European Polymer Journal 108 (2018) 274–285

Contents lists available at ScienceDirect

European Polymer Journal

journal homepage: www.elsevier.com/locate/europolj

Macromolecular Nanotechnology - Review

How do cellulose nanocrystals affect the overall properties of biodegradable T

polymer nanocomposites: A comprehensive review
⁎ ⁎
F.V. Ferreiraa,b, , A. Dufresnec, , I.F. Pinheiroa, D.H.S. Souzad, R.F. Gouveiab, L.H.I. Meia,
L.M.F. Lonaa
a
School of Chemical Engineering, University of Campinas (UNICAMP), Campinas, SP 13083-970, Brazil
b
Brazilian Nanotechnology National Laboratory (LNNano), Brazilian Center for Research in Energy and Materials (CNPEM), Campinas, SP, Brazil
c
Univ. Grenoble Alpes, CNRS, Grenoble INP, LGP2, F-38000 Grenoble, France
d
Instituto de Macromoléculas Professora Eloísa Mano (IMA), Universidade Federal do Rio de Janeiro (UFRJ), Rio de Janeiro, RJ, Brazil

A R T I C LE I N FO A B S T R A C T

Keywords: Cellulose nanocrystals (CNCs) are considered as one of the most attractive renewable reinforcements for bio-
Cellulose nanocrystals degradable polymers due to their promising properties and broad range of applications in several fields.
Biodegradable polymer nanocomposites However, the knowledge of CNCs effect on the overall properties of these CNC-based nanocomposites is not fully
Rheological properties clarified. This review proposes a comprehensive understanding on the effect of CNCs on the rheological, thermal,
Thermal properties
mechanical, barrier and biodegradation properties of the main biodegradable polymers. This further under-
Mechanical properties
standing is expected to facilitate progress in various sectors of nanotechnology and materials science.
Biodegradation

1. Introduction as low cost, biodegradability, excellent mechanical properties and

Polymer nanocomposites offer attractive opportunities for auto-
motive [1], aeronautics [2], biomedical [3,4], and food packaging [5,6]
applications, because they are usually lighter than traditional materials
and show improved rheological, thermal, mechanical, barrier and bio-
degradation properties when compared to neat polymer [7]. When
nano-reinforced polymer composites were presented to the public for
the first time in the 90s by Research Laboratory of Toyota a huge
market opportunity has emerged [8–10]. Since then, researches de-
voted to the development of polymer nanocomposites have increased
significantly [11,12]. Accordingly, new nanocomposites with improved
properties have emerged and prospective application of these materials
has been expanded [13]. However, despite the reported market op-
portunity and proven benefits of polymer nanocomposites, the presence
of these materials in the main markets is far from the expectation [14].
A reasonable explanation for this behavior might be given by identi-
fying the four major obstacles, which hinder their broader expansion.
(i) The cost, environmental concerns, and availability of the nanofiller
are issues that must be taken into account. Several nanofillers are
expensive, non-biodegradable and their production at large scale is
still challenging [15]. In this context, cellulose nanocrystals (CNCs)
have attracted great attention due to their amazing properties such
abundance in nature.
(ii) The choice of the polymer matrix is also of fundamental im-
portance because several issues caused by polymer materials on
the environment have been reported [16,17]. Thus, exploring the
biodegradability of polymers is a hot topic.
(iii) Manufacturing challenges of nanocomposites exist which must be
overcome. The main of them consists in achieving the homo-
geneous dispersion and strong interaction between the nano-
particles and the polymeric matrix during processing [18]. The
surface modification of the nanofiller and appropriate processing
methods of nanocomposites have shown an alternative to improve
the dispersion and nanofiller-matrix interaction [19–23].
(iv) The industry and academia share a common scientific goal, i.e.
understanding the fundamental relationship between processing
and the final performance of materials. In this context, some
questions still remain: could the alteration of the polymers prop-
erties be attributed to the addition of nanofillers? How can the
basic characteristics of polymers be altered after their addition in
the matrix? Is there any correlation between nanofiller-polymer
interface and the properties of the nanocomposite? How the na-
nofiller chemical characteristics interfere in the final properties of
nanocomposites? Based on these questions, a comprehensive un-
derstanding on the effect of CNC on the overall properties of

⁎
Corresponding authors at: School of Chemical Engineering, University of Campinas (UNICAMP), Campinas, SP 13083-970, Brazil.
E-mail addresses: filipevargasf@gmail.com (F.V. Ferreira), alain.dufresne@pagora.grenoble-inp.fr (A. Dufresne).

https://doi.org/10.1016/j.eurpolymj.2018.08.045
Received 12 July 2018; Received in revised form 10 August 2018; Accepted 27 August 2018
Available online 27 August 2018
0014-3057/ © 2018 Elsevier Ltd. All rights reserved.
F.V. Ferreira et al. European Polymer Journal 108 (2018) 274–285

biodegradable polymers is thus of fundamental importance and
can contribute to the advancement of research on nanocomposites
materials based on CNCs.
The main contribution of this review of the literature is focused on
the effect of CNCs on the overall properties of biodegradable nano-
composites with emphasis on their rheological, thermal, mechanical,
barrier and biodegradation properties. At first, a brief introduction on
cellulose and the extraction of CNCs from different raw materials
sources are presented. Important issues related to the fabrication of
CNCs-based nanocomposites, processing issues, dispersion and surface
modification of CNCs are addressed in the subsequent sections. The
fundamental knowledge of the effect of CNCs on the nanocomposites
properties is covered. We discuss the addition of CNCs as a strategy to
produce nanocomposites with improved performance, correlating the
variations in the nanocomposites properties with the CNC-polymer in-
terface. Finally, the conclusions and perspectives are presented.
Therefore, this review is a further understanding of polymer materials
reinforced with nanofillers.
2.1. Surface modification of CNCs
In general, surface modification is a versatile method to manipulate
and tune the surface properties of nanomaterials; essential condition to
expand their potential applications [55,56]. Several papers have re-
ported the functionalization of CNCs using different functional groups
[57,58], while other authors reported the importance of functionali-
zation to manufacturing biodegradable nanocomposites with enhanced
performances [59]. Hence, this aspect is not discussed deeply here.
What is needed to know at present is that there are two main types of
functionalization: covalent and non-covalent. Covalent functionaliza-
tion is responsible for irreversible bond formation [60], while non-
covalent is related to secondary reversible interactions such as van der
Waals or hydrogen bonding forces [61]. Additionally, the properties
and applications of CNCs can be adjusted by surface modification
[62,63]. For further information about functionalization of CNCs, the
reader is referred to the following papers [64–67].
3. Biodegradable polymers

Polymeric materials are broadly used worldwide today. Because of

2. Cellulose
Cellulose is the most abundant renewable polymer on Earth and it
can be found in plants [24], algae [25], tunicates [26], and some
bacteria [27–29]. Cellulose is a linear homopolysaccharide with highly
ordered structure of β-1.4-linked anhydro-D-glucose units, which ag-
gregate to form cellulose fibrils [30–32]. The extraction of the crys-
talline domains from amorphous portion, after deconstruction of cel-
lulose fibrils by acid hydrolysis, generates the so-called cellulose
nanocrystals [33]. Several factors are listed as playing a significant role
in the characteristic of CNCs, such as cellulose source [34–43]
(Table 1), acid concentration [44], time and temperature of the acidic
treatment [45,46], type of acid [47,48] and centrifugal force [49] used
during the extraction process. In general, CNCs are elongated rod-like
particles with a highly crystalline structure, bending strength of about
10 GPa, tensile strength of up to 7.5 GPa, and Young’s modulus of ap-
proximately 150 GPa [50,51]. In addition, crystalline cellulose is a
lightweight material with density of 1.5–1.6 g cm−3 compared to e.g.
glass with a density around 2.5 g cm−3. These properties make CNCs
suitable to be used as reinforcement in nanocomposites [52]. However,
the inherent hydrophilicity of cellulose leads to inadequate dispersion
and weak interaction with hydrophobic polymers. Thus, the critical
challenge during the preparation of CNC-based nanocomposites con-
sists in obtaining a uniform dispersion of CNC in the polymer matrix
and strong CNC/matrix interaction [53]. Surface modification of CNCs
is an effective route to overcome the drawbacks related to dispersion
and filler/matrix interaction [54].
their recalcitrant nature and consequent accumulation in the environ-
ment, several problems related to polymers in the natural environment
have been reported [68–70]. There is therefore a strong demand for the
replacement of non-biodegradable polymers by biodegradable ones in
specific sectors, such as food packaging and medical devices, whose
recycling is not recommended.
Biodegradable polymers can be classified as natural-based materials
and synthetic polymers. Polysaccharides [25,33,71–74] and other es-
sential macromolecules such as proteins [75,76] belong to natural-
based materials. This article focuses on the most commonly used bio-
degradable polymers as matrix in CNC-based nanocomposites: poly
(butylene adipate-co-terephthalate) (PBAT), poly(lactic acid) (PLA),
poly(ε-caprolactone) (PCL), poly(butylene succinate) (PBS) and poly-
hydroxybutyrate (PHB).
3.1. Poly(butylene adipate-co-terephthalate) – PBAT
Poly(butylene adipate-co-terephthalate) is a synthetic biodegrad-
able polymer prepared by polycondensation reaction of 1,4-butanediol
with both adipic and terephthalic acids [77–79]. PBAT is considered as
one of the most attractive biodegradable polymer due to its biode-
gradability, thermal and mechanical properties such as melting tem-
perature of about 110–120 °C, glass transition temperature around (Tg)
−30 °C, Young’s modulus of 20–60 MPa, tensile strength of 32–36 MPa,
and elongation at break higher than 600% [80–82]. These properties
make PBAT suitable for several applications ranging from packaging
materials [83,84] to biomedical fields [85–87].

3.2. Poly(lactic acid) – PLA

Table 1
Characteristics of cellulose nanocrystals obtained from various cellulose sources
Poly(lactic acid) is a biodegradable aliphatic polyester obtained
by acid hydrolysis: length (L), diameter (D) and aspect ratio (L/D).
from biomass sources, which can be synthetized mainly by ring opening
Source L (nm) D (nm) Aspect Reference polymerization (ROP) and polycondensation [88–90]. Different poly-
ratio (L/D)
merization routes can lead to polymer with different properties [91,92].
Corn (Zea mays) 940 ± 70 6±2 157 [34] In general, PLA shows a melting temperature of 173–178 °C, Tg near to
Soy Hulls 503 ± 155 4.9 ± 1.1 100 [35] 64 °C, Young’s modulus of 0.35–3.5 GPa, tensile strength of about
Capim Dourado 300 ± 93 4.5 ± 0.9 67 [37] 50 MPa, and low elongation at break (less than 5%) [93–95]. Due to the
(Syngonanthus nitens)
chirality of the lactic acid molecule, PLA has stereoisomers such as poly
Spruce bark (Picea abies) 175 ± 62 2.8 ± 0.8 63 [36]
Luffa cylindrica fibers 242 ± 86 5.2 ± 1.3 46.5 [38] (L-lactide) (PLLA), poly(D-lactide) (PDLA), and poly(DL-lactide)
Sugarcane bagasse 413 ± 52 10 ± 2.5 41 [39] (PDLLA) [96]. These stereoisomers have different properties: PLLA and
Agave tequilana 323 ± 113 11 ± 4 28 [43] PDLA are crystalline, isotactic and optically active, while PDLLA is
Acacia mangium 199 ± 22 7.44 ± 1.49 26 [42] amorphous relatively atactic and optically inactive [97]. PLA was first
Balsa wood (Ochroma 176 ± 68 7.5 ± 2.9 24 [40]
reported as material for the repair of mandibular fractures of dogs [98].
pyramidalis)
Ramie 134 ± 59 10.8 ± 4.5 12 [41] Currently, PLA and its stereoisomers can be used in several

275
F.V. Ferreira et al. European Polymer Journal 108 (2018) 274–285

applications, especially as packaging [99] and biomedical materials 4. CNCs-based nanocomposites

