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Bionanocomposites as industrial materials, current and future perspectives: a


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Article  in  Emergent Materials · November 2020


DOI: 10.1007/s42247-020-00133-x

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Emergent Materials
https://doi.org/10.1007/s42247-020-00133-x

REVIEW

Bionanocomposites as industrial materials, current and future


perspectives: a review
Blessy Joseph 1 & Saravanan Krishnan 2 & V. K. Sagarika 3 & Abhimanyu Tharayil 4 & Nandakumar Kalarikkal 1 &
Sabu Thomas 1,4

Received: 26 August 2020 / Accepted: 9 October 2020


# Qatar University and Springer Nature Switzerland AG 2020

Abstract
The use of biopolymers in industrial applications remain elusive due to their hydrophilicity, poor barrier properties, etc. It has
been of great interest to the research community to modify the inherent nature of bio-based materials by incorporating nanoscale
fillers into the matrix. The resulting bionanocomposites show versatility as future biomaterials, providing a deft alternative to
plastics. In general, bionanocomposites are made up of a matrix which is a biopolymer (continuous phase) and the reinforcing
agent (dispersed phase), consisting of particles with dimensions in the range of 1–100 nm. The increased research in this field is
driven by the biodegradable, biocompatible, and renewable nature of biomaterials. Bionanocomposites find broad applications in
food packaging, automobile industries, electronic industries, cosmetics, textile industries, water purification sectors, tissue
engineering, etc. A range of approaches have been utilized for the preparation of bionanocomposites including solution casting
and 3D printing. However, much more green and sophisticated processing techniques should be developed for industrial
applications. Furthermore, precise control over geometry, porosity, internal architecture, etc. is still challenging and need to be
overlooked carefully.

Keywords Bionanocomposites . Industry . Nanoparticles . Cost effective . Automobile . Water purification

1 Introduction environment. Recent advances in material science revolution-


ized the field of bionanocomposites, resulting in the effective
Plastic wastes are raising general global concern, and disposal development of environmentally friendly composites that can
methods are limited. We do not have enough means to recycle replace non-degradable plastics for diversified industrial ap-
plastic, and moreover, the practice of using single-use plastics plications. The bionanocomposites can be defined as the ma-
has become a pervasive problem. For instance, majority of terials that are comprise of particles with at least one dimen-
plastics include petroleum-based synthetic polymers like sion in the range of 1–100 nm and a constituent(s) of the
polypropylene and polyethylene that usually take longer time biological origin or may be biopolymers [1]. The nomencla-
to degrade, preventing the breakdown of the other biodegrad- ture “bionanocomposite or nanobiocomposite” typically ap-
able materials. They cause severe detrimental effects on the plies to materials that have particles with at least one dimen-
sion in the nanometer regime. Generally, a bionanocomposite
comprises a biopolymer or biodegradable polymer (usually
* Sabu Thomas cellulose, polycaprolactone, polylactic acid, chitin) with ap-
sabuthomas@mgu.ac.in propriate nanofillers (nanoclay, zinc oxide, titanium dioxide,
1
silver nanoparticles, etc.). Nanofillers have large surface to
International and Inter University Centre for Nanoscience and
Nanotechnology, Mahatma Gandhi University,
volume ratio which enhances the polymer matrix-filler inter-
Kottayam, Kerala 686560, India actions, resulting in overall enhancement of material perfor-
2
Indian Institute of Technology, Chennai, Tamil Nadu 600036, India
mance [2]. The reinforcement effect is obtained even at small-
3
er filler content which is not usually possible with convention-
Indian Institute of Science Education and Research, Tirupati,
Mangalam, Tirupati, Andhra Pradesh 517507, India
al composites that require higher proposition of fillers.
4
Nanofillers also improve the thermal and barrier characteris-
School of Energy Materials, Mahatma Gandhi University,
Kottayam, Kerala 686560, India
tics of polymers. The bionanocomposite materials have
emergent mater.

