Energy Nexus 7 (2022) 100134

Contents lists available at ScienceDirect

Energy Nexus
journal homepage: www.elsevier.com/locate/nexus

Recycling of major agriculture crop residues and its application in polymer

industry: A review in the context of waste to energy nexus
Aishwarya S. Mohite, Ameya R. Jagtap, Madhavi S. Avhad, Aarti P. More∗
Department of Polymer and Surface Engineering, Institute of Chemical Technology, Mumbai, Maharashtra, India

a r t i c l e i n f o a b s t r a c t

Keywords: The depletion of petroleum-based resources such as natural gas, coal, and minerals is an alarming sign for the
Agricultural residue sustainability of mankind. Thus, the focus has majorly turned towards renewable energy resources. It can be seen
Crop that environment-friendly resources are preferred over petroleum products at places wherever feasible. One of
Waste
such abundant resources includes agricultural residue, which is luxuriantly available at a low cost. It generally
Cellulose
consists of both pre-harvested and post harvested residue. This residue generally includes crop stems, leaves,
Bio-plastic
Polymer composites peels, husk, and ash which are studied for their constituents and properties. The residue being lignocellulosic
acts as a potential source of cellulose, hemicellulose, lignin, and pectin, which are extracted and further treated.
In this work, locally and considerably obtained crops such as cereals, millets, and fruits are investigated. They are
studied for their applications in polymer domains such as potential absorbents, fillers in polymers, bio-plastics,
lightweight construction materials, packaging substitutes, etc. This paper gives an insight into the work carried
on Agro-waste and its potential applications replacing exhausting resources.

1. Introduction to be taken to move towards a sustainable world [1,2,4-6]. Besides, they

Petroleum products such as chemicals, gases, etc. are getting ex-
hausted day by day with the increasing population. Thus, knowing about
the fore-coming energy crisis, major steps are to be taken in the direc-
tion of renewable resources that are found worldwide. The innovative
ways to develop alternative energy sources and materials include nat-
urally available substitutes, such as agriculture waste [1,2]. Biomass
from agriculture waste is a perfect example of continuous carbon cycle
as shown in Fig. 1. As it is already utilised for energy production, the rich
chemical composition of biomass can be exploited for the other appli-
cations in different industry. In the polymer industry, conventional raw
materials are derived from fossil fuels. Thus, shifting focus from fossil
fuel-based raw material to bio-based materials which are functionally
equivalent; can prevent atmospheric CO2 build-up [3]. Already major
attention is given to the use of naturally available fillers in the polymer
industry [4] but this work focuses on the use of agriculture waste, [5] its
recycling, and its use in polymer industry applications.
This paper discusses in detail about crops and their residues that
were grown locally and bountiful such as rice, wheat, maize, local fruits,
jowar, ragi, etc. As this field is very vast, efforts have been taken to cover
major crop residues, and stress has been given on their application in
the polymer industry. The polymer industry utilizes major petroleum
products, such as monomers, fillers, and other additives, thus steps have
boost the rural economy [7]. The major use of agro waste was found
to be for extraction of cellulose, pectin and hemicellulose, and also for
extraction of active ingredients [8,9].
The attention was driven towards the work related to polymer bio-
composites, also their use in fields of packaging which also included
edible packaging [10]. It has also found its application in the field of
construction, automobile, and its use as reinforcement in polymers in the
form of carbon nanotubes, cellulose, lignin carbon nanofibers which are
derived from agro-waste [11,12]. Table 1 depicts chemical constituents
of common agro waste.
2. Rice
Rice is one of the basic foods which is consumed by nearly 40% of the
world’s population [13]. Globally, Asia alone contributes to 90% pro-
duction of rice [14,15]. Among them, China stands first in the produc-
tion of rice followed by India and Indonesia [16]. The age-old method
of getting rid of this agricultural crop waste was to burn them on the
fields [17]. But burning leads to the loss of important constituents and
also leads to emissions of greenhouse gases which in turn increases the
global temperature. Thus, to prevent global warming, this agro waste
can be utilized in manufacturing of biocomposites. Below Fig. 2 shows
the major uses of rice residue in the polymer industry.

∗
Corresponding author.
E-mail address: ap.more@ictmumbai.edu.in (A.P. More).

https://doi.org/10.1016/j.nexus.2022.100134
Received 13 May 2022; Received in revised form 4 August 2022; Accepted 17 August 2022
Available online 19 August 2022
2772-4271/© 2022 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/)
A.S. Mohite, A.R. Jagtap, M.S. Avhad et al. Energy Nexus 7 (2022) 100134

Table 1
Chemical constitution of cereals and millets waste.

Agro Waste Hemicellulose (%) Cellulose (%) Lignin (%) Ash Content (%) References

Rice Husk 22.48 31.12 22.34 - [184,185]

Rice Straw 21.64 39.04 16.2 18 [185,186]
Wheat Straw 24.5 32.7 16.8 4.7 [187]
Wheat Husk 18 36 16 - [68]
Corn Straw 31.12 48 16 - [188]
Corn Husk 43.96 47 4.13 2.93 [189]
Sorghum Straw 19.4 35.4 10.3 5.3 [190]
Pearl Millet 25 52 10 9.4 [191]

strength and tensile modulus values increased [21]. Apart from their us-
age as filler, they also can take part in polymerization reactions. Aparna
Mukherjee et al. grafted methyl methacrylate with rice straw fibers, re-
sulting in improved durability and flame-retardant properties of the ma-
terial [22].

2.2. Rice husk

Fig. 1. Bio-mass and its correlation with carbon cycle [183].
2.1. Rice straw
It is studied that biomass briquettes can be made from rice straw
[18]. It has a high amount of cellulose and hemicellulose which can
be hydrolyzed to sugars and fermented, but the process requires pre-
treatment, and also it has high silica content [19]. Xiaolang Chen et al.
extracted cellulose fibers from rice straw by a mechanical-high pressure
steam technique [20]. Rice straw and unsaturated polyester resin com-
posites were prepared and the composites were tested for their mechan-
ical properties with the straw loading being done between 0 to 40%.
On an increase in straw content in composite, it was found that tensile
Rice husk (RH) is a protective layer of rice grain and makes 0.23 tons
per ton of rice [R24]. It is light brown, and its chemical constituents in-
clude cellulose (50%), lignin (30%), and other inorganic contents [23].
Rice husk is majorly used for power generation because it is better
than rice straw due to its easy logistics, lower trading value, and easy
availability [24–27]. Conventionally, they have been used as bedspreads
for animals, absorbing material, filler in construction, and to augment
growth of seeds/grains [27]. In addition, rice husk being the source of
lignocellulose was used for bio-ethanol production [19],28-31]. The rice
husk can be also used for the production of cellulose and hemicellulose
[32,33]. Besides, rice husk was used for the synthesis of furfural, thus
finding its application in different resin chemistries [34]. As discussed
above, rice husks contain high amounts of silica due to which they are
used for the manufacturing of ceramics [35]. While, Ahmed A. Moosa
et al. converted silica obtained from RH into silica nanoparticles, which
were incorporated with epoxy to produce epoxy-nanocomposite [36].
Marco Cespugli et al. found that modified rice husks can act as a cata-
lyst and sustainably synthesize polyester with restricted structure [37].

Fig. 2. Use of rice residue in the polymer industry.

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A.S. Mohite, A.R. Jagtap, M.S. Avhad et al. Energy Nexus 7 (2022) 100134

Fig. 3. Thermal and Mechanical performance of RH filled PP

composite [41].

