j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 5 : 3 1 6 1 e3 1 7 0

Available online at www.sciencedirect.com

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

Original Article

Biocomposites based on poly(hydroxybutyrate) and

the mesocarp of babassu coconut (Orbignya
phalerata Mart.): effect of wax removal and maleic
anhydride-modified polyethylene addition

Nata
lia Fernanda Inoc^encio Silva a, Jos
e Elson Soares Filho a,*,
Tiago Galdino Cabral Santos a, J
essica da Silva Chagas a,
Suelen Alves Silva Lucena de Medeiros a, Eduardo Braga Costa Santos a,
Renate Maria Ramos Wellen a, Lucineide Balbino da Silva a,
Laura Carvalho b, Ma
rio Andr
e Brito Seixas Nunes c,
Am
elia Severino Ferreira e Santos a
a

ria, s/n, Castelo Branco,
Department of Materials Engineering, Federal University of Paraı́ba, Cidade Universita
~o Pessoa, PB, 58051-900, Brazil
Joa
b
Academic Unit of Materials Engineering, Federal University of Campina Grande, Av. Aprı́gio Veloso, 882,
Bodocong
o, Campina Grande, PB, 58429-900, Brazil
c
UFPB: Universidade Federal da Paraiba, Brazil

article info abstract

Article history: Aiming to adds value to agricultural products and develop environmental-friendly and
Received 13 March 2021 cost-effective materials, the present work investigates the influence of babassu mesocarp
Accepted 3 September 2021 (BM) flour extractives and the addition of maleic anhydride-modified polyethylene
Available online 20 September 2021 (MAPE), as a coupling agent, on the properties of additivated polyhydroxybutyrate
(PHBad)/BM biocomposites. The extractives were partially and completely removed from
Keywords: BM flour by detergent and soxhlet extraction, respectively, before biocomposites melt
Biocomposite processing. The thermal, mechanical, structural, morphological, and flow properties of
Babassu coconut biocomposites with extracted BM flours were determined and compared to the properties
Mesocarp of biocomposite with BM flour in natura. In addition, the influences of MAPE incorporation
Particle-reinforcement in the properties of each biocomposite were also studied, in order to understand their role
Surface treatment in biocomposite compatibilization. The particle treatments resulted in biocomposites
with lower tensile strength than biocomposites with BM in natura. Despite the low
compatibility of MAPE with PHB, the addition of MAPE increased the tensile strength of
the respective PHB biocomposite, reaching values of tensile strength similar or slightly
higher than the PHBad-MAPE matrix. Therefore, MAPE acted as an effective additive for

* Corresponding author.
E-mail address: elsinhofilho@gmail.com (J.E. Soares Filho).
https://doi.org/10.1016/j.jmrt.2021.09.008
2238-7854/© 2021 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).
3162 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 5 : 3 1 6 1 e3 1 7 0

BM flour, probably, due to reactive processing with the starch polar surface groups. Since
BM was abundantly and cheaply available, its use with PHB and MAPE resulted in
biodegradable material with similar mechanical properties of neat PHB and concomitant
reduction in cost.
© 2021 The Author(s). Published by Elsevier B.V. This is an open access article under the CC
BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