received considerable attention from the industry and academia develop bionanocomposites as a promising candidate in pack-
owing to their unique properties such as excellent biodegradabil- aging applications [9]. Bionanocomposites having antimicrobial
ity, cost-effectiveness, and sustainability. Optically transparent property can be used to improve the shelf life and safety of food
bionanocomposites made of polylactic acid (PLA) is an interest- products by decreasing the growth of post-processing pollutant
ing material for food industry. Other polymers used in packag- microorganisms [10].In a previous study, AgNPs (silver nano-
ing industry include poly-(butylene succinate) (PBS), particles) were incorporated into the HPMC (hydroxypropyl
polyhydroxybutyrate (PHB), and starch [3, 4]. Cellulose nano- methylcellulose) matrix to produce a bactericidal food packag-
fibers are explored in automobile industries for developing du- ing films. These HPMC-AgNP nanocomposites have shown
rable load-bearing parts, automotive parts, and building blocks excellent barrier properties and mechanical characteristics. The
in cars [5]. Nanocellulose-based composites also act as cost- nanofillers have resulted in the high tensile strength of the nano-
effective and reusable adsorbents in water treatment industries composite films, and the study concluded that these films can be
for the removal of contaminants like fluoride and chlorophenols used as an active antimicrobial coating in the food packaging
[6]. The performance of bionanocomposites is dependent on the industry. In another study, nano-silica was introduced into the
effective dispersion of nanoparticles in the polymer matrix. The PLA (polylactic acid) matrix to synthesize a biodegradable coat-
uniform distribution of nanoparticles in a bulk polymer depends ing material through the sol-gel process. From the results, it was
on various factors like choice of solvent, type of mixing, and clear that the water vapor and gas barrier properties of the PLA/
size of nanoparticles. The nanofillers are usually surface modi- SiO2 (silica) nanocomposite films were improved making it
fied by using techniques like plasma modification, grafting or suitable for food packaging applications [11]. Researches have
coating with bio moieties, and chemical modifications to im- been done about the usage of bionanocomposite films contain-
prove their dispersion in polymer matrix. Surface modification ing chitosan, PVA (polyvinyl alcohol), and TiO2 nanoparticles
techniques also enhance the biocompatibility and for packaging of soft brined cheese. In this composite film, high
hydrophobicity/hydrophilicity of the bionanocomposites. hydrophilic and bio-inert properties of PVA and antimicrobial
There are various factors that affect the final properties of characteristics of TiO2 are combined to create a mechanically
bionanocomposites like the nature of biopolymer used, size of robust material for packaging [10].
nanofillers, stoichiometric ration of components involved, and The poor oxygen barrier property of PLA (polylactic acid)
cross-linking effectiveness [7]. Improved understanding of sur- is a limiting factor for its usage in packaging applications. In a
face chemistry enabled functionalizing nanoparticles, to im- study, Thellen et al. revealed that the PLA/MMT (polylactic
prove the mechanical and biological properties. Several other acid/montmorillonite) bionanocomposites possess improved
criteria like controlling the crystallinity of nanoparticles and oxygen barrier properties by 15–48% as compared to that of
tuning their size and shape are also considered for fabricating pure PLA. Also, the water vapor transition rate was decreased
high-performance bionanocomposites [8]. For biomedical appli- by 40–50% for PLA/MMT bionanocomposites as opposed to
cations, it is very important that the bioactivity of the nanocom- that of neat PLA. Similarly, to overcome the poor gas barrier
posites should be preserved even after processing. Hence, choice properties of PHA (polyhydroxyalkanoates), nanoclay can be
of processing technique is also very important. It is however incorporated into the PHA matrices resulting in lower oxygen
worth to elucidate the underlying structure property relationship and water permeability. And hence, these PHA/ nanoclay
and polymer-filler interactions at the interface for the design of a bionanocomposites can be used for food packaging [13].
bionanocomposites. Considering the versatile properties of these Studies have been conducted regarding the synthesis of
materials, the present review focuses on the application of bionanocomposite films using modified MMT (Cloisite 20A
bionanocomposites in selected industries involving food, water and Cloisite 30B) and soy protein isolates. It was found that
purification/treatment, tissue engineering, cosmetics, electron- the nanocomposite with 5% Cloisite 20A and Cloisite 30B
ics, textile, and automobiles. exhibited superior viscoelastic, water barrier, and mechanical
properties as compared to natural MMT composite films.
Also, it was reported that the films made from 10% concen-
2 Bionanocomposites for food industry tration of Cloisite 30B possess similar mechanical character-
istics as that of some plastics currently being used in the food
Food packaging materials play a vital role in maintaining the packaging industry [14]. Bionanocomposite films for food
quality and safety of food products by creating a barrier against packaging were developed by incorporating chitosan nanopar-
the passage of moisture, chemical contaminants, light, CO2, O2, ticles and Origanum vulgare essential oil (OEO) into fish
and microorganisms. Recently, many efforts have been reported gelatin matrix using solution casting technique. The neat films
to replace the non-degradable petroleum-derived plastic food presented a rough morphology (Fig. 1b), and with addition of
packaging materials by biopolymer-based materials. To enhance essential oil, the roughness decreased as evident from atomic
the mechanical properties of biodegradable, renewable, and hy- force microscopy images (Fig. 1c). This is because the liquid
drophilic biopolymers, nanofillers are incorporated onto them to state of oil fills in the irregularities of polymer films; however,
emergent mater.

Fig. 1 AFM images of a chitosan


nanoparticles, b control and FG/
CSNP composite films containing
c 0.4 and d 1.2% (w/v) OEO
(black dots in image). Mean
values with different superscript
in small letters for Ra and in cap-
ital letters for Rq are significantly
different (p < 0.05). Scan size
50 × 50 m and resolution< 0.1 nm
[12]

with further addition of oil (1.2%, w/v), an increase in rough- and enhanced adsorption rate for the removal of contaminants
ness parameters could be observed (Fig. 1d). This could be from water. For example, Shi et al. manufactured magnetic
attributed to the lipid aggregation and creaming during the chitosan nanocomposites using amine-functionalized magne-
drying step [12]. The films also exhibited antimicrobial activ- tite nanoparticles to remove heavy metal ions for water puri-
ity against test food pathogens, Staphylococcus aureus, fication. In the presence of ultrasound radiation, these metal
Listeria monocytogenes, Salmonella enteritidis, and ions can be removed from chitosan in weak acidic deionized
Escherichia coli. water due to the reversible interactions between chitosan and
Nanotechnology has resulted in the development of antimi- metal ions. Hence, the created magnetic chitosan nanocom-
crobial food packaging materials with improved mechanical posites can be utilized as a recyclable tool for heavy metal ion
and oxidation stability, barrier properties, and biodegradability. removal from water [15].
These packaging materials are very important in food industries In a recent work to remove the textile dyes (AR88-acid red
in order to enhance the quality and freshness of food materials. 88) from wastewater, biosilica/chitosan nanocomposite was
The applications of bionanocomposites should not only be lim- applied [16]. In this work, the adsorbed dye increased with
ited to packaging materials but should be extended to biosen- the increase in reaction time and adsorption concentration and
sors that will allow easy detection of spoiled or contaminated a decrease in temperature and initial pH (Fig. 2a). When the
foods, detect the presence of microorganisms, and so on. adsorption dosage was increased from 1 to 3 (g L−1), a huge
increase in adsorption was observed (Fig. 2b). But, the further
increase in adsorption dosage caused a minor increase in the
3 Bionanocomposites for water adsorption.
purification/treatment industries For the removal of methylene blue (MB) dye from aqueous
solution, batch adsorption methods were performed applying
Previous research works have shown that the chitosan-based CTS-g-PAA/MMT (chitosan-g-poly(acrylic acid)/montmoril-
magnetic nanocomposites exhibit better adsorption efficiency lonite) nanocomposite as adsorbent [17]. An increase in the
emergent mater.

