Journal of Macromolecular Science, Part A

Pure and Applied Chemistry

ISSN: (Print) (Online) Journal homepage: https://www.tandfonline.com/loi/lmsa20

Green composites of bio-based epoxy and waste

tea fiber as environmentally friendly structural
materials

Nobomi Borah & Niranjan Karak

To cite this article: Nobomi Borah & Niranjan Karak (2023) Green composites of bio-based
epoxy and waste tea fiber as environmentally friendly structural materials, Journal of
Macromolecular Science, Part A, 60:3, 217-229, DOI: 10.1080/10601325.2023.2177171

To link to this article: https://doi.org/10.1080/10601325.2023.2177171

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JOURNAL OF MACROMOLECULAR SCIENCE, PART A: PURE AND APPLIED CHEMISTRY
2023, VOL. 60, NO. 3, 217–229
https://doi.org/10.1080/10601325.2023.2177171

Green composites of bio-based epoxy and waste tea fiber as environmentally

friendly structural materials
Nobomi Borah and Niranjan Karak
Advanced Polymer and Nanomaterial Laboratory (APNL), Department of Chemical Sciences, Tezpur University, Napam, Tezpur, Assam, India

ABSTRACT ARTICLE HISTORY

Bio-derived epoxy green composites were fabricated using waste tea fibers and their durability Received December 2022
was studied under aggressive environments. The fibers were first mercerized and subsequently Accepted January 2023
functionalized with maleic anhydride. Functionalization resulted in improved adhesion as well as
KEYWORDS
uniform distribution of the fibers in the matrix. Although, the tensile strength was lower than the
Biocomposite; durability;
pristine, improvements were recorded in their mechanical strengths (tensile strength up to natural fibers; polymer-
16.1 MPa) compared to un-modified ones, with good elongation at break (23.8%). The green com- matrix composite;
posites also demonstrated good thermal stability up to 244
C. On investigating the durability thermosetting resins
toward disparate chemical and physical environments, all the materials exhibited high resistance
under extreme temperatures (2 and 70
C) and UV irradiation and showed remarkable enhance-
ments in tensile strength after aging (up to 65.8% and 49.5%, respectively). This study ensured
promising outdoor applications of this green composite derived using waste materials as a benign
durable material.

GRAPHICAL ABSTRACT

1. Introduction formulated to alleviate environmental hazards by practicing

raw materials from natural renewable resources to offer
The incessant drainage of naphtha derivatives and the bur-
optimum sustainability to the material without losing their
geoning awareness toward environment have shifted the cur-
competence.[3]
rent scenario of material research toward greener aspects by Amongst the commercially exploited thermosetting poly-
promoting bio-based renewable resources as the synthons. mers in the biocomposite industry, epoxy thermoset has
Revolutionary changes have been recorded in the field of been considered as a front runner. However, their depend-
structural materials on replacing the expensive, heavy ency on the nonrenewable resources raises questions on sus-
weighted materials like metals, and alloys. by easily process- tainability which can be addressed by using greener
able polymers.[1] Polymeric composites are such inexpensive precursors for obtaining the epoxies. Different greener or
and light weight replacements that are designed so far for bio-based epoxy resins have been synthesized in recent times
high performance structural applications. They generally that serves as potential replacements for petroleum-based
composed of synthetic polymers and synthetic carbon, glass, ones.[4] For this purpose, a bio-based epoxy was synthesized
aramid, etc. fibers derived from nonrenewable resources that using tannic acid (TA) as the starting material in our previ-
make them non-biodegradable and less environment ous work via a facile method.[5] Further, to address the
friendly.[2] In this milieu, biocomposites have been problems elevated from their brittleness character, the epoxy

CONTACT Niranjan Karak [email protected] Advanced Polymer and Nanomaterial Laboratory (APNL), Department of Chemical Sciences, Tezpur
University, Napam, 784028, Tezpur, Assam, India
Supplemental data for this article can be accessed online at https://doi.org/10.1080/10601325.2023.2177171.
ß 2023 Taylor & Francis Group, LLC
218 N. BORAH AND N. KARAK

