,important plasticizers
such as rice,
accomplished for
corn,
by the sample production.
and tapioca.
following: Then, 95
The measured
weighing mL
out materialsof distilled
starch water
at powder
suitable is the
stand
istoadded to a beaker. They are combined by using a glass rod. The weighted
the beaker, followed by the preparation of the plasticizers, 5 mL of glycerol, an starch content
els, such as the starch content of the corn, rice, and tapioca that are essentially r
tol, making
for which are
the required as important
sample. The first stage plasticizers for sample
in the procedure production.
is to calculate Then, 9
the appropri
distilled water is added to a beaker. They are combined by using a glass
of each starch, such as rice, corn, and tapioca. The measured starch powder is rod. The
thew
starch
to contentfollowed
the beaker, beaker isbythen filled with the
the preparation plasticizer
of the mixture,
plasticizers, 5 mL which is then
of glycerol, an
Polymers 2023, 15, 3760 8 of 25
beaker is then filled with the plasticizer mixture, which is then quickly mixed with it using
the same glass rod to produce a turbid white solution. The magnetic hot plate device that
had been used to heat the solution is turned on. Meanwhile, the glass rod is used to stir the
solution continuously to ensure full coagulation of the solution. After reaching a paste-like
state, a basic glass plate with an aluminum foil covering is made. The paste mixture is then
distributed across the whole glass sheet plate, giving a sample a definite sheet structure
when it is allowed to cool for three to four consecutive days. Different compositions of
sample a definite sheet structure when it is allowed to cool for three to four consecutive
materials are presented in Table 1.
days. Different compositions of materials are presented in Table 1.
Table 1. Composition of the bioplastics.
Table 1. Composition of the bioplastics.
Calcium(g)
Sample No. Corn Starch (g) Rice Starch (g) Tapioca Starch (g) Glycerol (mL) Sorbitol (mL) Calcium Carbonate
Sample No. Corn Starch (g) Rice Starch (g) Tapioca Starch (g) Glycerol (mL) Sorbitol (mL)
Sample 1 16 2 12 5 0 Carbonate
0 (g)
Sample
Sample21 816 4 2 8 12 5 5 0 0 0 0
Sample
Sample32 108 4 4 4 8 5 5 0 0 2 0
Sample43
Sample 1610 2 4 8 4 5 5 0 0 4 2
Sample54
Sample 1616 6 2 8 8 0 5 5 0 0 4
Sample65
Sample 1416 2 6 4 8 0 0 5 5 0 0
Sample 6 14 2 4 0 5 0
Sample 7 17 4 8 0 5 1
Sample 7 17 4 8 0 5 1
Sample 8 12 4 4 2.5 2.5 0
Sample 8 12 4 4 2.5 2.5 0
Sample
Sample99 1616 4 4 8 8 2.5 2.5 2.5 2.5 2 2
3.1. Preparation of Rice Starch

3.1. Preparation of Rice Starch
To obtain rice starch in powder form, 1 kg of paddy rice is placed in a container with
enough To water
obtaintorice starch
cover in powder
it, and form,
the rice is 1 kg to
allowed ofsoak
paddy
forrice is placed
around 2–3 h.inThen
a container with
the mixture
enough water to cover it, and the rice is allowed to soak for around 2–3 h. Then the mixture
of rice and water is blended in a mixer grinder to obtain a semi-liquid form. To separate
of rice and water is blended in a mixer grinder to obtain a semi-liquid form. To separate
the water content and husk from this combination, by using a fine, lint-free white cloth.
the water content and husk from this combination, by using a fine, lint-free white cloth.
The dissolved starch is present in the water; thus, when the water content is dried off, the
The dissolved starch is present in the water; thus, when the water content is dried off, the
starch will be in powder form.
starch will be in powder form.
3.2.
3.2.Characterization
CharacterizationMethodsMethods
3.2.1.
3.2.1.Solubility
Solubilityin inWater
Water
In
In total,
total, nine
nine bioplastic
bioplastic sample
sample pieces
pieces totaling
totaling 1.5 cm22 were
1.5 cm were cut.
cut. ItIt isis weighed
weighed and
and
measured
measured to to determine
determine the the sample’s
sample’s starting
starting weight
weight (W(W11).).The
Thesample
sampleisisthenthensubmerged
submerged
in
in50
50mLmL of of distilled
distilled water and left there for
for 24
24 hh at
at room
roomtemperature,
temperature,as asshown
shownininFigure
Figure8.
8. The samples were removed from the water by filtering it after 24 h. The
The samples were removed from the water by filtering it after 24 h. The remaining samples remaining sam-
ples
that that
had hadbeenbeen filtered
filtered werewere dried
dried inoven
in an an oven ◦
at 85at 85 °C for
C for 24 h24before
h before
beingbeing weighed
weighed as
as the
the final
final product
product (W2(W 2). The
). The following
following formula
formula waswas
usedused to determine
to determine thethe solubility
solubility in wa-
in water:
ter:
W − W2
Solubility in water (%) = 1 × 100 (1)
Solubility in water (%) = W1 100 (1)
W11—weight
W —weightof
ofthe
theinitial
initialsample
samplein
ing,g,W
W2—weight
2 —weightof
ofthe
thedried
driedsample
sampleining.g.
Solubilityin
Figure8.8.Solubility
Figure inwater.
water.
3.2.2. Solubility in Alcohol

Nine bioplastic sample pieces totaling 1.5 cm2 were cut. It is weighed and measured to
determine the sample’s starting weight (W1). It is then submerged for 24 h at room temper-
ature in 3 mL of ethanol in a 10 mL test tube that is sealed, as depicted in Figure 9. The
Polymers 2023, 15, 3760 9 of 25
3.2.2. Solubility in Alcohol

Nine bioplastic sample pieces totaling 1.5 cm2 were cut. It is weighed and measured
to determine the sample’s starting weight (W1 ). It is then submerged for 24 h at room
temperature in 3 mL of ethanol in a 10 mL test tube that is sealed, as depicted in Figure 9.
The
thatsamples were filtered
had been extracted were
from the ethanol
dried in anafteroven
24 h by filtering
at 85 it. The
°C for 24 hremaining
before being w
samples that had been filtered were dried in an oven at 85 ◦ C for 24 h before being weighed
final
as product
the final product(W(W2). The following formula was used to determine the solubil
2 ). The following formula was used to determine the solubility
in alcohol:
Solubility inSolubility
alcohol (%) =
W1 − W2 )(%) =
in(alcohol × 100 100(2)
W1
WW 1—weight
1 —weight of theof thesample
initial initialinsample in g, of
g, W2 —weight Wthe
2—weight of in
dried sample the
g. dried sample
Figure
Figure 9. Solubility
9. Solubility in alcohol.
in alcohol.
3.2.3. Moisture Content

3.2.3. Moisture
Nine Content
bioplastic sample pieces totaling 1.5 cm2 were cut. It is weighed and measured
to determine
Ninethe sample’s starting
bioplastic sample weight (W1 ).totaling
pieces The samples
1.5were
cm2prepared in anItoven
were cut. at
is weighed
85 ◦ C for 24 h, according to Figure 10, and the final weight of the samples was calculated
to2 ).determine
(W the
The following sample’s
formula starting
was used weight
to determine the (W 1). The
moisture samples were prepared
content:
85 °C for 24 h, according to Figure 10, and the final weight of the samples
(W1 − W2)
(W2). The following formula
Moisture was
content (%)used
= to
W1
determine
× 100 the moisture content:
(3)
W1 —weight of the initial sample in g, W2 —weight

Moisture contentof (%) = sample in g. 100
the dried
3.2.4. Absorption of Water

W1—weight of the initial sample in g, W2—weight of the dried sample
All the samples of 1.5 cm2 bioplastics were dried in an oven at 85 ◦ C for 24 h. The dried
samples were then weighed and measured (W1 ). The dried samples were then submerged
for 24 h at room temperature in 50 mL of distilled water. The weight of wet samples was
weighed and measured after 24 h (W2 ). The following formula was used to determine
water absorption:
( W2 − W1 )
Absorption of water (%) = × 100 (4)
W1
W1 —weight of the initial dried sample in g, W2 —weight of the final wet sample in g.
to determine the sample’s starting weight (W1). The samples were prepared in an
85 °C for 24 h, according to Figure 10, and the final weight of the samples was cal
(W2). The following formula was used to determine the moisture content:
Moisture content (%) = 100

Polymers 2023, 15, 3760 10 of 25
W1—weight of the initial sample in g, W2—weight of the dried sample in g.
Figure 10.Bioplastic
Figure 10. Bioplastic samples.
samples.
3.2.5. Biodegradability Test