[100–102].
Polymer composites are hybrid materials with one or more particle
3.3. Poly(ε-caprolactone) – PCL components (fillers) within a polymer matrix. The addition of micro
size filler as reinforcement was heralded in the 60 s as a way to prepare
Poly(ε-caprolactone) is a semicrystalline aliphatic linear polyester polymer materials with improved properties [121]. Similar tendency
with melting temperature of about 58–63 °C, Tg around −60 °C, good using “nano” reinforcement has been observed. Currently, several na-
drug permeability, biocompatibility, water and solvent resistance nomaterials with different sizes and shapes have been used as re-
[103,104]. PCL can be synthetized by free radical ring opening poly- inforcement, such as carbon nanotube [122–124], graphene [125],
merization (ROP) of 2-methylene1,3dioxepane [105], but ROP of ε- graphene oxide [126,127], layered double hydroxides [128], carbon
caprolactone is the most widely used method to obtain high-molecular- nanofiber [129] and CNCs [130]. Among these nanofillers, the use of
weight PCL [106]. This biodegradable polymer has been studied espe- CNC as reinforcement in different biodegradable polymeric matrices is
cially for use as medical implants [107] and controlled drug release a growing area of nanomaterials. This growth stems from the possibility
applications [108,109]. to prepare nanocomposites with improved properties maintaining the
biodegradability of the matrix. CNC-based nanocomposites have been
3.4. Poly(butylene succinate) – PBS prepared mainly by solvent casting, melt mixing and in-situ poly-
merization. Several review papers detail recent developments in pro-
PBS is a biodegradable polymer synthetized by polycondensation cessing of these nanocomposites [131,132]. The advantages and dis-
reaction of succinic acid (a very attractive biobased raw material) and advantages of the main processing methods used to obtain CNC-based
1,4-butanediol [110,111]. This aliphatic polyester has high flexibility, nanocomposites are summarized in Table 3.
with Tg around −32 °C, melting point near to 114 °C, about 230%
elongation at break, 42 MPa tensile strength, Young's modulus of about
4.1. Rheological properties of CNC-based nanocomposites
690 MPa and good thermal and chemical resistance [112]. These
properties make PBS a good material to be used as packaging, among
Cellulose nanocrystals lodge themselves between the polymer
other applications [113].
chains, affecting the microstructure (viscoelastic properties) of the
matrix [133]. Accordingly, the materials can show transition in rheo-
3.5. Polyhydroxybutyrate – PHB logical behavior from liquid-like to pseudo-solid-like or solid-like after
addition of the nanofiller [134]. Thus, rheological measurements are
Polyhydroxybutyrate, a member of Polyhydroxyalkanoate family, is powerful tools used to access this effect of the CNCs on the viscoelastic
a thermoplastic polyester produced by bacterial sources [74,114,115]. properties of the polymer. Moreover, the rheological results may also
PHB is a highly crystalline polymer, with melting temperature near provide information on the degree of dispersion and interactions be-
177 °C , tensile strength of 43 MPa and elongation at break of about 5% tween CNCs and polymer matrices [133,135]. The rheological behavior
[116–118]. This biodegradable polymer is also biocompatible with of polymers is studied mainly through their storage modulus (G'), loss
potential application in agriculture and biomedical fields [119,120]. modulus (G″) and complex viscosity (η*) as a function of frequency. G′
However, practical use of neat PHB has been limited due to its brit- and G″ may be used to classify polymer based solutions [136–139], as
tleness and narrow processing window [93]. Main properties of the summarized in Table 4. Moreover, both G′ and G″ may be used to in-
most commonly used biodegradable polymers used as matrix in CNC- vestigate the state of CNCs dispersion. When CNCs are homogeneously
based nanocomposites are summarized in Table 2. dispersed in a polymer matrix, an increase in both G′ and G″ is usually
observed due to efficient filler-matrix load transfer [140,141]. This
Table 2
stress transfer is affected as the agglomeration of the nanoparticles in-
Main properties of the most commonly used biodegradable polymers used as
creases, which decreases G′ and G″ [142]. Regarding the complex
matrix in CNC-based nanocomposites.
viscosity, generally η* increases with the addition of CNCs in a polymer
Polymer Properties matrix and this effect should be more pronounced with increasing filler
content [143]. However, this behavior is not fully understood.
Melting Tg (°C)* Young’s Tensile Elongation at
temperature modulus strength break (%) According to Einstein–Batchelor theory [145,146], the viscosity of
(°C) (MPa) (MPa) the system always increases with the addition of particles. This beha-
vior is reported by several authors studying CNC-based nanocomposites
PBAT 110–120 −30 20–60 32–36 > 600**
[147–149]. Mariano et al. [147] prepared CNC-based nanocomposites,
PLA 173–178 64 350–3500 50 < 5**
PCL 58–63 −60 – – – using PLLA modified with imidazolium group (Im-PLLA) as surfactant
PBS 114 −32 690 42 230 and PLA as matrix, and observed that the addition of high amount of
PHB 177 – – 43 5 CNC (10 and 20 wt% CNCs) increases the viscosity of the nanocompo-
sites. Similar behavior was observed by Zhang et al. [141] working with
* Glass transition temperature.
CNC/PBAT nanocomposites. They observed that the addition of 3 wt%
** > higher than and < less than.
CNC increases the complex viscosity of the polymer. However, other

Table 3
Advantages and disadvantages of the main processing methods of CNC-based nanocomposites.
Methods Advantages Disadvantages

Solvent casting Ease preparation; possibility of forming a three-dimensional CNC network inside Use of hazardous solvents (environmental issues); small scale
polymer matrix. production.
Melt mixing Potential to large-scale mass production; hazardous solvents are not required. CNCs can degrade during the process; high shear applied during the
process does not allow the 3D CNC network to form.
In situ polymerization Formation of a polymer network with CNCs embedded relatively uniform; Temperature can degrade CNCs during polymerization; CNCs
possibility of covalent bond between CNCs and polymer matrix potential to large dispersion in the monomer phase can lead to low degree of
scale production. polymerization.

276
F.V. Ferreira et al. European Polymer Journal 108 (2018) 274–285

Table 4 weak percolating network. According to authors, the differences ob-

Relative value of the storage modulus and loss modulus for classifying polymer- served in the rheological properties of the nanocomposites prepared by
based solutions. extrusion are related to four combined effects: polymer chain scission,
Classification Relationship between G′ and G″ Reference mechanical degradation of CNCs, orientation effect and aggregation
induced by the process.
Dilute solution G′ > G″* [137]
Entanglement network system G′ = G″ [138,139]
Weak gel G′ < G″** [136] 4.2. Thermal properties of CNC-based nanocomposites
Strong gel G′ ≪ G″** [144]
The effect of CNC on the crystallization and the spherulite growth of
* Viscous behavior. biodegradable polymers from the melt have been intensively in-
** Elastic behavior.
vestigated by differential scanning calorimetry (DSC). Several authors
reported that CNCs act as nucleating agent, increasing especially the
researchers reported a decrease in viscosity when adding CNCs, which
melting temperature (Tm), crystallization temperature (Tc) and degree
contrasts with expectations based on the Einstein–Batchelor theory.
of crystallinity (Xc) of the polymer. An increase in Tm can be related to
Pinheiro et al. [150] studied the effect of modified CNC on the rheo-
the presence of thicker polymer crystalline lamellae [168], while the
logical behavior of CNC/PBAT nanocomposites and observed that the
decrease of this temperature can result from the crystallization of
viscosity of the system decreases as the concentration of modified CNC
slightly less perfect polymer crystals [169]. When a nanofiller acts as
increases. Additionally, other authors observed a peculiar behavior
nucleating agent, usually Tc of the nanocomposite is shifted to a tem-
when CNCs are added in the polymer matrix. Ben Azouz et al. [151]
perature slightly higher than that of the neat polymer, which is directly
studied the rheological properties of poly(oxyethylene) (PEO) filled
related to an increased number of heterogeneous nuclei for crystal-
with CNCs (aqueous solution) and reported that the viscosity of the
lization [170]. On the other hand, when CNCs act as anti-nucleating
suspension first decreases as the CNC content increases up to 6 wt%,
agent, a decrease in Tc is observed, as reported by Chen et al. [171]. The
and then increases for the 9 wt% suspension. According to these au-
authors studied the crystallization of PHB-based nanocomposites filled
thors, the viscosity first decreases due to strong affinity between PEO
with unmodified and modified CNCs. They observed that the un-
chains and the CNCs surface [152]. Above the critical value (6 wt% of
modified CNC acted as nucleating agents, increasing the Tc value of
CNCs), the PEO chains are adsorbed by the great amount of CNC.
PHB; while polylactide-grafted CNC (CNC-g-PLA) acted as anti-nucle-
Therefore, less free PEO chains are available in the solution which in-
ating agent, resulting in a reduction in Tc of the polymer. Accordingly,
creases the viscosity of the system.
the nanocomposites filled with CNC-g-PLA showed lowest crystal-
These contradictory results occur because of the filler size
lization rate than the neat polymer and the nanocomposites filled with
[153,154], free volume introduced by the filler [155], interaction be-
unmodified CNCs. The same trend was observed by Lv et al. [172]
tween the filler and the matrix [156], which are unique for each system
studying the crystallization of CNC/PCL nanocomposites.
[157] and they affect differently the viscosity of the polymer solution
Other papers showed that the change in Tc can also be related to the
[158]. The filler size can change the free volume of the system, which
spherulite morphology of the polymer. Chen et al. [173] studying the
affect the viscosity of the polymer system [150]. Moreover, particles
effect of CNC and microcrystalline cellulose (MCC) on spherulite mor-
with small size can plasticize the polymer matrix, decreasing the visc-
phology of PHB showed that the crystallization temperature of this
osity of the system [159–161]. Weak interfacial interaction (poor
polymer and the nano size of CNC affect the final morphology of
wetting) between the filler and the polymer due to difference in polarity
system. The authors showed (Fig. 1a) that the average band space in-
for example, typically leads to poor dispersion (or aggregation). The
creased as the crystallization temperature increased. On the other hand,
aggregation of the filler means an increase of particle size, which affect
this average band space decreased with the addition of CNC and MCC
the viscosity of the entire system [162–164].
(Fig. 1b), probably due to faster crystallization rate of PHB in the
In addition to the above considerations, the addition of CNCs in
composites when compared with neat PHB (Fig. 1c). Addition of CNC
polymer matrices can also affect the rheological properties due to the
and MCC (heterogeneous nuclei) unbalances the stresses at the filler/
formation of a three-dimensional (3D) network which connects the
matrix interface, resulting in insufficient time to PHB chain segments to
CNCs inside the polymer [140,165]. This strong 3D network is based on
relax and favoring the lamellae twist [174]. Thus, the ring-banded
hydrogen bonding between the nanoparticles and occurs when the CNC
spherulites are formed with smaller band space (Fig. 1b) [175,176].
content reach the percolation threshold, leading to changes in the
The crystallinity of the polymer is also affected by the addition of
viscosity of the polymer [140,148]. Several parameters are listed as
CNCs, and it is related not only to nucleation ability of CNCs, but also to
playing a significant role on the formation of the percolating network
the enhanced interfacial interaction among filler-matrix. Pei et al. [177]
such as particle morphology [166], surface of CNCs [136] and mainly
prepared PLLA-based nanocomposites reinforced with partially sily-
the method used to obtain the CNC-based nanocomposite [167]. El Miri
lated CNC by casting. They reported that the Xc value of the polymer
et al. [136] prepared bio-nanocomposite films of carboxymethyl cel-
increased from 14.3% to 30.4% after addition of 1 wt% of functiona-
lulose (CMC)/starch (ST) polysaccharide matrix reinforced with CNCs
lized CNCs and this significant increase was not observed when un-
using the solution casting method. The authors reported that the ad-
modified CNCs were used. According to these authors, the enhanced
dition of CNCs can lead to additional interfacial interactions between
crystallization power of modified CNCs is a result of good dispersion
the functionalized surface and the macromolecular chains of CMC and
and improved interfacial CNC-polymer interaction due to surface
ST. Alloin et al. [167] studied the influence of processing (casting/
modification. Similar results were also reported by other authors, using
evaporation and extrusion) on the rheological properties of PEO based
PBAT [169] and PLA [178,179] as matrices and modified CNCs.
nanocomposites. The authors reported a strong reinforcing effect of
On the other hand, differently from what is usually reported in the
CNCs in the polymer matrix for nanocomposites prepared by casting/
literature, some authors [169,180] observed no significant increase in
evaporation, suggesting the presence of a CNC percolating network. On
Xc after addition of CNC in the polymer matrices. Yu et al. [180] pre-
the other hand, the reinforcing effect of CNCs in the nanocomposites
pared CNC/PHBV nanocomposites by solution casting method and they
prepared by extrusion was reduced probably due to the absence or
reported that the crystallization of PHBV became easier due to the

277
F.V. Ferreira et al. European Polymer Journal 108 (2018) 274–285

Fig. 1. The corresponding intensity profiles measured from the centers of selected ring-banded spherulite of (a) neat PHB at different crystallization temperatures and
(b) neat PHB and its composite samples for Tc = 85 °C. The arrows in the micrographs indicate the measuring radial directions. Polarized optical photographs of final
crystalline morphology of (a) neat PHB, (b) MCC/PHB and (c) CNC/PHB crystallized at 109 °C with the scale bar of 200 μm. Adapted from ref [173] with permission
from Elsevier.

addition of CNCs (i.e. nanocrystals acting as nucleating agents). Despite
this, the crystallinity of the polymer decreased by 6.64%. According to
authors, the regularity of polymer chains was disturbed due to the
addition of CNCs. Morelli et al. [168] reported that despite the increase
in Tc as the amount of CNC increased, the crystallinity of PBAT did not
change considerably. Similar behaviors were also observed by Hameed
et al. [181] working with PHBV. In another work, Morelli et al. [182]
reported that Tc of PBAT increased, while Xc decreased after addition of
modified CNC with a low molecular weight poly(butylene glutarate). It
is well-known that the crystallization process of polymeric materials
depends on the level of dispersion of nucleating (in this case cellulose
nanocrystals), nanocomposite processing method, polymer chemical
structure, thermal history of the material, structure of the filler and so
on [165,183]. Therefore, these above contradictory results suggest that
cellulose nanocrystals (especially modified CNCs) can act as nucleating
agents (nucleation sites) affecting the interfacial interaction among
filler-matrix, Tc and Xc of the polymer. Therefore, it is recommended to
study the nucleation effect of the CNCs for each system, since it can
vary and modify the properties of the final material.
4.3. Mechanical properties of CNC-based nanocomposites
The enhancement of the mechanical properties of the host matrix sounds
natural because of the intrinsic mechanical function of cellulose in nature.
The use of CNCs in different polymer matrices to achieve nanocomposites
with adequate mechanical properties is important for the better employment
of these materials in the different fields where they are used [184]. For ex-
ample, when these materials are used as packaging, high elongation at break
and enhanced tear resistance are required [185]. In the case of biomedical
application, the material should be flexible with high elongation at break,
whereas for automotive applications, high stiffness and strength are essential
[186]. Several authors studied theoretically the effect of CNCs on the me-
chanical properties of polymer nanocomposites. Aitomäki and Oksman [187]
used micromechanical models such as Halpin–Tsai model [188] and rule of
mixture (ROM) model [189] to study the reinforcement effect of nanocellu-
lose in polymer nanocomposites. Sapkota et al. adapted the Ouali–Takaya-
nagi [190] model with the model reported by Schilling et al. [191] to in-
terpret the mechanical reinforcement in polymer nanocomposites reinforced
with CNCs.