Fig. 4. Mechanical properties of rice husk/UPR system.

In places such as Nigeria, rice husks along with starch and wood glue treated rice husk OH groups and NCO from isocyanate in PU leading to
were used locally to make water-resistant particleboard for the rainy reaction in the matrix. The 50% loading of filler contains about 55-60%
season [38]. Several studies have published results of utilization of RH of OH groups in RH, with further increase in filler these properties were
as filler for petroleum and biobased polymers [27,39,40], some of which reduced, which was attributed to decrease in homogenous PU matrix
are discussed in the subsequent paragraph. [45]. On top of that, RH can also be incorporated in recyclable plastic,
Rice husk-filled polypropylene composites were manufactured, and thus adding value to the recycled products [46,47]. In addition, they
it was reported that those samples showed an increase in melt flow in- can also be utilized in applications like energy storage devices [48].
dex and a slight decrease in flexural, tensile, and impact properties of
composites which is shown in Fig. 3 [41]. Rice husk and unsaturated
2.3. Rice husk ash
polyester resin composites were made using alkali-treated rice husk and
non-alkali treated rice husk [42,43]. It was found that non-alkali treated
Rice husk ash (RHA) is obtained after the thermochemical transfor-
RH showed poor interfacial bonding and provided a path for the failure
mation of rice husk [R4]. It is used as fillers for many polymer systems
of the product [43]. For alkali-treated rice husk, filler loading was done
[49,50], hence employed as filler in epoxidized natural rubber, natural
ranging from 0 to 50%, and the properties of the composite are shown
rubber vulcanizates [51–53]. It was used to replace talc in Polyamide-6
in Fig. 4. Thus, it was concluded that alkali treatment gave the com-
and polyamide-6,6, and successfully presented better mechanical prop-
posites better adhesion between filler and matrix [42]. Furthermore,
erties [54]. Furthermore, it was used as an adsorbent material with good
the type of chemical treatment decides the improvement in mechanical
efficiency [55,56]. Natalia Cardona-Uribe et al. [57] and Sevdalina Tur-
properties. To elaborate, Md. Rezaur Rahman et al. chemically treated
manova et al. [58] in their review reported possibilities and examples
RH with benzene diazonium salt in alkali, acidic, and neutral media.
of polymers composite using RHA in detail. Moosa et al. synthesized
The coupling reaction between diazonium salt and RH at high pH ac-
epoxy/SiO2 nanocomposite where silica nanoparticle (avg diameter - 53
corded the highest interfacial bonding in comparison to others, result-
nm) were prepared from rice husk ash. The inclusion of SiO2 nanopar-
ing in improvement of mechanical properties of composite system [44].
ticles (0.5 wt %) showed improvement in tensile strength of epoxy
Polyurethane (PU) composites were manufactured using rice husk (RH)
resin [36]. Faud et al. prepared biocomposite of polypropylene with
powder. The particle size for the loading was ranging from 150 to 250
3 types of rice husk ash (RHA). The Amorphous RHA (ARHA), White
microns. From Fig 5. And Fig 6. it can be seen that with about 50% of
RHA (WRHA), Black RHA (BRHA) were used at 10-40 wt %. Flexural
filler loading, flexural strength, flexural modulus, tensile strength, ten-
modulus was increased particularly with PP-BRHA composite decreas-
sile modulus, and elongation at break of the composite were found to
ing other mechanical properties such as tensile and impact strength and
be highest for lower particle size ranging 150-180 micron. With lower
elongation at break. ARHA however improved the tensile strength of
particle size, the higher surface area was used for the interaction of un-
composite [59]. E.P. Ayswarya et al. synthesized RHA-HDPE composite

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A.S. Mohite, A.R. Jagtap, M.S. Avhad et al. Energy Nexus 7 (2022) 100134

Fig. 5. Effect of RH particle size:150-180 microns [45].

Fig. 6. Effect of RH particle size:180-250 microns [45].

using compatibilizer. Inclusion of compatibilizer improved the mechan- The wheat residue consists of about 15-20% of lignocellulose [68]. The
ical properties and thermal properties substantially [60]. crop residue from wheat cultivation and processing mainly consists of
wheat straw, wheat husk, and wheat bran. In the following paragraphs,
2.4. Rice bran we will discuss the usage of this waste in the polymer industry. Fig. 7
shows a pictorial representation of value-added polymer products made
Rice bran is the portion that is present between husk and grain, from wheat waste.
which is usually removed during the polishing of grain. It has about 15-
3.1. Wheat husk
20% of oil content [42], hence is a natural source of oil [61–63]. Numer-
ous studies have converted rice bran oil into useful materials [64]. For
Wheat husk flour (WHF) was used as filler in thermoplastic poly-
instance, Ravindra D. Kale et al. chemically modify microcrystalline cel-
mers such as PP and HDPE to synthesize their composites using com-
lulose by the introduction of an acyl group from rice bran oil. The reason
patibilizing agents such as MA-g-PE and MA-g-PP. Addition of compat-
was to introduce hydrophobicity in hydrophilic polymers like cellulose
ibilizing agents shown to have improved compatibility between WHF
[65]. Further, to develop an antimicrobial food package, Abd El-Aziz A
and thermoplastic material. WHF filled composites showed lowered
El-Wakil et al. developed a composite of low-density polyethylene/ low-
degradation temperature. Fig 8. Shows HDPE biocomposites with MA-
density polyethylene-grafted methacrylic acid, tea tree oil (TTO) with
g-PE showed better mechanical properties than PP and MA-g-PP [69].
rice bran, where TTO act as an antimicrobial and anti-mycotoxin agent,
Recycled Polyurethane particles and wheat husks were used to man-
while rice bran helped in improving hardness value of the composite
ufacture thermal insulation panels, which achieved a good thermal
[66]. Further, although they have shown superiority they are challenged
insulation value of 0.0418-0.0574 W/(m.K). These insulation boards
by problems like poor mechanical properties at higher loading, storage
are reported to be used in environment-friendly structures (buildings).
for the long term, and poor UV stability of plastic products [67] thus,
Wheat husk was incorporated in biodegradable poly(butylene adipate-
posing requirements for development in manufacturing process of bio-
co-terephthalate)/poly(lactic acid) (PBAT/PLA) blend using hot press
composites.
technology as filler [70,71].

3. Wheat 3.2. Wheat straw

Wheat being the second most cultivated cereal all over the world con- Wheat straw soda pulp was used to synthesize nano cellulose [72].
tributes towards more agro-waste substances. Similar to rice waste, even Novel waterborne coupling agents were used for manufacturing com-
wheat straw is consumed by animals and used as construction material. posite from wheat straw and recycled LDPE. These coupling agents used