3.2.4. Absorption of Water
2
Nine samples of 1.5 cm bioplastics were weighed, and the initial weight was noted
(W1 ). All
The the samples
styrofoam cupsofare1.5
used bioplastics
cmto2 collect were
the garden dried
soil. in an oven
The samples were at 85 °C
stored at for 24
room temperature
dried samples werefor 5 days
thenafter being buried
weighed in 2 cm of damp
and measured (W1soil. Fordried
). The five days, the soilwere th
samples
needs to be
merged forkept
24moist.
h at The
room samples were takeninafter
temperature 50 five
mLdays and dried water.
of distilled for 24 h The
in an weight
oven set to 85 ◦ C [11]. The dried samples were weighed and recorded as final weight after
24 h (W2 ). The following formula was used to determine the biodegradability:
( W1 − W2 )
Biodegradability (%) = × 100 (5)
W1
W1 —weight of the initial sample in g, W2 —weight of the dried sample in g.
3.2.6. Tensile Strength

Using the universal testing machine (UTM), samples of bioplastics were tested for
tensile strength according to ASTM D638-03 standards [61]. The samples were divided
into cross sections that measured 60 mm in length by 15 mm in breadth, with a 40 mm gap
between each strip. The machine runs at a crosshead speed of 10 mm/min. Each sample’s
tensile strength was noted, and all the samples were tested.
3.2.7. Scanning Electron Microscope (SEM) Analysis

Using a scanning electron microscope (HITACHI-Japan made, Tokyo, Japan), the
morphological structure of the bioplastics samples was examined. Samples of 1.5 cm2 in
size were used, and a 62 µm emission current was used to power the gadget. For various
magnifications, the accelerating voltage of 10 kV was applied at a working distance of
9 mm. The gold was used to layer the samples before the analysis of SEM.
Polymers 2023, 15, 3760 11 of 25
3.2.8. Fourier Transform Infrared Spectroscopy (FTIR)

All samples of bioplastics were subjected to FTIR analysis using the FTIR-8400S
equipment (Shimadzu, Kyoto, Japan) with 24 scans, 1 cm−1 resolution, and wavenumbers
between 4000 cm−1 and 500 cm−1 . The peaks are obtained for the corresponding wavenum-
bers. The bonding type of molecules like O-H, C-H, and other compounds was determined
by the peaks. The spectrum in graphical form was obtained and analyzed in the results.
The graphical spectrum was obtained and examined in the outcomes.
3.2.9. Thermal Analysis

In the instrument TGA 5500, thermogravimetric analysis (TGA) was carried out. The
temperature was raised from room temperature to 400 ◦ C, while increasing by 15 ◦ C/min
for the bioplastic samples, which ranged in weight from 2.6 to 8.3 mg.
3.3. Statistical Analysis

The Grey Relational Analysis of the Taguchi method is used for the optimization
procedure. Here, components such as starch, glycerol, sorbitol, and fillers are considered.
The results from tests for solubility in water and alcohol, water absorption, moisture
content, biodegradability, and tensile strength are used to determine the outcomes. Here,
the Taguchi analysis makes use of a three-level design and L9 runs. Finding the normalizing
sequence of experimental data with a range of 0–1 is the first stage in the Grey Relational
Analysis. The values of solubility in water and alcohol, water absorption test, and moisture
content in this process all adhere to the principle of “smaller is better,” which is expressed
as follows:
maxxi (k ) − xi (k )
xi ∗ = (6)
maxxi (k) − minxi (k)
The values of biodegradability and tensile strength adhere to the principle of “bigger
is better”, which is expressed as follows:
xi (k ) − minxi (k)
xi ∗ = (7)
maxxi (k) − minxi (k)
where xi * (k) is the value following Grey Relational Generation (i = 1, 2, 3,. . .9), min xi (k)
is the least value of xi (k), max xi (k) is the greatest value of xi (k), and k = 1, 2, 3 for the
kth results. Table 2 displays the results normalization sequence and Table 3 presents the
deviation sequence.
Table 2. Normalizing sequence.
Solubility in Solubility in Absorption of Moisture Tensile

Samples Biodegradability
Water Alcohol Water Content Strength
Sample 1 0.000 0.056 0.000 0.000 0.159 0.000
Sample 2 0.361 0.000 0.876 0.306 0.512 1.000
Sample 3 0.656 0.851 0.723 0.455 0.215 0.986
Sample 4 0.484 0.125 0.746 0.156 0.360 0.736
Sample 5 0.818 0.469 0.938 0.414 0.132 0.047
Sample 6 0.401 0.447 0.166 0.651 1.000 0.716
Sample 7 0.942 0.765 1.000 0.489 0.000 0.303
Sample 8 0.330 0.804 0.008 0.781 0.215 0.541
Sample 9 1.000 1.000 0.661 0.609 0.122 0.104
Polymers 2023, 15, 3760 12 of 25
Table 3. Deviation sequence.

Sample 1 1.000 0.944 1.000 1.000 0.841 1.000
Sample 2 0.639 1.000 0.124 0.694 0.488 0.000
Sample 3 0.344 0.149 0.277 0.545 0.785 0.014
Sample 4 0.516 0.875 0.254 0.844 0.640 0.264
Sample 5 0.182 0.531 0.062 0.586 0.868 0.953
Sample 6 0.599 0.553 0.834 0.349 0.000 0.284
Sample 7 0.058 0.235 0.000 0.511 1.000 0.697
Sample 8 0.670 0.196 0.992 0.219 0.785 0.459
Sample 9 0.000 0.000 0.339 0.391 0.878 0.896
Finding the deviation sequence is necessary after calculating the normalizing sequence.
It is the difference and the reference sequence ( x 0∗ (k) compatibility sequence xi (k), and

which can be expressed as follows:
∆oi = x0∗ (k) − xi (k) (8)
where x0* (k) = 1.000.

To illustrate the link between the ideal and real normalized experimental results, the
Grey Relational Coefficient (GRC), which is derived as follows:
∆min + ψ∆max
ξi ( k ) = (9)
∆oi (k) + ψ∆max
ψ—distinguishing coefficient, which lies between 0 and 1.

Here, take as ψ = 0.5. ∆min —minimum value of deviation sequence and
∆max —maximum value of deviation sequence.
Table 4 shows the Grey Relational Coefficient. After finding the Grey Relational
Coefficient, the Grey Relational Grade is calculated by averaging the Grey Relational
Coefficient.
Table 4. Grey Relational Coefficient.

Sample 1 1.000 0.899 1.000 1.000 0.759 1.000
Sample 2 0.580 1.000 0.363 0.620 0.494 0.333
Sample 3 0.433 0.370 0.409 0.524 0.700 0.336
Sample 4 0.508 0.800 0.401 0.762 0.581 0.405
Sample 5 0.379 0.516 0.348 0.547 0.791 0.913
Sample 6 0.555 0.528 0.750 0.434 0.333 0.411
Sample 7 0.347 0.395 0.333 0.506 1.000 0.623
Sample 8 0.602 0.383 0.985 0.390 0.699 0.480
Sample 9 0.333 0.333 0.431 0.451 0.804 0.827
A greater GRG value indicates that the matching sequence is nearer to the optimal
according to the GRG results. Sample 1 has a higher GRG value, per the GRG results; thus,
it might be selected as optimal.
The Taguchi analysis in Minitab software (version 19) is then run after feeding the
causes and answers. The response table for GRG is likewise prepared after calculating the
mean of GRG for the other parameters. The rank and delta values are also provided. The
ideal graphs for GRG are produced between the factors and mean values. According to
the response table and graph, the highest-grade values for each factor are chosen, making
starch (Level 1), glycerol (Level 3), sorbitol (Level 1), and fillers (Level 1) the best choices.
Polymers 2023, 15, 3760 13 of 25
The final product is made up of a combination of 20 g of starch, 5 mL of glycerol, 0 mL of

sorbitol, and 0 g of filler. Table 5 shows the response for Grey Relational Grade. Table 6
shows the Grey Relational Grade.
Table 5. Response for Grey Relational Grade.
Level Starch Glycerol Sorbitol Filler

1 0.6567 0.5792 0.7225 0.6851
2 0.5535 0.498 0.5261 0.5338
3 0.5513 0.6844 0.5653 0.5427
Delta 0.1054 0.1864 0.1965 0.1513
Rank 4 2 1 3
Table 6. Grey Relational Grade.
Samples Grade
Sample 1 0.943
Sample 2 0.565
Sample 3 0.462
Sample 4 0.576
Sample 5 0.582
Sample 6 0.502
Sample 7 0.534
Sample 8 0.590
Sample 9 0.530
4. Results and Discussion