thermosets were reinforced with fibers and particulates vary- durability and performance under disparate environmental
ing from macro to nano dimensions that enhanced their conditions.[19] Alsaadi et al. studied the interlaminar fracture
crack-resistance ability.[6] One of such in-line reinforcements behavior of glass fiber/sewage sludge ash/epoxy composite
used in the production of biocomposites is natural lignocel- under accelerated UV radiation which revealed a significant
lulosic fibers which are renewable, biodegradable, cost effect- loss of weight and strength after 250 h of aging.[20]
ive, easily processible, and have low density and high Durability of a coriander straw/polypropylene composite
volume that make them efficient and sustainable replace- was studied in UV and hygrothermal aging conditions
ments of synthetic fibers.[7,8] Fibers obtained from the seeds, where declinations were recorded in tensile, flexural and
stems, and leaves of hemp, sisal, flex, jute, rice straw, coco- impact strength that questioned it’s suitability for outdoor
nut, etc. have been extensively utilized as the reinforcing applications.[21] These facts demanded the designing of a
agents in the fabrication of epoxy biocomposites.[9] sustainable green composite that could offer superior resist-
Yet, natural tea fibers produced in millions of tons every ance toward extreme weathering conditions. Nevertheless,
year in the tea factories of India and other countries as the the engineering materials highlighted above are although
by-product is a waste material that requires judicious man- thought to be biobased and environment friendly, but the
agement.[10] Discarding this tea waste into the surrounding actual environmental impact (EI) they may impart in their
not only pollutes the environment but also results in loss of
lifetime, starting from the production to dissimilation, is
great volume of resources that can be recovered from the
enigmatic and hence needs critical investigation. In this
wastes. Therefore, valorization of these tea waste is of prime
regard, a method called life cycle assessment is adopted uni-
importance and different approaches have been already
versally to study the impact of a material on disparate envir-
adopted for their uses as food in poultry, raw materials for
onmental parameters during its lifetime via a “cradle to
caffeine extraction, biofertilizer production, etc.[10] A signifi-
grave” approach.[22] Interestingly, studies presenting such
cant amount of research have already been dedicated to the
analysis on natural fiber reinforced biocomposites have been
utilization of tea waste, particularly in the area of material
engineering.[11,12] For example, cellulose nanocrystals, [13] concluded to consume about 60% lesser energy than the
cellulose nanofibers,[14] etc. were derived from the waste synthetic alternatives which inspires the practice of these
brewed tea leaves. A hybrid epoxy biocomposite was pre- materials for biocomposite fabrication.[23]
pared by Prabhu et al. by employing glass, kenaf, and waste The present work, therefore, has been objectified to util-
tea leaf fibers together as the reinforcing agent in an epoxy ize waste tea fibers as reinforcing agent in a biobased epoxy
matrix that showed high tensile strength (70.8 MPa) with (TAE) derived from TA for the production of a green com-
10% glass, 25% kenaf, and 5% tea fibers and exhibited posite. Instead of using nonrenewable resource based syn-
debasement in strength with the increase of tea fiber load- thetic reinforcing agents or renewable well-known plant
ing.[15] Hussin et al.[16] derived a biocomposite from unsat- fibers, we have chosen waste tea fibers as the reinforcing
urated polyester as the matrix and brewed tea waste as the agent so as to minimize waste generation as well as to bring
natural filler. However, the biocomposites yielded lower in sustainability into the developed material. The waste tea
mechanical strength (15.7–4.3 MPa) compared to the bare fibers were first mercerized and subsequently functionalized
polyester (23.5 MPa). This lowering of mechanical strength with MAH on the surface prior to their use as the reinforc-
was attributed to the poor interaction between the matrix ing agent in the epoxy matrix. Functionalization of tea fibers
and the fibers which can be improved by lowering the with MAH resulted in superior adhesion of the epoxy on
amorphous content of the fibers or by modification. In this the fiber surface that led to changes in their overall perform-
context, different surface modification methods including ance. Different aging tests were conducted to determine the
silane coupling, acrylation, KMnO4 treatment, peroxide weathering resistance and durability of the green composites
treatment, etc. were applied on the natural fibers.[17] against disparate environmental conditions.
However, very less efforts have been attempted for utiliza-
tion of tea fibers with their modification. Maleic anhydride
(MAH) is a renowned modifier and compatibilizer, that has 2. Experimental
been utilized in the biocomposite industry primarily for 2.1. Materials
grafting of natural or synthetic polymers by radical initiated
polymerization process.[18] Direct functionalization of MAH Waste tea fibers were collected from a local tea factory of
on fiber surface is rarely explored until Mishra et al. used it Assam, India. TA and epichlorohydrin (ECH) used for the
for surface modification of three different fibers by subject- preparation of TAE were purchased from Sigma Aldrich and
ing them to 2% MAH solution for 16 h.[18] Incorporation of Sisco Research Laboratory (SRL) Private Ltd., India, respect-
MAH on the surface of tea fibers to be used as reinforcing ively. Sodium hydroxide (NaOH), sodium chloride (NaCl),
agent for an epoxy biocomposite (green composite) has not and sodium sulfate anhydrous (Na2SO4) used for various
been reported so far and thus it paves new horizons of purposes were obtained from Merck, India. Poly(amido
research in this field. amine) hardener was obtained as a gift sample from Asian
These natural fiber reinforced biocomposites are widely Paints, India and used. Tetrahydrofuran (THF, used post
explored in the field of automobile, aerospace, and construc- distillation) and acetone were obtained from SD Fine
tion industries which necessitate investigation of their Chem., India. MAH was obtained from LobaChemie, India.
 JOURNAL OF MACROMOLECULAR SCIENCE, PART A: PURE AND APPLIED CHEMISTRY 219

2.2. Preparation of the bio-based epoxy (TAE)

The bio-based epoxy resin derived from TA was prepared
by following a previously reported procedure, the detail of
which is described in the Section SI.1.1 of Supporting
Information (SI).[5]