4
A.S. Mohite, A.R. Jagtap, M.S. Avhad et al.
Fig. 7. Application of wheat residue in polymer domain.
were polyacrylate latex (PAL) and another was, a blend of polymethy-
lene polyphenylene isocyanate (PAPI) and PAL. The composite study
showed PAL improved mechanical properties and reduced swell stabil-
ity. Also, the varying ratio of PAPI/PAL resulted in an evaluation of
mechanical properties. PAL coupling agent had OH groups on it which
formed hydrogen bonding with wheat straw. Varying the WS content
in the composite showed an impact on the internal bonding strength
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Energy Nexus 7 (2022) 100134
Fig. 8. Mechanical properties of thermoplastic biocomposites
[69].
Fig. 9. Effect of WS/Recycled LDPE ratio on composite prop-
erties [73].
as shown in Fig 9. [73]. A study was published on biocomposite of
wheat straw and recycled polystyrene (PS) using cold mixing and then
hot-pressing technology [74]. Similarly, wheat straw fiber and recycled
polyethylene biocomposites were manufactured and studied for their
various properties. It showed that with an increase in fiber length there
was an increase in L/D ratio and optimal tensile and flexural properties
were obtained. With the decrease in fiber length, there is agglomeration
A.S. Mohite, A.R. Jagtap, M.S. Avhad et al.
and reduction of mechanical properties [75]. A composite study was
made using wheat straw, inorganic filler, and recycled PP for their me-
chanical and thermal performance. Composites with wheat straw and
inorganic filler showed optimum water absorption properties than only
wheat straw/PP composites, also the thermal expansion of composites
was shown to have reduced with an increase in wheat straw loading
[76]. Wheat straw (WS)/bagasse fiber (BF) reinforced epoxy compos-
ites were made using varying quantities of bagasse fiber and wheat
straw. The wheat straw and bagasse fiber were alkali-treated and later
bagasse fiber was also treated with acrylic acid. With 20/80 and 40/60
WS/BF ratio in composite, the highest mechanical properties were ob-
tained which was attributed to the better mechanical performance of
bagasse fiber as shown in Fig 10. As BF had more amount of cellulose
content than WS and ultimately higher microfibrils content, resulted in
enhanced surface adhesion to the polymer matrix. Water absorption of
composites decreased with an increase in BF, which was attributed to
higher lignin content in BF thereby giving higher water resistance [77].
3.3. Wheat bran
A lot of research has been carried out on lignocellulose fillers for
wood polymer composites. An alternative to conventional used lignocel-
lulosic fillers is wheat bran as it is inexpensive. Aleksander Hejna et al.
investigated the ability of wheat bran as fillers for linear low-density
polyethylene products manufactured using rotational molding. The ten-
sile strength, elongation values, and rebound resilience decreased as
filler content increased. This could be associated with lower interfacial
bonding between them. However, an unusual trend was noted for hard-
ness values on increasing filler content. It dropped when wheat bran
proportion was 2.5% and then improved consequently, which may be
because of rigid wheat bran structure that counterbalances its porosity
[78]. Furthermore, Łukasz Majewski et al. have found that wheat bran
can be successfully incorporated in LDPE to manufacture products us-
ing injection molding equipment. The products can be targeted to have
lower-cost products, improve degradation temperature, and lower the
weight of the product [79]. Besides, the feruloylated oligosaccharides
present in wheat bran can be used in nutraceutical foods to accord an-
timicrobial activity [80].
4. Maize (Corn)
Another major crop grown worldwide is corn [81]. Thus, measures
have to be taken for the recycling of corn crop residue. The common
application of corn residues includes nutrients for the soil, animal feed-
stock, and energy production [82]. The major residues of corn are corn
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Energy Nexus 7 (2022) 100134
Fig. 10. Mechanical properties of WSF/BF epoxy
blended composites [77].
stover which majorly includes corn straw, corn cob, corn husk, etc.
Fig. 11 represents the major uses of corn residue.
4.1. Corn straw
Cellulose, hemicellulose, and lignin are the main components of
corn straw [82]. Traditionally, polyurethanes are made from an ad-
ditional reaction of polyether polyol or polyester polyol with polyiso-
cyanates. Among them, polyol raw material can be partly replaced by
corn straw as a source of polyol components and as filler [82]. The wood
plastic composite (WPC) was made using waste fiber reinforced plastic
(FRP), corn straw fiber, and Polyvinyl chloride (PVC). This use of corn
straw fibers in WPC had led to improvement in mechanical properties
as shown in Table 2 the study showed that WPC can be stronger us-
ing corn straw fiber instead of conventional wood fibers. Alkali treated
straw gave improved properties [83]. Extraction of cellulose from corn
straw was carried out using different methods such as using ionic liq-
uids, high-temperature systems, and low-temperature laccase systems
[84,85]. Numerous studies are carried out on the utilization of straw
as a superabsorbent hydrogel. Wei-Min Cheng et al. prepared super-
absorbent hydrogel wherein after extraction of lignin from corn straw,
the resultant was grafted with 2-acrylamido-2-methylpropanesulfonic
acid to produce sulfonated cellulose. It was further copolymerized with
acrylic acid [86]. While Weishuai Wang et al. modified straw cellulose-
g-AA with polyvinyl alcohol and ammonium polyphosphate [87]. Shup-
ing Jin et al. composed superabsorbent material of AA and powdered
corn straw [88] Fig 12. Thus, depending on the modification done, sev-
eral astonishing superabsorbent hydrogels could be synthesized. Follow-
ingly, biodegradable films [89] and dust suppressants [90] from corn
straw were synthesized.
4.2. Corn cob
Corn cob is one of the most important corn residues. It contains a pith
at the centre which is surrounded by wood rings and subsequently by
chaff [91]. They were used for the synthesis of furfural compounds [92].
Hydrophobic imidazolium ionic liquids with magnetic-chitosan metallo-
porphyrin were used to convert cellulose to 5-hydroxymethylfurfural
(5-HMF) [93]. Xylan-type hemicellulose was extracted from the corn-
cob using ultrasound-assisted extraction [94]. The xylan is potent as
polymeric material for drug delivery systems because of its ability to
behave as an inhibitory function against mutagenicity activity, antiphlo-
gistic effects, etc [95]. A study found out that corn cob properties were
comparable with expanded clay, cork was used along with extruded
polystyrene. It was found to replace conventional materials and can
be used to manufacture thermal insulation products, ceiling coating,
A.S. Mohite, A.R. Jagtap, M.S. Avhad et al. Energy Nexus 7 (2022) 100134

Fig. 11. Value added products obtained from corn crop residue.

Table 2
Effect of corn straw fibers on WPC composite [83].

WPS with

Waste FRP NaOH treated Untreated corn

content (phr) Wood Fiber corn straw Fiber straw Fiber

Tensile Strength (MPa) 0 20.5 19 17

10 21 20.5 18
20 22 21 20.5
30 28 24 21.5
40 22 19.5 19

Flexural Strength (MPa) 0 55 54 52

10 62 60 56
20 63 63 60
30 68 65 62
40 64 61 59

Fig. 12. Synthesis of corn straw-co-amps-co-aa superabsorbent hydrogel [88].

furniture, etc [96,97]. Acoustic insulation properties of corn cob par-
ticle board are also found to be comparable with traditional materials
used such as glass wool [98]. Corn cob-filled chitosan composites films
were prepared. SEM analysis showed that there was weak interaction
between corn cob filler and chitosan thus mechanical properties such
as tensile strength and elongation at break were reduced, whereas ten-
sile modulus was increased [99]. R. R. F. Ramos et al. developed green
composites comprising polypropylene (PP) and corncob. It was found
that the properties followed by these composites were comparable to
neat PP and provided lower density and final product value [91]. A
composite was prepared using corn cob filler, wood ash, PP, malenated
PP as a compatibilizer, and stearic acid as a lubricant. Wood ash was
used as filler with its content varied from 1 to 10 wt%. Table 3 shows
that tensile strength and elongation at break were found to decrease
with an increase in filler loading. Flexural modulus and tensile modu-
lus increased with an increase in filler loading [100]. Shiliu Zhu et al.
investigated water absorption, mechanical and crystalline properties of
Corncob powder-filled high-density polyethylene (HDPE) composites.