Table 5
Mechanical property improvements for CNC-based polymer nanocomposites.
CNC source Polymer matrix Preparation procedure Filler content (wt%) σ* (MPa) E* (GPa) ε* (%) Year Ref

University of Maine, USA PBS In situ polymerization 0.5 42.1 > 54.3 0.69 > 0.83 230 > 357 2018 [112]
MCC PBAT Melt mixing 7 22.0 < 12.4 0.05 > 0.08 544.5 < 567.4 2017 [150]
MCC PBAT Casting 10 6.3 > 7.2 0.06 > 0.12 10.2 < 5.8 2016 [168]
MCC PBAT Melt mixing 10 5.8 = 5.8 0.06 > 0.08 30 < 20 2016 [169]
MCC PBAT Melt mixing 0.5 11.0 < 9.7 0.04 > 0.12 927 < 558 2016 [141]
MCC PLA Casting 5 55 < 54 1.3 > 1.6 9<7 2015 [179]
MCC PHB Casting 5 25 < 23 1.4 > 1.8 4<3 2015 [179]
MCC PLA Casting 2.5 40 > 51 – 4.3 > 5.6 2013 [192]
MCC PLA Melt mixing 5 43 > 46 2400 > 4400 90 < 18 2012 [178]
Cotton PLLA Casting 2 48.3 > 58.6 1.1 > 1.4 31.1 < 8.3 2010 [177]

* σ – strength; E – modulus of elasticity; ε – elongation at break. The properties were compared between CNC-based nanocomposites and neat polymer. >
improved and < decreased properties.

278
F.V. Ferreira et al. European Polymer Journal 108 (2018) 274–285

Other authors have highlighted experimentally improvements in the mechanical properties of the nanocomposite such as nanofiller size
mechanical properties of different polymer matrices through the addi- [196,197], method of preparation of the nanocomposite [167], ex-
tion of CNC as reinforcement [192]. Table 5 summarizes these im- traction method [198], surface modification of CNCs [59] and so on
provements in mechanical properties for CNC-based polymer nano- [132]. Thus, the above discussion allows us to conclude that the ad-
composites. Siqueira et al. [38] prepared PCL-based nanocomposites dition of CNCs affects the mechanical properties of the nanocomposites.
and observed an increase in tensile modulus with the addition of CNCs. The overall mechanical improvements of CNC-based nanocomposites
Morelli et al. [168] reported an increase of about 40% in yield stress for are related to a synergistic effect of the increased crystallinity of the
PBAT-based nanocomposites after addition of 10 wt% of modified polymer matrix due to nucleation ability of CNCs and the CNCs re-
CNCs. Similar result were observed by other research group [192]. The inforcing effect, obeying a nanofiller limit concentration for each
increase in the mechanical properties of nanocomposites can be related system [199].
to the addition of a hard phase (CNCs) in the comparatively softer
polymer matrix, which absorb part of the external stress due to their
4.4. Barrier properties of CNC-based nanocomposites
high Young’s modulus and also dissipate this external stress by particle-
particle and particle-polymer friction as mentioned earlier [193,194].
Barrier properties (gas and moisture barrier) are important re-
Moreover, the improvement in mechanical performance can also be
quirements for several applications, especially when the biodegradable
related to the increase in the polymer crystallinity, as observed by Pei
polymer is used as packaging [200]. Several authors have reported a
et al. [177]. The author prepared PLLA-based nanocomposites with
positive impact on gas and moisture barrier performances for biode-
partially silylated CNC (SCNC). They reported that the increase in
gradable polymers after addition of CNCs [201,202]. Ambrosio-Martín
tensile modulus (27%) and in the tensile strength (21%) observed for
et al. [203] prepared PLA-based nanocomposites using CNCs modified
the nanocomposite filled with 1 wt% SCNC can be related to the in-
with lactic acid oligomers (OLLA–BCNCs) as nanofiller. The authors
creased degree of crystallinity resulting from the addition of CNCs.
observed improvements in the water and oxygen barrier properties due
Fortunati et al. [178] prepared PLA-based nanocomposites re-
to the addition of well-dispersed OLLA–BCNCs. According to the au-
inforced with CNC modified with surfactant (acid phosphate ester of
thors, the nanofillers act as blocking agents within the polymeric ma-
ethoxylated nonylphenol) and observed an increase of 83% in the
trix, promoting a tortuous path to permeation of the water and gas
Young modulus value after addition of 5 wt% of modified CNCs.
molecules, and therefore increasing the barrier properties of the ma-
However, the authors observed a decrease in the elongation at break,
terial. Fig. 2 shows the schematic representation of tortuous path to
which is a common trend observed for thermoplastic nanocomposites
permeation of the water and gas molecules due to the addition of CNCs.
(as shown in Table 5). The addition of CNCs can lead to substantial
In this context, the morphology, orientation and good dispersion of the
local stress concentrations in the polymer matrix, reducing the elon-
CNCs within the polymer matrix lead to higher tortuosity effects, im-
gation at break of the material [195]. Despite this trend, some authors
proving the barrier properties of the material [204,205]. Sanchez-
observed a slightly different behavior studying CNC/PBAT nano-
Garcia et al. [206] reported that the water permeability decreased by
composites. Pinheiro et al. [150] observed that the elongation at break
82% and the oxygen permeability reduced by 90% when adding CNC in
of PBAT increased with the addition of modified CNCs. Moreover, this
PLA matrix. On the other hand, different results were reported by
property decreased as the CNC content increased from 3 (theoretical
Espino-Pérez et al. [192], working with n-octadecyl-isocyanate-grafted-
percolation threshold) to 7 wt%. This behavior may be surprising at
CNCs and PLA as matrix. The authors reported that O2 permeability did
first sight since the reinforcement effect of nanofiller should be more
not reduce after addition of CNCs into PLA. These contradictory results
pronounced as the CNC content increases. However, the addition of
between the work of Sanchez-Garcia et al. [206] and Espino-Pérez et al.
CNCs up to the theoretical percolation threshold leads to homogeneous
[192] can be related to the permeability value of neat polymer. San-
dispersion of CNCs in the polymer matrix (partially organized struc-
chez-Garcia et al. reported the blank value
ture), which favors the dissipation of external stress. This partially or-
(1.37 × 10−17 m3 m m−2 s−1 Pa−1) one order of magnitude higher
ganized structure tends to be destroyed when passing from a percolated
than that of Espino-Pérez et al. (2.4 × 10−18 m3 m m−2 s−1 Pa−1),
system to a non-percolated one, resulting in CNC agglomeration. The
while the nanocomposites showed the same range (about 1.6 and 2.3
agglomeration not only induces stress concentration spots in the
10−18 m3 m m−2 s−1 Pa−1).
polymer matrix, but it also affects the dissipation of external stress
Besides the barrier properties to water and gas by tortuosity effects,
through particle-polymer interaction, resulting in the reduction of the
some authors reported that the improvement of barrier properties of the
elongation at break. Other process parameters can also affect the
polymer can be related to the changes in its crystallinity due to the

Fig. 2. Schematic representation of the more tortuous path for water and gas molecules to diffuse due to addition of CNCs. The figure is based on the work of Ferrer
et al. [201] and Nair et al. [202].