avoid environmental damage, because they decompose

1. Introduction
The Babassu (Orbignya phalerata Mart.) Is a genuinely Bra-
zilian palm tree found naturally in the North, Northeast and
Midwest regions of Brazil. There is a valuable economic po-
tential and generates income to the extractive families. The
Babassu palm tree produces fruits that are composed of a
protective peel rich in lignin and cellulosic material and co-
conuts rich in vegetable oil. The composition of Babassu co-
conut is shown in Fig. 1.
Babassu mesocarp (BM) is mainly used as flour for human
consumption (biscuits, breads and cereal bars), animal feed
and biomass energy source [1,2]. Investigations of the use of
the mesocarp as starch source has been intensified in the last
years [1,2]. The use of babassu mesocarp flour to produce
starch rich films or polymer biocomposites without any pre-
treatment have also been evaluated. Nevertheless, there is
relatively little studies trying to use integral babassu meso-
carp flour or investigate how its impurities, or starch extrac-
tion methodology affect film end uses properties [2].
Its chemical composition consists of starch (50e70 wt.%),
moisture, proteins, dietary fibers (10e37%), lipids, soluble
carbohydrates, mineral salts, ashes, and other components
[1e3]. As a babassu coconut component, the development of
processes or new market for BM adds value to this residue,
reduce its current underuse and brings socio-economic ad-
vantages for the communities involved in the coconut
extractivism [1,3].
Looking for the challenges in biotechnology and more
specifically to the babassu mesocarp (BM) agroindustry, in this
study it was evaluated its potential to be incorporated as
natural filler within the plastic industry. Since BM is a
renewable and biodegradable material, natural or synthetic
biodegradable polymers are classified as real alternatives to
Fig. 1 e Babassu coconut composition.
without leaving any traces of toxic or dangerous residues,
when disposed in safe areas under appropriate environmental
conditions, such as temperature, humidity, and available ox-
ygen [1,4].
Polyhydroxybutyrate (PHB) is a biodegradable semi-
crystalline thermoplastic polymer with high chain regularity
and processing similar to high-density polyethylene (HDPE). It
can be obtained through bacterial fermentation of sugar cane,
however, it can also be extracted from some plants, such as
potatoes (Solanum tuberosum) and tobacco (Nicotiana tabacum)
[1,3].
Due to the biodegradability and the excellent character-
istics, the PHB has a high power of insertion in the industrial
production and market and may be of interest in the manu-
facture of products for quick use, such as disposables, pack-
aging for cosmetics, compound materials, food, pesticides,
automotive industry products, among others [4]. However,
the fragility at room temperature makes it difficult to use and,
therefore, the use of additives as a nucleating agent and
plasticizer is required for the processing, as they generally
improve the mechanical properties by inhibiting secondary
crystallization and reducing the size of spherulites [5,6].
Furthermore, the high production cost discourages large-
scale applications, which favors the use of PHB compounded
with other bidegradable polymers, as well as fillers aiming at
cost reductions along with the improvement of material
properties [7].
As BM is abundantly and cheaply available filler naturally
occurring in the North, Northeast and Midwest regions of
Brazil, its use in blending with PHB will result in completely
biodegradable, and low-cost material with socio-economic
benefits. Furthermore, both PHB and BM have brownish color
[2] and their compound will have natural wood appearance.
The biodegradable compounds are used in the manufac-
ture of eco-friendly materials in the areas of technology and
engineering and have a strong capability to reduce
manufacturing input costs. Furthermore, natural fibers or
fillers can act as reinforcement in structure, which, generally,
improves the thermo-mechanical performance. However,
before the incorporation in the polymer, the natural fibers/
particles can be treated to remove extractives, which could
negatively influence its interaction with the matrix, making it
difficult for the fiber/particle and matrix to adhere [8e11,12].
However, the isolation of neat starch should not be interesting
because the lack of affinity between PHB and starch, main
component of BM, resulting in blends with poor performance
[13,14]. Therefore, the evaluation of BM flour in natura is
interesting and the dietary fibers present in its chemi-
cal composition could enhance the physical-mechanical
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 5 : 3 1 6 1 e3 1 7 0 3163

compared to the properties of biocomposite with BM flour in

natura. In addition, the influences of MAPE addition in the
properties of each biocomposite was also studied.