4.1. Solubility in Water
The interaction between the molecules of starch and the plasticizers, such as glycerol
and sorbitol, with the addition of water can be used to explain this technique of experiment.
The solubility in the water experiment yields results that improve the material’s intended
water resistance. Figure 11 can be used to explain these experiments. When compared to
other samples, like Sample 5, Sample 9, and Sample 2, Sample 1 has the widest range of
solubility in water. According to this, the sample made with the inclusion of glycerol as
a plasticizer has a higher solubility in water than the sample made with sorbitol as the
plasticizer (Sample 5).
These findings also show that Sample 7, a sample made using calcium carbonate as
filler, has a lower water solubility than the other samples. According to these findings,
glycerol is more attracted to the hydrogen bond, and because they have a lower molecular
weight than sorbitol, this occurs. The protein composition based on the starch used to
prepare the samples affects the solubility in water. These experimental findings indicate
that the sample’s solubility in water depends on the interactions between the amylose
and amylopectin contents of the starch. Previous studies have indicated that a bioplastic’s
solubility in water is influenced by the type of plasticizer [62]. The properties of these
sample findings vary depending on the amount of sorbitol, calcium carbonate, and glycerol
added as fillers.
Polymers 2023, 15, 3760 glycerol as a plasticizer has a higher solubility in water than the sample made14with
of 25 sorbito
as the plasticizer (Sample 5).
Figure11.
Figure 11.Water
Water and
and alcohol
alcohol solubility
solubility on bioplastic
on bioplastic samples.
samples.
4.2. Solubility in Alcoholalso show that Sample 7, a sample made using calcium carbonate a
These findings
These
filler, has results
a lower arewater
similarsolubility
to the features
thanofthe solubility in water and
other samples. follow theto
According results
theseoffindings
solubility in water. According to the graph shown in Figure 11, samples made
glycerol is more attracted to the hydrogen bond, and because they have a lower molecula with glycerol
as a plasticizer had a higher solubility in alcohol than samples made with sorbitol alone or
weight than sorbitol, this occurs. The protein composition based on the starch used to
in combination with both plasticizers. Sample 2 has a higher solubility in the alcohol, which
prepare
is composed the ofsamples affects
plasticizers suchtheassolubility in water.
glycerol. Samples These
8 and experimental
9 had findings
reduced solubility in indicat
that the sample’s solubility in water depends on the interactions between
alcohol since they were made by mixing glycerol and sorbitol. The solubility of a substance the amylose and
isamylopectin contents
mostly determined of the
by the starch. Previous
disappearance studies
of glycerol have indicated
or sorbitol, thatmarginally
which is only a bioplastic’s sol
ubility in water is influenced by the type of plasticizer [62]. The properties
soluble in alcohol in comparison to water due to the starch content, which is insoluble of these
in sampl
alcohol
findings at vary
ambient temperature.
depending on the amount of sorbitol, calcium carbonate, and glycerol added
The
as fillers.samples created by adding calcium carbonate as a filler produce different out-
comes. The solubility level of samples of bioplastic is reduced by the addition of fillers
like calcium carbonate. This may be demonstrated using Samples 3, 7, and 9, which were
4.2. Solubility in Alcohol
created by adding fillers such as calcium carbonate. The inclusion of fillers typically causes
These results
the material’s porosity,arewhich
similar to the itfeatures
prevents from beingof solubility
soluble in in wateraccording
alcohol and follow the result
to the
of solubility
results of earlierinstudies
water.[63].
According to the graph shown in Figure 11, samples made with
glycerol as a plasticizer had a higher solubility in alcohol than samples made with sorbito
4.3. Moisture
alone or in Content
combination with both plasticizers. Sample 2 has a higher solubility in th
alcohol, which of
The values is the moistureofcontent
composed are shown
plasticizers in Figure
such as 12 Samples
glycerol. and note 8 the moisture
and 9 had reduced
content of the prepared bioplastic samples. It was found that samples
solubility in alcohol since they were made by mixing glycerol and sorbitol.made from glycerol
The solubility
have a high moisture level, with Sample 1 having a moisture value of 29.63%. When
of a substance is mostly determined by the disappearance of glycerol or sorbitol, which i
compared to bioplastic samples made from glycerol, the sorbitol sample has a moisture
only
contentmarginally
that is lesssoluble in alcohol
than 20%, innoteworthy.
which is comparisonThisto water due tothe
is because thepresence
starch content,
of the which
is insoluble
starch in alcohol
molecules’ at ambient
long-lasting temperature.
hydrogen bonds with them will result in a lesser attraction
The samples
for water molecules. created by adding calcium carbonate as a filler produce different out
comes. The solubility level of samples of bioplastic is reduced by the addition of fillers lik
calcium carbonate. This may be demonstrated using Samples 3, 7, and 9, which were cre
ated by adding fillers such as calcium carbonate. The inclusion of fillers typically cause
the material’s porosity, which prevents it from being soluble in alcohol according to th
results of earlier studies [63].
content of the prepared bioplastic samples. It was found that samples made from glycero
have a high moisture level, with Sample 1 having a moisture value of 29.63%. When com
pared to bioplastic samples made from glycerol, the sorbitol sample has a moisture con
tent that is less than 20%, which is noteworthy. This is because the presence of the starch
Polymers 2023, 15, 3760 molecules’ long-lasting hydrogen bonds with them will result in a lesser15attraction
of 25 fo
water molecules.
Figure12.
Figure 12.Moisture
Moisture content
content andand biodegradability
biodegradability on bioplastic
samples.
Glycerol,
Glycerol, onon thethe
other hand,
other contains
hand, a hydroxyl
contains groupgroup
a hydroxyl that promotes the formation
that promotes the formation
of
of hydrogen bonds and increases the attraction of water molecules. Sample 8,was
hydrogen bonds and increases the attraction of water molecules. Sample 8, which which wa
created by combining sorbitol and glycerol to create bioplastic samples,
created by combining sorbitol and glycerol to create bioplastic samples, had the lowes had the lowest
moisture content measurement, at 6.5%; moreover, the moisture content value increased
moisture content measurement, at 6.5%; moreover, the moisture content value increased
slightly if the filler, i.e., calcium carbonate (CaCO3 ), was added to the sorbitol. It should be
slightly if the filler, i.e., calcium carbonate (CaCO3), was added to the sorbitol. It should
noted that adding a filler caused the moisture content to rise by 5%. A drop in moisture
be noted
content thatwas
value adding
seen aiffiller caused
the filler wasthealsomoisture
added tocontent to rise
the glycerol by 5%.
at the sameAtime.
dropThe
in moistur
content content
moisture value was valueseen if theby
increased filler was also
5% when added
the filler was to the to
added glycerol at the
the mixture same time. Th
of glycerol
moisture
and sorbitol.content value increased
Such outcomes were seen byin5% when
earlier the filler
research wasasadded
studies to the mixture of glyc
well [64].
erol and sorbitol. Such outcomes were seen in earlier research studies as well [64].
4.4. Biodegradability Test
4.4. The physiochemical
Biodegradability Testcharacteristics of a bioplastic sample, such as its chemical struc-
ture, affinity for water, molecular weight, and others, determine its biodegradability. With-
out theTheusephysiochemical characteristics
of fillers, it has been observed thatof abiodegradation
bioplastic sample, will such as its chemical
rise. There will be struc
ture, affinity for water, molecular weight, and others, determine
a decrease in the percentage of biodegradability when the fillers are added. It has been its biodegradability
Without the
discovered thatuse
theofmixture
fillers,ofit sorbitol
has been observed
and that biodegradation
glycerol-based samples (Sample will rise.a There
8) has high will b
a decrease
capacity in the percentage
for biodegradation due toofthe
biodegradability
samples’ affinity when the Half
for water. fillers are samples’
of the added. It ca-has been
pacity to degrade
discovered thatwhen combined
the mixture of with theseand
sorbitol plasticizers is reduced
glycerol-based when fillers
samples are added
(Sample 8) has a high
(Sample
capacity9),for
as depicted in Figuredue
biodegradation 12. Both
to thebiodegradation
samples’ affinity and oxidation
for water.are supported
Half of the bysamples
natural fillers. Following a previous study, the amount of filler increased
capacity to degrade when combined with these plasticizers is reduced when fillers ar the biodegradation
(weight loss percentage) of biocomposites, and that increase was proportional to the filler’s
added (Sample 9), as depicted in Figure 12. Both biodegradation and oxidation are sup
amount [65].
ported by natural fillers. Following a previous study, the amount of filler increased th
But when samples are made using sorbitol, fillers do not impact how quickly they
biodegradation
degrade. (weight
An increased filler loss
weightpercentage) ofabiocomposites,
will result in modest improvement and inthat increase was propor
biodegradability,
tional to the filler’s amount [65].
which also applies to Sample 4. Sample 3 has an extremely poor biodegradation capacity,
with a 25.73% score. It can be the result of the sparing use of fillers. These findings support
the notion that prepared samples have higher biodegradability.
But when samples are made using sorbitol, fillers do not impact how quickly the
degrade. An increased filler weight will result in a modest improvement in biodegrada
bility, which also applies to Sample 4. Sample 3 has an extremely poor biodegradatio
capacity, with a 25.73% score. It can be the result of the sparing use of fillers. These find
Polymers 2023, 15, 3760 ings support the notion that prepared samples have higher biodegradability. 16 of 25
4.5. Absorption of Water