279
F.V. Ferreira et al.
addition of the nanofiller [207]. Fortunati et al. [208] reported that
PLA/CNC nanocomposites showed improvements in barrier properties
simultaneously with increased crystallinity due to the addition of CNCs.
In order to better understand the origin of barrier properties, separating
the blocking agent effect of CNCs from that of the nucleating effect
which affects the crystallinity of the polymer, Espino-Pérez et al. [209]
studied the system CNC/PLA nanocomposites with a high D-lactic acid
content (which cannot crystallize under commonly used processing
conditions) as matrix. They considered separately the blocking agent
effect of CNCs from that of the nucleating effect that affects the crys-
tallinity of the polymer. The authors concluded that the tortuosity effect
of CNC on the oxygen barrier properties is limited. However, a sig-
nificant improvement in the water vapor barrier properties was ob-
served after addition of modified CNC. Unmodified CNCs swell during
the mass transport of water due to their hydrophilicity, which favors
the pathway for mass transport. This behavior is not observed when
modified CNCs are used because the surface modification decreases the
hydrophilicity of the nanoparticles [57]. Follain et al. [210] reported
that other features can be listed as playing a significant role on gas and
moisture barrier performances of CNC-based nanocomposites. The au-
thors prepared PCL-based nanocomposites reinforced with N-octadecyl
isocyanate modified CNC and observed that the permeability and dif-
fusivity of the gases N2, O2 and CO2 were increased despite the per-
colating dense CNC phase formed. According to the authors, the for-
mation of a three-dimensional network and intimate interfacial
adhesion between CNC and PCL chains can cause structural defects in
the matrix, which facilitate the gas transfer.
Therefore, the results for barrier properties of CNC-based nano-
composites here presented allow us to conclude that the tortuosity ef-
fect induced by CNCs, the structure of the nanocomposite, CNC surface
chemistry and mainly the change in crystallinity of the host matrix play
a role on gas and moisture barrier performances of the material.
4.5. Biodegradation properties of CNC-based nanocomposites
Biodegradation is an important requirement for packaging industry,
agricultural mulches and biomedical materials based on plastics, due to
their great amount of use of these items that tends to growth. This gives
rise to the current and growing concern about environmental issues.
The preparation of polymer materials with improved biodegradation
properties has been challenging and an excellent alternative to mitigate
the problems of landfills, mainly in countries that have not adopted the
composting technique. Studies have highlighted improvement in bio-
degradation properties for different biodegradable polymer matrices
through the addition of CNC as filler [150,211]. This behavior is related
to depolymerization of the polymer by water and hydrophilic nature of
CNC [212]. The polymer degradation occurs by non-enzymatic
(thermal degradation, chemical hydrolysis) and enzymatic routes (de-
gradation by aerobic and anaerobic bacteria and fungi present in the
natural environment) [213]. In the case of non-enzymatic degradation,
the polymer degradation rate is strongly increased by water, which
causes hydrolysis of polymer chains, mainly those polymers of hetero-
geneous chains like polyesters [87].
The addition of CNCs increases the hydrophilicity of the polymer
[211], consequently enhances the biodegradability of the matrix. In the
case of enzymatic degradation, aerobic bacteria that act during the
biodegradation process are hydrophilic and consume CNCs during de-
gradation [214]. The consumption of CNCs by microorganisms leads to
a more porous polymer matrix, which favors the rate of bio-disin-
tegration of the material [215]. In this context, the surface modification
of CNCs affects negatively the degradation of the matrix since it de-
creases the nanofiller hydrophilicity [216]. Pinheiro et al. [150] pre-
pared PBAT-based nanocomposites filled with unmodified and modified
CNCs. The authors observed that the incorporation of unmodified CNCs
resulted in greater weight loss probably due to the hydrophilic nature of
the nanocrystals that accelerated the hydrolysis of PBAT. Other authors
280
European Polymer Journal 108 (2018) 274–285
[212] reported similar results and observed that the hydrophilic nature
of the reinforcement favors the degradation of the polymer. The crys-
tallinity [217] and crystal size [218,219] have also been reported
playing an important role in the degradation rate of the matrix, since
crystalline regions are more resistant to hydrolysis [220,221].
Since the biodegradation of polymers occurs in the environment, its
impact in the soil must be examined in order to follow any ecotox-
icological effects arising from the process. In this context, Palsikowski
et al. [222] reported their research with PLA and PBAT and their non-
cytotoxic, -phytotoxic, -genotoxic and -mutagenic behaviors against
Allium cepa meristematic cells. Other authors [223,224] reported that
the polymers PCL, PBS and PHB are also non-toxic in soil. However, as
the number of new biodegradable reinforced materials grows in the
market every year, the study of their biodegradation and the effect of
this process in the environment should be investigated.
5. Potential applications of CNC-based nanocomposites in the
industry
The interest from industrial sector by cellulose-based materials has
attracted increasing investment, which will certainly continue to grow
driven by sustainability trends [225]. These materials have been shown
great potential to be used in different fields such as flexible printed
electronics applications [226], fire retardant paperboard for semi
structural applications [227], food packaging [228], etc. However,
there are several challenges to solve especially related to development
of suitable processing technologies for large scale. The processing step
of these materials is crucial because it is related to their final perfor-
mance. Further studies are needed to prepare cellulose-based nano-
composites in industrial production, and they are appearing [229],
which reinforces the optimism for the replacement of non-biodegrad-
able polymers by environment-friendly materials.
6. Conclusions and perspectives
Cellulose nanocrystals (CNCs) have been widely studied as re-
inforcement phase in biodegradable polymers due to their biodegrad-
ability, wide availability, highly crystalline structure and ability to
improve the properties of composites. The rheological, thermal, me-
chanical, barrier and biodegradation properties of the polymer are
improved after addition of CNCs, inspiring the scientific community to
understand how CNCs affect the overall properties of the nanocompo-
sites. However, this fundamental knowledge is not fully clear.
As a general conclusion, CNCs can affect differently the viscosity of
the polymer depending on size, free volume introduced by the CNCs,
percolating network, processing method of the nanocomposites, dis-
persion and interfacial interaction of CNCs with the polymer matrix. A
number of papers have emphasized nucleation effect of CNCs, which
increases the crystallinity of the polymer. The increased crystallinity
has been associated with improved mechanical properties of the na-
nocomposite. Moreover, good dispersion and strong CNC-matrix inter-
action contributes to dissipate energy from external stresses, which
enhances the mechanical properties of the nanocomposites. The pre-
sence of CNCs in polymer matrices leads a more tortuous path to per-
meation of water and gas molecules, improving the barrier properties,
whereas enhancing the biodegradation rate of the inherently biode-
gradable polymer. The further understanding of the effect of CNCs on
the overall properties of CNC-based nanocomposites here reported is
useful information to researchers and may facilitate progress in mate-
rials science.
Acknowledgements
The authors gratefully acknowledge the financial support received
from FAPESP [Grant 2016/09588-9; Ph.D. fellowship of F.V.F] and
CNPq. The authors thank Dr. Marcos Mariano for the valuable
F.V. Ferreira et al.
discussions. LGP2 is part of the LabEx Tec 21 (Investissements d’Avenir
– grant agreement no. ANR-11-LABX-0030) and of PolyNat Carnot
Institute (Investissements d’Avenir – grant agreement no. ANR-16-
CARN-0025-01).
References
[1] A.K. Naskar, J.K. Keum, R.G. Boeman, Polymer matrix nanocomposites for auto-
motive structural components, Nat. Nanotechnol. 11 (2016) 1026–1030, https://
doi.org/10.1038/nnano.2016.262.
[2] W. Francisco, F.V. Ferreira, E.V. Ferreira, L.S. Cividanes, A. dos R. Coutinho,
G.P. Thim, Functionalization of multi-walled carbon nanotube and mechanical
property of epoxy-based nanocomposite, J. Aerosp. Technol. Manage. 7 (2015)
289–293, https://doi.org/10.5028/jatm.v7i3.485.
[3] S. Mondal, Preparation, properties and applications of nanocellulosic materials,
Carbohydr. Polym. 163 (2017) 301–316, https://doi.org/10.1016/j.carbpol.2016.
12.050.
[4] R. Scaffaro, F. Lopresti, M. D’Arrigo, A. Marino, A. Nostro, Efficacy of poly(lactic
acid)/carvacrol electrospun membranes against Staphylococcus aureus and
Candida albicans in single and mixed cultures, Appl. Microbiol. Biotechnol. 102
(2018) 4171–4181, https://doi.org/10.1007/s00253-018-8879-7.
[5] S.A. Attaran, A. Hassan, M.U. Wahit, Materials for food packaging applications
based on bio-based polymer nanocomposites, J. Thermoplast. Compos. Mater. 30
(2017) 143–173, https://doi.org/10.1177/0892705715588801.
[6] A.M. Youssef, S.M. El-Sayed, H.H. Salama, H.S. El-Sayed, A. Dufresne, Evaluation
of bionanocomposites as packaging material on properties of soft white cheese
during storage period, Carbohydr. Polym. 132 (2015) 274–285, https://doi.org/
10.1016/j.carbpol.2015.06.075.
[7] H. Kargarzadeh, M. Mariano, J. Huang, N. Lin, I. Ahmad, A. Dufresne, S. Thomas,
Recent developments on nanocellulose reinforced polymer nanocomposites: a re-
view, Polym. (Guildf) (2017), https://doi.org/10.1016/j.polymer.2017.09.043.
[8] Y. Kojima, A. Usuki, M. Kawasumi, A. Okada, Y. Fukushima, T. Kurauchi,
O. Kamigaito, Mechanical properties of nylon 6-clay hybrid, J. Mater. Res. 8
(1993) 1185–1189, https://doi.org/10.1557/JMR.1993.1185.
[9] A. Usuki, Y. Kojima, M. Kawasumi, A. Okada, Y. Fukushima, T. Kurauchi,
O. Kamigaito, Synthesis of nylon 6-clay hybrid, J. Mater. Res. 8 (1993)
1179–1184, https://doi.org/10.1557/JMR.1993.1179.
[10] P. Nawani, D. Burnett, R. Crawford, Modified Nano-Clay Materials and
Nanocomposites Made Therefrom, US Patent 20140275347 A1, 2013.
[11] A. Kausar, S. Anwar, Graphite filler-based nanocomposites with thermoplastic
polymers: a review, Polym. Plast. Technol. Eng. (2017) 1–16, https://doi.org/10.
1080/03602559.2017.1329438.
[12] L.S. Cividanes, W. Franceschi, F.V. Ferreira, B.R.C. Menezes, R.C.M. Sales,
G.P. Thim, How Do CNT affect the branch and crosslink reactions in CNT-epoxy,
Mater. Res. Express. 4 (2017) 105101, https://doi.org/10.1088/2053-1591/
aa8d31.
[13] S.K. Kumar, B.C. Benicewicz, R.A. Vaia, K.I. Winey, 50th anniversary perspective :
are polymer nanocomposites practical for applications? Macromolecules 50
(2017) 714–731, https://doi.org/10.1021/acs.macromol.6b02330.
[14] R. Pfaendner, Nanocomposites: industrial opportunity or challenge? Polym.
Degrad. Stab. 95 (2010) 369–373, https://doi.org/10.1016/j.polymdegradstab.
2009.11.019.
[15] F.V. Ferreira, L.D.S. Cividanes, F.S. Brito, B.R.C. de Menezes, W. Franceschi,
E.A. Nunes Simonetti, G.P. Thim, Functionalizing Graphene and Carbon
Nanotubes: A review, Springer International Publishing, Cham, 2016http://doi.
org/10.1007/978-3-319-35110-0.
[16] R. Geyer, J.R. Jambeck, K.L. Law, Production, use, and fate of all plastics ever
made, Sci. Adv. 3 (2017) e1700782, https://doi.org/10.1126/sciadv.1700782.
[17] L.C.M. Lebreton, J. van der Zwet, J.-W. Damsteeg, B. Slat, A. Andrady, J. Reisser,
River plastic emissions to the world’s oceans, Nat. Commun. 8 (2017) 15611,
https://doi.org/10.1038/ncomms15611.
[18] K. Oksman, Y. Aitomäki, A.P. Mathew, G. Siqueira, Q. Zhou, S. Butylina,
S. Tanpichai, X. Zhou, S. Hooshmand, Review of the recent developments in cel-
lulose nanocomposite processing, Compos. Part A Appl. Sci. Manuf. 83 (2016)
2–18, https://doi.org/10.1016/j.compositesa.2015.10.041.
[19] J.C. Natterodt, J. Sapkota, E.J. Foster, C. Weder, Polymer nanocomposites with
cellulose nanocrystals featuring adaptive surface groups, Biomacromolecules 18
(2017) 517–525, https://doi.org/10.1021/acs.biomac.6b01639.
[20] N. Lin, J. Huang, A. Dufresne, Preparation, properties and applications of poly-