2.3. Fiber isolation and modification

The factory tea waste has been utilized for tea fiber extrac-
tion. The tea waste fibers were first separated from the tea
waste by repeated sieving via sieves of different pore sizes
(0.5-1.5 mm). The residual fibers were then dipped in cold
distilled water for 24 h to remove dirt and impurities and
then dried in an oven at 50
C. The dried fibers were trans-
ferred to a round bottom flask with a magnetic stirrer and
subsequently were treated with 2% NaOH at 50
C for 2 h
by maintaining a fiber to solution ratio of 1/25 g.mL1. The
mixture was then vacuum filtered, washed with 1% acetic
acid solution followed by washing with distilled water sev-
eral times for neutralization. Finally, the fibers were washed Figure 1. (a) Schematic representation of the steps involved in the functionali-
zation and fabrication of green composites and (b) green composites as final
2–3 times with acetone and placed in an oven at 60
C for products.
drying until constant weight was obtained and coded
as MTF. 10 min for obtaining proper mixing of the resin and the
fibers. The resulted content was then evenly cast inside a
metal mold (inner dimensions of 10 cm  5 cm  0.1 cm)
2.4. Functionalization of MAH to MTF
placed above a 20 cm  15 cm Teflon sheet and kept at rt for
The mercerized tea fibers were further treated with MAH 24 h for the removal of free solvent.
for obtaining superior interaction between the fibers and the In the third step, the content was compressed and cured
epoxy matrix. For the treatment, 3 g of fibers were impreg- by a two-step curing process. Prior to the curing, the mold
nated in a 3% MAH solution in acetone (1/50 g.mL1 fiber with prepreg was placed under vacuum for 2–3 h to remove
to solution ratio) for a period of 16 h at 65 ± 2
C. After residual water or solvent trapped inside the prepreg. The
completion of the process, the modified MTF fibers were content was then subjected to compression molding in a
repeatedly washed with acetone to remove the excess MAH, hydraulic press under a pressure of 50–60 kN in two stages,
dried overnight at 60
C and stored in a desiccator (coded first at 80 ± 3
C for 30 min and then at 100
C for 45 min.
as MTF-f-MAH) for the subsequent usage. After cooling, the molded green composite was removed
The grafting percentage have been calculated by Soxhlet from the compression press and post cured at 120
C for
extraction of the modified fiber in acetone by using Eq. (1). 30 min. Fig. 1a represented the steps involved in the fabrica-
tion process with a digital image of the final product in Fig.
Grafting percentage ¼ ððW2  W1 Þ=W1 Þ  100 (1)
1b. As depicted in Table 1, different compositions of the
where W1 and W2 are the amount of MTF and pure MTF-f- green composite were prepared following the same proced-
MAH respectively.[24] ure using MTF and MTF-f-MAH as the reinforcing agents
and coded as GCx or MGCx respectively. The x refers to
the first digit of percentage of fiber weight present in the
2.5. Fabrication of green composite green composites with respect to the resin weight.
The preparation of the green composite comprises of three
stages. The first step involved wetting of the fibers with the
2.6. Characterization
epoxy resin. An amount of 5.0 g of TAE was taken in a
100 mL beaker and 2 mL of distilled THF was added into it to The detail of the instrumentations utilized in this work for
make a low viscous resin mixture. Then 1.5 g of MTF-f-MAH characterization and property evaluation of the composites
(30 weight % of TAE) was taken in a petri dish to which the is elaborated in Section SI.1.2 of SI.
resin solution was poured slowly and mixed homogeneously
with the fibers for proper wetting. The epoxy impregnated
2.7. Aging test
MTF-f-MAH was kept in a vacuum desiccator at room tem-
perature (rt) for 48 h to obtain good adhesion of the resin on To understand the suitability of the green composites under
the fiber surface. After completion of the wetting process, the the practical environmental conditions, samples were sub-
required amount of poly(amido amine) hardener was added jected to four different artificial aging conditions, viz. media
into the prepreg in the next step followed by hand mixing of with three different pH (4, 7 and 9), UV and two extreme
220 N. BORAH AND N. KARAK

Table 1. Compositions of the green composites.

Composite code TAE (g) MTF (g) MTF-f-MAH (g) Poly(amido amine) (g) Fiber to resin ratio (% of fiber w.r.t. resin)
GC2 6.0 1.2 — 2.0 1:5 (20%)
GC3 5.0 1.6 — 1.6 1:3 (30%)
GC4 4.0 1.6 — 1.5 1:2.5 (40%)
MGC2 6.0 — 1.2 2.0 1:5 (20%)
MGC3 5.0 — 1.6 1.6 1:3 (30%)
MGC4 4.0 — 1.6 1.5 1:2.5 (40%)

Figure 2. (a) Plausible mechanisms of MAH interaction with MTF, (b) crosslinking between MTF-f-MAH and TAE during impregnation, and optical microscope
images of (c) GC4 and (d) MGC4 showing fiber dispersion in the matrix.

temperatures exposure (2 and 70
C), and solvents (in THF thermoset). MAH is primarily used as a grafting agent for
and EtOH). The detail of the aging process is provided in polymers like polypropylene,[25] polystyrene,[18] poly(buty-
the SI under section SI.1.3. After the aging test was com- lene succinate),[26] where a radical initiated mechanism is
pleted, the mechanical properties of the composites were followed for grafting of MAH into the polymeric backbone
measured. that further acts as the compatibilizer for the fibers and the
matrix. Conversely, Mishra et al. carried-out MAH grafting
on banana, hemp and sisal fibers for preparing polystyrene-
2.8 Water absorption capacity fiber composites.[18] However, the mechanism of interaction
Water absorption ability of green composite was measured between the fiber surface and MAH remained unexplained.
to understand their moisture withstanding ability by follow- The percentage of MAH present on the fiber surface,
ing the ASTM D570-98 standard. The detail procedure obtained after repeated washing of the fibers with acetone
adopted is described in Section SI.1.4 of SI. using Soxhlet extraction, was found to be 18.2% as calcu-
lated from Eq. (1). Fig. 2a represented the two most prob-
able binding modes of MAH to MTF.[27] During the
2.9. Soil burial test modification process, the nucleophilic hydroxyl groups of
the fiber-surface would either open up the MAH ring con-
The soil burial test was carried for the composites in order verting it to maleic acid or bind the MAH ring to itself via
to find out their biodegradability. The experimental details hydrogen bonding as shown in Fig. 2a. Again, while impreg-
are provided in SI under Section SI.1.5. nation of MTF-f-MAH with TAE, the carboxylic acid groups
originating from MAH might be crosslinked with the epoxy
3. Result and discussion rings of TAE thereby acting as an interface between TAE
and the fiber in a similar way as shown in Fig. 2b.[28] To
The objective of preparing the green composites was to add understand the bonding mechanism, an ATR-FTIR analysis
value to tea waste, produced in a huge scale every year by was carried out for TAE impregnated MTF-f-MAH (codded
the tea factories, as well as to replace the synthetic or petro- as impMTF-f-MAH) and MGC for equivalently weighted
derived fillers by bio-derived ones. The advantage of these samples. Further, the FTIR spectrum and 1H NMR spectrum
green composites lies in their more bio-content compared to of TAE resin are presented in Figure SI.1 and Figure SI.2
the TAE thermosets. Addition of 20-40% tea waste fiber as along with their explanation in SI. From the absorbance ver-
the filler enhanced the bio-content of the green composites sus wavelength plots of impMTF-f-MAH and MGC, it was
from 32.9 to 37.3% (compared to 24.7% bio-content in TAE clear that some changes obviously took place as seen from
 JOURNAL OF MACROMOLECULAR SCIENCE, PART A: PURE AND APPLIED CHEMISTRY 221