Prepared
4.5. Absorption of bioplastic
Water samples have a significant absorption value that has an impact o
the Prepared
probability and of samples
bioplastic the samples.
have aFigure 13, for
significant example,
absorption in Sample
value that has1,anthe values
impact onshow th
the probability
highest rangeand of theinvolving
despite samples. Figure 13, for
glycerol as aexample, in Sample 1,
main plasticizer, the values
which show
induces thethe
composit
highest
starch range despite
particles thatinvolving glycerol
are closely as atogether.
bound main plasticizer, whichthe
Observing induces
compositethe composite
starch, the cor
starch
starchparticles
(1/3rd ofthat areweight)
total closely bound
has an together.
intensiveObserving the composite
rate of retentivity towards starch,
the the corn becaus
glycerol
starch (1/3rd of total weight) has an intensive rate of retentivity towards the glycerol
of the presence of amylose (a straight chain glucose molecule) and amylopectin (a com
because of the presence of amylose (a straight chain glucose molecule) and amylopectin
pounding polysaccharide structure, which enables correlation and continues chain bondin
(a compounding polysaccharide structure, which enables correlation and continues chain
of glucose
bonding molecules)
of glucose these two
molecules) thesepolymers
two polymersare responsible where
are responsible where these glucose
these glucosemolecule
are broken down it enables easy permeation of water. Similar findings
molecules are broken down it enables easy permeation of water. Similar findings were were made in th
earlier
made work
in the when
earlier workit was
whenshown that adding
it was shown sorghum
that adding sorghumstalk filler
stalk totoa abioplastic
filler bioplastic made o
sorghum
made starch starch
of sorghum increased the amount
increased of water
the amount thatthat
of water waswas
absorbed
absorbed [66].
[66].
Figure13.13.
Figure Absorption
Absorption of water
of water on bioplastic
samples.
Because
Becausesorbitol is a is
sorbitol significant plasticizer,
a significant the coagulation
plasticizer, and binding
the coagulation andofbinding
the compo-
of the com
nents occur well, and the contents exhibit less porosity, eliminating the inclusion
ponents occur well, and the contents exhibit less porosity, eliminating the inclusion of pores In o
Sample 7 the absorption value is the lowest of all of them. When both plasticizers are added,
pores In Sample 7 the absorption value is the lowest of all of them. When both plasticizer
the amount of calcium carbonate acts as a filler, which reduces the rate of absorptivity.
are added, the amount of calcium carbonate acts as a filler, which reduces the rate of ab
Samples 8 and 9 shows high and low values despite the contexts of starch proportions
sorptivity.
being Samples
the same, whereas 8 and 9 shows
the filler high and
on Sample 9, in low values
a small despite
amount, thecharacterize
would contexts ofthe starch pro
portions
least value.being the same, whereas the filler on Sample 9, in a small amount, would char
acterize the least value.
4.6. Tensile Strength
4.6. For use in
Tensile food packaging, it was crucial to examine the tensile strength of the bioplastic
Strength
samples. The tensile strength values for the bioplastic samples are shown in Figure 14. The
For use in food packaging, it was crucial to examine the tensile strength of the bio
tensile strength of the produced bioplastic samples was determined using the universal
plastic samples. The tensile strength values for the bioplastic samples are shown in Figur
testing machine. It was found that the plasticizers affect the manufactured bioplastic
14. The tensile
samples’ tensilestrength.
strengthWhen
of the produced
compared to abioplastic samples
sample made was determined
from sorbitol without theusing th
inclusion of fillers, the bioplastic samples made from glycerol have a lower tensile strength.
The bioplastic sample made from glycerol is found to have a maximum tensile strength
universal testing machine. It was found that the plasticizers affect the manufactured bio-
plastic samples’ tensile strength. When compared to a sample made from sorbitol without
Polymers 2023, 15, 3760 17 of 25
the inclusion of fillers, the bioplastic samples made from glycerol have a lower tensile
strength. The bioplastic sample made from glycerol is found to have a maximum tensile
strength of 7.38 MPa (Sample 2). When molecular interactions and hydrogen bonding de-
of 7.38 MPa (Sample 2). When molecular interactions and hydrogen bonding develop,
velop, the maximum tensile strength of the bioplastic sample made from sorbitol is found
the maximum tensile strength of the bioplastic sample made from sorbitol is found to be
to be 13.612 MPa (Sample
13.612 MPa (Sample 6).found
6). It was It wasthat
found that
adding adding
fillers fillersthe
improved improved the tensile
tensile strength of thestrength
of the bioplastic
bioplastic samplessamples proportionately.
proportionately. Similarwere
Similar findings findings were
obtained obtained
from from
an earlier studyan earlier
study
on theon the tensile
tensile strengthstrength of bioplastics
of bioplastics made frommadestarchfrom
[67]. starch [67].
14. Tensile
Figure 14.
Figure TensileStrength
Strengthonon
bioplastic samples.
bioplastic samples.
The inclusion of fillers, such as calcium carbonate (CaCO3 ), has an impact on the
The inclusion of fillers, such as calcium carbonate (CaCO 3), has an impact on the bi-
bioplastic sample’s tensile strength as well. It was discovered that the glycerol’s tensile
oplastic sample’s when
strength improved tensile strength
CaCO as well. It was discovered that the glycerol’s tensile
3 was added. The sorbitol’s tensile strength was decreased
strength improved when CaCO
when CaCO3 was introduced. The sorbitol 3 was added.
with The sorbitol’s
calcium tensile
carbonate (CaCOstrength was decreased
3 ) sample was
when CaCOto3 have
determined was the
introduced. Thestrength
lowest tensile sorbitolvalue,
withmeasuring
calcium carbonate (CaCO7).
0.85 MPa (Sample 3) sample
Both was
determined to have
plasticizers will affectthe
thelowest
tensile tensile
strengthstrength value,
of a sample measuring
when 0.85 MPa
they are mixed. (Sample
Better tensile7). Both
strength waswill
plasticizers produced.
affect The
the addition of calcium
tensile strength ofcarbonate
a samplewas found
when to have
they decreased
are mixed. the tensile
Better
tensile strength
strength (CaCO3 ). Also,
was produced. it was found
The addition that when
of calcium the starchwas
carbonate levelfound
rose, the samples’
to have decreased
ability to withstand tensile stress decreased. The samples made from glycerol
the tensile strength (CaCO3). Also, it was found that when the starch level rose, the sam- were also
substantially more flexible than those made from sorbitol.
ples’ ability to withstand tensile stress decreased. The samples made from glycerol were
also substantially
4.7. Scanning more
Electron flexible(SEM)
Microscope than those made from sorbitol.
SEM photographs on a composite proportion of nine samples are shown in Figure 15.
4.7.
On Scanning
analyzingElectron Microscope
these samples (SEM)
through SEM, it is inferred that all the samples that are
produced
SEM have been well-coagulated,
photographs on a composite thereby eliminating
proportion ofthe risks
nine of inducing
samples fine holes,
are shown in Figure
cracks, and disintegrated particles. The composite starch (Figure 15, samples
15. On analyzing these samples through SEM, it is inferred that all the samples that are1–9) contents
are dispersed well, with plasticizers showing that a proper homogenous distribution would
produced have been well-coagulated, thereby eliminating the risks of inducing fine holes,
increase its surface integrity and smoothness. Plasticizers like glycerol and sorbitol provide
cracks, and disintegrated particles. The composite starch (Figure 15, samples 1–9) contents
enough bonding attraction on the fine coarseness of starch, unlike sorbitol, using glycerol
are
useddispersed
to have morewell, with plasticizers
permeability; moreover, showing that the
this enables a proper
sample homogenous distribution
to accumulate more
would
capacityincrease
and spaceitsthan
surface integrity
its original and
size on smoothness.
exposed to thePlasticizers
environment. like glycerol and sorbitol
provide enough bonding attraction on the fine coarseness of starch, unlike sorbitol, using
glycerol used to have more permeability; moreover, this enables the sample to accumulate
more capacity and space than its original size on exposed to the environment.
Polymers 2023, 15, 3760 18 of 25
Figure 15. Scanning electron microscope results for various bioplastic samples (S1–30% starch, 5%
Figure 15. Scanning electron microscope results for various bioplastic samples (S1–30% starch, 5%
glycerol, S2–20% starch, 5% glycerol, S3–18% starch, 5% glycerol, S4–26% starch, 5% glycerol, S5–
glycerol, S2–20%
30% starch, starch, 5%
5% sorbitol, glycerol,
S6–20% S3–18%
starch, starch, 5%
5% sorbitol, glycerol,
S7–29% S4–26%
starch, starch, S8–20%
5% sorbitol, 5% glycerol, S5–30%
starch, 2.5%
starch, 5% sorbitol,
of glycerol S6–20%
and sorbitol, starch,
S9–30% 5% sorbitol,
starch, S7–29% starch,
2.5% of glycerol 5% sorbitol, S8–20% starch, 2.5% of
and sorbitol).
glycerol and sorbitol, S9–30% starch, 2.5% of glycerol and sorbitol).
A percentage increase (1–2 g) in addition to calcium carbonate (Figure 15, Sample 3,
A percentage increase (1–2 g) in addition to calcium carbonate (Figure 15, Sample
Sample 4, Sample 7, Sample 9) from the overall percentage of components (20–30 g) in-
3, Sample 4, Sample 7, Sample 9) from the overall percentage of components (20–30 g)
creases ductility on the sample and shows reduced thickness and leaves more suspended
increases ductility on the sample and shows reduced thickness and leaves more suspended
particles. Besides the contrast towards thickness, the sorbitol-prepared sample (Figure 15,
particles. Besides the contrast towards thickness, the sorbitol-prepared sample (Figure 15,
Sample 5, Sample 6, Sample 7) eliminates water inclusion because of having better bond-
Sample 5, Sample 6, Sample 7) eliminates water inclusion because of having better bonding
ing on the composite material, which prevents permeability. Similar types of morphology
on the composite material, which prevents permeability. Similar types of morphology
have also been discovered in earlier investigations [28]. Abnormal bulges on the samples
have also been discovered in earlier investigations [28]. Abnormal bulges on the samples
(Figure 15, Sample 5, Sample 7, Sample 9) clearly shows that adequate mixing at continu-
(Figure 15, Sample 5, Sample 7, Sample 9) clearly shows that adequate mixing at continuous
ous interval enables the formation of microbubbles onto the samples, which reflects in an
uneven suspension of starch particles.
Polymers 2023, 15, 3760 19 of 25

