Food Packaging and Shelf Life 31 (2022) 100807

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Food Packaging and Shelf Life

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

Development of sustainable food packaging material based on

biodegradable polymer reinforced with cellulose nanocrystals
Marcio S. Andrade a, Otávio H. Ishikawa a, Robson S. Costa a, Marcus V.S. Seixas a, Rita C.L.
B. Rodrigues b, Esperidiana A.B. Moura a, *
a
Instituto de Pesquisas Energéticas e Nucleares, Centro de Química e Meio Ambiente, 2242 Prof. L. Prestes Av., 05508-000 São Paulo, SP, Brazil
b
Universidade de São Paulo, Escola de Engenharia de Lorena, 12602-810 Lorena, SP, Brazil

A R T I C L E I N F O A B S T R A C T

Keywords: The increased environmental impact and sustainability issues related to conventional food packaging have
Cellulose nanocrystals gained attention and led to a global concern. The massive consumption of conventional food packaging has
Sustainable packaging increased disposal of non-eco-friendly packaging waste, severely damaging the environment. The replacement by
Bionanocomposite film
sustainable packaging is an important alternative to reduce the enormous volume of plastic waste. In this work,
Agro-waste
bionanocomposite films composed of PBAT/PLA blend and cellulose nanocrystals (CNCs) extracted from agro-
Sugarcane bagasse
Biomass pretreatment waste were investigated. Characterization of CNCs confirmed that nanocrystals were obtained. Bio­
nanocomposite films presented better hydrophobic character and thermal stability than the blend film. In
addition, the tensile strength, elongation at break, and Young’s modulus was around 52%, 29%, and 118%,
respectively, higher than blend films. These mechanical values were comparable to values of commercial plastic
materials that are extensively used in food packaging. Thus, the prepared bionanocomposite films might be an
interesting alternative to produce sustainable food packaging materials.

1. Introduction packaging have increased non-eco-friendly packaging waste disposal,

severely damaging the eco and aqua systems and, consequently, human
Packaging materials based on conventional plastic petroleum- and animal health. Thus, the replacement of conventional packaging for
derived polymers are traditionally used in the food packaging in­ sustainable alternatives that easily and safely degrade is a vital alter­
dustry. A variety of practically non-degradable and not recyclable native to decrease disposal of plastic wastes in landfills, rivers, and
petroleum-derived plastic, metal, glass, paper, and board, in various marine environments (Gan & Chow, 2018; Raheem, 2013; Zhong,
combinations, are also employed to achieve the properties for essential Godwin, Jin, & Xiao, 2020).
functions of food packaging that maintain the quality and safety of food Some commercially available biopolymers are attractive alternatives
(Coles & Kirwan, 2003; Marsh & Bugusu, 2007). Although their excep­ to prepare sustainable food packaging materials. Among the commercial
tional properties, such as lightweight, water resistance, barrier against biopolymers, poly(lactic acid) (PLA) is a polyester polymer with high
the transfer of liquids and gases, good mechanical behavior, and heat modulus and strength comparable to that of petroleum-derived plastics,
sealability maintain the safety and quality of food products from pro­ and poly(butylene adipate-co-terephthalate) (PBAT), an aliphatic-
cessing and manufacturing to consumer use, the practically aromatic copolyester, is a highly flexible biopolymer whose properties
non-degradability, not recyclability, and other negative impacts at the are comparable to those of low-density PE (LDPE).
end of their short shelf life have increased the global environmental The blend of PLA and PBAT has drawn much attention as a promising
awareness and driven attention to developing alternative raw materials material for sustainable food packaging (Gan & Chow, 2018; Moustafa,
from renewable resources (Coles & Kirwan, 2003; Marsh & Bugusu, Youssef, Darwish, & Abou-Kandil, 2019; Vasile, 2018; Zhong et al.,
2007; Raheem, 2013). Although the packaging is indispensable for 2020). The high toughness of PBAT makes it the right candidate, and it is
maintaining the quality and freshness of food and extending its lifetime, industrially viable for blending with PLA to develop a more appropriate
the increased production and consumption of conventional food bionanocomposite for the sustainable packaging field. The high

* Corresponding author.
E-mail address: [email protected] (E.A.B. Moura).

https://doi.org/10.1016/j.fpsl.2021.100807
Received 13 April 2021; Received in revised form 27 November 2021; Accepted 30 December 2021
2214-2894/© 2022 Elsevier Ltd. All rights reserved.
M.S. Andrade et al. Food Packaging and Shelf Life 31 (2022) 100807

Fig. 1. Schematic representation for synthesis of CNCs.