2. Experimental

2.1. Methods

The workpieces of biocomposites used for characterization

and performance evaluation were obtained with PBH (with
processing additives), 0 and 2 wt% of the coupling agent,
(maleic anhydride-modified polyethylene e MAPE), and the
fiber in natura and treated by two routes of wax removal.
Aiming to avoid a negative influence of the coupling agente in
Fig. 2 e Flowchart of the experiment development. the mechanical properties of the biocomposite, was added
maximum 2 wt% of MAPE. Fig. 2 illustrates the experimental
procedures carried out as well as and Table 1 shows the
compositions adopted in this work.
Table 1 e Compositions adopted.
The PHB was donated by PHB Industrial S/A (Serrana, Sa ~o
Composition (wt.%) Paulo - Brazil) with a melt flow index (MFI) of 2.98 g$10 min
1.
1
PHBad 100 0 0 n.a* As additives for PHB composites, it was used 2 wt.% stearic
PHBad-MAPE 982 0 0 n.a* acid, 0.5 wt.% microcrystalline cellulose (MCC, MC-101), and 9.5
1 803 20 0 In natura wt.% glycerol as a lubricant agent, nucleating agent, and
2 784 20 2
plasticizer, respectively. The PHB processing aids was chosen
3 803 20 0 Route 1
4 784 20 2 Surfactant washing
based on the literature data [12,18,19]. Table 1 shows the adopt
5 803 20 0 Route 2 compositions in this work and the PBH percentages are already
6 784 20 2 Solvent extraction including the sum of the processing additives (12 wt.%).
1
Mixture of 88% of PHB with 12 wt.% of processing additives. The adopted coupling agent, maleic anhydride-modified
2
Mixture of 86% of PHB with 12 wt.% of processing additives. polyethylene - MAPE, was produced by Polyram Plastic In-
3
Mixture of 68% of PHB with 12 wt.% of processing additives. dustries LTD (Afula, Israel) and kindly provided by Parabor Ltda
4
Mixture of 66% of PHB with 12 wt.% of processing additives. (Sa~ o Paulo-SP, Brazil). The bio-filling material, BM, was sup-
*Not applicable. plied by Floresta Brasileira SA (Itapecuru-Mirim, Maranha ~o -
Brazil) presenting an average particle size of 32.9 mm.
Two physicochemical routes were performed on BM to
performance of PHB/starch matrix. Furthermore, starch remove as much wax as possible from the mesocarp. In the
granules are encapsulated by fiber, protein, and lipid present first route, the BM powder was submitted to extraction (via
in babassu mesocarp and the fiber residue generated during soxhlet) for 24 h with ethanol, followed by 24 h in cyclo-
its extraction presents high starch content, indicating a diffi- hexane. In the second route, the BM has immersed in 20% (v/v)
cult and an ineffective starch isolation [7]. aqueous solution of a commercial surfactant for dishware
Further fruitful investigations dealing biocomposite of PHB washing (alkylbenzene sodium sulfonate), under magnetic
with 20 wt.% of treated natural fibers from Cocos nucifera, stirring for 24 h [18]. Then, the BM fiber was filtered, washed,
Ananas erectifolius, Copernicia prunifera, Hymenolobium and dried in an oven for 16 h at 60  C.
petraeum Ducke are available in the literature [7e10] are The calculation of the extractive content for BM in natura
available in the literature and all investigations have shown and BM route 2 was carried out by the percentage weight
better mechanical performances with fibers incorporated. The variation of each kind of BM in relation to respective BM
polyolefin modified with maleic anhydride promotes esterifi- weight after soxhlet extraction for 24 h with ethanol, followed
cation reactions between the coupling agent and the hydroxyl by 24 h in cyclohexane. Since BM route 1 used soxhlet
groups available on the surface of the natural fiber/particle extraction, the determination of extractive content was not
[11], facilitating the interfacial adhesion between the fiber/ applicable to this sample. Moisture content was determined
particle and the matrix [13,15e17].
In this sense, the main goal of this study is to investigate the