Fig. 2 Varying of adsorbed AR88 with a adsorbent dosage and b initial pH [16]

pH value resulted in an increase in the adsorption capacity of gum alkylamine) biopolymeric matrix. And the produced
the CTS-g-PAA/MMT nanocomposite for MB cationic dye. bionanocomposites were tested in rat punch wound models
Overall, the study established that the prepared nanocompos- for wound healing applications. In the SEM studies, the good
ite is a suitable adsorbent for the removal of MB dye from dispersion of silver nanoparticles in the GGAA matrix was
aqueous solution. Saifuddin et al. prepared Ag/chitosan observed. In the wound healing studies, faster wound healing
bionanocomposites via a melt intercalation method during occurred for the AgNP-GGAA nanocomposite–treated group
which a chitosan solution and silver nitrate solution were as compared to that of silver alginate cream. The antimicrobial
mixed and microwave irradiation was applied. During irradi- properties of AgNPs and the hydrated surface provided by the
ation, the silver nitrate was reduced forming silver nanoparti- cationic guar gum matrix resulted in the proliferation and mi-
cles. And the Ag/chitosan nanocomposites were able to elim- gration of keratinocytes at the wound region to promote the
inate a higher amount of atrazine pesticide in column mode. healing process. Also, it was indicated that the hydroxypro-
Also, the chitosan-based nanocomposites exhibited a higher line, DNA, and total protein content of the tissues at the
elimination of organophosphate pesticides [18]. wound site were much higher in the AgNP-GGAA
Khan et al. fabricated antibacterial nanocomposites by dis- nanocomposite–treated group as compared with the commer-
persing zinc oxide (ZnO) nanofillers in the matrix of cellulose cially available silver alginate group [20].
acetate (CA). Every nanocomposite film (CA/ZnO weight ra- Díez-Pascual et al. prepared castor oil (CO)–based films
tios of 100/0 (CA), 100/2 (NC1), 100/3 (NC2), 100/4 (NC3), containing chitosan-modified zinc oxide (ZnO) nanoparticles
100/5 (NC4) films) exhibited antibacterial activity which in- using solution mixing and casting method. The thermal stabil-
creased with the increment in ZnO concentration. The selec- ity, biodegradability, cytocompatibility, viscoelastic, barrier,
tivity of nanocomposite films was examined towards Pb2+, antibacterial, and wound healing properties of the synthesized
Mn2+, Ni2+, Zn2+, Cd2+, Al3+, Sb3+, Fe2+, and Sr3+ metal ions films were evaluated. The chitosan-ZnO loading has increased
and was found that the antibacterial nanocomposites were the thermal stability, degree of porosity, water absorption,
more selective towards Fe2+ ion. The highest uptake capacity hydrophilicity, oxygen permeability, water vapor transmis-
towards Fe2+ was shown by NC1 nanocomposite (CA/ ZnO sion rate, and biodegradability of the films. The water vapor
weight ratio of 100/2), and the water permeability of NC1 was transmission rate and oxygen permeability values of the films
evaluated to investigate the role of antibacterial nanocompos- were within the range of commercial wound dressing mate-
ite films as a membrane for water purification. And the water rials. Results confirmed that the nanofillers were randomly
permeability data concluded that these materials are appropri- and uniformly distributed on the CO (castor oil) resin. The
ate for water purification applications [19]. antimicrobial activity of the nanocomposites was proven
against Gram-negative as well as Gram-positive bacteria in
the presence and absence of UV light. And the antimicrobial
4 Bionanocomposites for healthcare industry activity against M. luteus and S. aureus were higher than that
towards E. coli bacteria. From the in vivo healing studies, it
Several studies have been done focusing on the usage of the was noted that wounds treated with CO/chitosan-ZnO healed
biodegradable and biocompatible polymer materials as wound faster than CO and gauze-covered wounds. In total, the re-
healing scaffolds to restore the cellular continuity of tissue. search summarized that these nanocomposite films have great
Auddy et al. fabricated a novel bionanocomposite by embed- potential for use in the biomedical field, specifically in wound
ding silver nanoparticles (AgNP) into cationic GGAA (guar dressings [21].
emergent mater.