toughness of PBAT makes it the right candidate, and it is industrially alternating amorphous and crystalline domains (Dufresne, 2018; El
viable for blending with PLA to develop a more appropriate bio­ Fawal et al., 2020; Gan, Sam, Abdullah, & bin, Omar, 2020; Jamróz,
nanocomposite for the sustainable packaging field. Blends of PLA and Kulawik, & Kopel, 2019; Moustafa et al., 2019; Risyon et al., 2020;
PBAT are an excellent alternative to combine properties of both poly­ Yadav & Chiu, 2019; Zhong et al., 2020).
mers; however, they tend to result in immiscible blends, as their physical Thus, PBAT/`PLA/CNCs films have great potential in the food
properties are highly dependent on their morphological characteristics. packaging industry, requiring further studies in the literature. This work
However, miscible or compatible systems are commonly observed in aims to prepare sustainable bionanocomposite films composed of a
copolymer-homopolymer mixtures, even in the absence of specific in­ biodegradable poly(lactic acid)/poly(butylene adipate-co-
teractions (Rana, Mandal, & Bhattacharyya, 1993; Rana, Mandal, & terephthalate) blend containing different amounts of cellulose nano­
Bhattacharyya, 1996; Rana, Bag, Bhattacharyya, & Mandal, 2000). The crystals (CNCs, 0–2 wt.%), extracted from agro-waste using a twin-screw
compatibility between the PLA and PBAT blend can be evaluated by extruder and blown extrusion process. The synthesis techniques adopted
Fourier transform infrared (FTIR), nuclear magnetic resonance (NMR) in this work were innovative as the bionanocomposite was prepared by
spectroscopy, dynamic mechanical analysis, as well as observed by SEM extrusion process from a biodegradable blend, in a simple, rapid, eco-
and TEM. friendly, and easily reproducible manner. The cellulose nanocrystals
Therefore, for the PLA/PBAT blends to be suitable as a competitive, used to prepare the bionanocomposite were extracted from agro-waste
sustainable food packaging material compared to traditional ones, the and have an economic advantage because only small amounts of
thermal stability, UV, water vapor, and gas barrier properties must be nanofillers are needed to increase the performance of the film. The
improved. Different techniques have been highlighted to address these nanocomposite film packaging was produced by blown extrusion, an
limitations, such as chemical modification and reinforcing nanofillers industrial process. The effect of CNC content on the morphological,
(Kumar, Mukherjee, & Dutta, 2020; Moustafa et al., 2019; Vasile, 2018; mechanical, and thermal properties of the films was assessed to evaluate
Yadav & Chiu, 2019). The synergistic effects of fillers at the nanoscale the potential use of the bionanocomposite films for sustainable food
level are because of the higher surface/volume ratio – the smaller the packaging applications. These novel food packaging materials presented
particle size, the larger the ratio. Their interaction with biopolymers can mechanical values comparable to those of some commercial plastic-
results in food packaging material with adequate performance and based films used in flexible food packaging.
economic profitability, which can expand their commercial application
(Hai, Choi, Zhai, Panicker, & Kim, 2020; Papadopoulou et al., 2019; 2. Materials and methods
Risyon, Othman, Basha, & Talib, 2020; Rocca-Smith et al., 2019).
Several nanofiller types can be used to prepare bionanocomposite for 2.1. Materials
food packaging applications, including nanocellulose. The positive as­
pects of nanocellulose as a sustainable nanomaterial are its abundance, Sugarcane bagasse fiber (SBF) waste were obtained from Usina Ira­
renewability and biodegradability, high mechanical properties, high cema, São Martinho Group in Iracemápolis, São Paulo, Brazil. The
reinforcing capability, and low density. Two types of nanocellulose can moisture content of the raw SBF fibers was around 50 wt. %. PLA
be obtained from cellulose. One of the main constituents of plant cell Ingeo™ 2003D, from NatureWorks, PBAT (Ecoflex F C1200) from BASF.
walls is cellulose nanocrystals (or “nanowhiskers”) (CNCs), which The analytical grade chemicals used in this work were purchased from
exhibit a needle-like appearance. The other type is nanofibrillated cel­ Sigma-Aldrich and used without further purification.
lulose (CNF), which refers to long and flexible nanofillers composed of

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M.S. Andrade et al. Food Packaging and Shelf Life 31 (2022) 100807