interval enables the formation of microbubbles onto the samples, which reflects in an
uneven suspension of starch particles.
4.8.
4.8.Fourier
FourierTransmission
Transmission Infrared
Infrared Spectroscopy
Spectroscopy (FT–IR)
(FT–IR)
Based
Basedononthe
thesubstances
substancesgiven,
given,this
thisexperiment
experimentdemonstrates
demonstrateshow howseveral
severalfunctional
functional
groups
groups can
can exist.
exist. Based
Basedononthe
theplasticizers
plasticizersadded
addedto
tothe
thesamples,
samples,such suchasas glycerol
glycerol and
and
sorbitol,
sorbitol, as well as their combined nature, the graphical depiction has been categorizedas
as well as their combined nature, the graphical depiction has been categorized as
shown
shownin inFigures
Figures16–18.
16–18.Samples
Samples1,1,2,2,3,3,and
and44were
wereplasticized
plasticizedusing
usingglycerol,
glycerol,and
andwhen
when
compared, −1 − 1 reflect
compared,the thedistinctive
distinctivepeaks
peaksbetween
between3250 3250and
and3550
3550cm
cm reflect thethe
O-H stretching
O-H of
stretching
the alcohol
of the group.
alcohol Similar
group. peaks
Similar havehave
peaks also also
beenbeen
observed in samples
observed of starch-based
in samples bio-
of starch-based
plastic in earlier
bioplastic studies
in earlier [68].[68].
studies
Figure
Figure16.
16.FT−IR
FT−IRresults
resultsononsamples
samplesplasticized
plasticizedusing
usingglycerol.
glycerol.
These peaks show that the samples include glycerol, which has a hydroxyl group.
C-O-H groups can be seen at the level where between 1624 cm−1 and 1759 cm−1 pass from
one to the other. The peaks between 2883 cm−1 and 3000 cm−1 indicate the presence of
the C-H stretching group. The inclusion of starch has led to the presence of these groups.
These would resemble the samples that had been plasticized with glycerol.
The existence of the C=O=H group is indicated by the similar characteristic peaks
over Sample 2, Sample 7, and Sample 8 between 2350 cm−1 and 2500 cm−1 . This could be
brought on by the samples’ content of rice starch. The comparison of the graph’s fingerprint
area matches the distinctive qualities of the various plasticizers employed in the samples.
These findings would enable us to categorize the various functional groups based on the
components of the bioplastic samples.
Figure 17. FT−IR results on samples plasticized using sorbitol.

Polymers 2023, 15, 3760 20 of 25
Figure 16. FT−IR results on samples plasticized using glycerol.
Figure 17.
Figure FT−IRresults
17. FT−IR resultson
onsamples
samplesplasticized
plasticizedusing
usingsorbitol.
sorbitol.
Figure 18. FT−IR results on samples plasticized using glycerol and sorbitol.
Figure 18. FT−IR results on samples plasticized using glycerol and sorbitol.
4.9. Thermal Analysis
These peaks show of
The degradation that
thethe samplessamples
bioplastic include happened
glycerol, which
in threehasstages,
a hydroxyl
at 130 group.
◦ C, 290C-
◦ C,
O-H groups
◦ can be seen at the level where between 1624 cm −1 and 1759 cm−1 pass from one
and 390 C, as indicated by the graphs of the thermal analysis of the various compositions
toofthe
theother. The peaks
generated between
bioplastic 2883 according
samples cm−1 and 3000 cm−1 indicate
to Figures the presence
19–21. The of the
plasticizers C-H
(glycerol
stretching group. The inclusion of starch◦ has led to the presence of these
and sorbitol) start to evaporate at 220 C and are completely evaporated at 290 C. The groups. ◦These
would
entireresemble the samples
decomposition that had been
of the bioplastics plasticized
occurred with220
between glycerol.
◦ C and 390 ◦ C. It is observed
thatThe
the existence
evaporationof the C=O=H of
of moisture group is indicated
the bioplastics by the
made the similar at 130 ◦ C. peaks
characteristic
first stage
over Sample 2, Sample 7, and Sample 8 between 2350 cm and 2500 cm−1. This could be
−1
brought on by the samples’ content of rice starch. The comparison of the graph’s finger-
print area matches the distinctive qualities of the various plasticizers employed in the
samples. These findings would enable us to categorize the various functional groups
based on the components of the bioplastic samples.
4.9. Thermal Analysis