Figure SI.3. In case of impMTF-f-MAH, the absorbance cor- fibers.[11] Furthermore, to probe the interaction between
responding to carbonyl peak at 1714 cm1 which originated MAH and MTF after the modification, FTIR spectrum of
from free acids and ester groups was 0.172. While the same the MTF-f-MAH was analyzed. Characteristic peaks
in MGC decreased to 0.102 due to transesterification and appeared in the spectra indicated a successful functionaliza-
crosslinking with epoxide rings that consumed some acidic tion. The peaks were present at 1712 cm1 corresponds to
groups. At the same time, new peaks appeared at 1641 cm1 the C ¼ O group and at 1598 cm1 for the C ¼ C vibration
due to formation of amide linkages from the crosslinking of MAH moieties. Apart from these, peaks appearing at
with the hardener. Similarly, peak at 1590 cm1 with absorb- 1032 cm1 (C-O stretching vibration), 863 cm1 and
ance 0.152 that was due to the unsaturation originating 833 cm1 (C-O-C ring stretching), 760 cm1 (ring C-H
from the unsaturated moieties present in the benzene and bending) supported the functionalization reaction with
MAH rings. The peak became less intense in MGC with MAH.[26,29] This could also be perceived from the shifting
absorbance value 0.118 which might have happened con- and sharpening of the peak at 3352 cm1 corresponding to
sumption of some unsaturation through Michaels-type reac- OH stretching of the surface hydroxyl groups of the fibers.
tion as described later, while the benzene ring content was Fig. 3b showed the FTIR spectra of all the composites which
constant. Because of this interaction, strong adhesion of displayed characteristic absorption peaks namely: at
TAE with the MTF surface was achieved that improved their 3320 cm1 for OH stretching of hydroxyl groups of the
dispersion and alignment in the matrix and further boosted fibers and TAE, 2923 cm1 for aliphatic CH stretching origi-
the performance of the material. The optical microscope nating form cellulosic fibers and the hardener, 1707 cm1
images of the green composites clearly demonstrated the for C ¼ O stretching of MAH carbonyl and TAE ester
improvement in fiber dispersion, as properly distributed and groups, 1428 cm1 for N-H bending and 1204 cm1 for C-N
aligned fibers were seen in the recoded microscope images stretching originating from the amide groups of poly(amido
of MGC4 (Fig. 2d) compared to GC4 (Fig. 2c). The lack of amine) hardener, and 863 cm1 due to the aromatic C-H
coupling agent resulted in agglomeration between the fibers deformation, originated from the rings present in TA of
causing an indecorous distribution throughout the matrix TAE.[5]
for GCs.
3.2. Thermal analysis
3.1. FTIR spectral study
The thermal degradation profiles were presented in Fig. 4a,b
FTIR spectral study was performed to obtain the structural and in Table SI.1. As seen from the TGA thermograms and
characterization of the MTF, MTF-f-MAH and the green DTG graphs of MTF and MTF-f-MAH displayed in Fig. 4a,
composites. Fig. 3a displayed the FTIR spectra of MTF and initial 5–10% weight loss was because of the elimination of
MTF-f-MAH which supported a successful functionalization entrapped acetone and water in the fibers. The weight loss
of MAH on the fibers. The IR bands that matched different percentage of MTF-f-MAH for this early decomposition
functionalities present in the MTF appeared as: a broad stage was low compared to weight loss of MTF, signifying a
band at 3410 cm1 for OH stretching vibration of hydroxyl comparatively lower moisture content of MTF-f-MAH.[30]
groups present in cellulose as well as absorbed water moi- This might be attributed to the partial hydrophobicity
eties, at 2915 cm1 for CH stretching and a broad band at induced by functionalization of MAH on MTF which was
1642 cm1 corresponding to C ¼ O stretching vibrations.[13] inhabiting the surface sites and thus preventing the fibers
Another small peak present at 896 cm1 is due to the from adsorbing moisture. Nevertheless, MTF-f-MAH
ꞵ-glycosidic linkages between the sugar units present in the showed an advance second stage degradation profile staring

Figure 3. FTIR spectra of (a) MTF and MTF-f-MAH, and (b) green composites.
222 N. BORAH AND N. KARAK

Figure 4. (a) TGA profiles with inset DTG curves of MTF and MTF-f-MAH and (b) TGA and (c) DTG profiles of green composites.

matrix resulting in a good dispersion.[33] MGCs displayed

an extended region of first stage degradation up to tempera-
ture of 170
C owing to the decomposition of MAH moiety
present on the fiber surface. The second degradation stage
between 230
C and 380
C was attributed to the depolymer-
ization of lignocellulose and damage of glycosidic link-
ages.[32] The final degradation stage included degradation of
the lignin and celluloses leading to char formation near the
temperature range of 400
C to 600
C. The results obtained
are in aligned with the TGA profiles of some reported bio-
composites, showing greater char yield and hence better
thermostability of chemically treated fibers.[34]