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Table 3
Mechanical properties of corn biocomposites.

Tensile strength Impact strength Flexural Tensile modulus Flexural Elongation at

Sr. No. Bio-composite type Comp. (MPa) (KJ /m) strength (Mpa) (Mpa) modulus (GPa) break (%) Reference

1 Chitosan (CS): Corn 100/0 53 - - 2200 - 13.9 [99]

2 Cob (CC) 90/10 33 - - 2300 - 11
3 80/20 30 - - 2600 - 8.5
4 70/30 28 - - 2650 - 6.2
5 60/40 27 - - 2800 - 5
6 R-LDPE: Corn Husk 100/0 13.5 - - 166 - - [107]
7 95/5 24.7 - - 327 - -
8 90/10 24.3 - - 456 - -
9 85/15 17.9 - - 456 - -
10 80/20 17.7 - - 410 - -
11 Treated recycled 70/30 7 - - 1650 - - [109]
12 polystyrene(rPS): 60/40 10 - - 1800 - -
13 Corn husk fibers 50/50 13 - - 2150 - -
14 (CHF) 40/60 17 - - 2400 - -
15 Polypropylene (PP): 90/10 23.84 - - 2064.99 - 1.95 [112]
16 Red sea weed (RS) 80/20 19.99 - - 1853.79 - 1.28
17 70/30 17.85 - - 1344.14 - 1.71
18 Polypropylene (PP): 90/11 33.75 - - 2116.9 - 3.63
19 Brown sea weed (BS) 80/21 31.25 - - 2306.88 - 2.31
20 70/31 22.48 - - 1866.32 - 1.73
21 Polypropylene (PP): 70/30 27.98 15.68 65.03 - 7.58 - [114]
Wood flour (WF)
22 Polypropylene (PP): 70/30 25.6 15.85 60.55 - 6.17 -
Rice husk flour (RHF)
23 Polypropylene (PP): 70/30 22.28 15.35 53.29 - 5.39 -
Corn husk flour
(CHF)

They found that on increasing filler content water absorption content
increased which hampered the water-resistance performance of com-
posites structure. This is imputed because of the increase in cellulose
and hemicellulose content of the system. While the mechanical proper-
ties followed an unusual trend because of lower compatibility [101].
Many studies have been carried out on the production of nanocrys-
talline and microcrystalline cellulose from corncob [102]. Corn cob
cellulose on modification finds different applications such as catalyst
[103], metal extraction [104,105], etc. Furthermore, the polyol can be
derived from corn cob which can be used for the production of biobased
polyurethanes [106].
4.3. Corn husk
Recycled LDPE and corn husk fiber biocomposites were studied. With
the increase in filler content, mechanical properties such as moduli, ten-
sile strength, swelling properties, and the thermal stability of composites
were enhanced. These composites can be used for packaging film [107].
It can be seen in Table 3 that the incorporation of corn husk fibers in
polymers, increased its mechanical properties, but also increased wa-
ter absorption parameters for composites. Thus, corn husk fibers were
treated with NaOH to improve their surface properties and decrease
the moisture content into them [108]. Thus, in the study of recycled
Polystyrene (rPS) and corn husk fibers (CHF) composites, this concern
was considered. They treated corn husk fibers with NaOH. With treat-
ment of CHF, tensile strength, tensile modulus, thermal stability was
increased and water absorption tendency was reduced to about 29%.
It was attributed to better adhesion of rPS and treated-CHF leading to
filling of gaps between fiber and matrix [109]. Corn Husk fibers were
used to extract cellulose and further acetylated using a one-step acety-
lation process without any catalyst having the degree of substitution
in the range of 2.16-2.63. The Corn Husk Cellulose Acetate films thus
obtained were made from the green process and had comparable me-
chanical properties [110]. Hemicellulose (HC) extracted from corn husk
was acetylated using 2,3-epoxypropyltrimethylammonium chloride and
converted to cationic cellulose with the degree of substitution of 0.43.
The polymer made was used for sewage treatment in the municipal de-
partment. The performance of those obtained HC was compared with
conventional polymer (ACRIPOL C10) used for sewage treatment. Com-
paring the parameters such as color and turbidity for those two poly-
mers, it was seen that better results were delivered for cationic hemi-
cellulose than cationic polyacrylamide [111]. Corn Husk powder was
used as filler for PP composites. Filler loading was ranging from 10-30
wt%. Its mechanical, thermal, and morphological characteristics were
evaluated. Mechanical properties such as tensile strength, elongation at
break were decreased with an increase in filler loading, whereas tensile
modulus was increased. Corn Husk filler and PP are shown to have good
compatibility given by SEM analysis [112]. Corn Husk films were pre-
pared which are considered to be environmentally friendly. Corn Husk
was alkaline treated, washed then again treated with HCl. The pulp ob-
tained was mixed and mechanically stirred using chitosan and acetic
acid, and was cast into films using a casting knife. These films were
used as pots for growing seedlings. They showed complete biodegrad-
ability in 270 days. Also, used as a pot, it is shown to provide a better
environment for plant growth [113]. Corn Husk flour and PP composites
were synthesized and their mechanical properties were evaluated based
on the amount of filler loading and size of the filler. With an increase in
filler size, flexural strength was observed to be increased, also with the
increase in filler content flexural strength was reduced. It was attributed
to interactions between filler and polymer [114].
As the method of incorporation of the above-mentioned crop residues
is different, it is difficult to compare them. However, in Table 4 tensile
strength and modulus values of some crop residue is presented.
5. Millets
Millets are produced globally with surplus crop residues. India is one
of the largest producers of millets. In India, states like Rajasthan, Mad-
hya Pradesh and Maharashtra are ranked as highest in millet producing
states. Attention must be given to such crops because they are produced
on a large scale and thus may lead to the need for waste utilization. Ma-
jor millets produced include Jowar, Bajra and Ragi, out of which a lot of
work has been carried out on the waste utilization of Jowar and hence

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A.S. Mohite, A.R. Jagtap, M.S. Avhad et al. Energy Nexus 7 (2022) 100134

Table 4
Mechanical properties of common Agro-Waste.

Agro Waste Tensile Strength (MPa) Young’s Modulus (MPa) References

Rice Straws (Uncrushed) 74.60 3323 [21]

Rice Straw (Crushed) 69.72 2427 [21]
Bagasse fiber 20-290 17 [98]
Wheat straw fiber 32 6.6 [98]
Corn Straw 100-140 - [192]

it is discussed here in detail. Other millets and their waste (by-products)

recycling is also discussed here in a nutshell.