effect of the extractives on some properties of PHB/BM bio- Table 2 e Extractives and moisture content.
composites and role of maleic anhydride-modified polyethylene Filler Extractive Moisture
(MAPE), as coupling agent of biopolymer. As a result, extractives Content (%) Content (%)
were partially and completely removed from BM flour by using
BM in natura 8.5 ± 1.6 2.74 ± 0.4
surfactant (route 1) and soxhlet (route 2) extraction, respec- BM via route 2 2.9 ± 0.52 3.02 ± 0.7
tively, before preparation of biocomposites. The thermal, me- BM via route 1 n.a. 3.78 ± 0.1
chanical, structural, morphological, and flow properties of
n.a: Not applicable.
biocomposites with extracted BM flours were determined and
3164 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 5 : 3 1 6 1 e3 1 7 0
Fig. 3 e Thermogravimetric curve of BM flour in natura.
by weight loss of each kind of BM dried at 100  C until they
reach constant weight, as recommended by ASTM D 1348-94.
Both analyses were performed in triplicate.
The BM in natura, as well as after each route were charac-
terized by Fourier transform infrared spectroscopy (FTIR) and
scanning electron microscopy (SEM). Also wax obtained from
BM in natura extract after solvent evaporation was character-
ized by FTIR. FTIR analysis were gathered as average of 32
scans in the region from 600 to 4000 cm
1 in transmittance
mode, using a Shimadzu IR Prestige-m21 spectrophotometer.
Previously, fillers were sieved through 200 mesh and pressed
with potassium bromide as pellets shape.
2.2. Biocomposites processing and workpieces
preparation
Prior to the processing step, the components were completely
dried. The PHB was vacuum dried for 3 h at 80  C, and the BM
fibers were oven-dried for 24 h at 60  C. Then, the lubricant,
Fig. 4 e (a) - FTIR spectra of BM in natura and after the two physicochemical treatment routes. (b) e comparison between
FTIR of the wax obtained and BM in natura.
nucleating, and plasticizer agents were added, as suggested by
El-Hadi et al. [15] and Marinho et al. [20]. All the compositions
were processed for 5 min at 170  C and 50 rpm in the mixing
chamber (69 cm3) of a Thermo Scientific Haake Rheomix OS
with counter-rotating roller rotors.
The biocomposites formulations were manually cut into 3
mm particles and dried in a vacuum oven for 3 h at 80  C. Then
they were molded by compression in sheets of 150  150  2
mm in a hydraulic press Marconi MA098/A, at 180  C for 8 min
(3 min under a pressure of 3 Kgf and 5 min with 6 Kgf) After
pressing, the plates were immersed in an ice bath and dried
with absorbent paper. All characterizations and performance
evaluation tests were performed on workpieces taken from
these compression molded plates.
A Shimadzu's universal machine, model AG-X 10 KN, was
used to carry out the tensile test, following ISO 527e2 standard
(1993). The speed used in the was 5 mm/min. The tensile
strength data are based on the arithmetic mean and standard
deviation of 05 specimens for each composition.
The microstructures were accessed using a Zeiss LEO
scanning electron microscope at a voltage of 20 kV under a
high vacuum. The fibers, natural and treated, were glued in
a carbon ribbon and gold-sputtered for secondary electron
mode analysis. The fractured surface observation of the
composites workpieces was carried out after immersed in
liquid nitrogen for cryogenic fracture and subsequent gold
sputtering. DSC scans were acquired from a Shimadzu DSC-
60H, the applied thermal program was heating from room
temperature (~23  C) to 190  C, isothermal at 190  C for 3
minutes, cooling to 30  C and re-heating to 190  C, the
heating/cooling rate was 10  C$min
1, under inert nitrogen
atmosphere at 50 mL$min
1. The degree of crystallinity
(Xc) of reference matrices and their composites with BM
in natura, as well as after each route were measured using
Eq. (1).
DHm 100
Xc ¼ *
DH100% w
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 5 : 3 1 6 1 e3 1 7 0 3165