Table 1 2.2.3. Sonication treatment

Chemical composition of in natura sugarcane bagasse fiber (SBFin natura) and after In this work, sonication treatment was used to obtain cellulose
diluted sulfuric acid pretreatment (SBFacid), as sell as the first alkaline pre­ nanocrystal (CNC). For the sonication step, 2 g of freeze-dried cellulose
treatment (SBFalcali). fiber powder was added for every 250 ml of water/DMF (dime­
Constituent SBFin natura (mass %) SBFacid (mass%) SBFalcali (mass %) thylformamide)/ethanol solution in an 8:1:1 volume ratio. Sonication
Cellulose 45.07 ±2.08 62.57 ±3.86 85.96 ±1.51 treatment was performed using an ultrasonic processor, model VCX 750
Hemicellulose 29.78 ±1.50 0 0 (Sonics & Materials, Inc), with 20 kHz ultrasonic frequency at 70%, 750
Soluble Lignin 0.70 ±0.08 0.31 ±0.04 0.08 ±0.06 Watts. After sonication treatment, the cellulose nanocrystals were
Insoluble Lignin 12.27 ±1.74 34.21 ±6.86 13.50 ±7.61 visibly dispersed (Fig. 1).
Extractives 3.12 ±0.27 0 0
Ash 6.02 ±0.73 6.05 ±0.93 10.81 ±1.38
Total 96.97 ±6.40 103.1 5 ±11.6 110.34 ±10.57 2.2.4. Freeze-drying of cellulose nanocrystals
To incorporate the cellulose nanocrystals into the PBAT/PLA blend
through the extrusion process, the aqueous cellulose nanocrystal sam­
2.2. Isolation and Characterization of Cellulose Nanocrystals (CNCs) ples were frozen and freeze-dried for 24 hours in an MSSL-404 vial
freeze dryer with an internal platform and microprocessor vacuum,
2.2.1. Cellulose delignification (first stage) pressure stabilized at 60 mmHg and temperature of -42 ◦ C.
The CNCs were prepared from SBF waste using the dilute sulfuric
acid pretreatment process conducted in the Pilot Plant at Engineering
School of Lorena - University of São Paulo (EEL-USP). First, the SBF was 2.3. Preparation of blend and bionanocomposite films
sun-dried until it reached a humidity of about 12 wt.%. The dilute sul­
furic acid pretreatment (100 mg sulfuric acid/mg dry matter) was per­ The pellets of both PBAT and PLA were initially dried in an air
formed in a stainless steel AISI 316 reactor, with a total volumetric circulating oven at a temperature of 60 ◦ C for 24 hours, to remove
capacity of 50 liters, equipped with a jacket for indirect heating by moisture content to less than 2% before processing. Blend of PBAT/PLA
electric resistance. The reaction was conducted at 121 ◦ C for 10 min, the (70/30 wt. %) was mixed through a dry blender operated at 80 rpm and
ratio of solid: liquid was 1:10 (Rodrigues et al., 2010), obtaining the SBF 40 ◦ C temperature for 10 min. The neat premixed dry blend and blend
pretreated by diluted acid (cellulignin - SBFacid). The cellulignin from containing 1–2% (wt. %) of freeze-dried cellulose nanocrystals were
sugarcane bagasse pretreated by diluted sulfuric acid was washed until melt blended in a corotating twin-screw extruder Haake Rheomex with
neutral pH and dried to 50 wt. %. In the same pilot plant, the first stage 16 mm and L/D = 25 rate from Thermo Scientific. The temperature
of cellulignin delignification (Fig. 1) was performed by alkaline pre­ profile was 95/118/125/135/135/135 ◦ C. The screw speed was 50 rpm.
treatment using 1.0% (w/v) NaOH in the ratio of solid: liquid of 1:10 at The extrudates coming out of the extruder were cooled down for better
121 ◦ C and reaction time of 10 min (Mori, 2015). Then, the partially dimensional stability, pelletized by a pelletizer, dried again at 60 ± 2 ◦ C
delignified material (cellulignin) was separated from the soluble for 4 hours, and fed into extrusion blown film, single-screw extruder
lignin-rich black liquor fraction by centrifugation. The cellulignin frac­ Haake Rheomex with 16 mm and L/D = 25 rate from Thermo Scientific,
tion was washed with water to near neutral pH, dried in the air circu­ and flexible film samples were obtained. The temperature profile was
lating oven at 60 ◦ C, milled in a ball mill, and classified according to 120/125/130/130/135/135 ◦ C, the blow-up ratio (BUR) of the bubble
particle size. Cellulose with particle size smaller than 125 µm was sub­ was 2:1, and screw rotation was kept at 30 rpm.