5.1. Sorghum

Produced on a large scale with surplus crop residue, finds it nec-

essary for crop residue management. Mainly its stalks, bran and other
such parts are considered as waste from the crop. The stalk of the crop
was divided into three regions: bottom, middle, and top for its ease of
characterization. The main constituents of the stalk were found to be
lignin, cellulose, and hemicellulose. The stalks were stable below 200°C
and later found to have degraded [115]. Micro-fibrillated cellulose was
obtained via alkalization and acetylation of sorghum fibers. The alka-
lization was carried out using 10% NaOH at 80°C for 1 h, later it was
acetylated using acetic acid and in a later stage soaked with acetic anhy-
dride using sulphuric acid as a catalyst for about 10 min and 2 h. With
further acetylation and soaking in acetic anhydride for about 2 h, the
highest crystallinity index of 82.6% was obtained thereby removing all
lignin content from it [116,117]. Sorghum stem was treated in distilled
water for 3 hours and later its residue was alkali treated in KOH for 3
hours and initial filtrate was concentrated and precipitated in ethanol,
then obtained filtrate from residue was treated in ethanol for more than
3 hours. The yield obtained was about 76.3% and higher molecular
weight hemicellulose obtained were thermally stable [118]. Sorghum
straws were treated with phosphoric acid to synthesize furfural. These
Fig. 13. Other use of sorghum waste.
sorghum straws were used as a source of xylose, which is converted to
xylitol. It was also used for producing furfural. Optimum conditions for
the production of furfural from xylose, using acid hydrolysis were at 6%
H3 PO4 at 134°C for 300 min, which yielded about 13.7g/L of furfural,
2.9g/L of glucose and other ingredients [119]. tion at break and bending strength was also observed to be optimum
The Sorghum is very popular for polymer composites. The pop- [123]. Oriented sorghum fiber and HDPE composites were made using
ular composites based on Sorghum is shown in Fig. 13. Polylactic hot press technology. With about 10% of HDPE and 2% of adhesive,
acid/sorghum fiber biocomposites were made via compression mould- the composite showed better mechanical properties than sorghum com-
ing. For reducing the hydrophilicity of bio filler, it was treated with 4 posites without HDPE [124]. Sorghum bran like stalks was also used
different agents such as amino silicone oil, silane coupling agent, emul- for making polymer biocomposites. The study was made using recy-
sified wax, and titanate coupling agent. With modification of fiber, the cled LDPE and sorghum bran, in about loading percent ranging from
contact angle was found to increase showing improved water repellency. 5 to 20. Increasing sorghum bran resulted in increase in tensile strength
From the study it was seen that increase or decrease in hydrophilicity and moduli and decrease in hardness as shown in Fig. 14. The filler
did not directly affect the mechanical properties of sorghum composites. showed good adhesion to the polymer matrix and also good thermal
Table 5 shows that with lower water repellence, titanium coupling agent stability of composites [125]. Sorghum stem was used as filler for PP
sorghum composites had maximum flexural strength, even higher than composites. Various genotypes were used for making these composites.
that of control [120]. Particleboards were made using sorghum stalks There was variation observed with different genotypes used in mechan-
and an industrial mixture of hardwood. Urea-formaldehyde was used ad- ical properties such as tensile strength, which varied from 7.2 to 11.5
hesive with ammonium chloride as hardener. After studying its mechan- MPa and impact strength which varied from 4.4 to 6.2 KJ/m2 [126].
ical properties and manufacturing details it was stated that sorghum The major drawback a bio filler may face will be its incompatibility
stalks had potential to be used as supplementary fibrous material for with polymer matrix. Thus, various treatments are given to it, such as
making particle boards used for indoor application [121]. The work has alkalization-bleaching and alkalization-bleaching-acid hydrolysis. Thus,
also been reported, for manufacturing particle boards using sorghum on carrying out such treatments it was seen that composites with better
stalks (ST) and citric acid [122]. ST were used as filler in HDPE using tensile strength and compatibility [127]. A novel study was made us-
maleic grafted PE (MAPE) as compatibilizer. Filler loading varied from ing sorghum straw and PVA based composites using micro silica (MS)
0 to 10% along with MAPE varying from 0-3%. With a high amount and poly(acrylonitrile-styrene-acrylate) (ASA) as other additives. To test
of compatibilizer, its tensile properties were found to increase at 20% their performance in corrosive and harsh environmental conditions, sea
filler loading. With higher filler loading, not much changes were seen water and acid rain was used. It was shown that with 6% of microsilica
in properties due to compatibilizer not being able to depict its proper and 34% of ASA, the PVA and MS showed improved toughness, heat
functioning. At 20% of filler and 1% of MAPE loading highest elonga- resistance and strength [128].

9
A.S. Mohite, A.R. Jagtap, M.S. Avhad et al. Energy Nexus 7 (2022) 100134

Table 5
Mechanical properties of sorghum composites.

Tensile strength Flexural Tensile modulus Flexural Elongation at

Sr. No. Bio-composite type composition (MPa) strength (Mpa) (Mpa) modulus (GPa) break (%) Reference

1 PLA / Untreated Sweet 2/1 (wt/wt) 2.95 37 - - - [120]

Sorghum Fiber (UNT - F)
2 PLA / silane coupling 2/1 (wt/wt) 3 39 - - -
agent treated SSR (SCA -
F)
3 PLA / titanium coupling 2/1 (wt/wt) 4.6 60 - - -
agent treated SSR (TCA -
F)
4 PLA / emulsified wax 2/1 (wt/wt) 3.5 50 - - -
treated SSR (EW - F)
5 PLA / amino silicone oil 2/1 (wt/wt) 1 19 - - -
treated SSR (ASO - F)
6 HDPE: SSR: MAPE 80/20/0 15.5 - 950 14.5 8.5 [123]
7 79/20/1 17 - 850 9
8 77/20/3 19 - 975 15.5 8
9 80/40/0 16.5 - 1350 27 3.75
10 79/40/1 16.5 - 1050 4.5
11 77/40/3 17 - 1100 3.5
12 Oriented Sorghum fiber: 90/10 21 - 1100 - - [124]
13 HDPE composite (OFPC) 80/20 22 - 1050 - -
14 70/30 19.5 - 8050 - -
15 60/40 18 - 700 - -
16 PLA: Millet Husk Powder 90/10 - - - 1.5 [131]
17 (MHP) 80/20 - - - 4
18 70/30 - - - 2
19 60/40 - - - 2.8
20 PP: Coconut Shell 60/40 22 - - - 3.2 [133]
21 PP: Barley Husk 60/40 29 - - - 2.6
22 PP: Soft Wood 60/40 27 - - - 1.9
23 PP: Coconut Shell: Maleic 52/40/2 29 - - - 3.1
anhydride (MA)
24 PP: Barley Husk: Maleic 52/40/2 38 - - - 2.6
anhydride (MA)
25 PP: Soft Wood: Maleic 52/40/2 32 - - - 1.8
anhydride (MA)

Fig. 14. Mechanical properties of sorghum/recycled LDPE.

5.2. Other millets
Millet husk powder (PENNISETUM GLAUCUM) was used as filler
in HDPE polymer with variation in fiber size ranging from 250 to 750
micrometer along with variation in fiber loading from 10 to 40% by
weight. It was seen that with minimum fiber size and optimum load-
ing tensile strength was increased with of impact strength with increase
in filler loading [129,130]. Alkali treated Foxtail Millet were also used
as reinforcement agents in epoxy resin using vacuum bagging. Fibers
were alkali treated using NaOH in varying quantities and were washed
and dried for final use in making composite laminates. With increase
in NaOH quantity for treatment of fibers and filler loading, all the me-
chanical properties were improved. SEM analysis showed that with in-
crease in treatment, there existed an increase in bonding between ma-
trix and filler [131]. Silica aerogel was extracted from Ragi Husk Ash
by treating it with alkali forming sodium silicate solution and later
neutralizing using acid. The gel was then washed using deionized wa-
ter and alcohol and drying under atm pressure and 700°C gives opti-
mum amorphous silica content [132]. Barley husk with coconut shell
as fillers were also used to reinforce PP matrix along with MA-g-PP
as coupling agent. Barley husk having more inorganic content on the
surface showed 10% better tensile strength than soft wood composites.
Also, coconut shell and barley husk composites have higher elonga-
tion at break and impact strength than conventional soft wood compos-
ites [133]. Polyhydroxyalkanoate was biosynthesized using ragi husk
along with sesame oil cake via enzymatic reaction [134,135]. Fig. 15

10
A.S. Mohite, A.R. Jagtap, M.S. Avhad et al. Energy Nexus 7 (2022) 100134

Fig. 15. Typical applications of waste produced from

other millets.