Fig. 5 e Microstructure, as seen by SEM, of the BM fillers.

Fig. 6 e Microstructure, as seen by SEM, of the BM compisites.

Where: is the melting enthalpy, ¼ 146 J$g
1 (assumed as the

melting enthalpy for 100% crystalline PHB [18DSC] and w is
PHB weight fraction.
Melt flow rate (MFR) measurements of reference matrices
and their composites with BM in natura and after each route
were performed in triplicate, using a Ceast model 7023
plastometer, according to ASTM D 1238. Testing parameters
were 2.16 kg at 180  C with intervals of 6 seconds for melt
cutting. Previously, samples were vacuum dried for 3 hours
at 80  C.
3. Results and discussion
Table 2 shows the wax removal rates and moisture contents,
the BM in natura presented 8.5 wt% of extractives, corrobo-
rating with the first stage of decomposition process shown in
thermogravimetric curve in Fig. 3 that is related to moisture
and other small molecular species content of filler. In ther-
mogravimetric curve we also observe about of 25% of residue,
which is, probably, ash and carbonaceous residue from fibers,
3166 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 5 : 3 1 6 1 e3 1 7 0
minerals and other components [2]. BM treated by route 1
(Surfactant washing) presented 2.9% of extractives content,
which is attributed to non-fibrous constituents and residual
wax [14]. Although less efficient in removing extractives,
detergent treatment presents a lower environmental impact
besides cheaper than the organic solvent. The moisture rate
on the samples indicates that only organic solvent treatment
changed the hydrophilicity of the natural BM, suggesting
higher hydrophilic groups exposure on the filler surface,
corroborating to the residual extractives content found for BM
treated by route 2.
Fig. 4a addresses the FTIR spectra of natural BM and treated
via route 1 and 2. The wideband ranging from 3328 to
3600 cm
1 is due to free hydroxyl groups, associated with
cellulose and starch components of BM [18,20]. Displayed
bands in the range from 2800 to 3000 cm
1 are attributed to
CeH stretching vibrations. Related to FTIR bands in the region
between 1200 and 600 cm
1, they are attributed to carbohy-
drate vibrations, while between 912 cm
1 and 1080 cm-1 to the
CeOH stretching [21,22]. Around 1610 cm
1, absorption bands
are due to adsorbed H2O in MB [22]. It is noteworthy that bands
in 1700e1750 cm
1 region, characteristic of hemicellulose and
lignin, were not verified in FTIR spectrum of natural BM in,
indicating that aldehydes, ketones, acids, and esters are ab-
sent or below the equipment detection limit [23,24].
The spectra of BM in natura and the wax extracted from BM
are shown in Fig. 4b. In general, the spectrum of the wax from
BM did not present new bands, and carbonyl bands in the
region of 1700e1750 cm
1 were absent. The wideband ranging
between 3600 and 3100 cm
1 is due to the (n-OH) stretch,
which probably comes from starch, one of the extractives
components [12,21]. The spectral region between 2980 and
2850 cm
1 corresponds to (n-CH) of sp3 carbon type. At
1633 cm
1 is observed an absorption band related to (d)
deformation of (d-COH) bond usually found in biopolymers.
Displayed bands in the range from 1200 to 912 cm
1 corre-
spond to (n-CO) bonds, and in the range between 878 and
400 cm
1 are due to (d-CH) deformations in monosubstituted
aromatic rings. These bands from wax BM are proper to
characterize it as a nonpolar component [22,23], corroborating
with the increased hydrophilicity of BM filler after route 2
(Table 2).
SEM images in Fig. 5 present spherical particles, as already
observed by McCrum et al. [25]. BM aggregation was verified
after physicochemical treatments, being more pronounced in
route 1. Probably, partial wax removal from the filler surface
made them sticky, favoring coalescence. Subtle roughness is
verified in treated BM fillers since the initially smooth surface
is not observed afterward.
Fig. 6 shows the microstructures as seen SEM images of all
six investigated biocomposites compositions. In all micro-
structures, is possible to verify the uniformity in the disper-
sion of BM fibers throughout the PHB matrix. It was also
verified a lack of aggregates, indicating that melt processing
was adequately carried out in order to avoid aggregates.
At the interface, there are voids around the BM filler, and
consequently, several BM particles were pulled out from the
PHB matrix. The low interfacial adhesion between different
kinds of BM fillers and PHB matrix suggests a poorly affinity