Guadarrama-Reyes et al. studied the antibacterial proper- these polymer nanocomposites decreased with gradual decrease
ties of two suture threads, silk and catgut, coated with silver in pH values, which is due to the change in hydrogel volume as
nanoparticles (AgNPs). Chenopodium ambrosioides (perenni- a result of pH-dependent cross-linking reaction. These nanosys-
al herb) commonly known as Mexican tea was used as reduc- tems possess high colloidal stability even after 100 days of
ing agent for the preparation of nanoparticles. The synthesis of storage. Cytotoxicity studies revealed that L929 fibroblast cells
silver nanoparticles and the dispersion of AgNPs on both su- with nanoparticles at all tested concentration exhibited ≥ 90%
ture threads were ensured by the characterization studies. viability indicating it is non-toxic and biocompatible. Also, no
Inhibition zone tests were conducted to determine the antibac- change in cellular morphology or signs of cell death was ob-
terial properties of the bionanocomposites. The suture com- served during inverted light microscopy studies.
posites showed antibacterial activity towards Escherichia coli Biocompatible synthetic PEGylated copolymer–coated
and Staphylococcus aureus bacteria. In the inhibition of magnetic nanoparticles (10 nm) were developed [27]. These
S. aureus versus E. coli, there was no notable difference seen nanocomposites are super paramagnetic (55 emu/g) with spe-
statistically. These suture thread bionanocomposites could be cific absorption rate up to 17.44 W/g which is well suited for
used in oral or periodontal surgery to prevent the growth of magnetic hyperthermia. Silver nanoparticles bio-synthesized
pathogenic microorganisms [22]. using the leaf extract of Euphorbia helioscopia was reportedly
A novel three-dimensional polymer–based magnetic nano- loaded into chitosan-alginate and the polymer-based nanocom-
composite made up of poly(ε-caprolactone) (PCL), poly(eth- posites was prepared [28]. At the ratio of 2:1 of chitosan and
ylene glycol) (PEG), and 5% iron oxide nanoparticles alginate, maximum loading efficiency of about 95% was ob-
(250 nm) fabricated using the co-electrospinning method served. AgNP-loaded chitosan-alginate constructs displayed
was reported [23]. Interestingly, these nanocomposites as a good anti-bacterial efficacy (in terms of log reduction) against
membrane displayed low cytotoxicity with NIH 3T3 cells Staphylococcus aureus, Pseudomonas aeruginosa, Klebsiella
studied using MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphe- pneumoniae, Acinetobacter baumannii, Morganella morganii,
nyltetrazolium bromide) assay. More importantly, these cells and Haemophilus influenzae. Besides, these composites were
attach to the scaffold and grow densely which supports the biocompatible to normal cell lines (L929) and cytotoxic to
potentiality of this electrospun PCFC/Fe3O4 membrane in tis- HeLa cancer cells and thus could serve as potential candidates
sue engineering. In a separate study, the synthesis of iron for applications in biomedicine.
oxide-gold core shell nanoparticles (8.1 nm) stabilized by Thermo-sensitive nanocomposites containing chitosan
thiolated sodium alginate was reported [24]. About 23% of hydrogels with embedded poly(lactic-co-glycolic acid) nano-
polymeric content of nanocomposites was contributed by the particles for encapsulation of flavonoid extract of Cecropia
stabilizer, sodium alginate. Although the saturation magneti- glaziovii Snethl with known anti-viral properties against
zation (Ms) of these magnetic nanocomposite (41➔24 emu/g) Herpes infections was reported [29]. Incorporation of PLGA
was reduced due to gold coating, these composites demon- nanoparticles (226 nm) into chitosan hydrogels decreases the
strated good loading capacity (7.2 wt.%) with encapsulation thermal stability as that of pristine chitosan hydrogel.
efficiency of nearly 73% curcumin. These properties empha- Rheological properties (elasticity) were optimum at maximum
size the applicability of these nanocomposites as MRI/CT of 3% w/w PLGA nanoparticle concentration for these chito-
contrast agents and in targeted drug delivery. san hydrogel-(Ch-PLGA) nanocomposites. Cytotoxicity stud-
Similarly, the synthesis of dextran stabilized iron oxide ies of the Ch-PLGA (10%) nanocomposites were studied
nanoparticles (DINP) was reported [25]. The average core par- using MTT assay. Results revealed about > 70% Vero cells
ticle size of the ferrite nanoparticles was found to be 15.4 nm, were viable after 48-h incubation for all concentration (50 to
and coating them by dextran has shown to improve the stability 400 μg mL−1) of Ch-PLGA nanocomposites tested.
of nanoparticles in biological matrices. These nanocomposites Metal nanoparticle–incorporated polymeric scaffolds are
demonstrated good cytocompatibility as shown via (1) direct highly applicable in tissue engineering applications. Recently,
contact assay with L929 fibroblast cells showing no phenotypic titanium dioxide (TiO2) nanoparticles impregnated zein–
changes and maintained cellular integrity and (2) MTT assay polydopamine (PDA) polymeric scaffold was prepared and eval-
with 80% cells found viable. Systematic investigation of acute/ uated for wound healing properties [30]. Thermogravimetric
chronic oral, dermal, immunotoxicity, genotoxicity, carcinoge- analysis indicated that the thermal stability of these scaffolds
nicity, and bio-distribution study revealed that these dextran- was increased due to the uniform distribution of TiO2 nanopar-
capped iron oxide nanoparticles were considered as non-toxic, ticles into polymeric network. Compared to zein and zein-PDA,
safe, and biocompatible for biomedical applications. Hydrolytic zein-PDA-TiO2 nanofiber possesses enhanced proliferation and
synthesis of pH-responsive poly(aspartic acid) hydrogel-loaded viability of keratinocytes. In addition, the cell adhesion and mi-
Fe3O4 nanoparticles from cross-linked polysuccinimide on the gration properties of these nanofibers were significantly higher
surface of magnetite nanoparticles under mild alkaline condi- than that of the control. These properties of nanofibers were
tions was recently reported [26]. The hydrodynamic diameter of responsible to promote the healing process in the wound re-
emergent mater.