Table 6
Mechanical properties of jackfruit residue’s biocomposites.

Sr.No. Biocomposite type composition Tensile strength (MPa) Tensile modulus (Mpa) Elongation at break (%) Reference

1 LDPE/Jackfruit seed 95/5 9.5 120 40 [139]

2 flour (JFSF) 90/10 9.75 145 30
3 85/15 9.75 138 38
4 80/20 9 142 20
5 LDPE/Jackfruit seed 95/3.75/1.25 10 102 100
6 flour (JFSF)/Adipic Acid 90/7.5/2.5 9.5 82 85
7 (AA) 85/11.25/3.75 9 81 58
8 80/15/5 8.5 80 55
9 PVA/Jackfruit seed flour 70/30 3 - 155 [140]
10 (JFSF) 50/50 1 - 150
11 30/70 0.5 - 20
12 PP/Jackfruit seed flour 50/50 12 1900 - [193]
13 (JFSF) 30/70 10 2200 -
14 10/90 8.2 2600 -
15 LDPE/Jackfruit seed 97/3 9 125 230 [143]
16 flour (JFSF)-63 μm 95/5 8.7 105 210
17 90/10 8 100 165
18 85/15 7.8 90 160
19 80/20 7.3 80 150

shows typical use and application of other millet residue in the polymer
industry.
6. Fruits
Various crop residues such as millets, pulses are studied and utilized
widely, but the other important but to some extent neglected residues
are fruit waste. Fruit waste is generated when a consumer or concerned
industry utilizes the fruit yield for further processing, but sometimes it
can also be generated on the field. But major crops which have major
residual parts include jackfruit, watermelon, citrus fruits, and etc. Fruit
wastes generally consist of peels, seeds, rinds, and etc, and are used ef-
fectively for extraction of active ingredients such as polyphenols, dietary
fibers, enzymes and proteins from it [136].
6.1. Jackfruit peel and seeds
Jackfruit is a seasonal fruit, but has a high amount of waste which
includes peel and seeds [137]. Cellulose nanocrystals were extracted
from jackfruit peel with about 83.42% of crystallinity. Bleaching treat-
ment was given to separate out cellulose and hemicellulose from the
waste, further alkali treatment was given to extract cellulose, and lastly
it was treated with acid to remove amorphous regions of cellulose giv-
ing cellulose nanocrystals [138]. A study was made using jackfruit seed
flour and LLDPE to make biocomposites, and with compatibilization of
adipic acid. Table 6 shows that with compatibilization, tensile strength
and elongation at break were increased, but with increase in filler load-
ing it was found to decrease, and young’s modulus was found to increase
with increase in filler loading [139]. Biodegradable plastic was prepared
using Polyvinyl alcohol (PVA) and jackfruit seed powder. Its biodegrad-
ability was examined after incorporation of seed powder, which was
found to increase. With increase in seed powder content, mechanical
properties such as tensile strength, elongation at break were reduced,
thus it was suggested that better binders can be used during fabrica-
tion of the plastics [140]. A bioplastic was made using starch from rice
waste, jackfruit seeds, sorbitol, chitosan, glycerol and PVA as additives.
The effects of various additives on bioplastic were evaluated for its me-
chanical properties and biodegradability. With increase in glycerol in
plastic, tensile strength was found to decrease, whereas with chitosan it
was increased. With 2 gm of PVA and 2 ml of sorbitol optimum tensile
strength was obtained. With incorporation of glycerol and sorbitol, elon-
gation at break was increased and reduced with addition of PVA. The
bioplastic formulation showed 32.18% degradation after 14 days [141].
Jackfruit seed flour was also incorporated in PP to make biocomposites.
It showed that with increase in jackfruit seed content, tensile strength
was reduced but young’s modulus was increased. With increased compo-
sition of jackfruit seeds, it led to bioplastic with lower water absorption
[140]. Jackfruit seed starch was used for enhancing biodegradability
of PVA. Mechanical properties like tensile strength obtained were opti-
mum at 4wt% of starch loading and further decreased, while elongation
at break was found to be reduced. Biodegradation test was performed
and it showed that within 20 days under normal conditions, about 30

11
A.S. Mohite, A.R. Jagtap, M.S. Avhad et al.
wt% of mass was lost (Degraded). This shows improved biodegradabil-
ity of the blend [142]. Tensile properties of LDPE with jackfruit seed
flour (JSF) were also evaluated, with variation in particle size of JSF.
It was seen that with increasing JSF content from 0 to 20 wt%, tensile
strength and elongation at break were reduced and found lower than
virgin LDPE. Also, with lower particle size of JSF, the tensile proper-
ties were higher as compared to higher particle size filler [143]. The
environment-friendly films were prepared using starch from jackfruit
seed and PVA using banana skin powder. Starch was used to enhance
degradability of PVA and banana skin powder was used as filler to im-
prove strength, and films were made using solution casting methods.
Tensile strength and elongation at break were found to reduce by in-
creasing banana skin powder, but with 1 wt% loading, optimum prop-
erties were obtained. This was observed due to better adhesion between
filler and matrix, which on further addition of filler led to agglomeration
of fillers. Soil burial test showed that significant weight loss within 20
days of burial was seen due to incorporation of fillers than virgin PVA
[144].
6.2. Watermelon rind and seeds
Carbonized watermelon rind (CWRF) was used as filler in the poly-
mer industry. The novel work was made using carbonized watermelon
rind powder incorporated in unsaturated polyester resin (UPR), fur-
ther evaluated for its various properties. UPR along with cobalt octoate
as catalyst, methyl ethyl ketone peroxide as hardener and CWRF as
filler was used. Energy dispersive X-ray spectroscopy analysis showed
presence of minerals such as antimony, bromine, chromium, lead and
absence of cadmium and mercury. These metals detected were lower
than permitted values by IS 9833.19. At higher filler loading, analysis
showed that agglomeration of filler particles and thus at about 10 wt%
loading, optimum mechanical properties were observed. Hardness was
found to have an optimum value of 85 shore. It was seen that upon in-
creasing filler loading, time taken by samples to collapse was increased,
also no dripping was seen in thermal property evaluation [145]. Later
researchers developed hybrid composites based on pineapple, water-
melon peel nanoparticles along with inorganic with carbon, jute fab-
ric in epoxy resin. They experimented with several hybrid compos-
ite compositions such as jute/carbon epoxy, jute/pineapple epoxy, car-
bon/pineapple/watermelon epoxy, and etc. Fig 16. Depicts hybrid com-
posites made from carbon/Pineapple/Watermelon filled epoxy showed
best mechanical properties among all composites, due to presence of
fruit nanofiller particles along with inorganic carbon [146].
6.3. Orange
Orange peel characterization was shown to have low cellulose, hemi-
cellulose and lignin content but high fixed carbon content and was used
12
Energy Nexus 7 (2022) 100134
Fig. 16. Mechanical properties of different hy-
brid biocomposites [146].
for pectin extraction [147]. From orange peel Limonene, phenolic com-
pounds and essential oil were extracted [148–150]. Orange peel pow-
der was used in LLDPE to form sheets [151]. These orange peels were
used as reinforcing agents for epoxy resin along with hardeners. The
filler content was varied from 5 to 30 wt% and mechanical properties of
composites were evaluated. In Table 7, it can be seen that with 20 wt%
of filler loading, mechanical properties such as tensile strength, flexu-
ral strength, and hardness were reported to be higher than neat epoxy
as well as filled epoxy. SEM analysis of 20 wt% filled epoxy, showed
no debonding or crack formation on tensile testing thereby showing
strong bonding of matrix and reinforcement [152,153]. Orange peels
particles were also used as fillers to produce bio-composite using HDPE.
The orange peel powder used was carbonized at 1200°C and particle
size of 100 um was obtained. With 20 wt% of loading of carbonized or-
ange peel powder, high tensile strength, hardness, bending strength was
observed. The mechanical test results showed that fillers were evenly
loaded in the matrix [154]. Particle boards were made using the orange
peel powder and urea formaldehyde and phenol formaldehyde resins. As
the filler: polymer ratio approached 1, highest tensile strength was ob-
served. Properties such as non-flammability and water resistance were
improved for the biocomposite and found as an advantage over conven-
tional wood-based particle boards [155]. Eco-friendly packaging films
were made using polyvinyl alcohol and orange-peel powder. Mechani-
cal properties such as tensile strength, elastic modulus and elongation
at break at 10 wt% loading was reported to be 8.58 MPa, 236 MPa,
and 28.7% respectively and were highest among other loading %. These
films obtained were found to be better than other non-biodegradable
films [156]. Polyester was also reinforced with orange peel powder in
replacement of synthetic fillers. Mechanical properties such as hardness,
tensile strength were reported to be highest at 10 wt% of loading of or-
ange peel powder [157].
6.4. Lemon
Lemon waste is usually used for extraction of vital chemicals, dietary
fibers, bioactive compounds [158–160]. But newer technologies were
used to incorporate lemon waste in the polymer industry. LDPE films
with lemon aroma (heat resistant) were produced using citrus essential
oils for biscuits packaging. By incorporating lemon aroma/essential oils
it showed no changes in tensile strength but lowered elongation at break
but had potential for being used for packaging of films [161]. Another
such study was made using chitosan-lemon essential oil based coatings
for maintaining the quality of strawberry during transportation [162]. A
study was made earlier using C. Limetta reinforced polyester composites
for its tribological and physical properties evaluation. Later sweet lime
peels were used to reinforce epoxy resins. It showed that by incorporat-
ing filler, viscoelastic properties of epoxy were enhanced [163,164].
A.S. Mohite, A.R. Jagtap, M.S. Avhad et al. Energy Nexus 7 (2022) 100134