between these components [25]. Since the BM particles
remained in the form of granules dispersed in the PHB matrix,
the starch gelatinization did not occur during melt processing,
which characterizes a particle with a rigid and brittle matrix
[4]. The wax extractives vaporization at processing conditions
may also have contributed partially to this behavior, mainly,
in compositions from 1 to 4. As pointed out in the literature
[11,12], at melt processing temperatures, extractives may tend
to migrate to the natural particle/polymer matrix interface,
contributing to voids observed. The coupling agent (MAPE)
addition did not improve the filler/matrix interface, regardless
of BM treatment, indicating its poor efficiency as a coupling
agent for PHB/BM biocomposites.
As a result, composites with lower mechanical properties
than reference matrices will, probably, be produced [26,27].
Moreover, subtle porosity increases for detergent treated BM
composites was observed (Fig. 6ced), which may be associated
with the volatilization of residual surfactant from the filler
surface.
According to DSC data, showed in Table 3, BM addition
regardless of the performed treatment, as well as the coupling
agent addition reduced Tc of PHB. That can be translated at
hindered crystallization of PHB-MAPE matrix and PHB com-
posites with different kinds of BM fillers [24]. PHB-MAPE ma-
trix and PHB and PHB-MAPE composites with different kinds
of BM fillers displayed lower Tm than PHB, indicating a slight
reduction in their crystal perfection [24,28]. Additionally, PHB
composites with treated BM (PHB/BM by route 1 and PHB/BM
by route 2) presented higher Xc than PHB matrix and PHB/BM
composite. Table 3 reports melting and melt crystallization
parameters of PHB, PHB-MAPE, and their composites with BM
in natura and treated BM.
A significant increase in Xc was also observed for compo-
sitions 4 and 6, which might contribute to improving their
mechanical properties relative to the reference matrix
[29e31]. BM filler treated by route 1 displayed a slight nucle-
ating effect on the matrix, which can provide faster and lower-
cost processing.
The thermal behavior observed corroborates with the role
of proteins, lipids, and phenolic compounds in inhibiting
retrogradation of amylose and also with the plasticizing effect
of lipids in the starch matrix, both resulting in a less crystal-
line starch matrix, as it had already been observed by Maniglia
et al. [22]. Nevertheless, in the present study, these effects
were reflected on the PHBad matrix compounded with BM in
nature (compositions 1 and 2), mainly, if compared with
Table 3 e DCS parameters of the compositions.
Compositions Tm ( C)a Tc ( C)b Xc (%)c
PHBad 180.6 103.2 56.6
PHBad-MAPE 159.5 96.1 52.8
1 166.1 98.5 57.2
2 173.8 107.8 62.4
3 169.8 94.8 69.4
4 169.5 102.2 72.3
5 167.8 101.4 67.3
6 169.5 89.6 70.2
a
Tm: melting temperature.
b
Tc: crystallization temperature.
c
Xc: degree of crystallinity.
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 5 : 3 1 6 1 e3 1 7 0
Fig. 7 e Torque versus time curves of matrices and their composites.
respective biocomposite with treated BM. Among extractives,
the lipids might have the major contribution, since no sig-
nificant differences were observed between the two routes of
treatment.
PHB is a rigid polymer and so, right at the beginning of the
mixing process in the rheometer chamber, it exhibits a high
torque (Fig. 7a), which would make it difficult to mix with the
BM particles in the initial moments of mixing. Therefore, it
was necessary to carry out an additive in the PHB (PHBad)
which resulted in the reduction of the initial torque in the
mixing process. In addition, PHBad was mixed with MAPE
Table 4 e Melt flow rate of the compositions.
Compositions MFR (g/10min)a
1 2.5 ± 0.4a
2 2.0 ± 0.3a
3 2.7 ± 0.3a
4 2.1 ± 0.3a
5 3.5 ± 0.7a
6 3.0 ± 0.7a
a
Values are given on average ± SD. Values with same
lower superscript letters are not statistically significantly
different at type I error (a) of 0.05, using the Turkey-
Kramer test.
3167
compatibilizer (PHBad-MAPE) in order to verify its effect on
the properties of the composites, which also resulted in a
decrease in the initial mixing torque compared to pure PHB
and PHBad. Based on this result, PHBad and PHBad-MAPE were
used as matrices for the production of composites. The torque
flow versus time curves of the composites indicates that the
presence of MAPE in the composite containing BM in nature
(Fig .7b) made its mixing more difficult due to the increase in