saccharide nanocrystals in advanced functional nanomaterials: a review,
Nanoscale 4 (2012) 3274–3294, https://doi.org/10.1039/c2nr30260h.
[21] J.R. Capadona, O. Van Den Berg, L.A. Capadona, M. Schroeter, S.J. Rowan,
D.J. Tyler, C. Weder, A versatile approach for the processing of polymer nano-
composites with self-assembled nanofibre templates, Nat. Nanotechnol. 2 (2007)
765–769, https://doi.org/10.1038/nnano.2007.379.
[22] A. Maio, L. Botta, A.C. Tito, L. Pellegrino, M. Daghetta, R. Scaffaro, Statistical
study of the influence of CNTs purification and plasma functionalization on the
properties of polycarbonate-CNTs nanocomposites, Plasma Process. Polym. 11
(2014) 664–677, https://doi.org/10.1002/ppap.201400008.
[23] R. Scaffaro, A. Maio, S. Agnello, A. Glisenti, Plasma functionalization of multi-
walled carbon nanotubes and their use in the preparation of nylon 6-based na-
nohybrids, Plasma Process. Polym. 9 (2012) 503–512, https://doi.org/10.1002/
ppap.201100140.
[24] R.J. Moon, A. Martini, J. Nairn, J. Simonsen, J. Youngblood, Cellulose
281
European Polymer Journal 108 (2018) 274–285
nanomaterials review: structure, properties and nanocomposites, Chem. Soc. Rev.
40 (2011) 3941, https://doi.org/10.1039/c0cs00108b.
[25] D. Klemm, B. Heublein, H.P. Fink, A. Bohn, Cellulose: fascinating biopolymer and
sustainable raw material, Angew. Chemie – Int. Ed. 44 (2005) 3358–3393, https://
doi.org/10.1002/anie.200460587.
[26] I.A. Sacui, R.C. Nieuwendaal, D.J. Burnett, S.J. Stranick, M. Jorfi, C. Weder,
E.J. Foster, R.T. Olsson, J.W. Gilman, Comparison of the properties of cellulose
nanocrystals and cellulose nanofibrils isolated from bacteria, tunicate, and wood
processed using acid, enzymatic, mechanical, and oxidative methods, ACS Appl.
Mater. Interfaces 6 (2014) 6127–6138, https://doi.org/10.1021/am500359f.
[27] G. Pacheco, C.R. Nogueira, A.B. Meneguin, E. Trovatti, M.C.C. Silva,
R.T.A. Machado, S.J.L. Ribeiro, E.C. da Silva Filho, H. da S. Barud, Development
and characterization of bacterial cellulose produced by cashew tree residues as
alternative carbon source, Ind. Crops Prod. 107 (2017) 13–19, https://doi.org/10.
1016/j.indcrop.2017.05.026.
[28] I.M.S. Araújo, R.R. Silva, G. Pacheco, W.R. Lustri, A. Tercjak, J. Gutierrez,
J.R.S. Júnior, F.H.C. Azevedo, G.S. Figuêredo, M.L. Vega, S.J.L. Ribeiro,
H.S. Barud, Hydrothermal synthesis of bacterial cellulose–copper oxide nano-
composites and evaluation of their antimicrobial activity, Carbohydr. Polym. 179
(2018) 341–349, https://doi.org/10.1016/j.carbpol.2017.09.081.
[29] M. de Lima Fontes, A.B. Meneguin, A. Tercjak, J. Gutierrez, B.S.F. Cury, A.M. dos
Santos, S.J.L. Ribeiro, H.S. Barud, Effect of in situ modification of bacterial cel-
lulose with carboxymethylcellulose on its nano/microstructure and methotrexate
release properties, Carbohydr. Polym. 179 (2018) 126–134, https://doi.org/10.
1016/j.carbpol.2017.09.061.
[30] H. Miyamoto, U. Schnupf, J.W. Brady, Water structuring over the hydrophobic
surface of cellulose, J. Agric. Food Chem. 62 (2014) 11017–11023, https://doi.
org/10.1021/jf501763r.
[31] D.J. Gardner, G.S. Oporto, R. Mills, M.A.S.A. Samir, Adhesion and surface issues in
cellulose and nanocellulose, J. Adhes. Sci. Technol. 22 (2008) 545–567, https://
doi.org/10.1163/156856108X295509.
[32] C. Salas, T. Nypelö, C. Rodriguez-Abreu, C. Carrillo, O.J. Rojas, Nanocellulose
properties and applications in colloids and interfaces, Curr. Opin. Colloid Interface
Sci. 19 (2014) 383–396, https://doi.org/10.1016/j.cocis.2014.10.003.
[33] Y. Habibi, L.A. Lucia, O.J. Rojas, Cellulose nanocrystals: chemistry, self-assembly,
and applications, Chem. Rev. 110 (2010) 3479–3500, https://doi.org/10.1021/
cr900339w.
[34] M. Smyth, A. García, C. Rader, E.J. Foster, J. Bras, Extraction and process analysis
of high aspect ratio cellulose nanocrystals from corn (Zea mays) agricultural re-
sidue, Ind. Crops Prod. 108 (2017) 257–266, https://doi.org/10.1016/j.indcrop.
2017.06.006.
[35] W.P. Flauzino Neto, M. Mariano, I.S.V. da Silva, H.A. Silvério, J.-L. Putaux,
H. Otaguro, D. Pasquini, A. Dufresne, Mechanical properties of natural rubber
nanocomposites reinforced with high aspect ratio cellulose nanocrystals isolated
from soy hulls, Carbohydr. Polym. 153 (2016) 143–152, https://doi.org/10.1016/
j.carbpol.2016.07.073.
[36] M. Le Normand, R. Moriana, M. Ek, Isolation and characterization of cellulose
nanocrystals from spruce bark in a biorefinery perspective, Carbohydr. Polym. 111
(2014) 979–987, https://doi.org/10.1016/j.carbpol.2014.04.092.
[37] G. Siqueira, H. Abdillahi, J. Bras, A. Dufresne, High reinforcing capability cellulose
nanocrystals extracted from Syngonanthus nitens (Capim Dourado), Cellulose 17
(2010) 289–298, https://doi.org/10.1007/s10570-009-9384-z.
[38] G. Siqueira, J. Bras, N. Follain, S. Belbekhouche, S. Marais, A. Dufresne, Thermal
and mechanical properties of bio-nanocomposites reinforced by Luffa cylindrica
cellulose nanocrystals, Carbohydr. Polym. 91 (2013) 711–717, https://doi.org/10.
1016/j.carbpol.2012.08.057.
[39] F.V. Ferreira, M. Mariano, S.C. Rabelo, R.F. Gouveia, L.M.F. Lona, Isolation and
surface modification of cellulose nanocrystals from sugarcane bagasse waste: from
a micro – to a nano-scale view, Appl. Surf. Sci. 436 (2018) 1113–1122, https://doi.
org/10.1016/j.apsusc.2017.12.137.
[40] C.L. Morelli, J.M. Marconcini, F.V. Pereira, R.E.S. Bretas, M.C. Branciforti,
Extraction and characterization of cellulose nanowhiskers from balsa wood,
Macromol. Symp. 319 (2012) 191–195, https://doi.org/10.1002/masy.
201100158.
[41] A. Junior de Menezes, G. Siqueira, A.A.S. Curvelo, A. Dufresne, Extrusion and
characterization of functionalized cellulose whiskers reinforced polyethylene na-
nocomposites, Polym. (Guildf) 50 (2009) 4552–4563, https://doi.org/10.1016/j.
polymer.2009.07.038.
[42] L. Jasmani, S. Adnan, Preparation and characterization of nanocrystalline cellu-
lose from Acacia mangium and its reinforcement potential, Carbohydr. Polym. 161
(2017) 166–171, https://doi.org/10.1016/j.carbpol.2016.12.061.
[43] E. Espino, M. Cakir, S. Domenek, A.D. Román-Gutiérrez, N. Belgacem, J. Bras,
Isolation and characterization of cellulose nanocrystals from industrial by-pro-
ducts of Agave tequilana and barley, Ind. Crops Prod. 62 (2014) 552–559, https://
doi.org/10.1016/j.indcrop.2014.09.017.
[44] L. Chen, Q. Wang, K. Hirth, C. Baez, U.P. Agarwal, J.Y. Zhu, Tailoring the yield
and characteristics of wood cellulose nanocrystals (CNC) using concentrated acid
hydrolysis, Cellulose 22 (2015) 1753–1762, https://doi.org/10.1007/s10570-015-
0615-1.
[45] X.U.E.M.I.N. Dong, Effect of microcrystallite preparation conditions on the for-
mation of colloid crystals of cellulose, Cellulose 5 (1998) 19–32, https://doi.org/
10.1023/A:1009260511939.
[46] D. García-García, R. Balart, J. Lopez-Martinez, M. Ek, R. Moriana, Optimizing the
yield and physico-chemical properties of pine cone cellulose nanocrystals by dif-
ferent hydrolysis time, Cellulose 25 (2018) 2925–2938, https://doi.org/10.1007/
s10570-018-1760-0.
F.V. Ferreira et al.
[47] C. Liu, B. Li, H. Du, D. Lv, Y. Zhang, G. Yu, X. Mu, H. Peng, Properties of nano-
cellulose isolated from corncob residue using sulfuric acid, formic acid, oxidative
and mechanical methods, Carbohydr. Polym. 151 (2016) 716–724, https://doi.
org/10.1016/j.carbpol.2016.06.025.
[48] J. Araki, M. Wada, S. Kuga, T. Okano, Flow properties of microcrystalline cellulose
suspension prepared by acid treatment of native cellulose, Colloids Surf. A
Physicochem. Eng. Asp. 142 (1998) 75–82, https://doi.org/10.1016/S0927-
7757(98)00404-X.
[49] W. Bai, J. Holbery, K. Li, A technique for production of nanocrystalline cellulose
with a narrow size distribution, Cellulose 16 (2009) 455–465, https://doi.org/10.
1007/s10570-009-9277-1.
[50] M. Jonoobi, R. Oladi, Y. Davoudpour, K. Oksman, A. Dufresne, Y. Hamzeh,
R. Davoodi, Different preparation methods and properties of nanostructured cel-
lulose from various natural resources and residues: a review, Cellulose 22 (2015)
935–969, https://doi.org/10.1007/s10570-015-0551-0.
[51] M.A.S. Azizi Samir, F. Alloin, J.Y. Sanchez, N. El Kissi, A. Dufresne, Preparation of
cellulose whiskers reinforced nanocomposites from an organic medium suspen-
sion, Macromolecules 37 (2004) 1386–1393, https://doi.org/10.1021/
ma030532a.
[52] H.M.C. Azeredo, M.F. Rosa, L.H.C. Mattoso, Nanocellulose in bio-based food
packaging applications, Ind. Crops Prod. 97 (2017) 664–671, https://doi.org/10.
1016/j.indcrop.2016.03.013.
[53] M. Mariano, N. El Kissi, A. Dufresne, Cellulose nanocrystals and related nano-
composites: review of some properties and challenges, J. Polym. Sci. Part B Polym.
Phys. 52 (2014) 791–806, https://doi.org/10.1002/polb.23490.
[54] A. Boujemaoui, C. Cobo Sanchez, J. Engström, C. Bruce, L. Fogelström,
A. Carlmark, E. Malmström, Polycaprolactone nanocomposites reinforced with
cellulose nanocrystals surface-modified via covalent grafting or physisorption – A
comparative study, acsami.7b09009, ACS Appl. Mater. Interfaces (2017), https://
doi.org/10.1021/acsami.7b09009.
[55] F.V. Ferreira, L.D.S. Cividanes, F.S. Brito, B.R.C. de Menezes, W. Franceschi,
E.A.N. Simonetti, G.P. Thim, Functionalization of graphene and applications,
Funct. Graphene Carbon Nanotub. Springer International Publishing, 2016, pp.
1–29, , https://doi.org/10.1007/978-3-319-35110-0_1.
[56] F.V. Ferreira, W. Francisco, B.R.C. De Menezes, L.D.S. Cividanes, A.D.R. Coutinho,
G.P. Thim, Carbon nanotube functionalized with dodecylamine for the effective
dispersion in solvents, Appl. Surf. Sci. 357 (2015), https://doi.org/10.1016/j.
apsusc.2015.09.202.
[57] J. Tang, J. Sisler, N. Grishkewich, K.C. Tam, Functionalization of cellulose nano-
crystals for advanced applications, J. Colloid Interface Sci. 494 (2017) 397–409,
https://doi.org/10.1016/j.jcis.2017.01.077.
[58] E. Espino-Pérez, S. Domenek, N. Belgacem, C. Sillard, J. Bras, Green process for
chemical functionalization of nanocellulose with carboxylic acids,
Biomacromolecules 15 (2014) 4551–4560, https://doi.org/10.1021/bm5013458.
[59] F.V. Ferreira, I.F. Pinheiro, R.F. Gouveia, G.P. Thim, L.M.F. Lona, Functionalized
cellulose nanocrystals as reinforcement in biodegradable polymer nanocompo-
sites, Polym. Compos. 39 (2018) E9–E29, https://doi.org/10.1002/pc.24583.
[60] B.R.C. de Menezes, F.V. Ferreira, B.C. Silva, E.A.N. Simonetti, T.M. Bastos,
L.S. Cividanes, G.P. Thim, Effects of octadecylamine functionalization of carbon
nanotubes on dispersion, polarity, and mechanical properties of CNT/HDPE na-
nocomposites, J. Mater. Sci. 53 (2018) 14311–14327, https://doi.org/10.1007/
s10853-018-2627-3.
[61] F.V. Ferreira, L.D.S. Cividanes, F.S. Brito, B.R.C. de Menezes, W. Franceschi,
E.A.N. Simonetti, G.P. Thim, Functionalization of carbon nanotube and applica-
tions, Funct. Graphene Carbon Nanotub. Springer International Publishing, 2016,
pp. 31–61, , https://doi.org/10.1007/978-3-319-35110-0_2.
[62] D.O. de Castro, J. Bras, A. Gandini, N. Belgacem, Surface grafting of cellulose
nanocrystals with natural antimicrobial rosin mixture using a green process,
Carbohydr. Polym. 137 (2016) 1–8, https://doi.org/10.1016/j.carbpol.2015.09.
101.
[63] I. Capron, O.J. Rojas, R. Bordes, Behavior of nanocelluloses at interfaces, Curr.
Opin. Colloid Interface Sci. 29 (2017) 83–95, https://doi.org/10.1016/j.cocis.
2017.04.001.
[64] S. Eyley, W. Thielemans, Surface modification of cellulose nanocrystals, Nanoscale
6 (2014) 7764–7779, https://doi.org/10.1039/C4NR01756K.
[65] L. Wei, U.P. Agarwal, K.C. Hirth, L.M. Matuana, R.C. Sabo, N.M. Stark, Chemical
modification of nanocellulose with canola oil fatty acid methyl ester, Carbohydr.
Polym. 169 (2017) 108–116, https://doi.org/10.1016/j.carbpol.2017.04.008.
[66] B.L. Tardy, S. Yokota, M. Ago, W. Xiang, T. Kondo, R. Bordes, O.J. Rojas,
Nanocellulose–surfactant interactions, Curr. Opin. Colloid Interface Sci. 29 (2017)
57–67, https://doi.org/10.1016/j.cocis.2017.02.004.
[67] R. Sunasee, U. Hemraz, Synthetic strategies for the fabrication of cationic surface-
modified cellulose nanocrystals, Fibers 6 (2018) 15, https://doi.org/10.3390/
fib6010015.
[68] J.P. da Costa, P.S.M. Santos, A.C. Duarte, T. Rocha-Santos, (Nano)plastics in the
environment – sources, fates and effects, Sci. Total Environ. 566–567 (2016)
15–26, https://doi.org/10.1016/j.scitotenv.2016.05.041.
[69] C. Wilcox, N.J. Mallos, G.H. Leonard, A. Rodriguez, B.D. Hardesty, Using expert
elicitation to estimate the impacts of plastic pollution on marine wildlife, Mar.
Policy 65 (2016) 107–114, https://doi.org/10.1016/j.marpol.2015.10.014.
[70] C.J. Moore, Synthetic polymers in the marine environment: a rapidly increasing,
long-term threat, Environ. Res. 108 (2008) 131–139, https://doi.org/10.1016/j.