epithelialization studies in rats. Also, zein-PDA-TiO2 nanofibers detergent for better dispersion of CNC in PLA. The same group
showed better wound closure rate (15 days) and the tensile has reported the preparation of PLA-based nanocomposite film
strength of the newly formed tissue (1.283 MPa) than control with polyethylene glycol (PEG)-grafted TEMPO-oxidized
(Zein-PDA) which took 17 days for complete healing and CNC and rGO recently [35]. Unlike CTAB-capped CNC-
1.083 MPa strength, respectively. Interestingly, histopathological PLA nanocomposites, this nanocomposite with modified
studies by hematoxylin and eosin (H&E) staining revealed that CNC showed improved thermal and mechanical properties.
wound healing occurs in the presence of zein-PDA-TiO2 nano- Moreover, this nanocomposite was also found cytocompatible
fibers and is facilitated by better epithelialization, granulation to fibroblast cells C3H10T1/2. Formulation of polyethylene
tissue, and new hair follicle formation with improved collagen glycol–capped celecoxib-loaded liposomes of average size
deposition and decreased inflammation. 95 nm was recently developed for treating colon cancer and
Developing target-specific multifunctional up-converting arthritis [36]. Drug release kinetics indicated that continuous
metal nanoparticles is important for imaging and cancer thera- release of about 98.75% is released within a period of 24 h.
peutic applications. For instance, nanocomposite containing Nanocrystalline cellulose/alginate hydrogels immobilized with
phenanthriplatin (IV)-conjugated NaGdF4:Yb3+/Er3+ nanopar- silver nanoparticles were 3D printed. Both alginate (ALG) and
ticles, modified using polyethylenimine (PEI), and poly(ethyl- alginate/nanocrystalline cellulose hybrid (ALG/CNC) scaffolds
ene glycol) along with cancer-specific RGD peptide was report- had rough surface with pore size ranging from 174 to 201 μm
ed [31]. These nanocomposites (251-nm dia.) exhibited notice- as seen in Fig. 3a and 3c. Figure 3b shows the cross-sectional
able cytotoxic effect towards Hep-2 cells. The cellular internal- image of alginate scaffolds that displayed interconnected lay-
ization of these nanocomposites in cancer cell lines was studied ered porous structure in the interior. Hollow tubular fiber for-
using flow cytometry and ICP-MS analysis. Results revealed mation was interestingly observed for ALG/CNC composite
that cells taking up these nanocomposites showed lumines- (Fig. 3d). The EDS image clearly depicts how uniformly silver
cence under laser excitation at 960 nm, demonstrating their nanoparticles are distributed in alginate and ALG/CNC scaf-
applications as bio-imaging agents. In vivo studies demonstrat- folds (Fig. 3e and f) [33].
ed that these nanocomposites possess tumor inhibition ability in Hyaluronan (HA) is one of the main components of the
tumor-induced mice which could be due to the directed entry of extracellular matrix (ECM) and aids in cell proliferation and
nanosystem into cells by endocytic pathway and sustained re- migration. Bionanocomposites were fabricated using HA and
lease of pro-drug Phen-Pt (IV) from nanocomposites. bacterial cellulose (pure cellulose nanofibers) using solution
Recently, an innovative hybrid hydrogel with excellent an- impregnation method [37]. Briefly, the bacterial cellulose
tibacterial and anticancer properties was reported [32]. Here, films were dipped into various concentrations of hyaluronan
green synthesis of silver nanoparticles (10-nm dia.) is solution (0.05%, 0.1%, 0.2%, or 0.5% (wt./v)) for 24 h at
achieved using carboxymethyl cellulose (CMC) as a reducing room temperature. The composite films showed better water
agent and stabilizer and further conjugated with doxorubicin uptake ability than pure BC films. The BC-HA composite
(DOX), an anticancer drug. These nanoconjugates were cross- films promoted the growth of primary human fibroblast cells,
linked using citric acid to produce hybrid hydrogels. indicating that the films were cytocompatible. In vivo wound
Interestingly, gel fraction and swelling % of the hybrid nano- healing analyzed in Wistar rats were analyzed using H&E and
composites depends on the degree of carboxymethylation of Masson staining, 7 and 14 days after the surgery. Wound
CMC. These hydrogels demonstrated its anti-microbial activ- healing was investigated using 3 sets of samples (BC, BC-
ity against both Gram-positive and Gram-negative bacteria. HA composite films, and gauze samples). The wound region
In vitro study emphasized the synergistic killing effect in mel- covered with BC and the BC-HA composite films showed
anoma cancer cells due to the AgNPs and release of DOX. formation of new blood vessels; the BC-HA composite films
Incorporation of nanomaterials into the biomedical polymer with low HA concentrations of 0.05% HA and 0.1% HA
such as polylactic acid (PLA) to improve their overall proper- evidently promoted wound healing (Fig. 4).
ties for biomedical applications is gaining wide attention.
However, the uniform distribution of the nanomaterials in the
PLA matrix is a major concern. Pal et al. demonstrated the 5 Nanocomposites for automobile industry
fabrication of nanocomposite composed of PLA, cellulose
nanocrystals (CNCs), and reduced graphene oxide (rGO) using Due to their outstanding properties, polymer nanocomposites
melt-blending method [34]. These nanocomposites were non- are employed to address the emerging requirements in automo-
cytotoxic and biocompatible to HEK293 cells. Collectively, the bile industry. This includes paint, lubrication, electric and elec-
PLA matrix with 1% unmodified CNCs and rGO exhibited tronic devices and sensors, tyres, and self-cleaning for win-
maximum tensile strength and thermal stability as compared dows. Generally, natural rubber (NR), synthetic rubber, or their
to PLA matrix or other nanocomposites prepared by incorpo- blends form the basis of tyre tread compounds. Natural rubber
rating cetyltrimethylammonium bromide (CTAB), a cationic is considered as a degrading material; however, their
emergent mater.