mitted to the second delignification process on the laboratory scale. For
that, cellulose fiber was treated with 4% (w/v) NaOH solution at 70 ◦ C 2.4. Characterization of cellulose nanocrystal
and for 1 hour under constant magnetic stirring. This procedure was
repeated until the NaOH solution remained colorless after extraction. 2.4.1. X-ray diffraction (XRD) analysis
The second stage of cellulose delignification was to remove the lignin The crystalline structure and crystallinity index of SBF and cellulose
residue from the cellulose. The overall synthesis process of CNC is nanocrystal (CNC) were determined by XRD analysis. The XRD data
schematically summarized in Fig. 1. were collected using a Rigaku multiflex diffractometer. These mea­
The chemical composition of in natura sugarcane bagasse fiber (SBFin surements were performed using Cu Kα (λ=1,5418 Å), under the oper­
natura) and after diluted sulfuric acid pretreatment (SBFacid) and first ational conditions of 40 kV and 20 mA, over the 2θ range from 5◦ to 90◦ .
alkaline pretreatment (SBFalcali) are provided in Table 1. The crystallinity index of the samples was calculated using Eq. (1)
(Yadav & Chiu, 2019):
2.2.2. Cellulose delignification (second stage)
The cellulose fibers were bleached with 8% (w/v) NaOH solution and IC (%) = (((I002-Iar)/I002) x 100) (1)
24% (v/v) H2O2 at a ratio of 1:1 for 1 hour at 50 ◦ C under magnetic Where IC is the crystallinity index; I002 is the intensity of the crys­
stirring, using 1 g fiber to 10 mL solution ratio. After the bleaching step, talline region of cellulose (2θ=22.5◦ ); Iar is the intensity of the amor­
the solution of cellulose fibers was vacuum filtered and dried in a phous region (2θ=16.5◦ ) (Yadav & Chiu, 2019).
circulating oven at 60 ◦ C. After the bleaching step, the cellulosic mate­
rial was hydrolyzed using a 65% (w/w) aqueous sulfuric acid solution, 2.4.2. Thermogravimetric analysis (TGA)
maintaining the ratio of 1 g fiber to 10 ml H2SO4 solution at 45 ◦ C for The thermal degradation of all cellulosic samples (SBF and CNC) was
60 min under magnetic stirring. The acid hydrolysis allows a chemical investigated using thermogravimetric analysis. Thermogravimetric
attack on the amorphous regions most susceptible to reaction with sul­ analysis (Mettler-Toledo – TGA/SDTA 851) was performed under a ni­
furic acid. In turn, after the addition of sulfuric acid, the crystalline re­ trogen atmosphere (50 mL min-1). The samples (approximately 10 mg)
gions of cellulose remain unchanged. The high concentration of sulfuric were heated from 30 to 800 ◦ C at a heating rate of 10 ◦ C/min. The
acid was used to guarantee the efficiency of the chemical attack on the weight loss (%) was evaluated by measuring the residual weight at 770
amorphous region. After acid hydrolysis, the cellulose was subsequently ◦
C.
dialyzed with distilled water in a cellulose membrane (Sigma-Aldrich:
D9402) until the pH value between 6 and 7 to reduce the excess acidity 2.4.3. Transmission electron microscopy (TEM)
of the solution and interrupt the chemical reaction of the cellulose fiber The suspensions containing 10, 30, and 50 mg/mL of cellulose
with sulfuric acid. Then it was frozen and freeze-dried for 24 hours to nanocrystals in water were prepared for transmission electron micro­
obtain the powder. scopy analysis. A droplet of diluted suspension was deposited on a

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M.S. Andrade et al. Food Packaging and Shelf Life 31 (2022) 100807

copper screen covered with a carbon support film. The prepared samples Table 2
were stained with a 1.5% solution of uranyl acetate, dried at room Crystallinity index of SBF and CNC samples.
temperature, and observed by TEM using a Tecnai FEI G20 with an ac­ Samples I002 IAR IC (%)
celeration voltage of 200 kV. Measurements of cellulose nanocrystal
Sugarcane Bagasse Fiber (SBF) 351 185 47.2
dispersion in water were also taken before and after lyophilization and Cellulose Nanocrystals (CNCs) 3429 1030 70.1
further dispersion by ultrasonic treatment.