3.3. Mechanical properties

Figure 5. Tensile strength of the green composites with TAE (stress-strain curve
of TEA is reproduced from reference 5 for better understanding, To apprise the effect of chemically modified fiber reinforce-
Copyright@2022, Wiley). ment on the green composites, the mechanical properties, in
particular, stress, elongation at break, impact resistance,
from 125
C to 177
C with a peak degradation temperature hardness, and scratch resistance (hardness) of the compo-
at 155
C (shown in the inset of Fig. 4a), which can be sites were determined, and the average values are listed in
ascribed to the breakage of MAH moieties incorporated on Table SI.2. The green composites exhibited lower tensile
the fiber surface.[31] The appearance of such degradation strength than the pristine thermoset as shown in Fig. 5. This
profile was evident of a successful functionalization. This may be due to the improper adhesion of the matrix into the
was followed by a third degradation stage between 200
C to fibers, especially un-modified waste tea fibers. The max-
380
C resulting from the damage of lignocellulose. Such imum tensile strengths recorded were 12.74 MPa and
peculiar behavior was absent in MTF that displayed the 16.17 MPa, respectively for GC4 and MGC4, with 40% fiber
second degradation stage for lignocellulosic damage.[32] loading, whereas pristine TAE thermoset showed 17.2 MPa
Moreover, the char residue obtained for the MTF-f-MAH tensile strength. Similar results were obtained for a biocom-
was 1.39 times higher than the MTF revealing greater ther- posite made up of polystyrene and tea waste where the bio-
mostability of the former. The evaluation of the thermal composites showed lower tensile strength than the bare
data, along with the FTIR spectral analysis supported the polymer.[16] Other reports where waste tea fibers were used
success of the functionalization on the MTF surface. also revealed similar kind of results.[12] The biocomposites
The degradation of all the GCs and MGCs commenced of tea mill waste fibers embedded in polypropylene and
with an initial 2–8% weight loss within the temperature high-density polyethylene exhibited maximum stress of
range of 50–110
C accredited to the loss of absorbed water 17.02 MPa and 22.24 MPa and strain of 7.78% and 6.39%,
or solvent molecules. A clear increment (around 100
C) in respectively for 10% fiber loading.[12] For the MGCs, how-
the first degradation peak temperatures was observed in the ever, reinforcement of MTF-f-MAH imparted a bolstering
green composites compared to the fibers indicating effect in the green composites leading to the improvements
enhanced thermostability of the materials as shown in the in the tensile strengths in comparison to the GCs of similar
DTG curves in Fig. 4c. The better thermostability of the composition. This could be attributed to the fact that a
green composites MGCs compared to GCs could be ascribed proper interfacial adhesion is required between the fibers
to the improved interfacial adhesion of the resin to the and resin for gaining optimum mechanical strength, which
fibers after functionalization with MAH. As stated by other is dependent on the surface chemisorption of the resin on
reported studies, modification of the fibers altered the polar- the fibers.[35] In this situation, MAH acted as an interface
ity of the fibers which enhanced their miscibility over the between the fibers and the matrix which improved the
 JOURNAL OF MACROMOLECULAR SCIENCE, PART A: PURE AND APPLIED CHEMISTRY 223

3.4. Scanning electron microscopy (SEM)

The SEM images of tensile fractured surfaces of the green
composites were recorded for understanding the interactions
of fibers with the matrix. Fig. 6a–d displayed the SEM
images of the fractured surfaces of GC2, GC3, GC4, and
MGC4, respectively. The last image explicitly revealed a
strong fiber-matrix bonding present between the epoxy
matrix and the waste tea fibers in MGC4. This is owing to
the comparatively improved adhesion between epoxy and
the MAH treated fibers. However, a comparable roughness
was observed for the fractured surfaces of GCs and MGCs.
Further, the presence of fiber bundles instead of evenly dis-
tributed fibers in the case of GC2, GC3 and GC4 was
observed in Fig. 6a–c. This image also showed the voids as
created by the pulling-out of fibers. From 500 magnifica-
tion of GC3 shown in Fig. 6b, pulled out fibers are seen
Figure 6. SEM images of the fractured surfaces for (a) GC2 at 330, (b) GC3 at which clearly indicated the poor adhesion of fibers with the
500, (c) GC4 at 500, and (d) MGC4 at 500.
epoxy matrix. Furthermore, the distinct fiber-matrix inter-
face observed in Fig. 6a–c revealed the presence of poor
compatibility between these otherwise incompatible compo-
adhesion of the matrix to the fibers resulting from improper
nents ensuing evenly aligned and dispersed fibers through- wetting. In addition, cracks on the epoxy matrix surround-
out the material. MGC3 and MGC2 recorded slight ing the fiber bundles originated from the applied load were
improvement in the tensile strength values than GC3 and also visible in Fig. 6a–c indicating lower crack resisting abil-
GC2 as seen in Table SI.2. Further, the MGCs showed ity of MTF in GCs. Similar kind of fiber bundling and
enhancement in elongation at break values (24.2%, 23.9%, cracks were also observed in starch-jute epoxy biocompo-
and 23.8% for MGC2, MGC3, and MGC4, respectively) site.[2] A porous structure, matrix and fiber breakages were
compared to the GCs (13.8%,16.8%, and 16.5% for GC2, observed in a pineapple, sisal fibers and TiO2 reinforced
GC3, and GC4 respectively) owing to their improved fiber- hybrid epoxy composite which was due to the improper
resin bonding. Apart from the cellulosic structure present in adhesion of the matrix into the fiber surface.[37] In the case
the fibers and the aliphatic chains of poly(amido amine) of MGC4, the fiber-matrix interface was clearly suggesting
hardener, the aliphatic moiety is also resulted from the an adequate adhesion of the epoxy around the fibers. The
opening of MAH rings and ester linkages might be playing imprints left by the pull-out fibers visible in Fig. 6a for
a crucial role in enhancing flexibility of the material. GC2, 6c for GC4 and 6d for MGC4 reflected ability of the
Nevertheless, the anomaly recorded in elongation at break matrix to partially transfer the load to the fibers during the
values might have originated from the diverse sized fibers fracture under tensile load.[27]
available in the composite that effected their elasticity to dif-
ferent extents. Similar results were also obtained in the
3.5. Aging tests
starch jute fiber biocomposite coated with epoxy.[2]
The toughness values of the green composites are given For achieving prospective applications of the designed green
in Table SI.2 and the results displayed an increasing trend composites, evaluation of their weather resistance and dur-
with the increase of fiber content. The MTF-f-MAH ability under different environmental conditions is crucial.
reinforcement remarkably enhanced the toughness of the To inspect the same, all the composites were subjected to
green-composites with a maximum recorded value of disparate aging environments. The mechanical strengths and
231.2 J/m3 assigned to MGC4. Similar trend was observed their weight losses were determined to understand their
for the hardness (Shore A) values as well, which exhibited a combating ability on post aging process. The subsequent
maximum of 98 for MGC4. The impact energies of the sub-sections described the results obtained from the differ-
materials were also measured by the standard falling ball ent aging processes for the fabricated green composites.
method. As observed from Table SI.2, there is no significant
difference between the impact energies of the GC2, GC3, 3.5.1. Chemical aging
and GC4; albeit MAH functionalization enhanced the The tensile strength values of the green composites after
impact energies of MGC2, MGC3 and MGC4. This could be chemical aging are presented in Fig. 7a. The pristine
attributed to the upgraded matrix-fiber interaction via the thermoset suffered significant debasement in strength on
coupling agent MAH which acted as the stress transfer agent exposure to these media as evident from Fig. 7a.
to spread the stress from the fiber to the matrix and helped Comparatively, the green composites exhibited good resist-
in withstanding the sudden impact experienced by the com- ance, while marginal enhancements in the tensile strengths
posites.[36] The scratch hardness values recorded for the were observed in acidic medium for some compositions that
materials indicated their high toughness values. reflected their superiority over similar kind of
224 N. BORAH AND N. KARAK