torque, peak width, and time to reach the steady state of the
mixture. . This behavior is an indication of interfacial inter-
action between the reinforcement and PHBad-MAPE. On the
other hand, for composites containing BM (routine 1) (Fig. 7c),
the addition of MAPE had little effect on the mixing process of
these composites, which were practically equal in terms of
peak width and time to reach the state mixing stationary. The
BM composites after soxhlet treatment (sample 6) (Fig. 7d)
show intermediate behavior in terms of torque and time
required for the homogenization of the mixture in relation to
the other composites.
Gathered data for mechanical properties are presented in
Fig. 8. BM additions to PHB matrix, regardless of treatment
applied, reduced PHB tensile strength, due to low interfacial
adhesion between different kinds of BM fillers and PHB
[12,16,19,32], as shown in Fig. 6.
The elongation at break behaved analogously to PHBad
matrix independent of the kind of BM filler used. It suggests
3168 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 5 : 3 1 6 1 e3 1 7 0
that neither the observed porosity on the matrix, nor the re-
sidual extractives content of BM by route 1 (composition 3)
affected its mechanical properties. For PHBad-MAPE com-
posites, the BM by route 2 (composition 6) presented similar
elongation at break relative to respective PHBad-MAPE matrix.
All other PHBad-MAPE composites improved their elongation
at break relative to reference matrix. Again the MAPE effect on
tensile strength was reproduced in elongation at break of
composites.
The coupling agent (MAPE) addition to PHBad reduced tensile
strength, an indication of poor compatibility between compo-
nents. Nevertheless, MAPE addition to PHBad composites with
BM promoted increased tensile strength relative to respective
MAPE-free composites (compositions 1, 3 and 5). Otherwise, the
PHBad-MAPE composites have similar or greater tensile
strength compared to reference matrix (PHBad-MAPE). These
results suggest that starch hydroxyls groups from BM surface
favors physicochemical interaction with the maleic anhydride
part of coupling agent by means of strong ester linkage, result-
ing in starch granules more stronger and flexible than starch
granules without MAPE addition [7,9,10,16,32]. As a result,
despite poor interfacial adhesion between BM particles and
polymer matrix, composite properties were improved.
As PHBad-MAPE biocomposites with BM in nature (compo-
sition 2) exhibited the best tensile strength and elongation at
break among all PHBad biocomposites, and PHBad with BM in
nature (composition 1) the second highest tensile strength of
prepared biocomposites, these behaviors might have contri-
bution of lipids and proteins (extractives) present in the nat-
ural filler. As evidenced in thermal analysis (Table 3), the lipids
have plasticizing effect on starch matrix [6]. Therefore, the
starch from BM in nature is more flexible than starch from
treated BM. On the other hand, zein protein has been suc-
cessfully used as coupling agent for natural fibers and hy-
drophobic polymer matrices [15,19,21], and any further effect
of BM flour proteins in composite compatibilization is a hy-
pothesis that cannot be disregarded. Mainly, because the
worse mechanical performance was just acquired for PHBad
composites with BM prepared by route 2, and the nonpolar
nature of extractives [26,27] was confirmed by FTIR analysis
(Fig. 4B).
Fig. 8 e Tensile strength and elongation at break of the
compositions.
The Melt Flow Rate - MFR data for the compositions are
presented in Table 4. The coupling agent addition, i.e., stearic
acid, modified flow properties of PHB-MAPE composites with
different kinds of BM fillers (compositions 2, 4 and 6) relative
to PHBad composites. MFR data are almost similar since they
are into standard deviation intervals. Thus, interaction dif-
ferences between BM in natura and treated BM with PHB ma-
trix, as verified in the tensile strength test, could not be
confirmed through MFR experiments.
Only the MFR of composition 5 composite showed a slight
increase relative to the others. Higher MFR may be associated
with higher BM (treated by route 2) hydrophilicity (Table 2) and
PHB susceptibility to hydrolysis [14]. Furthermore, there is also
the moisture plasticizing effect in starch viscosity during melt
processing [8]. Moisture acts as starch plasticizer, forming
strong bonding interactions with starch, weaking starch chain
interactions and facilitating movement among starch mole-