envres.2008.07.025.
[71] A. Dufresne, Nanocellulose: a new ageless bionanomaterial, Mater. Today 16
(2013) 220–227, https://doi.org/10.1016/j.mattod.2013.06.004.
[72] M.A. Azizi Samir, F. Alloin, A. Dufresne, Review of recent research into cellulosic
282
European Polymer Journal 108 (2018) 274–285
whisker, their properties and their application in nanocomposites field,
Biomacromolecules 6 (2005) 612–626, https://doi.org/10.1021/bm0493685.
[73] M.N. Ravi Kumar, A review of chitin and chitosan applications, React. Funct.
Polym. 46 (2000) 1–27, https://doi.org/10.1016/S1381-5148(00)00038-9.
[74] R.V. Nonato, P.E. Mantelatto, C.E.V. Rossell, Integrated production of biode-
gradable plastic, sugar and ethanol, Appl. Microbiol. Biotechnol. 57 (2001) 1–5,
https://doi.org/10.1007/s002530100732.
[75] A.K. Mohanty, M. Misra, L.T. Drzal, Sustainable bio-composites from renewable
resources: opportunities and challenges in the green materials world, J. Polym.
Environ. 10 (2002) 19–26, https://doi.org/10.1023/A:1021013921916.
[76] C.H. Goh, P.W.S. Heng, L.W. Chan, Alginates as a useful natural polymer for mi-
croencapsulation and therapeutic applications, Carbohydr. Polym. 88 (2012)
1–12, https://doi.org/10.1016/j.carbpol.2011.11.012.
[77] D. Mondal, B. Bhowmick, M.M.R. Mollick, D. Maity, N. Ranjan Saha,
V. Rangarajan, D. Rana, R. Sen, D. Chattopadhyay, Antimicrobial activity and
biodegradation behavior of poly(butylene adipate-co-terephthalate)/clay nano-
composites, J. Appl. Polym. Sci. 131 (2014) 1–9, https://doi.org/10.1002/app.
40079.
[78] U. Witt, R.J. Muller, W.D. Deckwer, New biodegradable polyester-copolymers
from commodity chemicals with favorable use properties, J. Environ. Polym.
Degrad. 3 (1995) 215–223, https://doi.org/10.1007/BF02068676.
[79] K. Zhu, W.-P. Zhu, Y.-B. Gu, Z.-Q. Shen, W. Chen, G.-X. Zhu, Synthesis and
characterization of poly(butylene adipate-co- terephthalate) catalyzed by rare
earth stearates, Chin. J. Chem. 25 (2007) 1581–1583, https://doi.org/10.1002/
cjoc.200790292.
[80] P. Bordes, E. Pollet, L. Averous, Nano-biocomposites: biodegradable polyester/
nanoclay systems, Prog. Polym. Sci. 34 (2009) 125–155, https://doi.org/10.1016/
j.progpolymsci.2008.10.002.
[81] V. Nagarajan, M. Misra, A.K. Mohanty, New engineered biocomposites from poly
(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV)/poly(butylene adipate-co-ter-
ephthalate) (PBAT) blends and switchgrass: fabrication and performance evalua-
tion, Ind. Crops Prod. 42 (2013) 461–468, https://doi.org/10.1016/j.indcrop.
2012.05.042.
[82] Y. Iwakura, Y. Li, K. Nakayama, H. Shimizu, Strengthening of poly(butylene adi-
pate-co-terephthalate) by melt blending with a liquid crystalline polymer, J. Appl.
Polym. Sci. 109 (2008) 333–339, https://doi.org/10.1002/app.28123.
[83] J.S. Pereira da Silva, J.M. Farias da Silva, B.G. Soares, S. Livi, Fully biodegradable
composites based on poly(butylene adipate- co -terephthalate)/peach palm trees
fiber, Compos. Part B Eng. 129 (2017) 117–123, https://doi.org/10.1016/j.
compositesb.2017.07.088.
[84] K. Fukushima, M.H. Wu, S. Bocchini, A. Rasyida, M.C. Yang, PBAT based nano-
composites for medical and industrial applications, Mater. Sci. Eng. C 32 (2012)
1331–1351, https://doi.org/10.1016/j.msec.2012.04.005.
[85] G.F. Santana-Melo, B.V.M. Rodrigues, E. da Silva, R. Ricci, F.R. Marciano,
T.J. Webster, L.M.R. Vasconcellos, A.O. Lobo, Electrospun ultrathin PBAT/nHAp
fibers influenced the in vitro and in vivo osteogenesis and improved the me-
chanical properties of neoformed bone, Colloids Surf. B Biointerfaces 155 (2017)
544–552, https://doi.org/10.1016/j.colsurfb.2017.04.053.
[86] J.G. de Castro, B.V.M. Rodrigues, R. Ricci, M.M. Costa, A.F.C. Ribeiro,
F.R. Marciano, A.O. Lobo, Designing a novel nanocomposite for bone tissue en-
gineering using electrospun conductive PBAT/polypyrrole as a scaffold to direct
nanohydroxyapatite electrodeposition, RSC Adv. 6 (2016) 32615–32623, https://
doi.org/10.1039/C6RA00889E.
[87] F.V. Ferreira, L.S. Cividanes, R.F. Gouveia, L.M. Lona, An overview on properties
and applications of poly(butylene adipate-co-terephthalate)-PBAT based compo-
sites, Polym. Eng. Sci. (2017), https://doi.org/10.1002/pen.24770.
[88] Computational Studies on the Selective Polymerization of Lactide Catalyzed by
Bifunctional Yttrium NHC Catalyst, Inorganics. 5 (2017) 46. http://doi.org/10.
3390/inorganics5030046.
[89] Y. Yu, G. Storti, M. Morbidelli, Ring-opening polymerization of L, L-lactide: kinetic
and modeling study, Macromolecules 42 (2009) 8187–8197, https://doi.org/10.
1021/ma901359x.
[90] M. Jamshidian, E.A. Tehrany, M. Imran, M. Jacquot, S. Desobry, Poly-lactic acid:
production, applications, nanocomposites, and release studies, Compr. Rev. Food
Sci. Food Saf. 9 (2010) 552–571, https://doi.org/10.1111/j.1541-4337.2010.
00126.x.
[91] S. Inkinen, M. Hakkarainen, A.-C. Albertsson, A. Södergård, From lactic acid to
poly(lactic acid) (PLA): characterization and analysis of PLA and its precursors,
Biomacromolecules 12 (2011) 523–532, https://doi.org/10.1021/bm101302t.
[92] K. Van de Velde, P. Kiekens, Biopolymers: overview of several properties and
consequences on their applications, Polym. Test. 21 (2002) 433–442, https://doi.
org/10.1016/S0142-9418(01)00107-6.
[93] L. Tan, X. Yu, P. Wan, K. Yang, Biodegradable materials for bone repairs: a review,
J. Mater. Sci. Technol. 29 (2013) 503–513, https://doi.org/10.1016/j.jmst.2013.
03.002.
[94] R. Scaffaro, L. Botta, F. Lopresti, A. Maio, F. Sutera, Green nanocomposites-based
on PLA and natural organic fillers, Handb. Compos. from Renew. Mater. John
Wiley & Sons Inc., Hoboken, NJ, USA, 2017, pp. 637–669, , https://doi.org/10.
1002/9781119441632.ch146.
[95] J.-M. Raquez, Y. Habibi, M. Murariu, P. Dubois, Polylactide (PLA)-based nano-
composites, Prog. Polym. Sci. 38 (2013) 1504–1542, https://doi.org/10.1016/j.
progpolymsci.2013.05.014.
[96] R. Scaffaro, L. Botta, F. Lopresti, A. Maio, F. Sutera, Polysaccharide nanocrystals as
fillers for PLA based nanocomposites, Cellulose 24 (2017) 447–478, https://doi.
org/10.1007/s10570-016-1143-3.
[97] L. Bouapao, H. Tsuji, K. Tashiro, J. Zhang, M. Hanesaka, Crystallization, spherulite
F.V. Ferreira et al.
growth, and structure of blends of crystalline and amorphous poly(lactide)s,
Polym. (Guildf) 50 (2009) 4007–4017, https://doi.org/10.1016/j.polymer.2009.
06.040.
[98] R.K. Kulkarni, E.G. Moore, A.F. Hegyeli, F. Leonard, Biodegradable poly(lactic
acid) polymers, J. Biomed. Mater. Res. 5 (1971) 169–181, https://doi.org/10.
1002/jbm.820050305.
[99] R. Auras, B. Harte, S. Selke, An overview of polylactides as packaging materials,
Macromol. Biosci. 4 (2004) 835–864, https://doi.org/10.1002/mabi.200400043.
[100] N. Monmaturapoj, A. Srion, P. Chalermkarnon, S. Buchatip, A. Petchsuk,
W. Noppakunmongkolchai, K. Mai-Ngam, Properties of poly(lactic acid)/hydro-
xyapatite composite through the use of epoxy functional compatibilizers for bio-
medical application, J. Biomater. Appl. 32 (2017) 175–190, https://doi.org/10.
1177/0885328217715783.
[101] L.C. Lins, F. Wianny, S. Livi, I.A. Hidalgo, C. Dehay, J. Duchet-Rumeau, J.-
F. Gérard, Development of bioresorbable hydrophilic-hydrophobic electrospun
scaffolds for neural tissue engineering, Biomacromolecules 17 (2016) 3172–3187,
https://doi.org/10.1021/acs.biomac.6b00820.
[102] R. Scaffaro, L. Botta, A. Maio, G. Gallo, PLA graphene nanoplatelets nano-
composites: physical properties and release kinetics of an antimicrobial agent,
Compos. Part B Eng. 109 (2017) 138–146, https://doi.org/10.1016/j.
compositesb.2016.10.058.
[103] R.A. Gross, B. Kalra, Biodegradable polymers for the environment, Science (80-)
297 (2002) 803–807, https://doi.org/10.1126/science.297.5582.803.
[104] F. Hajiali, S. Tajbakhsh, A. Shojaei, Fabrication and properties of polycaprolactone
composites containing calcium phosphate-based ceramics and bioactive glasses in
bone tissue engineering: a review, Polym. Rev. (2017) 1–44, https://doi.org/10.
1080/15583724.2017.1332640.
[105] G. Pitt, M. Gratzl, G. Kimmel, J. Surles, A. Sohindler, Aliphatic polyesters II. The
degradation of poly (DL-lactide), poly (ε-caprolactone), and their copolymers in
vivo, Biomaterials 2 (1981) 215–220, https://doi.org/10.1016/0142-9612(81)
90060-0.
[106] F. Weng, X. Li, Y. Wang, W.-J. Wang, S.J. Severtson, Kinetics and modeling of ring-
opening copolymerization of L-lactide and ε-caprolactone, Macromol. React. Eng.
9 (2015) 535–544, https://doi.org/10.1002/mren.201500009.
[107] A. Nasajpour, S. Ansari, C. Rinoldi, A.S. Rad, T. Aghaloo, S.R. Shin, Y.K. Mishra,
R. Adelung, W. Swieszkowski, N. Annabi, A. Khademhosseini, A. Moshaverinia,
A. Tamayol, A multifunctional polymeric periodontal membrane with osteogenic
and antibacterial characteristics, Adv. Funct. Mater. 28 (2018) 1703437, https://
doi.org/10.1002/adfm.201703437.
[108] X. Kang, Y. Xie, H.M. Powell, L. James Lee, M.A. Belury, J.J. Lannutti, D.A. Kniss,
Adipogenesis of murine embryonic stem cells in a three-dimensional culture
system using electrospun polymer scaffolds, Biomaterials 28 (2007) 450–458,
https://doi.org/10.1016/j.biomaterials.2006.08.052.
[109] P. Gunatillake, Biodegradable synthetic polymers for tissue engineering, Eur. Cells
Mater. 5 (2003) 1–16, https://doi.org/10.22203/eCM.v005a01.
[110] K. Bahari, H. Mitomo, T. Enjoji, F. Yoshii, K. Makuuchi, Radiation crosslinked poly
(butylene succinate) foam and its biodegradation, Polym. Degrad. Stab. 62 (1998)
551–557, https://doi.org/10.1016/S0141-3910(98)00041-X.
[111] H.S. Cho, H.S. Moon, M. Kim, K. Nam, J.Y. Kim, Biodegradability and biode-
gradation rate of poly(caprolactone)-starch blend and poly(butylene succinate)
biodegradable polymer under aerobic and anaerobic environment, Waste Manage.
31 (2011) 475–480, https://doi.org/10.1016/j.wasman.2010.10.029.
[112] T. Kim, H. Jeon, J. Jegal, J.H. Kim, H. Yang, J. Park, D.X. Oh, S.Y. Hwang, Trans
crystallization behavior and strong reinforcement effect of cellulose nanocrystals
on reinforced poly(butylene succinate) nanocomposites, RSC Adv. 8 (2018)
15389–15398, https://doi.org/10.1039/C8RA01868E.
[113] A. Bhatia, R. Gupta, S. Bhattacharya, H. Choi, Compatibility of biodegradable poly
(lactic acid) (PLA) and poly (butylene succinate) (PBS) blends for packaging ap-
plication, Korea-Australia Rheol. J. 19 (2007) 125–131.
[114] Y. Inoue, N. Yoshie, Structure and physical properties of bacterially synthesized
polyesters, Prog. Polym. Sci. 17 (1992) 571–610, https://doi.org/10.1016/0079-
6700(92)90002-G.
[115] A. Khardenavis, M. Sureshkumar, S. Mudliar, T. Chakrabarti, Biotechnological
conversion of agro-industrial wastewaters into biodegradable plastic, poly β-hy-
droxybutyrate, Bioresour. Technol. 98 (2007) 3579–3584, https://doi.org/10.
1016/j.biortech.2006.11.024.
[116] M. Yokouchi, Y. Chatani, H. Tadokoro, K. Teranishi, H. Tani, Structural studies of
polyesters: 5. Molecular and crystal structures of optically active and racemic poly
(β-hydroxybutyrate), Polym. (Guildf) 14 (1973) 267–272, https://doi.org/10.
1016/0032-3861(73)90087-6.
[117] G.-Q. Chen, Q. Wu, The application of polyhydroxyalkanoates as tissue en-
gineering materials, Biomaterials 26 (2005) 6565–6578, https://doi.org/10.1016/
j.biomaterials.2005.04.036.
[118] L. Savenkova, Z. Gercberga, V. Nikolaeva, A. Dzene, I. Bibers, M. Kalnin,
Mechanical properties and biodegradation characteristics of PHB-based films,
Process Biochem. 35 (2000) 573–579, https://doi.org/10.1016/S0032-9592(99)
00107-7.
[119] Z. Chen, Y. Song, J. Zhang, W. Liu, J. Cui, H. Li, F. Chen, Laminated electrospun
nHA/PHB-composite scaffolds mimicking bone extracellular matrix for bone tissue
engineering, Mater. Sci. Eng. C 72 (2017) 341–351, https://doi.org/10.1016/j.
msec.2016.11.070.
[120] G.-Q. Chen, A microbial polyhydroxyalkanoates (PHA) based bio- and materials
industry, Chem. Soc. Rev. 38 (2009) 2434, https://doi.org/10.1039/b812677c.
[121] T. Ramanathan, A.A. Abdala, S. Stankovich, D.A. Dikin, M. Herrera-Alonso,
R.D. Piner, D.H. Adamson, H.C. Schniepp, X. Chen, R.S. Ruoff, S.T. Nguyen,
I.A. Aksay, R.K. Prud’Homme, L.C. Brinson, Functionalized graphene sheets for
283
European Polymer Journal 108 (2018) 274–285
polymer nanocomposites, Nat. Nanotechnol. 3 (2008) 327–331, https://doi.org/
10.1038/nnano.2008.96.
[122] S. Iijima, T. Ichihashi, Single-shell carbon nanotubes of 1-nm diameter, Nat. Lett.
363 (1993) 603–605.
[123] R. Scaffaro, A. Maio, Enhancing the mechanical performance of polymer based
nanocomposites by plasma-modification of nanoparticles, Polym. Test. 31 (2012)
889–894, https://doi.org/10.1016/j.polymertesting.2012.06.006.
[124] F.V. Ferreira, B.R.C. Menezes, W. Franceschi, E.V. Ferreira, K. Lozano,
L.S. Cividanes, A.R. Coutinho, G.P. Thim, Influence of carbon nanotube con-