samples were performed in triplicate, and the average values were re­
2.5. Characterization of blend and bionanocomposite films ported. The water absorbency of the bionanocomposite films was eval­
uated in terms of swelling. Each film sample was sectioned into a 2×2
2.5.1. Thermogravimetric analysis (TGA) cm2 piece, dried at 45 ± 2 ◦ C for 24 hours in a circulating air oven, and
Thermogravimetric analysis (Mettler-Toledo – TGA/SDTA 851) was preweighed. The preweighed samples were immersed in a petri dish
performed under a nitrogen atmosphere (50 mL min-1). The samples filled with 20 mL of deionized water and remained undisturbed for
(approximately 10 mg) were heated from 25 to 600 ◦ C at a heating rate 24 hours at room temperature until an equilibrium swelling was
of 10 ◦ C/min. The weight loss (%) was evaluated by measuring the re­ reached. The samples were removed from deionized water, quickly
sidual weight at 600 ◦ C. wiped with filter paper to remove droplets on the surface, and then
weighed. The samples were weighed at specific intervals of time until
2.5.2. Differential Scanning Calorimetry (DSC) analysis the equilibrium swelling was reached. The swelling ratio was calculated
DSC analyses were carried out using a Mettler Toledo DSC 822e from using the following expression, Eq. (3) (Yadav & Chiu, 2019):
25 to 250 ◦ C at a heating rate of 10 ◦ C/min under a nitrogen atmosphere
(50 ml/min). All samples were first heated from 25 to 250 ◦ C at a rate of Swelling Ratio(%) = ((Ws -Wd )/(Wd ) × 100 ) (3)
10 ◦ C/min, rapidly cooled to 25 ◦ C, and reheated to 250 ◦ C at 10 ◦ C/min
to provide thermal history. Tm and ΔHm were determined considering Where Ws = weight of the swollen samples, Wd = weight of the dry
the heat capacity change observed on the second heating. Furthermore, samples in all three replicates.
since the PBAT fraction is the crystalline phase of the films and PLA is an
amorphous phase, the degree of crystallinity (Xc) was determined from 2.5.6. Field emission scanning electron microscopy (FESEM) analysis
the sample melting enthalpy considering only the PBAT fraction as being The surface morphologies of the cryofractured bionanocomposite
the crystalline phase of the films. The PBAT degree of crystallinity (Xc) samples under liquid nitrogen were analyzed by scanning electron mi­
was determined by Eq. 2 (Xiao, Lu, & Yeh, 2009): croscopy (SEM) using a JEOL-JSM-6701F, microscope accelerating
( / ) voltage of 1-30 kV, using EDS Thermo-Scientific mod. Noran System Six
Xc = ΔHm ΔHm 0 (1-WPBAT ) × 100% (2) software, in carbon, sputtered samples.

Where Xc is the degree of crystallinity, ΔHm is the sample melting 2.5.7. Mechanical tests
enthalpy, ΔHm0 is the melting enthalpy of 100% crystalline PBAT, and Tensile tests were determined using an INSTRON Testing Machine
WPBAT is the mass fraction of the PBAT in the blend. The ΔHm0 value model 5564, according to ASTM D 882-91, to evaluate the mechanical
used for the PBAT was 114 J.g-1 (Xiao et al., 2009). behavior of the bionanocomposite film samples. Each value obtained
represented the average of five samples.
2.5.3. X-ray diffraction (XRD) analysis
The crystallinity of polymer composite strongly influences its 3. Results and discussion
chemical and mechanical properties. Moreover, the addition of fillers,
such as CNC, depending on the filler concentration, can potentially alter 3.1. Cellulose nanocrystal characterization
the crystallinity of the polymer matrix, acting as nucleating agents (Gan
et al., 2020). The crystalline nature of the PBAT/PLA blend and its 3.1.1. X-ray diffraction (XRD) analysis
bionanocomposite film samples were analyzed using a Siemens - D5000 The crystalline structure and the crystallinity index of sugarcane
diffractometer operated at 40 kV and 40 mA, with CuKα radiation (λ= bagasse fiber and cellulose nanocrystal were determined by XRD anal­
15.4 Å). ysis. XRD patterns were collected from 5◦ to 90◦ (2θ). The SBF and
cellulose nanocrystal (CNC) exhibited characteristic crystalline peak
2.5.4. Water contact angle measurements related to the crystalline structure of cellulose I at around 2θ = 22.5◦ ,
The absorption of water by the surface of the material is linked to the which corresponded to the lattice plane (002), and one broad peak at 2θ
wettability process of the water on the material surface and, conse­ = 16.5◦ , corresponded to the lattice plane (110) related to the amor­
quently, the hydrophilic/hydrophobic character of the material surface. phous domains of cellulose. The crystallinity index (Ic) of SBF and CNC
A high degree of wettability between water and material means a greater calculated from Eq. (1) is presented in Table 2. The Ic of the SBF and
contact area between them and a greater probability of absorption and CNC were around 47% and 70%, respectively. These results indicate a
more hydrophilic material. Wettability is commonly assessed by the predominance of crystalline.
contact angle of the liquid with the solid surface. In this phenomenon,
the greater the contact angle, the lower the wettability, that is, the 3.1.2. Thermogravimetric analysis (TGA)
material has a hydrophobic character when the liquid wets less the solid According to the obtained TGA and DTG curves of SBF and CNC, two
surface in contact. The surface wettability of bionanocomposite films main stage degradations were observed during the thermal analysis of
was determined through water contact angle (WCA) measurements the SBF. The first stage degradation, which occurred at 30–142 ℃,
using a KSV Theta standard goniometer equipped with a camera to presented a slight weight loss (WL) of about 2% and was attributable to
capture the images of water droplets and then determine the contact the evaporation of residual water present in the material. The second
angles. Deionized water was used to evaluate the wettability properties degradation, which exhibited the higher WL of about 62%, occurred at
of these films. Angle measurements were performed in triplicate, and 230–400 ℃ and referred to the process of thermal decomposition of
their average values were taken. cellulose, including dehydration, decomposition, and depolymerization
of the glycoside units (Yadav & Chiu, 2019). The slow and gradual
2.5.5. Water absorbency test decreased in WL of about 7.8% observed from 400 to 770 ℃ was
Water absorbency measurements of the bionanocomposite film