cules [8]. Nevertheless, the observed lipids plasticizing effect
in the solid state of compositions 1 and 2 (Table 3) did not
prevail in the molten state. Another approach can be associ-
ated with the lower content of total phenolic compounds in
the PHBad and PHBad-MAPE composites with BM filler treated
by route 2 [6], as compared to the BM in nature. Nevertheless,
this hypothesis can be neglected because only a small amount
of phenolic compounds have been enough to provide the
antioxidant activity for starches with different phenolic
compounds content [6]. However, in the couple agent (MAPE)
presence, the increased MFR of composition 6 was not sig-
nificant compared to the PHB-MAPE matrix. Probably, some
interaction of MAPE with BM (route 2) may have subtly
contributed to increase composite viscosity [32], counter-
balancing the above-mentioned opposite effect of increased
BM hydrophilicity, discussed for composite 5. Moreover, MAPE
addition significantly reduced the MFR of PHBad-BM in nature
composites, increasing the viscosity of these composites (1
and 2), as also observed in the torque curves (Fig. 7b). From
this point of view, a possible hypothesis is that there is an
improvement in the physicochemical interaction of MAPE
with BM in nature, and consequently an improvement in the
tensile strength data of PHBad-MAPE composites with BM in
nature. Although the single addition of MAPE reduced MFR of
PHBad matrix and PHBad composite with BM in natura, this
decrease was not within the same order of magnitude than
those pointed out for MAPE addition to PHBad composites
with treated BM.
4. Environmental impacts
In view of these results, it is possible to conclude that the
compound with the treated fiber improves the adhesion in the
polymer matrix, the treatment by
Soxhlet exhibited better removal of wax, however the
treatment by a surfactant is an environmentally correct
alternative that can be used, besides saving costs produc-
tion and favoring environmental aspects, reducing the use
of solvents, reduces the risk of possible diseases such as
organic psycho syndrome (PSO) that is developed by
exposed employees, with great frequency of handling sol-
vents [31].
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 5 : 3 1 6 1 e3 1 7 0
The use of natural fibers contributes to the development of
new products of environmentally friendly technology, allow-
ing to mitigate environmental impacts related to the irregular
degradation of the environment.
5. Conclusions
From the use of BM in the polymer matrix, it was possible to
develop all biocomposites, reducing manufacturing costs and
valuing natural filler. The ecological biocomposites developed
have emerged as an alternative raw material for application in
plastic wood composites without any further treatment, since
composition 2 has shown the highest tensile strength among
the biocomposites. Results showed promise of using BM
additivated with MAPE as an all-natural, environmentally
friendly, and cost-effective filler for PHB matrix.
The BM treatment by route 2 altered its hydrophilicity and
successfully removed non-polar components from natural
filler, which showed to have an important role in bio-
composite compatibilization. Despite the low compatibility of
MAPE with PHB, in the added content, the addition of MAPE
increased the tensile strength of PHBad composites with the
treated BM. In addition, PHBad-MAPE composites resulted in
tensile strength similar to or higher than the PHBad-MAPE
matrix. Therefore, MAPE acted as an effective additive for
BM fillers, probably, due to reactive processing with the starch
polar surface groups.
Since BM was abundantly and cheaply available, its use in
blending with PHB and MAPE additive will result in biode-
gradable material with similar mechanical properties of neat
PHB and concomitant reduction in cost. Nevertheless, for a
completely biodegradable material, it might also be used, for
example, as a coating material for food packaging.
Declaration of Competing Interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgment
The authors are grateful for the funding of the Coordination
for the Improvement of Higher Education Personnel - CAPES
and the National Council for Scientific and Technological
Development CNPq, within the framework of the Post-
graduate Program in Materials Science and Engineering.
Especial thanks to all raw materials suppliers and technical
staff of the university. The support was essential to carrying
out the present work.
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