Figure 7. (a) Tensile strengths of the aged green composites and TAE at pH 4, 7, and 9; and (b) weight loss (%) profiles in the tested media.

from Table SI.3, the diffused water and alkali molecules

through the fibers to the epoxy network disturbed their
mutual interactions and imparting unusual softness to the
material. At pH 7, a maximum retention of 74.3% was
shown by GC2, while at pH 9, GC4 showed the maximum
retention of 93.5% as provided in Table SI.3. In parallel, the
alkali and water molecules may hydrolyze the ester or ether
linkages of the polymer and damage the fibers, causing not-
able erosion of the surface. This was reflected in the weight
loss percentages of the green composites as shown in Fig.
7b. The low weight loss recorded for GCs might be
explained from the presence of fiber bundles instead of
evenly dispersed fibers which rendered greater exposure of
the fibers to the solutions. Similar outcomes were reported
Figure 8. Tensile strengths of the green composites and TAE after UV and heat by Saadatmanesh et al.,[40] where composites made up of
aging.
loose glass fibers laminates were exposed to alkaline, neutral
and acidic media (pH 12.5, 10, 7 and 2.5). Their results
biocomposites, as reported earlier.[38] The elevation or reten-
showed significant declination in the tensile strength values,
tion percentages in tensile strengths obtained after aging are
while unidirectional and bidirectional bundled glass fiber
presented in Table SI.3. The green composites showed eleva-
laminates showed better performance in these solutions
tion in tensile strengths ranging between 5.3% to 6.2% for
owing to lower penetration rate.[40]
GC2 and GC4 when exposed to acidic medium, others
showing declination in the same. These might have occurred
due to two counteracting phenomena happening simultan- 3.5.2. UV aging
eously inside the material framework. The diffusion of the The UV resistance of the fiber reinforced green composites
solute molecules from the solution caused their inhabitation established to be a crucial aspect for designing outdoor-
in the interstitial voids present throughout the polymer net- based prospective applications. The specimens exhibited
work. These residing solute molecules subsequently weak- superior resistance toward UV irradiation revealing their
ened the interfacial interaction between the matrix and inordinate efficiency for exterior practices as demonstrated
fibers decreasing the crosslinking density and hence the in Fig. 8 showing the observed strength of the composites
strength.[39] At the same time, they originated secondary after UV exposure. The elevation observed in the tensile
crosslinking with the fibers and the epoxy network through strength of all the compositions ranged from 16.6 to 49.5%
Van der Waals forces or hydrogen bonding further rigidify- as computed in Table SI.3. The process of UV irradiation
ing the material to offer greater mechanical strength. involved a complex mechanism including chain sessions,
Moreover, the formation of new ether linkages in the acidic rearrangement, cracking of the surface, crosslinking, etc.,
medium might have resulted in this improvement in tensile leading to apparent stiffening of the materials. The presence
strength.[39] As a result, marginal changes were recorded in of epoxy and fibers further enhanced the intricacy of the
the green composites exposed to acidic medium. All the process as both these components performed in opposite to
compositions however suffered from visible debasement in each other during the aging. The traces of lignocellulose pre-
their tensile strength values when exposed to neutral and sent in the fibers absorbed the UV light causing to degrade
alkaline media. As seen from the retentions (%) in strength the epoxy present around them, while the epoxy resisted the
 JOURNAL OF MACROMOLECULAR SCIENCE, PART A: PURE AND APPLIED CHEMISTRY 225

Figure 9. Tensile strength of the green composites and TAE after solvent aging in THF and EtOH, and (b) weight loss (%) with inset digital images of surface ero-
sion during solvent aging.