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M.S. Andrade et al. Food Packaging and Shelf Life 31 (2022) 100807

Table 3 show the efficiency of acid hydrolysis treatment to obtain cellulose

Onset temperature (Tonset), maximum temperature (Tmax), and residual weight nanocrystals from sugarcane bagasse fiber. The TEM image confirmed
(RW) obtained from TGA analysis. the presence of nanocrystals in the suspensions, which consists mainly of
Samples Tonset (ºC) Tmax (◦ C) RW (770 ◦ C) (%) individual fibrils of elongated length and diameter in the order of
Sugarcane Bagasse Fiber (SBF) 276 330 28.2
magnitude of nanometers, with needle-like in shape, and with size in the
Cellulose Nanocrystals (CNCs) 230 270 23.6 range of 50− 150 nm (length) and 1− 10 nm (diameter) with a relatively
high aspect ratio.

assigned to the decomposition of lignin, whereas that of lignin had a

broader degradation temperature range between 220 and 600 ℃ (Jiang, 3.2. Blend and bionanocomposite films characterization
Lawrence, Hussain, Ansell, & Walker, 2019). The onset temperature
(Tonset) is defined as the temperature at which the WL of the sample 3.2.1. Thermogravimetric analysis (TGA)
becomes apparent, while the maximum temperature (Tmax) is the The TGA curves and derivative thermogram (DTG) curves of PBAT/
maximum thermal degradation temperature, which is the peak of the PLA blend and its bionanocomposite films were obtained. Based on the
derivative TGA curve (Herrera et al. 2018). The Tonset and Tmax of SBF DTG, two-step degradations were observed for the PBAT/PLA blend and
were at around 276 ℃ and 330 ℃, respectively. The measured value of its bionanocomposite films. Similar findings were reported by Shriv­
residual weight (RW) at 770 ℃ was at around 28.2%. The degradation astava, Wooi, Hassan, & Inuwa (2018). Furthermore, TGA/DTG results
process of CNC occurred in three main stages. The first degradation with presented a significant difference in residue weight and onset temper­
a slight WL of about 2.7% occurred at 30–144 ℃ and was attributable to ature (Tonset) of the neat blend compared to bionanocomposite films, as
the evaporation of residual water present in the material. shown in Table 4. The thermal stability of the bionanocomposite films
The second stage degradation, which exhibited a higher WL of about increased with the increased CNC content, which can be corroborated
53.4%, started at around 185 ◦ C and ended at approximately 336 ◦ C. In from the lower residue weight value of PBAT/PLA blend film compared
this stage, hydroxyl groups were replaced by acid sulfate groups in the to those of bionanocomposite films and with the Tonset, Tmax, and Tfinal
acid hydrolysis step, decreasing the activation energy for the cellulose values presented in Table 4. Considering that improvement in thermal
degradation. The sample becomes less resistant to pyrolysis, with stability is usually related to an increase in Tonset and Tmax, the film
dehydration reactions taking place, releasing water, and catalyzing its content of 2 wt. % CNC (PBAT/PLA/CNC 2) exhibited optimum thermal
decomposition. The third stage, from 336 to 770 ◦ C, presented a gradual stability with more than 25 ◦ C of enhancement in Tonset.
WL at around 20.2% as a function of temperature and was associated As observed from Table 4, the Tmax of this film increased from 395 to
with cellulose pyrolysis that occurs in the 300 to 600 ◦ C range, and was 400 ◦ C, and the Tfinal from 406 to 415 ◦ C. The improvement in thermal
attributed to the breakdowns of the internal cellulose molecules, which stability can be attributed to the CNC particles, which were diffused
did not make contact with sulfuric acid in acid hydrolysis, for the homogeneously into the matrix and firmly combined, despite the pres­
oxidation and breakdown of charred residues to form gaseous products ence of some CNC aggregates, as can be seen in FESEM images (Fig. 4).
of low molecular weight. The CNC showed a Tonset around 230 ℃ and The collected data clearly indicate that the thermal stability of
Tmax at approximately 270 ℃. The RW at 770 ℃ was around 23.6% and
lower than those of SBF. A similar trend was reported in the literature Table 4
and was related to the insertion of sulfate groups on the surface of CNC Thermogravimetric (TGA) and differential scanning calorimetry (DSC) analysis
during hydrolysis with sulfuric acid (El Achaby et al., 2017; Roman & results of PBAT/PLA blend and its bionanocomposite films.
Winter, 2004; Sahlin et al. 2018). The onset temperature (Tonset), the
Samples Tonset Tmax Tfinal RW Tm ΔHm Xc
maximum temperature (Tmax), and the RW obtained for SBC and CNC (◦ C) (◦ C) (◦ C) (%) (◦ C) (Jg-1) (%)
are summarized in Table 3. Although the thermal stability of CNC was
PBAT/PLA 341 395 406 2.6 154.8 4.5 13.2
lower than SBF, it remained high enough for most practical applications. Blend
Moreover, the thermal stability of the CNC makes it suitable for the PBAT/ 347 399 410 6.4 154.3 7.6 21.7
development of sustainable food packaging material based on the PLA/CNC
PBAT/PLA blend, as proposed in this work, since both the temperature 1a
PBAT/ 368 400 415 4.5 154.9 9.5 26.5
of the processing and the work of these packaging materials are less than
PLA/CNC
the degradation temperature of CNC. 2b

3.1.3. Transmission electron microscopy (TEM) analysis

a
The TEM image of the cellulose nanocrystals (CNCs) in aqueous PBAT/PLA content of 1 wt. % of CNC.
b
suspension of 0.03 g/mL concentration is in Fig. 2a and 2b. The images PBAT/PLA content of 2 wt. % of CNC.