Polymers 2023, 15, 3760 21 of 25
Figure 19.
19. TGA
Figure19. TGA curves
curves for
for samples
samples prepared
prepared using
using glycerol.
glycerol.
Figure
Figure 19.TGA curves
TGA for samples
curves prepared
for samples using glycerol.
prepared using glycerol.
Figure
Figure 20.
Figure20.
20. TGA
TGA
TGA curves
curves for
for samples
for samples
curves prepared
prepared
samples using
using sorbitol.
using sorbitol.
prepared sorbitol.
Figure 20. TGA curves for samples prepared using sorbitol.
Figure 21.
Figure TGA curves samples prepared using glycerol and sorbitol.
Figure 21.
21. TGA
TGA curves
curves samples
samples prepared
prepared using
using glycerol
glycerol and
and sorbitol.
sorbitol.
Figure 21. TGA curves samples prepared using glycerol and sorbitol.
This is due to the evaporation of the water. The acquired breakdown graphs revealed
5.
5. Conclusions
that 50% of weight reduction occurs at 315 ◦ C for the glycerol-based Sample 2. The graph
Conclusions
5. Conclusions
showsComposite
a progressive decline in weight between 220 ◦two
C and 350 ◦ C. The temperature of
◦ Composite samples
samples are
are prepared
prepared using
using two different
different starch
starch concentration
concentration ra ra
308 CComposite
causes a 50%samples
weight drop for
are the glycerol
prepared with CaCO
using two 3 Sample 4.starch
different For sorbitol-based
concentration ra
g, 40 g) in order to consolidate the samples in accordance with the
g, 40 g) in order to consolidate the samples in accordance with the test results. Thtest results. Th
g, 40 g) in order to samples
ulated consolidate the samples in accordanceproperties
with the test results. Th
ulated compounds
compounds samples possesspossess adequate
adequate mechanical
mechanical properties like like withstand
withstand
ulated
tensile compounds samples possess adequate mechanical propertiesundergoing
like withstand
tensile strength
strength at
at aa desired
desired level
level and
and the
the capability
capability ofof the
the samples
samples undergoing 40 40
tensile strength at aanalysis.
thermogravimetric desired level
The and the capability
following conclusionsof the samples
were drawn undergoing
from the 40
resu
thermogravimetric analysis. The following conclusions were drawn from the resu
thermogravimetric analysis. The following conclusions were drawn from the resu
Polymers 2023, 15, 3760 22 of 25
samples (Sample 6), a weight decreases of 50% occurs at 316 ◦ C. According to the research,
weight loss occurs in three stages, which are more comparable to the present study [27].
The obtained results showed that 2–70% of weight reduction occurred in 45–332 ◦ C.
In total, 50% of weight reduction occurs at the temperature of 321 ◦ C for the combination
of glycerol and sorbitol-based samples (Sample 9). The decomposition temperature of the
bioplastics is nearly 390 ◦ C. From this, it could be concluded that the prepared bioplastics
samples are suitable for temperatures below 390 ◦ C.
5. Conclusions
Composite samples are prepared using two different starch concentration ratios
(30 g, 40 g) in order to consolidate the samples in accordance with the test results. The
coagulated compounds samples possess adequate mechanical properties like withstanding
the tensile strength at a desired level and the capability of the samples undergoing 400 ◦ C
on thermogravimetric analysis. The following conclusions were drawn from the results.
• The scanning electron microscope image specifications show the compound binding
nature and pores permeability for water inclusion. Though the characterizations of
these samples are explicit to high and low of varying nature based on aggregating all
these values of their results, S4 shows an acceptable proportion as in the best sample,
ensuring the optimal signs for product development;
• Functional groups and potential chemical changes brought on by the addition of
plasticizers and fillers were identified using the FTIR analysis. All of the bioplas-
tic samples that were analyzed showed the characteristic peaks between 2925 and
3011 cm−1 , indicating = C-H stretching, which is caused by the presence of starch;
• Maximum tensile strength of 13.612 MPa was achieved by Sample 6 with sorbitol
bioplastic due to molecular interactions and hydrogen bonds. When calcium carbonate
was added, the tensile strength decreased. Furthermore, the samples’ ability to resist
tensile stress decreased with increasing starch content. In addition, the glycerol-based
samples were much more flexible than those containing sorbitol;
• The corn concentration and glycerol help in the easy binding of other compounds and
enable strength. Some ratios need to be at a level that is predictive of lower values,
even while the sample needs better findings to be used and implemented. Examples
of such constraints are a lower degradation rate and a greater water absorptivity level.
Commercialized packaging will be impacted by the development of bio-based plastic
applications as substitutes for food packaging. By doing so, it would be clear that these
results would have an impact on large-scale manufacturing. The effects of additional
plasticizers on the mechanical properties of the created bioplastics may be investigated in
further studies. Finding effective fabrication techniques is a potential additional area of
attention for this work.
Author Contributions: Conceptualization, R.J.H.N.; methodology, M.K.G.; validation, M.K.G. and