Fig. 3 Scanning electron


microscope images at different
magnifications of a ALG 5%
(w/v) scaffold (80×); b ALG 5%
(w/v) scaffold (360×); c ALG/
CNC (5% and 3% w/v) scaffold
(80×); d ALG/CNC (5% and 3%
w/v) scaffold cross section (80×).
Energy-dispersive X-ray spec-
troscopy (EDS) map distribution
and EDS spectrum of Ag in e
ALG 5% (w/v) scaffold (80×); f
ALG/CNC (5% and 3% w/v)
scaffold (80×) [33]

degradation rate is low. Carbon black and silica are used as and graphene are explored as reinforcing fillers. ZnO
reinforcing fillers to enhance the properties of rubber. With nanoparticle–doped graphene (nano-ZnO-GE) could signifi-
the outbreak of nanotechnology, several nanomaterials like cantly improve the tensile strength, modulus, and tear strength
clay, kaolin, multi-walled carbon nanotubes (MWCNT), silica, of natural rubber composites even at low filler content [38].
emergent mater.

Fig. 4 Representative HE-stained


tissue sections of subcutaneously
implanted wound dressings with
BC-HA composite films, BC, and
gauze, respectively, on 7 days and
14 days after implantation. Blood
vessels are indicated by black ar-
rowheads. All scale bars equal
100 μm [37]

NR/graphene nanocomposites (NR/GE) and NR/nano-zinc ox- from light vehicles to 95 g/km by 2020 [40]. The other major
ide (nano-ZnO) nanocomposites were used as reference sam- issue is the reduction of petroleum sources, whereas plant-
ples to evaluate the mechanical performance as seen in Fig. 5. It based products as fuels mostly remain underutilized. So, the
could be clearly observed that low content of nano-ZnO-GE time has come for bringing about a change in consumer habits
provided greater reinforcing effect when compared with control and work towards the sustainability of environment.
samples. This could be related to the effective dispersion of One of the important design strategies is the reduction of
graphene sheets, thus preventing stress concentration sites, automobile kerb weight, which has the added advantage of
leading to efficient stress transfer. The nano-ZnO-GE could less emissions and better drive performance. There are two
also effectively act as cure-activator during vulcanization pro- ways to achieve this, one is the architectural design of the
cess, resulting in formation of excellent cross-linked network. automobile and second is the substitution of existing materials
The automotive industry is one of the fastest growing indus- with new better functional materials. The practicality of using
tries worldwide and is one of the biggest markets for polymers natural fiber as a potential high-quality automotive material
after industrial construction market. Plastics account for around requires extensive understanding of the crystallization behav-
25% weight of the car body and around 15–20 different poly- ior, moisture repellant properties, degree of polymerization,
mers being used in a single car body. The polymer composite etc.
markets for automotive industry had a market size valued at Processing temperature is a significant factor in case of
6.40 billion USD in 2016, which is expected to grow to 11.6 natural fiber composite as mostly fiber degrades at around
billion USD by 2025. Polypropylene (PP), polyurethane (PU), 160 °C when exposed over a considerable duration of time
and polyvinyl chloride (PVC) are the most commonly used [41]. So, the important factor is to obtain rapid reaction rate
polymers which constitute around 65% of the total plastic ma- and development of low-temperature processing. The
terial used [39]. Even though automotive industry is one of the manufacturing route plays a very important role in the perfor-
key industrial sectors, it faces numerous challenges in both the mance of the final desired product. The processing involves
developed and developing markets globally. The foremost of interrelationships between several key factors: the interfacial
this is the reduction of greenhouse gas emissions. The EU has contact angle between the matrix and fiber, orientation of fi-
enacted legislation which reduces carbon dioxide emissions bers, moisture control, etc. to name a few. The compounding
emergent mater.

Fig. 5 Comparison of mechanical


properties of NR/nano-ZnO-GE,
NR/nano-ZnO, and NR/GE
nanocomposites. a Tensile
strength; b elongation at break; c
modulus at 300% strain; d tear
strength. The symbol α represents
5 phr for conventional-ZnO, and
β, χ, δ, and ε represent 0.5, 1.0,
1.5, and 2.0 phr for nano-ZnO-
GE; or 0.4225, 0.8450, 1.2675,
and 1.6900 phr for nano-ZnO; or
0.0775, 0.1550, 0.2325, and
0.3100 phr for GE, respectively
[38]