Fig. 2. TEM image of CNC (a) at magnification of 6500 X and (b) 13000 X, respectively.

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M.S. Andrade et al. Food Packaging and Shelf Life 31 (2022) 100807

Fig. 3. DSC results, (a) non-isothermal DSC curves for PBAT, PLA and for the PBAT/PLA and PBAT/PLA/CNC blends and (b) glass transition temperatures (Tg).

Fig. 4. FESEM images of the PBAT/PLA Blend: (a)1.000 X, (b) 6.000 X; PBAT/PLA/CNC1: (c) 3.000 X, (d)12.000 X; PBAT/PLA/CNC2: (e)3.000 X, (f)12.000 X.

bionanocomposite films was strongly influenced by the intermolecular recently reported by Gan et al. (2020). Mandal & Chakrabarty (2014)
bonding between the CNC and the PBAT/PLA blend matrix since the found that the incorporation of nanocrystalline cellulose (NCC) from
bond dissociation energy needed for chain cleavage of the polymer could sugarcane bagasse in PVOH significantly improved the thermal stability
be enhanced by strong intermolecular bonding. Similar trends were of NCC–PVOH nanocomposites by enhancing the NCC-matrix

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M.S. Andrade et al. Food Packaging and Shelf Life 31 (2022) 100807

Fig. 5. Image of the water droplet on the surfaces of bionanocomposite films for the contact angles measured: (a) PBAT/PLA Blend; (b) PBAT/PLA/CNC1; (c) PBAT/
PLA/CNC2.

interaction through hydrogen bonding. Hai et al. (2020) observed 3.2.3. Field emission scanning electron microscopy (FESEM) analysis
improved thermal stability of chitin nanofiber (CTNF) and bamboo Fig. 4 is FESEM images of cryofractured surfaces of the bio­
cellulose nanofiber (BACNF) nanocomposites when investigating the nanocomposite films. Fig. 4a and 4b present an overview of PBAT/PLA
thermal degradation of a green nanocomposite. Mondragon, blend with magnifications of 1.000× and 6.000×, respectively, illus­
Peña-Rodriguez, González, Eceiza, & Arbelaiz (2015) also reported a trating the characteristic morphology of immiscible blends with low
significant increase in the thermal stability of a bionanocomposite based adhesion and uniform dispersion of PLA, which is the dispersed phase on
on the incorporation of nanocrystalline cellulose (NCC) in the gelatin the slightly rough surface of the PBAT matrix. The FESEM image of the
matrix. surface of PBAT/PLA films containing CNCs reveal a smooth surface
structure with a homogeneous distribution of CNCs and well-defined
3.2.2. Differential scanning calorimetry (DSC) analysis occurrence of some aggregated particles on the surface of films, but
Fig. 3(a) shows the non-isothermal DSC curves for PBAT and PLA as without any visible cracks or holes, as shown in Fig. 4c and 4d of PBAT/
well as the PBAT/PLA and PBAT/PLA/CNC blends, and Fig. 3(b) pre­ PLA/CNC1 with magnifications of 3.000× and 12.000× and Fig. 4e and
sents the glass transition temperatures (Tg). For PLA, its Tg can be seen 4f of PBAT/PLA/CNC2 with magnifications of 3.000× and 12.000×,
in the temperature range between 34 and 43 ◦ C. Then a complex respectively. The aggregation of CNCs increased with increasing CNCs
endothermic peak is observed, which refers to the melting of PLA, with content. This effect was mainly due to the existence of strong in­
peak temperature at 88 ◦ C. PBAT exhibits an endothermic peak with low teractions between the surface of hydroxyl groups of the CNC at the
intensity, referring to its fusion, with peak temperature at 118 ◦ C. In the higher loading level as well as the attractive van der Waals forces
PBAT/PLA blends, the Tg can not be identified in Fig. 3(b), suggesting (George & Sabapathi, 2015; Klemm et al., 2018; Lee et al. 2019; Tayeb,
that the addition of PBAT in PLA shifted the Tg of PLA to lower tem­ Amini, Ghasemi, & Tajvidi, 2018). Both the strong interactions between
peratures below the range used in the analysis, since PBAT Tg occurs the hydroxyl groups of the CNCs and the van der Waals forces contrib­
around -33 ◦ C to -39 ◦ C (Kilic, Can, Kodal, & Ozkoc, 2019; Nayak 2010). uted to the increased concentration of CNCs, which led to a rapid
With the addition of CNC, the Tg of PLA shifts to higher temperatures collision between the CNCs particles during the dispersion process in the
between 37 ◦ C and 46 ◦ C, indicating the immiscibility of the blends and PBAT/PLA matrix.
that the nanocrystals made it difficult to move the amorphous phase, In this case, the CNC-CNC interaction became dominant over the
requiring more energy for the event to occur. CNC–matrix interaction, which induced the CNC particles to stick
Arrieta et al. (2014) reported similar results for poly(lactic acid)/p­ together and form aggregates, and the contact area between CNCs and
oly(hydroxybutyrate)/cellulose nanocrystals (PLA/PHB/CNCs) blends. PBAT/PLA matrix was reduced. Its homogeneous dispersion in the ma­
The incorporation of PHB in PLA shifted its Tg to lower temperatures trix was restricted. Such occurrence has been observed in previous
from 58.8 ◦ C to 53.5 ◦ C, and the addition of CNCs in the PLA/PHB blend studies (Azizi et al. 2014; Chakrabarty & Teramoto, 2018; Dufresne,
shifted the Tg of PLA to higher temperatures (62.5 ◦ C). 2018; El Miri et al., 2016; Klemm et al., 2018; Risyon et al., 2020).
The melting temperature and enthalpy as well as the crystallinity Unlike what the aggregated CNCs presented on the surface of the
degree of the PBAT/PLA blend and its bionanocomposite films are PBAT/PLA/CNC1 film, Figs. 4c and 4d, the surface of the PBAT/PLA/
presented in Table 4. Table 4 indicates that compared to blend, the CNC2 film, Fig. 4e and 4f, displays aggregations of needle-shaped CNCs
endothermic melting enthalpy and crystallinity degree of bio­ with lengths up to several microns. Despite the presence of aggregated
nanocomposite films increased with the amount of CNC added, but the CNCs, Fig. 4 suggests good adhesion between CNCs and PBAT/PLA
melting temperature was not changed. The increases in the melting blend matrix, which plays an essential role in improving the mechanical
enthalpy and crystallinity degree can be attributed to the high crystal­ performance of the resulting bionanocomposite films.
linity degree of CNC.
3.2.4. X-ray diffraction (XRD) analysis
The X-Ray diffraction patterns of PBAT/PLA blend and bio­
nanocomposite films had peaks at around 2θ = 9.6◦ , 17.6◦ , 18.8◦ , 26.7◦ ,
Table 5 28.6◦ , and 29.6◦ , attributed mainly to PBAT, and abroad, amorphous
Contact angle degree and swelling ratio of the PBAT/PLA blend film and its halo in the range of 16◦ to 24.8◦ , which might be the contribution of
bionanocomposite films. PLA. According to literature, the characteristic diffractogram of neat
Samples Contact angle Swelling ratio water absorbency PLA displays a broad, amorphous halo, indicating its amorphous state,
(degree) (%) reduction (%) with the prominent peaks at 2θ = 16.6◦ and 19.1◦ , and two smaller peaks
PBAT/PLA 50.5±1.3 8.6±0.5 - at 2θ = 14.7◦ and 22.3◦ (Papadopoulou et al., 2019). The diffractograms
Blend of the bionanocomposite films revealed significant increases in the in­
PBAT/PLA/ 71.0±1.0 3.9±0.3 - 55 tensity of crystalline peaks, which were approximately 2θ = 9.6◦ , 18.8◦ ,
CNC 1a
28.6◦ , and 29.6◦ , with the increased amount of CNC content. On the
PBAT/PLA/ 54.0±0.3 2.5±0.2 - 70
CNC 2b other hand, the characteristic crystalline peak related to CNC was not
a
visible in all bionanocomposite films. This can presumably be ascribed
PBAT/PLA content of 1 wt.% of CNC.
b to good interactions between the PBAT/PLA blend and CNC, which
PBAT/PLA content of 2 wt.% of CNC