M.P.N.; investigation, R.J.H.N. and J.B.K.; resources, R.J.H.N.; writing—original draft preparation,
M.K.G. and R.J.H.N.; writing—review and editing, M.P.N. and J.B.K.; supervision, R.J.H.N. and J.B.K.;
project administration, M.P.N.; funding acquisition, M.P.N. All authors have read and agreed to the
published version of the manuscript.
Funding: This publication is developed with the support of Project BG05M2OP001-1.001-0004 UNITe,
funded by the Operational Programme “Science and Education for Smart Growth”, co-funded by the
European Union through the European Structural and Investment Funds.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Acknowledgments: Author N.R.J. acknowledge the support of Ulam NAWA Postdoctoral Fellowship
of the Polish National Agency for Academic Exchange programme, Contract No Agreement no.
BPN/ULM/2022/1/00133/U/00001.
Conflicts of Interest: The authors declare no conflict of interest.
Polymers 2023, 15, 3760 23 of 25
References
1. Khalid, M.Y.; Arif, Z.U.; Ahmed, W.; Arshad, H. Recent Trends in Recycling and Reusing Techniques of Different Plastic Polymers
and Their Composite Materials. Sustain. Mater. Technol. 2022, 31, e00382. [CrossRef]
2. Khalid, M.Y.; Arif, Z.U.; Hossain, M.; Umer, R. Recycling of Wind Turbine Blades through Modern Recycling Technologies: A
Road to Zero Waste. Renew. Energy Focus 2023, 44, 373–389. [CrossRef]
3. Arif, Z.U.; Khalid, M.Y.; Sheikh, M.F.; Zolfagharian, A.; Bodaghi, M. Biopolymeric Sustainable Materials and Their Emerging
Applications. J. Environ. Chem. Eng. 2022, 10, 108159. [CrossRef]
4. Abraham, A.; Park, H.; Choi, O.; Sang, B.I. Anaerobic Co-Digestion of Bioplastics as a Sustainable Mode of Waste Management
with Improved Energy Production—A Review. Bioresour. Technol. 2021, 322, 124537. [CrossRef]
5. Ebrahimzade, I.; Ebrahimi-Nik, M.; Rohani, A.; Tedesco, S. Towards Monitoring Biodegradation of Starch-Based Bioplastic in
Anaerobic Condition: Finding a Proper Kinetic Model. Bioresour. Technol. 2022, 347, 126661. [CrossRef] [PubMed]
6. Fredi, G.; Dorigato, A. Recycling of Bioplastic Waste: A Review. Adv. Ind. Eng. Polym. Res. 2021, 4, 159–177. [CrossRef]
7. Gurunathan, M.K.; Hynes, N.R.J.; Al-Khashman, O.A.; Brykov, M.; Ganesh, N.; Ene, A. Study on the Impact and Water Absorption
Performance of Prosopis Juliflora & Glass Fibre Reinforced Epoxy Composite Laminates. Polymers 2022, 14, 2973. [CrossRef]
8. Sankaranarayanan, R.; Rajesh Jesudoss Hynes, N.; Senthamarai Kannan, P.; Khan, A.; Asiri, A.M. Mechanical Behavior of
Self-Healing Polyethylenimine/Polyacrylic Acid Multilevel Polymer Films. In Self-Healing Composite Materials: From Design to
Applications; Woodhead Publishing: Sawston, UK, 2019.
9. Kumar, R.; Rajesh Jesudoss Hynes, N.; Senthamaraikannan, P.; Khan, A.; Rangappa, S.M.; Siengchin, S.; Sundara Bharathi, S.R.;
Asiri, A.M.; Khan, I. Self-Repairing Fiber Polymer Composites: Mechanisms and Properties. In Self-Healing Composite Materials:
From Design to Applications; Woodhead Publishing: Sawston, UK, 2019.
10. Khalid, M.Y.; Al Rashid, A.; Arif, Z.U.; Ahmed, W.; Arshad, H. Recent Advances in Nanocellulose-Based Different Biomaterials:
Types, Properties, and Emerging Applications. J. Mater. Res. Technol. 2021, 14, 2601–2623. [CrossRef]
11. Shafqat, A.; Al-Zaqri, N.; Tahir, A.; Alsalme, A. Synthesis and Characterization of Starch Based Bioplatics Using Varying
Plant-Based Ingredients, Plasticizers and Natural Fillers. Saudi J. Biol. Sci. 2021, 28, 1739–1749. [CrossRef]
12. Alonso-González, M.; Felix, M.; Romero, A. Influence of the Plasticizer on Rice Bran-Based Eco-Friendly Bioplastics Obtained by
Injection Moulding. Ind. Crops Prod. 2022, 180, 114767. [CrossRef]
13. Atiwesh, G.; Mikhael, A.; Parrish, C.C.; Banoub, J.; Le, T.A.T. Environmental Impact of Bioplastic Use: A Review. Heliyon 2021,
7, E07918. [CrossRef] [PubMed]
14. Alonso-González, M.; Felix, M.; Guerrero, A.; Romero, A. Rice Bran-Based Bioplastics: Effects of the Mixing Temperature on
Starch Plastification and Final Properties. Int. J. Biol. Macromol. 2021, 188, 932–940. [CrossRef] [PubMed]
15. Henning, F.G.; Ito, V.C.; Demiate, I.M.; Lacerda, L.G. Non-Conventional Starches for Biodegradable Films: A Review Focussing
on Characterisation and Recent Applications in Food Packaging. Carbohydr. Polym. Technol. Appl. 2022, 4, 100157. [CrossRef]
16. Alves, J.S.; Dos Reis, K.C.; Menezes, E.G.T.; Pereira, F.V.; Pereira, J. Effect of Cellulose Nanocrystals and Gelatin in Corn Starch
Plasticized Films. Carbohydr. Polym. 2015, 115, 215–222. [CrossRef] [PubMed]
17. Babaremu, K.; Oladijo, O.P.; Akinlabi, E. Biopolymers: A Suitable Replacement for Plastics in Product Packaging. Adv. Ind. Eng.
Polym. Res. 2023, in press. [CrossRef]
18. Fakhoury, F.M.; Maria Martelli, S.; Canhadas Bertan, L.; Yamashita, F.; Innocentini Mei, L.H.; Collares Queiroz, F.P. Edible
Films Made from Blends of Manioc Starch and Gelatin—Influence of Different Types of Plasticizer and Different Levels of
Macromolecules on Their Properties. LWT 2012, 49, 149–154. [CrossRef]
19. Shaikh, S.; Yaqoob, M.; Aggarwal, P. An Overview of Biodegradable Packaging in Food Industry. Curr. Res. Food Sci. 2021, 4,
503–520. [CrossRef]
20. Bishop, G.; Styles, D.; Lens, P.N.L. Environmental Performance Comparison of Bioplastics and Petrochemical Plastics: A Review
of Life Cycle Assessment (LCA) Methodological Decisions. Resour. Conserv. Recycl. 2021, 168, 105451. [CrossRef]
21. Morreale, M.; Scaffaro, R.; Maio, A.; La Mantia, F.P. Effect of Adding Wood Flour to the Physical Properties of a Biodegradable
Polymer. Compos. Part. A Appl. Sci. Manuf. 2008, 39, 503–513. [CrossRef]
22. Khalid, M.Y.; Imran, R.; Arif, Z.U.; Akram, N.; Arshad, H.; Al Rashid, A.; Márquez, F.P.G. Developments in Chemical Treatments,
Manufacturing Techniques and Potential Applications of Natural-Fibers-Based Biodegradable Composites. Coatings 2021, 11, 293.
[CrossRef]
23. Jõgi, K.; Bhat, R. Valorization of Food Processing Wastes and By-Products for Bioplastic Production. Sustain. Chem. Pharm. 2020,
18, 100326. [CrossRef]
24. Pruncu, C.I.; Vladescu, A.; Hynes, N.R.J.; Sankaranarayanan, R. Surface Investigation of Physella Acuta Snail Shell Particle
Reinforced Aluminium Matrix Composites. Coatings 2022, 12, 794. [CrossRef]
25. Amin, M.R.; Chowdhury, M.A.; Kowser, M.A. Characterization and Performance Analysis of Composite Bioplastics Synthesized
Using Titanium Dioxide Nanoparticles with Corn Starch. Heliyon 2019, 5, E02009. [CrossRef] [PubMed]
26. Sankaranarayanan, R.; Hynes, N.R.J.; Li, D.; Chrysanthou, A. Electromagnetic Riveting Technique of Joining Metals to Polymer
Composites in Hybrid Multi-Material Aerospace Structures. Trans. Indian Inst. Met. 2021, 74, 2909–2924. [CrossRef]
27. Gómez-Heincke, D.; Martínez, I.; Stading, M.; Gallegos, C.; Partal, P. Improvement of Mechanical and Water Absorption Properties
of Plant Protein Based Bioplastics. Food Hydrocoll. 2017, 73, 21–29. [CrossRef]
Polymers 2023, 15, 3760 24 of 25
28. Yang, J.; Dong, X.; Wang, J.; Ching, Y.C.; Liu, J.; Chunhui, L.; Baikeli, Y.; Li, Z.; Mohammed Al-Hada, N.; Xu, S. Synthesis and
Properties of Bioplastics from Corn Starch and Citric Acid-Epoxidized Soybean Oil Oligomers. J. Mater. Res. Technol. 2022, 20,
373–380. [CrossRef]
29. Chowdhury, M.A.; Hossain, N.; Badrudduza, M.D.; Rana, M.M. Development and Characterization of Natural Sourced Bioplastic
for Food Packaging Applications. Heliyon 2023, 9, E13538. [CrossRef]
30. Ollé Resa, C.P.; Jagus, R.J.; Gerschenson, L.N. Effect of Natamycin, Nisin and Glycerol on the Physicochemical Properties,
Roughness and Hydrophobicity of Tapioca Starch Edible Films. Mater. Sci. Eng. C 2014, 40, 281–287. [CrossRef]
31. Asrofi, M.; Sapuan, S.M.; Ilyas, R.A.; Ramesh, M. Characteristic of Composite Bioplastics from Tapioca Starch and Sugarcane
Bagasse Fiber: Effect of Time Duration of Ultrasonication (Bath-Type). Mater. Today Proc. 2020, 46, 1626–1630. [CrossRef]
32. Zoungranan, Y.; Lynda, E.; Dobi-Brice, K.K.; Tchirioua, E.; Bakary, C.; Yannick, D.D. Influence of Natural Factors on the
Biodegradation of Simple and Composite Bioplastics Based on Cassava Starch and Corn Starch. J. Environ. Chem. Eng. 2020,
8, 104396. [CrossRef]
33. Méité, N.; Konan, L.K.; Tognonvi, M.T.; Doubi, B.I.H.G.; Gomina, M.; Oyetola, S. Properties of Hydric and Biodegradability of
Cassava Starch-Based Bioplastics Reinforced with Thermally Modified Kaolin. Carbohydr. Polym. 2021, 254, 117322. [CrossRef]
[PubMed]
34. Iriani, E.S.; Sunarti, T.C.; Richana, N.; Mangunwidjaja, D.; Hadiyoso, A. Utilization of Corn Hominy as a New Source Material for
Thermoplastic Starch Production. Procedia Chem. 2012, 4, 245–253. [CrossRef]
35. Wang, B.; Gao, W.; Kang, X.; Dong, Y.; Liu, P.; Yan, S.; Yu, B.; Guo, L.; Cui, B.; Abd El-Aty, A.M. Structural Changes in Corn Starch
Granules Treated at Different Temperatures. Food Hydrocoll. 2021, 118, 106760. [CrossRef]
36. Vignesh, N.J.; Velu, P.S.; Hynes, N.R.J. Physicochemical Analysis of Biobased Composites. In Biobased Composites: Processing,
Characterization, Properties, and Applications; John Wiley & Sons, Inc.: Hoboken, NJ, USA, 2021.
37. Shanmathy, M.; Mohanta, M.; Thirugnanam, A. Development of Biodegradable Bioplastic Films from Taro Starch Reinforced with
Bentonite. Carbohydr. Polym. Technol. Appl. 2021, 2, 100173. [CrossRef]
38. Behera, L.; Mohanta, M.; Thirugnanam, A. Intensification of Yam-Starch Based Biodegradable Bioplastic Film with Bentonite for
Food Packaging Application. Env. Technol. Innov. 2022, 25, 102180. [CrossRef]
39. Vieira, M.G.A.; Da Silva, M.A.; Dos Santos, L.O.; Beppu, M.M. Natural-Based Plasticizers and Biopolymer Films: A Review. Eur.
Polym. J. 2011, 47, 254–263. [CrossRef]
40. Yusoff, N.H.; Pal, K.; Narayanan, T.; de Souza, F.G. Recent Trends on Bioplastics Synthesis and Characterizations: Polylactic Acid
(PLA) Incorporated with Tapioca Starch for Packaging Applications. J. Mol. Struct. 2021, 1232, 129954. [CrossRef]
41. Razzaq, H.A.A.; Pezzuto, M.; Santagata, G.; Silvestre, C.; Cimmino, S.; Larsen, N.; Duraccio, D. Barley β-Glucan-Protein Based
Bioplastic Film with Enhanced Physicochemical Properties for Packaging. Food Hydrocoll. 2016, 58, 276–283. [CrossRef]
42. Velu, P.S.; Vignesh, N.J.; Hynes, N.R.J. Processing Methods for Manufacture of Biobased Composites. In Biobased Composites:
Processing, Characterization, Properties, and Applications; John Wiley & Sons, Inc.: Hoboken, NJ, USA, 2021.
43. Gonzalez-Gutierrez, J.; Partal, P.; Garcia-Morales, M.; Gallegos, C. Development of Highly-Transparent Protein/Starch-Based
Bioplastics. Bioresour. Technol. 2010, 101, 2007–2013. [CrossRef]
44. Martínez, I.; Partal, P.; García-Morales, M.; Guerrero, A.; Gallegos, C. Development of Protein-Based Bioplastics with Antimicrobial
Activity by Thermo-Mechanical Processing. J. Food Eng. 2013, 117, 247–254. [CrossRef]
45. Kumar, R.; Rajesh Jesudoss Hynes, N.; Saravanakumar, S.S.; Senthamaraikannan, P.; Khan, A.; Asiri, A.M.; Khan, I.; Khan, M.M.A.;
Nagarajan, S. Concept of Self-Repair and Efficiency Measurement in Polymer Matrix Composites. In Self-Healing Composite
Materials: From Design to Applications; Woodhead Publishing: Sawston, UK, 2019.
46. Dintcheva, N.T.; La Mantia, F.P. Durability of a Starch-Based Biodegradable Polymer. Polym. Degrad. Stab. 2007, 92, 630–634.
[CrossRef]
47. Rajesh Jesudoss Hynes, N.; Sankaranarayanan, R.; Senthil Kumar, J.; Mavinkere Rangappa, S.; Siengchin, S. Mechanical Behavior
of Synthetic/Natural Fibers in Hybrid Composites. In Hybrid Fiber Composites; John Wiley & Sons, Inc.: Hoboken, NJ, USA, 2020.
48. Jerome, J.; Rajesh Jesudoss Hynes, N.; Sankaranarayanan, R. Mechanical Behavioural Testing of Fibre Metal Laminate Composites.
In Proceedings of the 3RD International Conference on Condensed Matter and Applied Physics (ICC-2019), Bikaner, India, 14–15
October 2019; Volume 2220.
49. Arif, Z.U.; Khalid, M.Y.; Noroozi, R.; Hossain, M.; Shi, H.H.; Tariq, A.; Ramakrishna, S.; Umer, R. Additive manufacturing of
sustainable biomaterials for biomedical applications. Asian J. Pharm. Sci. 2023, 18, 100812. [CrossRef] [PubMed]
50. Khalid, M.Y.; Arif, Z.U. Novel Biopolymer-Based Sustainable Composites for Food Packaging Applications: A Narrative Review.
Food Packag. Shelf Life 2022, 33, 100892. [CrossRef]
51. Karan, H.; Funk, C.; Grabert, M.; Oey, M.; Hankamer, B. Green Bioplastics as Part of a Circular Bioeconomy. Trends Plant Sci. 2019,
24, 237–249. [CrossRef] [PubMed]
52. Vignesh, N.J.; Rajesh Jesudoss Hynes, N.; ShenbagaVelu, P.; Pravin, R. A Survey on Characterization of Natural Fibers. In
Proceedings of the Advances in Basic Science (ICABS 2019), Bahal, India, 7–9 February 2019; Volume 2142.
53. Wu, C.S. Renewable Resource-Based Composites of Recycled Natural Fibers and Maleated Polylactide Bioplastic: Characterization
and Biodegradability. Polym. Degrad. Stab. 2009, 94, 1076–1084. [CrossRef]
54. Mukesh, A.M.; Rajesh Jesudoss Hynes, N. Corrosion Behaviour of Fibre Metal Laminates and Control by Inhibitors. In Proceedings
of the Advances in Basic Science (ICABS 2019), Bahal, India, 7–9 February 2019; Volume 2142.
Polymers 2023, 15, 3760 25 of 25
55. Glenn, G.M.; Orts, W.; Imam, S.; Chiou, B.S.; Wood, D.F. Starch Plastic Packaging and Agriculture Applications. In Starch
Polymers: From Genetic Engineering to Green Applications; Elsevier B.V.: Amsterdam, The Netherlands, 2014; pp. 421–452.
ISBN 9780444537300.
56. Arif, Z.U.; Khalid, M.Y.; Ahmed, W.; Arshad, H.; Ullah, S. Recycling of the Glass/Carbon Fibre Reinforced Polymer Composites:
A Step towards the Circular Economy. Polym.-Plast. Technol. Mater. 2022, 61, 761–788. [CrossRef]
57. Dang, K.M.; Yoksan, R. Thermoplastic Starch Blown Films with Improved Mechanical and Barrier Properties. Int. J. Biol. Macromol.
2021, 188, 290–299. [CrossRef]
58. Arif, Z.U.; Khalid, M.Y.; Noroozi, R.; Sadeghianmaryan, A.; Jalalvand, M.; Hossain, M. Recent Advances in 3D-Printed Polylactide
and Polycaprolactone-Based Biomaterials for Tissue Engineering Applications. Int. J. Biol. Macromol. 2022, 218, 930–968.
[CrossRef]
59. Byun, Y.; Kim, Y.T. Utilization of Bioplastics for Food Packaging Industry. In Innovations in Food Packaging: Second Edition; Elsevier
Ltd.: Amsterdam, The Netherlands, 2013; pp. 369–390. ISBN 9780123946010.
60. Sharma, S.; Luzinov, I. Whey Based Binary Bioplastics. J. Food Eng. 2013, 119, 404–410. [CrossRef]
61. ASTM D638-03; Standard Test Method for Tensile Properties of Plastics. ASTM International: West Conshohocken, PA, USA, 2012.
62. Chiumarelli, M.; Hubinger, M.D. Evaluation of Edible Films and Coatings Formulated with Cassava Starch, Glycerol, Carnauba
Wax and Stearic Acid. Food Hydrocoll. 2014, 38, 20–27. [CrossRef]
63. Chen, X.; Chen, J.; You, T.; Wang, K.; Xu, F. Effects of Polymorphs on Dissolution of Cellulose in NaOH/Urea Aqueous Solution.
Carbohydr. Polym. 2015, 125, 85–91. [CrossRef] [PubMed]
64. Mohan, T.P.; Devchand, K.; Kanny, K. Barrier and Biodegradable Properties of Corn Starch-Derived Biopolymer Film Filled with
Nanoclay Fillers. J. Plast. Film. Sheeting 2017, 33, 15–26. [CrossRef]
65. Kim, H.S.; Kim, H.J.; Lee, J.W.; Choi, I.G. Biodegradability of Bio-Flour Filled Biodegradable Poly(Butylene Succinate) Bio-
Composites in Natural and Compost Soil. Polym. Degrad. Stab. 2006, 91, 1117–1127. [CrossRef]
66. Darni, Y.; Dewi, F.Y.; Lismeri, L. Modification of Sorghum Starch-Cellulose Bioplastic with Sorghum Stalks Filler. J. Rekayasa Kim.
Lingkung. 2017, 12, 22–30. [CrossRef]
67. Maulida, S.M.; Tarigan, P. Production of Starch Based Bioplastic from Cassava Peel Reinforced with Microcrystalline Celllulose
Avicel PH101 Using Sorbitol as Plasticizer. J. Phys. Conf. Ser. 2016, 710, 012012. [CrossRef]
68. Yin, Y.; Li, J.; Liu, Y.; Li, Z. Starch Crosslinked with Poly(Vinyl Alcohol) by Boric Acid. J. Appl. Polym. Sci. 2005, 96, 1394–1397.
[CrossRef]
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1 Department of Mechanical Engineering, Mepco Schlenk Engineering College,