process like injection molding, extrusion, and high shear Nanocellulose has comparatively lower density and would
mixing provides a great degree of consistency to the compos- be able to address the requirement for lower weight vehicle
ite material. Injection molding method has the advantage of [44]. It can be seen that over the last several years, there has
producing intricate shapes and short cycling times. been continuous adoption of cellulose-based materials in the
Compression molding has the advantage of a fast processing automotive industry [5]. Many automotive manufacturers like
time along with low fiber attrition. Compression molding Ford have already started replacing glass fiber–based filler
techniques have the advantage of reduced fiber degradation materials with cellulose nanoparticles. A new thermoplastic-
and lesser knit lines. Foaming techniques are extensively used based composite material was developed under the name
in upholstery making. THRIVE [45]. Here, cellulose obtained from tree pulp is used
Many global automotive manufacturers are embarking on as the nanofiller, which has the added advantage of high
the idea of sustainable manufacturing and production tech- strength, temperature resistance, durability, and wear resis-
niques. DaimlerChrysler uses around 60 components in its tance. This also has the additional advantage of reducing the
European vehicles that are derived from natural bio-based weight of the automobile thereby reducing the fuel consump-
resources. BMW uses considerable amount of renewable tion and carbon footprint. Cellulose-based nanofibrils have the
raw materials in their manufacturing processes. General biggest disadvantage of compatibility at the fiber matrix inter-
Motors has used wood fibers as cushioning in the seatbacks, face and require extensive modification and surfactants to im-
cargo area of floor of Cadillac Deville and GMC Envoy, re- prove their dispersion properties [46]. A water-soluble poly-
spectively [43]. Goodyear Tire manufactures have infused mer-like polyvinyl alcohol (PVA) can be used as the matrix
corn stacks in their tyre to find that the rolling resistance is that can encapsulate the nanocellulose fibrils and provide bet-
comparatively less compared to conventional tyres thereby ter dispersion. Recently a nanocellulose vehicle (NCV) has
improving fuel resistance. Kenaf fibers are also extensively been developed by Kyoto University in Japan. The automo-
used by Toyota in their many concept model cars. Many au- bile had a profile that is derived from natural cellulose material
tomotive components are produced from this bio-based natu- that has its origin from wood pulp which is exciting alternative
ral fiber materials and are outlined in Table 1. to the conventional automobile materials. This wood pulp was
emergent mater.

Table 1 Automotive parts produced from natural fibers [42] toxicity (epidermal skin model-EpiDerm™) or irritation
Vehicle part Material used (OECD TG 439) was not observed and the cell viability re-
mains unaffected for migration extracts upon exposure to skin
Glove box Wood/cotton fibers; molded flax/sisal cells. Recently, the polymer nanocomposite made out of poly-
Door panels Flax/sisal with thermoset resin vinyl alcohol, bentonite, and gold, silver, or zinc oxide nano-
Seat coverings Leather/wool backing particles for the preparation of facial mask was reported [50].
Seat surface Coconut fiber/natural rubber Importantly, this formulation was stable for up to 12 weeks
Trunk panel Cotton fiber and non-irritant to skin.
Insulation Cotton fiber
Trunk floor Cotton with PP/PET fibers
Floor panels Flax mat with PP 7 Bionanocomposites for textile industry

The durability of textile materials is of primary importance, and


therefore, it is very necessary to functionalize cotton fabrics. The
waste products or leftovers from agricultural waste, making it common approaches include plasma treatment, grafting, and de-
more environment-friendly. The advantage is that the positing nanoparticles on the surface. Incorporation of nanopar-
cellulose-based material is reported to be 80% lighter than ticles imparts special properties like antimicrobial activity, ultra-
steel, with strength levels around five times the metal [47]. violet protection, and enhanced hydrophobicity. Busila et al. re-
Biocomposites have the advantage that they are lightweight ported the synthesis of antimicrobial textiles by incorporation of
and reduce greenhouse gas emissions. Biocomposites are also Ag (silver)/ZnO/hybrid nanoparticles in chitosan (CS) matrix
advantageous for manufacturing of low load-bearing automo- along with suitable binders in cotton (100%) and cotton/
bile interiors like wood trim, interior panels, seat fillers, and polyester (50:50) using pad-dry-cure method [51]. The antimi-
thermoacoustic insulation. The preparation of biocomposites crobial activity of the textile coated with biopolymer nanocom-
can involve thermoplastic and thermosetting polymers as re- posite was tested against Gram-negative bacteria Escherichia
inforcements. The biodegradable polyesters like PLA, PHB, coli and Gram-positive Micrococcus luteus by tetrazolium/
PBS and natural polymers like cellulose, natural rubber are the formazan-test (TTC) method. Results showed that antimicrobial
most used thermoplastic matrix material. The thermosetting efficacy of modified cotton and cotton/polyester for both the
material includes resin with bio-based components like bio- bacterial species follows the order: Ag:ZnO/CS ≥ Ag/CS ≥
epoxy and bio-polyurethane. ZnO/CS > CS. A similar study was reported which involves
the preparation of antimicrobial textiles by coating the cotton
fabrics with SnO2/ZnO/chitosan bionanocomposites through
6 Polymer-based nanocomposites sonochemical process. The coated cotton fabrics displayed anti-
for cosmetics industry microbial activity against E. coli and Streptococcus aureus. After
several washes, antimicrobial activity was still retained with
Morlando et al. reported the use of natural polymer chitosan modified cotton fabrics which were due to the presence of chito-
for the inactivation of the photocatalytic activity of titanium san as complexing agent and citric acid as cross linker. With the
dioxide (TiO2), an inorganic ultraviolet (UV) filter used for interest of fabricating next-generation multifunctional smart tex-
sun blocking applications [48]. The photocatalytic property of tiles, textile (wool/nylon)-based e/touch-sensors decorated with
TiO2 in the presence of UV irradiation generates reactive ox- polyethylene glycol (PEG)/(poly (3,4-ethylenedioxythiophene),
ygen species which damages the sunscreen formulation and poly(styrenesulfonate) (PEDOT:PSS)/reduced graphene oxide
skin. Encapsulation of TiO2 by chitosan by spray drying meth- (rGO) nanosheets were developed. These multifunctional textiles
od reduces its photoactivity from 95 to 39.5% and thus useful exhibited high electrical conductivity (90.5 S cm−1), thermal
in the preparation of inactive protective coating material. As a conductivity (0.81 W/mK), and EMI (electromagnetic induction)
potential replacement to conventional plastics used as pack- shielding efficiency of 73.8 dB. This textile was found to be taser
aging materials, the use of biodegradable packaging material proof which can absorb electrical shocks as microwave shock
using the polylactic acid (PLA)-organoclay nanocomposite absorber and can be used in the manufacturing of soft touch
was developed and tested for cosmetic formulations [49]. switches to lighten up household bulbs or through WIFI-
Migration studies of the nanocomposite in cosmetic formula- connected textile-based touch switches.
tions and related stimulants were investigated for 10 days post Zinc oxide nanoparticles were grown on the polydopamine
incubation at 40 °C as per EU-Plastics Regulation 10/2011. templated cotton fabrics by Ran et al. [52]. The antimicrobial
Results indicated the total migration level of PLA nanocom- activity of the neat cotton fabrics and ZnO-modified cotton
posites was 0.88 mg/dm2 which were far less than maximum fabrics against Gluconobacter cerinus was studied using col-
legislative migration limit (10 mg/dm2). Especially, adverse ony count method, as shown in Fig. 6. The neat cotton fabrics
emergent mater.