Table 7
Mechanical properties of orange residue’s biocomposites.

Tensile strength Bending Flexural Tensile modulus Flexural

Sr. No. Biocomposite type composition (MPa) strength (MPa) strength (MPa) (MPa) modulus (GPa) Hardness Reference

1 Epoxy: Orange peel 95/5 19.25 - 48.23 742.46 5.146 18.28 [152,153]
2 particles 90/10 22.69 - 56.98 1313.63 9.631 19.68
3 80/20 25.85 - 62.35 1271.69 10.97 20.72
4 70/30 21.34 - 57.89 938.96 8.334 18.95
5 HDPE: Uncarbonized 95/5 3.9 82 - - - 3.2 [154]
6 Orange peel particles 90/10 4.5 84 - - - 4.3
7 85/15 6 91 - - - 6.2
8 80/15 4.7 94 - - - 6.4
9 75/25 4.6 73 - - - 7.3
10 HDPE: Carbonized 95/5 4.7 84 - - - 10
11 Orange peel particles 90/10 5.2 86 - - - 10.8
12 85/15 5.3 110 - - - 12.2
13 80/15 5.9 89 - - - 13.6
14 75/25 5.8 64 - - - 14

6.5. Other fruits
Other fruits such as banana, pomegranate, dates, apricot, walnuts,
rambutan, wood-apple were also considered to be used as fillers in the
polymer industry. These wastes were earlier considered to be used for
biogas production or for composting. The waste was earlier used for
extraction of cellulose, hemicellulose, lignin and other inorganic and
active ingredients [165]. But later they were used as bio-based fillers
in the polymer industry. Banana peel is considered as waste and con-
stitutes about 40% of total banana weight, and also its decomposition
is not favored due to emission of harmful gases as reported in some
of the literature. Also they were used for extraction of active ingredi-
ents [166–168]. Banana peel powder (BPP) was used with chitosan for
wound dressing purpose, showed highest antimicrobial activity against
bacteria and yeast at 12 wt% concentration, and showed lowest water
absorption at 24 and 48 h. It was seen that BPP acted as ionic crosslinker
for chitosan and reinforced the polymer matrix and reduced its swelling
behavior [169]. Banana peel and egg shell were used for making bio
composites [170]. Pomegranate peel was used as an antimicrobial and
reinforming agent for hydroxypropyl high amylose starch. At about 4-
6% of pomegranate peel powder, the mechanical properties of film ob-
tained were optimum. Also, at high loading of 12-14% the antimicrobial
activity obtained was highest. Since the ingredients used were also safe
for ingestion, edible films for packaging can be made from it [171].
Another such interesting study was made using pomegranate rind hy-
brids for making antimicrobial films using polycaprolactone and starch.
Combinations of samples were prepared using starch, pomegranate rind
individually and both together as filler. At about 20% of both the fillers
used, the highest microbial inhibition area was achieved. Checking for
its other properties it was seen that at 20 % loading of each filler, op-
timum mechanical properties were obtained. Thus, these films can be
used for delivering antimicrobial properties [172]. Another such break-
through was made using bio waste filler to reinforce polymers. It used
Wood-Apple and coconut shells as reinforcement for epoxy resin along
with hardener. The reinforcement varied from 5-20%, with 15% of load-
ing for each of the filler highest tensile and flexural strength were ob-
served as shown in Fig 17. And Fig 18. From SEM analysis it was seen
that at 15% loading there was higher bonding between filler and matrix
for wood apple samples than coconut shell samples [173]. Opuntia indica
(prickly pear fruits) peels were used for extraction of cellulose microfib-
rils, separating the rest of its components through various analytical
techniques [174]. An excellent research was carried out using rambutan
peel flour in LLDPE and its mechanical properties were evaluated. The
particle sizes of the flour used ranged from 63 um to 250 um. With 5%
loading of filler and particle size of 63um, highest elongation at break
and tensile strength was obtained Fig 19. With increase in filler content,
the properties were found to decrease in number which was attributed
to polar nature of filler and non-polar nature of plastic, thus note was
made using a filler treatment or coupling agent to improve that draw-
back [175]. An interesting study was carried out using date seed flour
along with PP-g-MA and stearic acid for enhancing flame retardancy,
mechanical properties of polyamide-6 (PA-6). It was seen that good hy-
drogen bonding existed at the surface of filler and compatibilizer and
later at matrix, thus at 20% filler and 5% of compatibilizer, better me-
chanical properties were obtained than neat PA-6 Fig. 20 represents the
flame-retardant properties of Date seed-based composites [176]. To im-
prove thermal properties of phenolic resin, varying proportions of areca
fiber and Pongomia shell powder was used. The areca fiber was chem-
ically treated before use as its pH was above 7, and may have reacted
with phenolic resin causing negative impact. The fire resistance was
increased with filler content, and at 15% Areca fiber and 20% Pongo-
mia pod powder optimum properties were obtained with LOI of 28.45%
and tensile modulus of 245 MPa [177]. Mangosteen peel powder was
dried and later used in natural rubber latex gloves thereby showing anti-
microbial properties and also improved mechanical properties such as
tensile strength and elongation at break than neat rubber gloves [178].
Preparation of biocomposites films was carried out using apricot and
walnut shell powder in starch. With both the fillers used individually,
reduced water vapor transmission rate and improved barrier properties
of film was achieved. Higher tensile strength was observed for the films
with filler and also at optimum loading of both the fillers, higher elonga-
tion at break was also observed. This was attributed to good adhesion be-
tween filler and matrix. Fig. 21 represents the properties of such compos-
ite [179]. Phenolic novolac epoxy was used in making bio-composites
because of their excellent heat resistance, good adhesion and chemi-
cal resistance. They were turned into composites using treated apricot
kernel shells (AKS). AKS were alkali treated to form shell-O-Na, later
it was treated with glacial acetic acid to form shell-O-OCOCH3 . Also,
alkali treated shells were treated with levulinic acid (LA) to form shell-
O-COC2 H4 COCH3 as another variant of the same filler. It was seen that
with LA treated shell composites showed highest tensile and elongation
at break at 20 wt% loading followed by acetic acid treated. Hardness
of all the samples were found to be the same irrespective of filler load-
ing. It was seen that LOI of composites increased with increase in filler
loading and highest LOI was seen for NaOH-treated shells used as filler,
followed by LA modified at 50 wt% loading. Thus, environment friendly
composites can be made out using these biofillers [180]. With adding
value to agriculture residues and avoiding tedious chemical treatment
for low yield extraction from them, these fillers can also be used as
biofillers for polymer matrix. PP biocomposites were made using SEBS-
g-MA as compatibilizer and various fillers such as almond shell powder,
coir, apricot, argan, wood and their mixture. It was seen that composites
shown increase its mechanical properties with increase in filler content
linearly [181]. Peach waste was also used to make biocomposites using