centration and sonication temperature on mechanical properties of HDPE/CNT
nanocomposites, Fullerenes Nanotub. Carbon Nanostruct. 25 (2017), https://doi.
org/10.1080/1536383X.2017.1359553.
[125] A.K. Geim, K.S. Novoselov, The rise of graphene, Nat. Mater. 6 (2007) 183–191,
https://doi.org/10.1038/nmat1849.
[126] F.V. Ferreira, F.S. Brito, W. Franceschi, E.A.N. Simonetti, L.S. Cividanes,
M. Chipara, K. Lozano, Functionalized graphene oxide as reinforcement in epoxy
based nanocomposites, Surf. Interfaces 10 (2018), https://doi.org/10.1016/j.
surfin.2017.12.004.
[127] A. Maio, R. Scaffaro, L. Lentini, A. Palumbo Piccionello, I. Pibiri,
Perfluorocarbons–graphene oxide nanoplatforms as biocompatible oxygen re-
servoirs, Chem. Eng. J. 334 (2018) 54–65, https://doi.org/10.1016/j.cej.2017.10.
032.
[128] R. Botan, I.F. Pinheiro, F.V. Ferreira, L.M.F. Lona, Correlation between water
absorption and mechanical properties of polyamide 6 filled with layered double
hydroxides (LDH), Mater. Res. Express. 5 (2018), https://doi.org/10.1088/2053-
1591/aac680.
[129] K. Lozano, E.V. Barrera, Nanofiber-reinforced thermoplastic composites. I.
Thermoanalytical and mechanical analyses, J. Appl. Polym. Sci. 79 (2001)
125–133, https://doi.org/10.1002/1097-4628(20010103)79:1<125:: AID-
APP150>3.0.CO;2-D.
[130] F.A. dos Santos, G.C.V. Iulianelli, M.I.B. Tavares, The use of cellulose nanofillers in
obtaining polymer nanocomposites: properties, processing, and applications,
Mater. Sci. Appl. 7 (2016) 257–294, https://doi.org/10.4236/msa.2016.75026.
[131] G. Siqueira, J. Bras, A. Dufresne, Cellulosic bionanocomposites: a review of pre-
paration, properties and applications, Polymers (Basel). 2 (2010) 728–765,
https://doi.org/10.3390/polym2040728.
[132] H. Kargarzadeh, M. Mariano, D. Gopakumar, I. Ahmad, S. Thomas, A. Dufresne,
J. Huang, N. Lin, Advances in cellulose nanomaterials, Cellulose (2018), https://
doi.org/10.1007/s10570-018-1723-5.
[133] Y.C. Ching, M. Ershad Ali, L.C. Abdullah, K.W. Choo, Y.C. Kuan, S.J. Julaihi,
C.H. Chuah, N.-S. Liou, Rheological properties of cellulose nanocrystal-embedded
polymer composites: a review, Cellulose 23 (2016) 1011–1030, https://doi.org/
10.1007/s10570-016-0868-3.
[134] M.H. Al-Saleh, U. Sundararaj, Review of the mechanical properties of carbon na-
nofiber/polymer composites, Compos. Part A Appl. Sci. Manuf. 42 (2011)
2126–2142, https://doi.org/10.1016/j.compositesa.2011.08.005.
[135] V. Rubentheren, T.A. Ward, C.Y. Chee, P. Nair, Physical and chemical reinforce-
ment of chitosan film using nanocrystalline cellulose and tannic acid, Cellulose 22
(2015) 2529–2541, https://doi.org/10.1007/s10570-015-0650-y.
[136] N. El Miri, K. Abdelouahdi, A. Barakat, M. Zahouily, A. Fihri, A. Solhy, M. El
Achaby, Bio-nanocomposite films reinforced with cellulose nanocrystals: rheology
of film-forming solutions, transparency, water vapor barrier and tensile properties
of films, Carbohydr. Polym. 129 (2015) 156–167, https://doi.org/10.1016/j.
carbpol.2015.04.051.
[137] A.H. Clark, S.B. Ross-Murphy, Structural and mechanical properties of biopolymer
gels, Biopolymers, Springer-Verlag, Berlin/Heidelberg, 1987, pp. 57–192, ,
https://doi.org/10.1007/BFb0023332.
[138] X. Xu, W. Liu, L. Zhang, Rheological behavior of Aeromonas gum in aqueous so-
lutions, Food Hydrocoll. 20 (2006) 723–729, https://doi.org/10.1016/j.foodhyd.
2005.06.012.
[139] A. Silva-Weiss, V. Bifani, M. Ihl, P.J.A. Sobral, M.C. Gómez-Guillén, Polyphenol-
rich extract from murta leaves on rheological properties of film-forming solutions
based on different hydrocolloid blends, J. Food Eng. 140 (2014) 28–38, https://
doi.org/10.1016/j.jfoodeng.2014.04.010.
[140] M. Mariano, N. El Kissi, A. Dufresne, Structural reorganization of CNC in injection-
molded CNC/PBAT materials under thermal annealing, Langmuir 32 (2016)
10093–10103, https://doi.org/10.1021/acs.langmuir.6b03220.
[141] X. Zhang, P. Ma, Y. Zhang, Structure and properties of surface-acetylated cellulose
nanocrystal/poly(butylene adipate-co-terephthalate) composites, Polym. Bull. 73
(2016) 2073–2085, https://doi.org/10.1007/s00289-015-1594-y.
[142] M. Mariano, C. Chirat, N. El Kissi, A. Dufresne, Impact of cellulose nanocrystal
aspect ratio on crystallization and reinforcement of poly(butylene adipate- co
-terephthalate), J. Polym. Sci. Part B Polym. Phys. 54 (2016) 2284–2297, https://
doi.org/10.1002/polb.24139.
[143] A. Durmus, A. Kasgoz, C.W. Macosko, Linear low density polyethylene (LLDPE)/
clay nanocomposites. Part I: structural characterization and quantifying clay dis-
persion by melt rheology, Polym. (Guildf) 48 (2007) 4492–4502, https://doi.org/
10.1016/j.polymer.2007.05.074.
[144] M. Mariano, N. El Kissi, A. Dufresne, Cellulose nanomaterials: size and surface
influence on the thermal and rheological behavior, Polímeros (2018), https://doi.
org/10.1590/0104-1428.2413.
[145] A. Einstein, On the theory of Brownian movement, Ann. Phys. 19 (1906) 371–381.
[146] G.K. Batchelor, The effect of Brownian motion on the bulk stress in a suspension of
spherical particles, J. Fluid Mech. 83 (1977) 97, https://doi.org/10.1017/
S0022112077001062.
[147] M. Mariano, F. Pilate, F.B. de Oliveira, F. Khelifa, P. Dubois, J.-M. Raquez,
F.V. Ferreira et al.
A. Dufresne, Preparation of cellulose nanocrystal-reinforced poly(lactic acid) na-
nocomposites through noncovalent modification with PLLA-based surfactants,
ACS Omega 2 (2017) 2678–2688, https://doi.org/10.1021/acsomega.7b00387.
[148] N.E. Marcovich, M.L. Auad, N.E. Bellesi, S.R. Nutt, M.I. Aranguren, Cellulose
micro/nanocrystals reinforced polyurethane, J. Mater. Res. 21 (2006) 870–881,
https://doi.org/10.1557/jmr.2006.0105.
[149] D. Liu, X. Chen, Y. Yue, M. Chen, Q. Wu, Structure and rheology of nanocrystalline
cellulose, Carbohydr. Polym. 84 (2011) 316–322, https://doi.org/10.1016/j.
carbpol.2010.11.039.
[150] I.F. Pinheiro, F.V. Ferreira, D.H.S. Souza, R.F. Gouveia, L.M.F. Lona, A.R. Morales,
L.H.I. Mei, Mechanical, rheological and degradation properties of PBAT nano-
composites reinforced by functionalized cellulose nanocrystals, Eur. Polym. J. 97
(2017), https://doi.org/10.1016/j.eurpolymj.2017.10.026.
[151] K. Ben Azouz, E.C. Ramires, W. Van den Fonteyne, N. El Kissi, A. Dufresne, Simple
method for the melt extrusion of a cellulose nanocrystal reinforced hydrophobic
polymer, ACS Macro Lett. 1 (2012) 236–240, https://doi.org/10.1021/
mz2001737.
[152] M.A.S. Azizi Samir, F. Alloin, J.-Y. Sanchez, A. Dufresne, Cellulose nanocrystals
reinforced poly(oxyethylene), Polym. (Guildf) 45 (2004) 4149–4157, https://doi.
org/10.1016/j.polymer.2004.03.094.
[153] H.M. Hassanabadi, D. Rodrigue, Effect of particle size and shape on the reinforcing
efficiency of nanoparticles in polymer nanocomposites, Macromol. Mater. Eng.
299 (2014) 1220–1231, https://doi.org/10.1002/mame.201300442.
[154] H. Hassanabadi, D. Rodrigue, Effect of nano-particles on flow and recovery of
polymer nano-composites in the melt state, Int. Polym. Process. 28 (2013)
151–158, https://doi.org/10.3139/217.2631.
[155] M.E. Mackay, T.T. Dao, A. Tuteja, D.L. Ho, B. Van Horn, H.-C. Kim, C.J. Hawker,
Nanoscale effects leading to non-Einstein-like decrease in viscosity, Nat. Mater. 2
(2003) 762–766, https://doi.org/10.1038/nmat999.
[156] K. Nusser, G.J. Schneider, W. Pyckhout-Hintzen, D. Richter, Viscosity decrease and
reinforcement in polymer-silsesquioxane composites, Macromolecules 44 (2011)
7820–7830, https://doi.org/10.1021/ma201585v.
[157] H.M. Hassanabadi, M. Wilhelm, D. Rodrigue, A rheological criterion to determine
the percolation threshold in polymer nano-composites, Rheol. Acta 53 (2014)
869–882, https://doi.org/10.1007/s00397-014-0804-0.
[158] S. Cheng, S.-J. Xie, J.-M.Y. Carrillo, B. Carroll, H. Martin, P.-F. Cao, M.D. Dadmun,
B.G. Sumpter, V.N. Novikov, K.S. Schweizer, A.P. Sokolov, Big effect of small
nanoparticles: a shift in paradigm for polymer nanocomposites, ACS Nano 11
(2017) 752–759, https://doi.org/10.1021/acsnano.6b07172.
[159] A. Tuteja, M.E. Mackay, S. Narayanan, S. Asokan, M.S. Wong, Breakdown of the
continuum Stokes−Einstein relation for nanoparticle diffusion, Nano Lett. 7
(2007) 1276–1281, https://doi.org/10.1021/nl070192x.
[160] L.-H. Cai, S. Panyukov, M. Rubinstein, Mobility of nonsticky nanoparticles in
polymer liquids, Macromolecules 44 (2011) 7853–7863, https://doi.org/10.1021/
ma201583q.
[161] U. Yamamoto, K.S. Schweizer, Microscopic theory of the long-time diffusivity and
intermediate-time anomalous transport of a nanoparticle in polymer melts,
Macromolecules 48 (2015) 152–163, https://doi.org/10.1021/ma501150q.
[162] V. Ganesan, V. Pryamitsyn, M. Surve, B. Narayanan, Noncontinuum effects in
nanoparticle dynamics in polymers, J. Chem. Phys. 124 (2006) 221102, https://
doi.org/10.1063/1.2209241.
[163] J.T. Kalathi, G.S. Grest, S.K. Kumar, Universal viscosity behavior of polymer na-
nocomposites, Phys. Rev. Lett. 109 (2012) 198301, https://doi.org/10.1103/
PhysRevLett. 109.198301.
[164] M. Wang, R.J. Hill, Anomalous bulk viscosity of polymer-nanocomposite melts,
Soft Matter. 5 (2009) 3940, https://doi.org/10.1039/b905686f.
[165] A. Dufresne, Nanocellulose: From Nature to High Performance Tailored Materials,
Walter de Gruyter, 2013.
[166] V. Khoshkava, M.R. Kamal, Effect of cellulose nanocrystals (CNC) particle mor-
phology on dispersion and rheological and mechanical properties of poly-
propylene/CNC nanocomposites, ACS Appl. Mater. Interfaces 6 (2014)
8146–8157, https://doi.org/10.1021/am500577e.
[167] F. Alloin, A. D’Aprea, A. Dufresne, N. El Kissi, F. Bossard, Poly(oxyethylene) and
ramie whiskers based nanocomposites: influence of processing: extrusion and
casting/evaporation, Cellulose 18 (2011) 957–973, https://doi.org/10.1007/
s10570-011-9543-x.
[168] C.L. Morelli, M.N. Belgacem, M.C. Branciforti, R.E.S. Bretas, A. Crisci, J. Bras,
Supramolecular aromatic interactions to enhance biodegradable film properties
through incorporation of functionalized cellulose nanocrystals, Compos. Part A
Appl. Sci. Manuf. 83 (2016) 80–88, https://doi.org/10.1016/j.compositesa.2015.
10.038.
[169] C.L. Morelli, N. Belgacem, R.E.S. Bretas, J. Bras, Melt extruded nanocomposites of
polybutylene adipate-co-terephthalate (PBAT) with phenylbutyl isocyanate mod-
ified cellulose nanocrystals, J. Appl. Polym. Sci. 133 (2016) 1–9, https://doi.org/
10.1002/app.43678.
[170] F.V. Ferreira, W. Franceschi, B.R.C. Menezes, F.S. Brito, K. Lozano, A.R. Coutinho,
L.S. Cividanes, G.P. Thim, Dodecylamine functionalization of carbon nanotubes to
improve dispersion, thermal and mechanical properties of polyethylene based
nanocomposites, Appl. Surf. Sci. 410 (2017), https://doi.org/10.1016/j.apsusc.
2017.03.098.
[171] J. Chen, D. Wu, K.C. Tam, K. Pan, Z. Zheng, Effect of surface modification of
cellulose nanocrystal on nonisothermal crystallization of poly(β-hydroxybutyrate)
composites, Carbohydr. Polym. 157 (2017) 1821–1829, https://doi.org/10.1016/
j.carbpol.2016.11.071.
[172] Q. Lv, C. Xu, D. Wu, Z. Wang, R. Lan, L. Wu, The role of nanocrystalline cellulose
during crystallization of poly(ε-caprolactone) composites: nucleation agent or not?
284
European Polymer Journal 108 (2018) 274–285
Compos. Part A Appl. Sci. Manuf. 92 (2017) 17–26, https://doi.org/10.1016/j.
compositesa.2016.10.035.
[173] J. Chen, C. Xu, D. Wu, K. Pan, A. Qian, Y. Sha, L. Wang, W. Tong, Insights into the
nucleation role of cellulose crystals during crystallization of poly(β -hydro-
xybutyrate), Carbohydr. Polym. 134 (2015) 508–515, https://doi.org/10.1016/j.
carbpol.2015.08.023.
[174] D. Wu, T. Yang, Y. Sun, T. Shi, W. Zhou, M. Zhang, Banded spherulites of elec-
trospun poly(trimethylene terephthalate)/carbon nanotube composite mats,
Polym. Int. 60 (2011) 1497–1503, https://doi.org/10.1002/pi.3108.
[175] D. Patel, D.C. Bassett, On the formation of S-profiled lamellae in polyethylene and
the genesis of banded spherulites, Polym. (Guildf) 43 (2002) 3795–3802, https://
doi.org/10.1016/S0032-3861(02)00178-7.
[176] Y. Zhang, H. Fang, Z. Wang, M. Tang, Z. Wang, Disclosing the formation of ring-
banded spherulites for semicrystalline polymers through the double-layer film
method, CrystEngComm 16 (2014) 1026–1037, https://doi.org/10.1039/
C3CE42083C.
[177] A. Pei, Q. Zhou, L.A. Berglund, Functionalized cellulose nanocrystals as biobased
nucleation agents in poly(l-lactide) (PLLA) – crystallization and mechanical
property effects, Compos. Sci. Technol. 70 (2010) 815–821, https://doi.org/10.
1016/j.compscitech.2010.01.018.
[178] E. Fortunati, I. Armentano, Q. Zhou, A. Iannoni, E. Saino, L. Visai, L.A. Berglund,
J.M. Kenny, Multifunctional bionanocomposite films of poly(lactic acid), cellulose
nanocrystals and silver nanoparticles, Carbohydr. Polym. 87 (2012) 1596–1605,