Abstract: It is crucial to find an effective, environmentally acceptable solution, such as bioplastics or

Keywords: bioplastics; starch; fillers; packaging

Citation: Navasingh, R.J.H.;

Polymers 2023, 15, 3760. https://doi.org/10.3390/polym15183760 https://www.mdpi.com/journal/polymers

on by heat or radiation, and it can be accelerated by adding catalysts. Considerable

A cassava-based bioplastic degrades substantially more effectively than a corn-based bio-

Figure 1. Lifecycle of the bioplastics.

Figure 2. Corn starch.

Figure 3. Rice starch.

Polymers 2023, 15, x FOR PEER REVIEW

Figure 4. Tapioca starch.

Polymers 2023, 15, x FOR PEER REVIEW

3.1. Preparation of Rice Starch

3.2.2. Solubility in Alcohol

3.2.2. Solubility in Alcohol

3.2.3. Moisture Content

W1 —weight of the initial sample in g, W2 —weight

3.2.4. Absorption of Water

Moisture content (%) = 100

W1—weight of the initial sample in g, W2—weight of the dried sample in g.

3.2.5. Biodegradability Test

W1 —weight of the initial sample in g, W2 —weight of the dried sample in g.

3.2.6. Tensile Strength

3.2.7. Scanning Electron Microscope (SEM) Analysis

3.2.8. Fourier Transform Infrared Spectroscopy (FTIR)

3.2.9. Thermal Analysis

3.3. Statistical Analysis

Table 2. Normalizing sequence.

Solubility in Solubility in Absorption of Moisture Tensile

Table 3. Deviation sequence.

Solubility in Solubility in Absorption of Moisture Tensile

which can be expressed as follows:

∆oi = x0∗ (k) − xi (k) (8)

where x0* (k) = 1.000.

ψ—distinguishing coefficient, which lies between 0 and 1.

Table 4. Grey Relational Coefficient.

Solubility in Solubility in Absorption of Moisture Tensile

The final product is made up of a combination of 20 g of starch, 5 mL of glycerol, 0 mL of

Table 5. Response for Grey Relational Grade.

Level Starch Glycerol Sorbitol Filler

Table 6. Grey Relational Grade.

4. Results and Discussion

as the plasticizer (Sample 5).

4.5. Absorption of Water

Polymers 2023, 15, x FOR PEER REVIEW 18 of 24

Figure 17. FT−IR results on samples plasticized using sorbitol.

Figure 16. FT−IR results on samples plasticized using glycerol.

Polymers 2023, 15, x FOR PEER REVIEW 19 of 24

4.9. Thermal Analysis

Author Contributions: Conceptualization, R.J.H.N.; methodology, M.K.G.; validation, M.K.G. and

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