diffusion of oxygen restricting the photodegradation of the elevations could be attributed to the physicochemical
fibers assisted by radical formation. Moreover, the antioxi- changes, initiated in the composites by extreme temperature
dants; lignin and TA present in the fibers and the resin exposures. At the near freezing temperature, the polymer
TAE, respectively prevented the oxidation process via radical chains are restricted from movement which lowered their
scavenging effect.[21] These contradicting processes presum- flexibility and increased the stiffness. This could be the rea-
ably boosted the resistance of the green composites toward son for the observed increase in tensile strength and
UV irradiation and improvement was recorded in their ten- decrease in elongation at break values. When the specimens
sile strengths as seen from Table SI.3. The earlier reported were exposed to elevated temperature, the post curing might
studies have also presented good resistance of epoxy bio- have occurred in the epoxy system that increased the cross-
composites toward UV exposure and borderline improve- linking density of the polymer network offering changes in
ments in their tensile strengths.[34] The carbon fiber epoxy the molecular arrangements. The high crosslinking density
composites prepared by Barbosa et al. when subjected to at high temperature resulted in embrittlement of the materi-
accelerated UV aging, suffered a marginal inclination in als that showed in steep rise of their tensile strengths. The
their tensile strengths owing to the post curing reactions results obtained in our study apparently symbolized the
occurring under the UV radiation.[41] However, the green advantages of the prepared materials over other earlier
composites prepared in this study exhibited superiority over reported ones for extreme temperature-based applications
other similar earlier reported biocomposites by displaying a without compromising their performance.[42] Table SI.4 pro-
significant elevation in the tensile strength with a maximum vides a comparison between the green composites with
growth up to 49.5% corresponding to GC2. MGCs, however, some recent reports on biocomposites in terms of changes
displayed relatively lower growth (22% to 37%) in tensile in tensile strength after heat and UV aging. As evident from
strength values. This might be ascribed to the MAH moiety the table, the present green composites exhibited superior
assisted cross-linkages in the epoxy network resisting the durability on exposure to extreme temperature and UV radi-
occurrence of additional crosslinking under UV exposure. A ation compared to others.
peculiar downtrend was observed in the elongation at break
values of all the composites, which might be endorsed to the
3.5.4. Solvent aging
chain scissoring followed by the rearrangement of bonds
The results obtained from solvent aging of the green compo-
that led to improved cross-linking and thus lowered the
sites were displayed in Fig. 9. Due to the diffusion of solvent
flexibility.[39]
molecules inside the polymer network during prolong
exposure, deformations were observed in the green compo-
3.5.3. Heat aging sites subject to THF as well as EtOH that resulted in signifi-
Generally, thermal aging of biocomposites results in mar- cant loss of strength as seen from the tensile strength values
ginal variations, may enhance or decrease the mechanical in Fig. 9a. Compared to EtOH, greater loss of strength was
strengths.[40,41] However, the prepared composites went recorded for THF with a maximum retention of only 50.7%
through noticeable improvement in their tensile strengths in compared to 63.5% in EtOH as apparent from Table SI.3.
both the temperatures as shown Fig. 8. The enhancement in However, the pristine thermoset displayed maximum lose in
tensile strength at 2
C was marginal compared to 70
C. A strength in both the solvents. Exposure to these solvents
maximum elevation of 13.1% was recorded for MGC3 at resulted in destructive effects on materials owing to the high
2
C, while showing an abrupt enhancement of 65.8% at solubility of the resin in THF and partial solubility in EtOH
70
C for MGC2 as reflected from Table SI.3. These as well as solubility of the extractable components of the
226 N. BORAH AND N. KARAK

Figure 10. Water absorption behavior of GCs and MGCs at (a) rt and (b) 70
C.

fibers in both. The solvent molecules would tend to disturb absorption characteristics upsurged with the increasing fiber
the polymer network as well as fibers of the composites to a loading ensuing a gradual rise in the weight gain of
great extent by dissolving some polymeric fractions and GC2 < GC3 < GC4. The results obtained were in consonance
lignocellulosic components of the fibers. This would cause with other previously reported results on water uptake behav-
significant leaching of small fragments from the surface as iors of biocomposites.[44] Contrarywise, the water uptake apti-
well as bulk of the materials. This phenomenon triggered tudes of the MGCs were lower compared to the GCs which
significant surface erosion and weight reductions of the was believed to be happening because of the improved inter-
composites ensuring deterioration of their strength. The facial adhesion between the fiber and the matrix. The MAH
weight loss values are presented Fig. 9b with inset digital functionalization on the surface -OH groups of the fibers
images of aged and unaged composites, reflecting the surface would prevent the accumulation water by occupying the fiber-
erosion of samples after immersion in THF. Similar phe- matrix interface and thus lower the water absorption capacity
nomenon was observed in the aging study of kraft lignin of the composites as observed in the case of MAH grafted
based biocomposites in water and acetone, where due to polypropylene and bamboo fiber reinforced biocomposites.[27]
partial solubility of lignin in acetone significant surface ero- Moreover, the hydrophobic nature of the TAE thermoset
sion was noted in the later that led to debasement in their would further tend to resist the water absorption even though
strengths.[43] However, compared to GCs, the weight loss increasing the fibers loading from MGC2 to MGC4 would
values were found to be lesser in MGCs, which might be speed up the process.[9] These counter acting aspects led to
due to the MAH modification of the fibers. anomalous water uptake profiles of MGCs displaying an initial
weight gain order of MGC2 < MGC4 < MGC3 followed by a
saturated weight gain order of MGC4 < MGC3 < MGC2 as
3.6. Water retention ability
evident from Fig. 10a.
The water sorption aptitude of the GCs was studied by meas- Furthermore, raising of the immersion temperature
uring the change in weight of the materials with time while resulted in lower water absorption by TAE thermoset and
being immersed in water. From the weight gain against time the green composites compared to water absorption at rt,
of exposure plots of the materials at rt as shown in Fig. 10a, it while the saturation period got shortened to 4-5 h. At the
is evident that the composites passed through a maximum elevated temperature, an irregularity was observed in the
sorption phase at near about 15 h of contact time and then time versus water uptake plots of the green composites and
acquired an apparent saturation level after 96 h. The graphs the weight gain of the MGCs were found to be greater than
displayed three stages of water absorption; an initial rapid the GCs. These might be happened because of the high tem-
absorption stage, then a relatively slower absorption followed perature that induced greater movement in the polymer
by an asymptotic stage which indicated a Fickian behavior to chains leading to softening of the materials and formation
be adopted by the green composites. Similar three staged water of micro-voids over the surface. However, after attaining the
absorption behavior was observed for polylactide/sisal biocom- maximum value, the weight gain percentages decreased rap-
posite in its hydrothermal aging study which showed increased idly with increasing immersion time as shown in Fig. 10b,
rate of water absorption and hence physical degradation on similar to some other earlier reported works.[45]
increasing the fiber content.[3] However, the green composites
exhibited a greater water absorption ability compared to the
3.7. Soil burial test
bare TAE thermoset which was manifested from the presence
of natural fibers in the former that would accelerate diffusion The biodegradability of the composites was investigated by
of water through capillary action. Henceforth, the water evaluating their weight loss after soil burial test conducted
 JOURNAL OF MACROMOLECULAR SCIENCE, PART A: PURE AND APPLIED CHEMISTRY 227