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M.S. Andrade et al. Food Packaging and Shelf Life 31 (2022) 100807

Table 6
Mechanical properties of the PBAT/PLA blend film and its bionanocomposite
films.
Bionanocomposite Thickness Tensile Elongation at Young’s
films (µm) strength at break (%) modulus
break (MPa) (MPa)

PBAT/PLA Blenda 60 ± 1.0 29.6 ± 1.6 370 ± 27 136 ± 10

PBAT/PLA/CNC 1b 64 ± 1.3 37.3 ± 2.5 460 ± 32 220 ± 12
PBAT/PLA/CNC 2c 63 ± 1.2 44.7 ± 2.3 478 ± 39 296 ± 17
a
PBAT/PLA blend.
b
PBAT/PLA content of 1 wt.% of CNC.
c
PBAT/PLA content of 2 wt.% of CNC.

Fig. 6. Stress-Strain curves for PBAT/PLA blend and its bio­ Table 7
nanocomposite films. Mechanical properties of commercial plastic-based films.
Commercial plastic-based Tensile Elongation at Young’s
contributed to an increase of crystallinity degree observed in the DSC films strength (MPa) break (%) modulus (MPa)
results, and consequently to improved thermal stability and mechanical Low-density polyethylene 7.00 – 34.5 50.0 – 1000 140 – 480
properties of bionanocomposite films when compared to PBAT/PLA (LDPE)
blend film. Linear low-density 10.0 – 37.3 0.80 – 1000 110 – 413
polyethylene (LLDPE)
High-density 23.0 – 40.0 400 – 1700 200 – 1350
3.2.5. Water contact angle measurements polyethylene (HDPE)
The water droplet image on the bionanocomposite film surfaces and Poly(vinyl chloride (PVC) 42.0 – 55.0 20.0 – 180 5.52 – 3230
the contact angle (WCA) measured for different cellulose nanocrystal Poly(propylene (PP) 27.0 – 98.0 200 – 1000 700 – 7510
content from 0 to 2 wt.% are shown in Fig. 5 and Table 5, respectively. Polyamide 66 (PA66) 31.0 – 45.0 40.0 – 170 400 – 3310
Poly(ethylene 2.10 – 90.0 4.00 – 600 107 – 3500
The WCA of the bionanocomposite film surface was measured to
terephthalate (PET)
evaluate the hydrophilic/hydrophobic character of the film. The water a
based on data presented by MatWeb(“Online Materials Information Resource -
contact angle of bionanocomposite films increased with increased CNC MatWeb,” 2002) and Otoni et al. (2017)
content from 0 to 2 wt. % (Fig. 5). The neat PBAT/PLA blend film pre­
sented a lower contact angle value of 50◦ , as expected due to the low
3.2.7. Mechanical tests
hydrophobic character of PBAT. The addition of 1 wt. % of CNCs
Typical stress-strain curves of PBAT/PLA blend and its bio­
increased the contact angle from 50 to 71◦ . However, when the CNC
nanocomposite films are in Fig. 6. These curves are based on average
content was 2 wt. %, the contact angle increased only 54◦ (Table 5). The
values calculated from the data obtained for five test specimens. Fig. 6
surface hydrophobicity of CNCs and their dispersion in the blend film
indicates that all film samples presented a mechanical behavior repre­
may explain these results. The surface hydrophobicity of CNC is better
sentative of ductile materials with a characteristic yield point, large
than that of the blend, which probably reduces diffusion of water mol­
plastic deformation, and high elongation values at break. A remarkable
ecules in the matrix. On the other hand, when the CNC content was
increase in tensile strength at break, Young modulus, and elongation at
increased to 2 wt. %, some CNC were not completely blended with
break of neat PBAT/PLA blend film due to the addition of CNCs were
PBAT/PLA matrix as shown at FESEM images (Fig. 4(c–f)), and aggre­
observed, contrary to the expected inverse relationship between tensile
gated CNC appeared on the surface of the bionanocomposite films. The
strength and elongation at break (Table 6).
amount of aggregated CNC drastically increased on the bio­
Similar mechanical behaviors were reported by Reddy & Rhim
nanocomposite surface with content of 2 wt. % of CNC. Whereas at 1 wt.
(2014), for crystalline nanocellulose incorporated into agar, and by
% of CNCs, the more homogenous dispersion on the blend surface and
Mandal & Chakrabarty (2014), in their study of the incorporation of
higher contact angle may suggest that the increase of aggregated CNC
nanocellulose from sugarcane bagasse into poly(vinyl alcohol).
decreased the contact angles of the bionanocomposite film. Similar
In the present experiment, the tensile strength, elongation at break,
findings have previously been reported (Goudarzi,
and Young’s modulus of the PBAT/PLA film content of 1 wt. % of CNCs
Shahabi-Ghahfarrokhi, & Babaei-Ghazvini, 2017; Hai et al., 2020;
increased by around 27%, 24%, and 62%, respectively, compared to
Yadav & Chiu, 2019).
PBAT/PLA blend film. The tensile strength, elongation at break, and
Young’s modulus were increased by around 52%, 29%, and 118%,
3.2.6. Water absorbency test
respectively, by increasing CNC content from 1 wt. % to 2 wt. %. This
The swelling ratio for water absorbency measurements of the bio­
behavior may be attributed to the inherent chain stiffness and rigidity of
nanocomposite films is presented in Table 5.
CNC (elastic modulus from 130 to 250 GPa) (Reddy & Rhim, 2014), the
As CNC content increased from 0% to 2%, the swelling ratio
high aspect ratio (1–10 nm in diameter and 50–150 nm in length), and
decreased from 8.6 to 2.5%. This indicates that the bionanocomposite
the strong interfacial interaction induced through hydrogen bonding
films containing 1 and 2 wt.% of CNC exhibited about 55% and about
between the CNC and the PBAT/PLA blend matrix. The improvement in
70% less water absorbency properties than the PBAT/PLA blend film,
the mechanical performance of the blend film containing 2 wt. % CNCs
respectively. Thus, incorporation of CNCs increased the hydrophobicity
suggests that the increase of the amount of CNC aggregates on the sur­
of the films, which is essential for food packaging applications due to the
face of the film, as can be noted in the FESEM image (Fig. 4e and 4f), was
greater crystallinity of the CNCs than PBAT/PLA blend, which, upon
not large enough to lead to non-uniform stress distribution in the films.
incorporation, acts as a barrier hindering PBAT/PLA blend molecules
This was able to reduce the interaction between the CNCs and PBAT/­
from swelling and thereby lessening the water absorbency. Furthermore,
PLA blend matrix, and consequently reduce the mechanical behavior of
as the CNCs are crystalline particles, they could inhibit the water
the film.
diffusion through the PBAT/PLA blend. This result is consistent with
The increases in percent elongation at break, which measures flexi­
other studies (Fortunati et al., 2014; Wang et al., 2016; Wu, Farnood,
bility or ductility of films, in tensile strength and Young’s modulus,
O’Kelly, & Chen, 2014; Yadav & Chiu, 2019).
make these bionanocomposite films strong and tough, the main

8
M.S. Andrade et al. Food Packaging and Shelf Life 31 (2022) 100807

Fig. 7. Visual appearance of bionanocomposite films: (a) PBAT/PLA Blend, (b) PBAT/PLA/CNC1, and (c) PBAT/PLA/CNC2.

mechanical characteristic required for food packaging applications. Declaration of Competing Interest
Furthermore, the mechanical test values of the bionanocomposite films
are comparable to those of some commercial plastic-based films used in The authors declare that they have no known competing financial
food packaging, as can be seen in Tables 6 and 7, which was based on interests or personal relationships that could have appeared to influence
data presented by MatWeb (2002) and Otoni et al. (2017). However, the work reported in this paper.
Young’s modulus of the films was smaller than those of the poly­
propylene (PP) and polyamide 66 (PA66) film grades (Table 6). In Acknowledgments
addition, the visual appearance of bionanocomposite films exhibited
transparency and no visual aggregates, which are important features for The authors wish to thank FAPESP(Brazil)/Process Number 2019/
use in food packaging (Fig. 7). The order of visual transparency of films 00862-9, IAEA-CRP(Vienna) No. 17760/RO, and CAPES(Brazil) for the
is as follows: support provided on this work.
PBAT/PLA Blend > PBAT/PLA/CNC1 > PBAT/PLA/CNC2
Appendix A. Supporting information

Supplementary data associated with this article can be found in the

4. Conclusions online version at doi:10.1016/j.fpsl.2021.100807.

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