does not possess any antibacterial effect; hence, bacterial trapping capability [55]. Ferritin is a highly stable iron storage
growth is visible (Fig. 6a). The growth was comparatively less protein and a widely used biomolecule produced by almost all
in PDA-templated cotton fabrics (Fig. 6b). However, there living organisms like bacteria, plants, and algae. Ferritin mul-
was complete reduction of bacterial growth in ZnO-coated tilayers showed switching abilities and can be utilized for the
cotton fabrics (Fig. 6c). This is attributed to the reactive oxy- creation of non-volatile memory. This was brought about by
gen production by ZnO nanoparticles resulting in the destruc- the charge trapping and releasing ability of the iron redox
tion of bacterial membrane. Even after five washing cycles, couples with ferritin [56]. A floating gate memory device
the antimicrobial property was retained (Fig. 6d). was fabricated using a Bombyx mori silk protein, multiwalled
carbon nanotube (MWCNT)/CdS composite system. The de-
vice showed good flexibility and transparency with a large flat
8 Polymer nanocomposites in electronic band voltage shift [57]. An antibody immunoglobulin G pro-
industry tein was attached to two gold nanoparticles which can be used
for the production of bioelectronics circuits [58]. A
Biomaterials have the disadvantage of having weak electron biocomponent blend film using carbon dots and silk were
transfer function, and thus, their application is limited in the produced as a phototunable carrier trapping layer showed
electronics industry [54]. When the bio-based materials are good optical programming and erasing process. This has the
combined to form composites with other functional materials, advantage that the synaptic-like behavior can be used in both
they can be readily used in electronics and other semiconduc- volatile and non-volatile modes and has the potential to be
tor industries. Bionanocomposites can be used in electronic used as a bioinspired photonic computing application [59].
devices such as resistive random access memory (RRAM), An amyloidogenic protein alpha synuclein was coated on gold
field-effect transistor (FET), resistive memory, artificial syn- nanoparticle arrays to create a monolayer that had a highly
apses, and artificial neural network simulation [53]. Chiu et al. tunable memory performance. The material showed good
prepared a glucose-based polysaccharide (maltoheptaose) tunneling/blocking properties and showed large density which
field effect transistor memory. The material showed high cur- is suitable for many electronic applications [60]. A protein
rent state and stable retention characteristics. The alpha glucan calmodulin (CaM)–modified silicon nanowire field effect
linker present in the glucose gave these material high charge transistor was manufactured for the detection of proteins and

Fig. 6 a Antimicrobial activity of


pristine cotton fabrics, b PDA-
templated cotton fabrics, c ZnO-
coated cotton fabrics, and d ZnO-
coated cotton fabrics after five
washing cycles [52]
emergent mater.

Fig. 7 Outline of
bionanocomposites in the
electronic device market [53]

calcium ions and finds their use as a biosensor [61]. A non- cost material also showed good on-off ratio and good data
volatile memory element is prepared by using DNA biopoly- retention time [65]. The biodegradability and bioactivity of
mer obtained from fish waste modified with hexadecyl the existing polymers can be used in the manufacture of im-
trimethyl ammonium chloride as gate dielectrics in a low- plantable bio electronic materials. A schematic representation
voltage application with very low hysteresis [62]. In another of the application of bionanocomposites in the electronic de-
study, wool keratin molecules were used in the incorporation vices market is given in Fig. 7 [53].
of gold nanoclusters in silk fibroin networks. This device has
the advantage of excellent switching abilities due to the tem-
plated β crystallite formation and can be used as an advanced 9 Conclusion
memristor [63]. Nagashima et al. prepared a highly flexible
silver–decorated cellulose nanofiber paper that showed its sta- The present review reports the use of bionanocomposites in the
ble non-volatile memory effects which has the potential to be industry as it is seen that in the last 10 years, an increasing
used in portable electronic applications [64]. A silver-doped number of researches in the area of bionanocomposites have
chitosan silver composite was prepared as solid polymer elec- been developed and reported. Several studies underline the
trolyte and applied to the resistive switching layer element in need to replace plastics with greener materials. Many biopoly-
ReRAM. It has the potential to be used in non-volatile mem- mers and inorganic nanoparticle filler materials are available
ory application with very less power requirements. This low- which can be finely tuned to obtain bionanocomposites with
emergent mater.

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