13
A.S. Mohite, A.R. Jagtap, M.S. Avhad et al.
HDPE as matrix. Peach waste is mainly composed of peels, seeds, trim-
mings, etc which would have mainly gone into landfill, liquid waste, an-
imal feed, and others. Peach seeds were processed into flour and along
with HDPE-g-MA incorporated into the HDPE matrix ranging from 2.5
to 20%. With about 2.5-5% of loading comparable mechanical proper-
ties were obtained and further incompatibility was obtained due to hy-
14
Energy Nexus 7 (2022) 100134
Fig. 17. Mechanical properties of wood apple shell compos-
ite [173].
Fig. 18. Mechanical properties of coconut shell composite
[173].
Fig. 19. Effect of 5 % loading of filler (rambutan peel flour)
[175].
drophobicity and hydrophilicity between matrix and filler respectively
[182].
Apart from application in polymer industry crop residues are also
popular for fuel production, in construction industry etc. Table 8 repre-
sents some of the application of crop residues in other industries.
A.S. Mohite, A.R. Jagtap, M.S. Avhad et al. Energy Nexus 7 (2022) 100134

Fig. 20. Flame retardant value of Date stone/polyamide (a) Time of ignition vs type of sample and (b) Time to flame out vs type of sample.

Fig. 21. Water vapour transmission rate vs concentration of

apricot shell and walnut shell powder.

Table 8
Usage of crop residue in other application sectors.

Sr. No. Type of residue Application Reference

1. Rice Straw Adsorbent material for Zn and Cu ion removal [194]

2. Rice Husk Production of Bio-ethanol [32,33]
3. Rice Husk Lightweight building material [195]
4. Rice Husk High Capacity lithium batteries [196]
5. Rice Husk Ash Production of silicon carbide [197,198]
6. Rice Husk Ash Synthesis of zeolites and mesoporous material [199]
7. Broken Rice Production of Lactic Acid [200,201]
8. Broken Rice Antioxidants, anti-aging used for cosmeceutics [202]
9. Wheat Husk Manufacture silica-based products such as zeolites, metal silicates, composites, aerogels [203]
10. Wheat bran Wheat bran polymer-based oil gelling agent [204]
11. Wheat bran Usage of arabinoxylans from wheat bran for production of food packaging films [205]
12. Corn Straw Production of Biogas [206]
13. Corn Cob Production of Biofuel [207,208]
14. Corn Cob Activated charcoal- water recycling [209]
15. Corn Cob Ash Blended with Cement [210–212]
16. Corn Cob Lightweight Mansory [213,214]
17. Corn Cob Pore Forming agent in ceramic bricks [215]
18. Corn Cob Synthesis of SiC nanoparticles [216]
19. Corn Cob Silica [217]
20. Corn Cob Synthesis of polymeric flocculant [218]
21. Watermelon rind and seeds For recycling of wastewater by removal of dyes [219–221]
22. Sorghum milling waste, sorghum bran Bioethanol [222]
23. Sorghum stalks Porous carbon for supercapacitor [223]
24. Sorghum stem and root Removal of chemical dyes and ions from wastewater [224]
25. Sorghum waste nanorods of SiC [225]
26. Sorghum waste Lightweight brick [226]
27. Sorghum bagasse Bio-oil – further treatment gives mixed phenol [227]
28. Rice bran and finger millet seed coat Extraction of xylan [228]
29. Pearl millet Biofuel [229]
30. Pearl Millet Husk Removal of dyes from wastewater [230]
31. Pearl millet straw Biogas production [231]

15
A.S. Mohite, A.R. Jagtap, M.S. Avhad et al.
7. Conclusion and future prospective
The crop residue can include pre-harvest and post-harvest of crops
such as Rice, Wheat, Maize, locally available fruits such as Jackfruit, Wa-
termelon, and citrus fruits and Millets. One of the most used techniques
to deal with crop residue is burning. But, the burning of crop residue
creates soil and air pollution, release huge amount of carbon dioxide,
carbon monoxide and sulphur dioxide, create a haze in the environment,
leads to increase in the temperature and it is threat to the environment,
leads to health problem due to the pollution. Hence, the need of sustain-
able techniques to deal with crop residue is need of today’s world. On
the other hand, polymer composites find application in various fields
such as automotive, space, agriculture, electronics, construction indus-
try etc. The reinforcement of filler to the polymer improves its strength,
dimensional stability, thermal stability, sound insulation properties etc.
based on the type of filler. The conventional fillers are obtained from
petroleum resources and considering the depleting sources of petroleum
sources there is a need of sustainable resources. The crop residue is one
of such kind of waste has huge potential in it, is sustainable in nature.
With its incorporation in polymer and making of polymer composites,
the minimization of polymer use can be achieved through its composites
form by having an eco-friendly reinforcing phase. The resource material
for fillers in composite could be agricultural waste obtained from cere-
als, fruits, and millets as they are widely grown with surplus residue.
The polymer composites are increasingly used in various sectors where
the mechanical, as well as morphological properties, are of immense im-
portance. The incorporation of fillers synthesized from crop residue with
some pre-treatment improves the mechanical properties of composite
substantially. The use of biocomposite is also cost-effective with respect
to replacing commercial fillers (e.g. carbon black, aluminium silicate)
and utilization of agricultural residue which otherwise are burned, com-
posted, or thrown away into landfills and thus missing an opportunity to
get utilized accord astonishing results. There is need of awareness and
establishment of proper channelling for the utilization of crop residue
in polymer industry for various applications.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
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