Figure 11. (a) Weight loss after soil burial, (b) FTIR of the green composites after degradation, and (c) FTIR spectra of GC2 before and after soil degradation.

for 30 days. As perceived from Fig. 11a, the weight loss aliphatic -C-H linkages present in the hardener.[48]
increased gradually with the increase of fiber loading. The Similarly, the degradation of the ester linkages present in
insertion of more and more fibers into the composite TA moiety was initiated by some esterase microorganisms
increased the rate of moisture absorption which further present in the soil.[48] However, due to the inherent anti-
improved their biodegradable behavior. However, MTF rein- microbial properties of TA, some partial antimicrobial char-
forced GCs suffered relatively higher weight loss than MTF- acter was transferred in to the composites which further
f-MAH reinforced MGC. This can be attributed to the poor rendered their rapid degradation by the soil microbes.[5] As
fiber matrix interaction in GCs that led to greater water a result of these two counteracting forces, the rate of biodeg-
absorption and subsequently faster biodegradation. radation of the composites in soil appeared to be slow and
Additionally, the increased hydrophobicity of the fibers after thus demanded longer duration for substantial degradation
MAH treatment also reduced the moisture absorption cap- to occur.
acity of the MGCs leading to a slower degradation rate.[46]
These results obtained are in good agreement with the pre-
4. Conclusion
viously reported studies.[47] The FTIR spectra of the
degraded composites were also recorded and presented in This study assessed the effects of MTF and MTF-f-MAH on
Fig. 11b and a slight decrease in the intensity of the different the performance of bio-derived epoxy green composites as a
bands were visible from the figure. For obtaining a clear replacement for synthetic composites. MAH functionaliza-
insight into the scenario, a comparison of the FTIR spectra tion improved the interaction between the waste tea fibers
of non-degraded GC2 composite with that of the degraded and the epoxy matrix as supported by FTIR, TGA and sur-
GC2 composite was presented in Fig. 11c. As seen from the face morphology studies. Although, the tensile strengths of
figure, a significant debasement in the intensities of the the green composites were lower than the bare epoxy, sig-
peaks at 2923 cm1, 1707 cm1, and 863 cm1 were noticed. nificant improvement was recorded after modification of the
These bands appeared due to the stretching vibrations of ali- fibers with MAH. The composites reinforced with MAH
phatic -C-H, -C ¼ O, and aromatic -C-H bonds, respectively functionalized fibers exhibited good mechanical properties
which might be due to the initial degradation of the hydro- (maximum stress up to 16.1 MPa) and thermal stability (up
carbon and ester linkages present in the polymeric network. to 244
C) compared to the un-modified ones. The durabil-
Some soil microorganisms that can effortlessly degrade ity and weather resistance on exposure to different chemical
hydrocarbon chains caused partial degradation of the and physical aging conditions demonstrated the advantages
228 N. BORAH AND N. KARAK

of the studied green composites over the pristine epoxy Compos. Part B 2019, 171, 87–95. DOI: 10.1016/j.compositesb.
thermoset as well as earlier reported biocomposites. The 2019.04.048.
[10] Chowdhury, A.; Sarkar, S.; Chowdhury, A.; Bardhan, S. Tea
maximum improvements of 65.8% and 49.5% was obtained Waste Management: A Case Study from West Bengal, India. J.
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Further, a temperature dependent water uptake behavior N.; Rajeshkumar, L.; Balaji, D.; Vigneshkumar, N.; Elango,
was noticed for the green composites with a short and low K. S.; Karpagam, J.; et al. Experimental Investigation on
Mechanical Properties of Flax/Banana/Industrial Waste Tea
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interfacial adhesion compared to GCs. The overall results 02.111.
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Waste Fibers Filled Thermoplastic Composites: The Effects of
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Acknowledgment Nanocrystals from Tea Leaf Waste Fibers. Polymers 2017, 9,
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The authors want to thank Sophisticated Analytical Instrumentation
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Cellulose Nano Fiber Reinforced Fully Bio-Based Waterborne
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