https://doi.org/10.1016/j.carbpol.2011.09.066.
[179] S. Gårdebjer, A. Bergstrand, A. Idström, C. Börstell, S. Naana, L. Nordstierna,
A. Larsson, Solid-state NMR to quantify surface coverage and chain length of lactic
acid modified cellulose nanocrystals, used as fillers in biodegradable composites,
Compos. Sci. Technol. 107 (2015) 1–9, https://doi.org/10.1016/j.compscitech.
2014.11.014.
[180] H. Yu, Z. Qin, Z. Zhou, Cellulose nanocrystals as green fillers to improve crystal-
lization and hydrophilic property of poly(3-hydroxybutyrate-co-3-hydro-
xyvalerate), Prog. Nat. Sci. Mater. Int. 21 (2011) 478–484, https://doi.org/10.
1016/S1002-0071(12)60086-0.
[181] N. Hameed, Q. Guo, F.H. Tay, S.G. Kazarian, Blends of cellulose and poly(3-hy-
droxybutyrate-co-3-hydroxyvalerate) prepared from the ionic liquid 1-butyl-3-
methylimidazolium chloride, Carbohydr. Polym. 86 (2011) 94–104, https://doi.
org/10.1016/j.carbpol.2011.04.016.
[182] C.L. Morelli, M.N. Belgacem, M.C. Branciforti, M.C.B. Salon, J. Bras, R.E.S. Bretas,
Nanocomposites of PBAT and cellulose nanocrystals modified by in situ poly-
merization and melt extrusion, Polym. Eng. Sci. 56 (2016) 1339–1348, https://
doi.org/10.1002/pen.24367.
[183] M. Šupová, G.S. Martynková, K. Barabaszová, Effect of nanofillers dispersion in
polymer matrices: a review, Sci. Adv. Mater. 3 (2011) 1–25, https://doi.org/10.
1166/sam.2011.1136.
[184] J. Lunt, Large-scale production, properties and commercial applications of poly-
lactic acid polymers, Polym. Degrad. Stab. 59 (1998) 145–152, https://doi.org/10.
1016/S0141-3910(97)00148-1.
[185] V.P. Martino, R.A. Ruseckaite, A. Jiménez, Thermal and mechanical character-
ization of plasticized poly (L-lactide-co-D, L-lactide) films for food packaging, J.
Therm. Anal. Calorim. 86 (2006) 707–712, https://doi.org/10.1007/s10973-006-
7897-3.
[186] W.A. Ribeiro Neto, A.C.C. de Paula, T.M.M. Martins, A.M. Goes, L. Averous,
G. Schlatter, R.E. Suman Bretas, Poly (butylene adipate-co-terephthalate)/hydro-
xyapatite composite structures for bone tissue recovery, Polym. Degrad. Stab. 120
(2015) 61–69, https://doi.org/10.1016/j.polymdegradstab.2015.06.009.
[187] Y. Aitomäki, K. Oksman, Reinforcing efficiency of nanocellulose in polymers,
React. Funct. Polym. 85 (2014) 151–156, https://doi.org/10.1016/j.
reactfunctpolym.2014.08.010.
[188] J.C.H. Affdl, J.L. Kardos, The Halpin-Tsai equations: a review, Polym. Eng. Sci. 16
(1976) 344–352, https://doi.org/10.1002/pen.760160512.
[189] J. Andersons, E. Spārniņš, R. Joffe, Stiffness and strength of flax fiber/polymer
matrix composites, Polym. Compos. 27 (2006) 221–229, https://doi.org/10.1002/
pc.20184.
[190] N. Ouali, J. Cavaille, J. Perez, Elastic, viscoelastic and plastic behavior of multi-
phase polymer blends, Plast. Rubber Compos. 16 (1991) 55.
[191] T. Schilling, M.A. Miller, P. van der Schoot, Percolation in suspensions of hard
nanoparticles: from spheres to needles, EPL (Europhysics Lett. 111 (2015) 56004,
https://doi.org/10.1209/0295-5075/111/56004.
[192] E. Espino-Pérez, J. Bras, V. Ducruet, A. Guinault, A. Dufresne, S. Domenek,
Influence of chemical surface modification of cellulose nanowhiskers on thermal,
mechanical, and barrier properties of poly(lactide) based bionanocomposites, Eur.
Polym. J. 49 (2013) 3144–3154, https://doi.org/10.1016/j.eurpolymj.2013.07.
017.
[193] F.V. Ferreira, W. Francisco, B.R.C. Menezes, F.S. Brito, A.S. Coutinho,
L.S. Cividanes, A.R. Coutinho, G.P. Thim, Correlation of surface treatment, dis-
persion and mechanical properties of HDPE/CNT nanocomposites, Appl. Surf. Sci.
389 (2016) 921–929, https://doi.org/10.1016/j.apsusc.2016.07.164.
[194] Long Jiang, E. Morelius, Jinwen Zhang, M. Wolcott, J. Holbery, Study of the poly
(3-hydroxybutyrate-co-3-hydroxyvalerate)/cellulose nanowhisker composites
prepared by solution casting and melt processing, J. Compos. Mater. 42 (2008)
2629–2645, https://doi.org/10.1177/0021998308096327.
[195] X. Colom, F. Carrasco, P. Pagès, J. Cañavate, Effects of different treatments on the
interface of HDPE/lignocellulosic fiber composites, Compos. Sci. Technol. 63
(2003) 161–169, https://doi.org/10.1016/S0266-3538(02)00248-8.
[196] S. Chatterjee, F. Nafezarefi, N.H. Tai, L. Schlagenhauf, F.A. Nüesch, B.T.T. Chu,
Size and synergy effects of nanofiller hybrids including graphene nanoplatelets
F.V. Ferreira et al.
and carbon nanotubes in mechanical properties of epoxy composites, Carbon NY
50 (2012) 5380–5386, https://doi.org/10.1016/j.carbon.2012.07.021.
[197] A.J. Crosby, J. Lee, Polymer nanocomposites: the “Nano” effect on mechanical
properties, Polym. Rev. 47 (2007) 217–229, https://doi.org/10.1080/
15583720701271278.
[198] H.-Y. Yu, Z.-Y. Qin, L. Liu, X.-G. Yang, Y. Zhou, J.-M. Yao, Comparison of the
reinforcing effects for cellulose nanocrystals obtained by sulfuric and hydrochloric
acid hydrolysis on the mechanical and thermal properties of bacterial polyester,
Compos. Sci. Technol. 87 (2013) 22–28, https://doi.org/10.1016/j.compscitech.
2013.07.024.
[199] S. Geng, J. Wei, Y. Aitomäki, M. Noël, K. Oksman, Well-dispersed cellulose na-
nocrystals in hydrophobic polymers by in situ polymerization for synthesizing
highly reinforced bio-nanocomposites, Nanoscale (2018), https://doi.org/10.
1039/C7NR09080C.
[200] D. LeCorre, A. Dufresne, M. Rueff, B. Khelifi, J. Bras, All starch nanocomposite
coating for barrier material, J. Appl. Polym. Sci. (131 2014), https://doi.org/10.
1002/app.39826.
[201] A. Ferrer, L. Pal, M. Hubbe, Nanocellulose in packaging: advances in barrier layer
technologies, Ind. Crops Prod. 95 (2017) 574–582, https://doi.org/10.1016/j.
indcrop.2016.11.012.
[202] S.S. Nair, J. Zhu, Y. Deng, A.J. Ragauskas, High performance green barriers based
on nanocellulose, Sustain. Chem. Process. 2 (2014) 23, https://doi.org/10.1186/
s40508-014-0023-0.
[203] J. Ambrosio-Martín, M.J. Fabra, A. Lopez-Rubio, J.M. Lagaron, Melt poly-
condensation to improve the dispersion of bacterial cellulose into polylactide via
melt compounding: enhanced barrier and mechanical properties, Cellulose 22
(2015) 1201–1226, https://doi.org/10.1007/s10570-014-0523-9.
[204] E. Espino-Pérez, J. Bras, G. Almeida, P. Relkin, N. Belgacem, C. Plessis,
S. Domenek, Cellulose nanocrystal surface functionalization for the controlled
sorption of water and organic vapours, Cellulose 23 (2016) 2955–2970, https://
doi.org/10.1007/s10570-016-0994-y.
[205] N. Follain, S. Belbekhouche, J. Bras, G. Siqueira, S. Marais, A. Dufresne, Water
transport properties of bio-nanocomposites reinforced by Luffa cylindrica cellulose
nanocrystals, J. Membr. Sci. 427 (2013) 218–229, https://doi.org/10.1016/j.
memsci.2012.09.048.
[206] M.D. Sanchez-Garcia, J.M. Lagaron, On the use of plant cellulose nanowhiskers to
enhance the barrier properties of polylactic acid, Cellulose 17 (2010) 987–1004,
https://doi.org/10.1007/s10570-010-9430-x.
[207] S. Charlon, N. Follain, C. Chappey, E. Dargent, J. Soulestin, M. Sclavons, S. Marais,
Improvement of barrier properties of bio-based polyester nanocomposite mem-
branes by water-assisted extrusion, J. Membr. Sci. 496 (2015) 185–198, https://
doi.org/10.1016/j.memsci.2015.08.043.
[208] E. Fortunati, M. Peltzer, I. Armentano, A. Jiménez, J.M. Kenny, Combined effects
of cellulose nanocrystals and silver nanoparticles on the barrier and migration
properties of PLA nano-biocomposites, J. Food Eng. 118 (2013) 117–124, https://
doi.org/10.1016/j.jfoodeng.2013.03.025.
[209] E. Espino-Pérez, J. Bras, G. Almeida, C. Plessis, N. Belgacem, P. Perré, S. Domenek,
Designed cellulose nanocrystal surface properties for improving barrier properties
in polylactide nanocomposites, Carbohydr. Polym. 183 (2018) 267–277, https://
doi.org/10.1016/j.carbpol.2017.12.005.
[210] N. Follain, S. Belbekhouche, J. Bras, G. Siqueira, C. Chappey, S. Marais,
A. Dufresne, Tunable gas barrier properties of filled-PCL film by forming perco-
lating cellulose network, Colloids Surf. A Physicochem. Eng. Asp. 545 (2018)
26–30, https://doi.org/10.1016/j.colsurfa.2018.02.040.
[211] D. Garcia-Garcia, J. Lopez-Martinez, R. Balart, E. Strömberg, R. Moriana,
Reinforcing capability of cellulose nanocrystals obtained from pine cones in a
biodegradable poly(3-hydroxybutyrate)/poly(ε-caprolactone) (PHB/PCL) ther-
moplastic blend, Eur. Polym. J. 104 (2018) 10–18, https://doi.org/10.1016/j.
eurpolymj.2018.04.036.
[212] S. Mohanty, S.K. Nayak, Biodegradable nanocomposites of poly(butylene adipate-
co-terephthalate) (PBAT) and organically modified layered silicates, J. Polym.
Environ. 20 (2012) 195–207, https://doi.org/10.1007/s10924-011-0408-z.
285
European Polymer Journal 108 (2018) 274–285
[213] A.A. Shah, F. Hasan, A. Hameed, S. Ahmed, Biological degradation of plastics: a
comprehensive review, Biotechnol. Adv. 26 (2008) 246–265, https://doi.org/10.
1016/j.biotechadv.2007.12.005.
[214] U. Witt, T. Einig, M. Yamamoto, I. Kleeberg, W.D. Deckwer, R.J. Müller,
Biodegradation of aliphatic-aromatic copolyesters: evaluation of the final biode-
gradability and ecotoxicological impact of degradation intermediates,
Chemosphere 44 (2001) 289–299, https://doi.org/10.1016/S0045-6535(00)
00162-4.
[215] C. Campbell, Soil microbiology, ecology, and biochemistry – edited by E.A. Paul,
Eur. J. Soil Sci. 59 (2008) 1008–1009, https://doi.org/10.1111/j.1365-2389.
2008.01052_2.x.
[216] J. Brand, G. Pecastaings, G. Sèbe, A versatile method for the surface tailoring of
cellulose nanocrystal building blocks by acylation with functional vinyl esters,
Carbohydr. Polym. 169 (2017) 189–197, https://doi.org/10.1016/j.carbpol.2017.
03.077.
[217] Y. Kanesawa, N. Tanahashi, Y. Doi, T. Saito, Enzymatic degradation of microbial
poly(3-hydroxyalkanoates), Polym. Degrad. Stab. 45 (1994) 179–185, https://doi.
org/10.1016/0141-3910(94)90135-X.
[218] K. Bahari, H. Mitomo, T. Enjoji, F. Yoshii, K. Makuuchi, Degradability of poly(3-
hydroxybutyrate) and its copolymer grafted with styrene by radiation, Polym.
Degrad. Stab. 61 (1998) 245–252, https://doi.org/10.1016/S0141-3910(97)
00147-X.
[219] G. Tomasi, M. Scandola, B.H. Briese, D. Jendrossek, Enzymatic Degradation of
Bacterial Poly(3-hydroxybutyrate) by a Depolymerase from Pseudomonas le-
moignei, Macromolecules 29 (1996) 507–513, https://doi.org/10.1021/
ma951067n.
[220] A. El-Hadi, R. Schnabel, E. Straube, G. Müller, S. Henning, Correlation between
degree of crystallinity, morphology, glass temperature, mechanical properties and
biodegradation of poly (3-hydroxyalkanoate) PHAs and their blends, Polym. Test.
21 (2002) 665–674, https://doi.org/10.1016/S0142-9418(01)00142-8.
[221] M.P. Arrieta, E. Fortunati, F. Dominici, J. López, J.M. Kenny, Bionanocomposite
films based on plasticized PLA–PHB/cellulose nanocrystal blends, Carbohydr.
Polym. 121 (2015) 265–275, https://doi.org/10.1016/j.carbpol.2014.12.056.
[222] P.A. Palsikowski, M.M. Roberto, L.R.D. Sommaggio, P.M.S. Souza, A.R. Morales,
M.A. Marin-Morales, Ecotoxicity evaluation of the biodegradable polymers PLA,
PBAT and its blends using allium cepa as test organism, J. Polym. Environ. 26
(2018) 938–945, https://doi.org/10.1007/s10924-017-0990-9.
[223] J.E. Mark, Physical Properties of Polymers Handbook, Springer, New York, New
York NY, 2007http://doi.org/10.1007/978-0-387-69002-5.
[224] J. Rydz, W. Sikorska, M. Kyulavska, D. Christova, Polyester-based (bio)degradable
polymers as environmentally friendly materials for sustainable development, Int.
J. Mol. Sci. 16 (2014) 564–596, https://doi.org/10.3390/ijms16010564.
[225] H. Kargarzadeh, J. Huang, N. Lin, I. Ahmad, M. Mariano, A. Dufresne, S. Thomas,
A. Gałęski, Recent developments in nanocellulose-based biodegradable polymers,
thermoplastic polymers, and porous nanocomposites, Prog. Polym. Sci. (2018),
https://doi.org/10.1016/j.progpolymsci.2018.07.008.
[226] F. Hoeng, A. Denneulin, J. Bras, Use of nanocellulose in printed electronics: a
review, Nanoscale 8 (2016) 13131–13154, https://doi.org/10.1039/
C6NR03054H.
[227] D.O. Castro, Z. Karim, L. Medina, J.-O. Häggström, F. Carosio, A. Svedberg,
L. Wågberg, D. Söderberg, L.A. Berglund, The use of a pilot-scale continuous paper
process for fire retardant cellulose-kaolinite nanocomposites, Compos. Sci.
Technol. 162 (2018) 215–224, https://doi.org/10.1016/j.compscitech.2018.04.
032.
[228] E. Fortunati, F. Luzi, W. Yang, J.M. Kenny, L. Torre, D. Puglia, Bio-based nano-
composites in food packaging, Nanomater. Food Packag. Elsevier, 2018, pp.
71–110, , https://doi.org/10.1016/B978-0-323-51271-8.00004-8.
[229] C.G. Otoni, B.D. Lodi, M.V. Lorevice, R.C. Leitão, M.D. Ferreira, M.R. de Moura,
L.H.C. Mattoso, Optimized and scaled-up production of cellulose-reinforced bio-
degradable composite films made up of carrot processing waste, Ind. Crops Prod.
121 (2018) 66–72, https://doi.org/10.1016/j.indcrop.2018.05.003.