Fibers and Polymers 2021, Vol.22, No.

11, 3203-3211 ISSN 1229-9197 (print version)

DOI 10.1007/s12221-021-0843-y ISSN 1875-0052 (electronic version)

Study on Mechanical and Thermal Properties of Amazon Fibers on the

Polymeric Biocomposites: Malva and Tucum
Juliana dos Santos Carneiro da Cunha1, Hilton Eduardo de Oliveira Neto1, Virginia Mansanares Giacon1,2,
Lizandro Manzato1,3, and Cristina Gomes da Silva1,4*
1
Postgraduate Program in Materials Science and Engineering, Federal University of Amazonas, 69080-900, Brazil
2
Materials Engineering Department, Federal University of Amazonas, 69080-900, Brazil
3
Federal Institute of Education, Science and Technology of Amazonas, 69075-351, Brazil
4
Department of Physics, Federal University of Amazonas, Manaus, 69080-900, Brazil
(Received July 20, 2020; Revised February 24, 2021; Accepted March 1, 2021)

Abstract: Amazon region found abundant vegetal fibers with diversified properties to the application. Tucum and malva
fibers regularly obtained in this region were applied as reinforcement in the polymeric biomatrix and as a substitute for
synthetic materials. Castor oil was used as the polyol to prepare the polyurethane biomatrix (PU). Amazon fibers were
incorporated in this biomatrix using high proportions (30, 50, and 70 wt.%; 30 mm length), TPU (tucum polyurethane
composite), and MPU (malva polyurethane composite). This study valorized regional materials and substituted synthetic
products by renewable source materials. The fibers’ characterization results showed a high cellulose percentage, promoting
high crystallinity values by XRD (X-ray diffraction) results (67.5 % for malva and 60.0 % for tucum). SEM (Scanning
Electron Microscopy) images revealed the arrangement/thickness of the fibers, as well as the composite morphology.
Thermolysis and mechanical properties investigate the composites in which the natural fibers were incorporated into the
polyurethane matrix in large percentages, maintaining the main properties. The composites presented high impact Izod
values, as 550 J m-1 for TPU-70 wt.% and 452 J m-1 for MPU-70 wt.%. In general, composites prepared with a high content
of natural products from renewable sources showed promising performances in the applied tests, with excellent potential for
replacing engineering materials.
Keywords: Malva, Tucum, Castor oil, Polyurethane, Composite

Introduction
The vegetal fibers are diversified and abundant in the
Amazon Region, and their acquisition was relatively easy at
Ong’s (non-governmental organization) or popular markets.
These fibers have a diversified property, which is an
attraction to the science and technology areas. Comprehending
these fibers’ main components and structure facilitates their
direct application in engineering materials (as reinforcement
fibers) or extraction of the major components (cellulose and
lignin) for later applications. Based on these arguments, this
study with composites applied malva and tucum fibers from
the Amazon region.
Tucum fibers grow into the Amazon rainforest in the
western region, from Venezuela to Peru and western Brazil;
their scientific name is Astrocaryum chambira Burret [1,2].
However, the fibers are manually extracted from the palm
tree, separated by the leaf vein, and being forcefully pulled
out at a bending point [1]. In Brazil, native indians from the
Tikunas tribe (localized between the county of Tabatinga and
São Paulo de Olivença on Amazonas state and at the border
with Acre State) cultivate the tucum trees [3,4].
Malva is a fibrous plant from the Malvaceae family
(Urena Lobata Linn) and is easily found in the Amazon
Region, Pará, and the Amazonas States, where the clime is
*Corresponding author: cristinaggs@gmail.com
propitious to the grown of this plant, humid and hot. Malva
is a similar plant to ramie; both are cultivated together in this
region. It is an essential plant in the economics of the local
people and the market. Previous works present promising
results, with excellent properties, chemical and mechanical
resistance [4-6].
Renewable natural resources are a source of energy and a
feedstock to produce new materials, and it has been
increasing in considerable proportions every year [7,8].
Sustainable materials have been the research centers’
motivation due to the scarcity of nonrenewable resources,
bio-friendly, and bio-degradability products [7,8]. The
vegetal fibers widely used as a reinforcement in polymer
matrices it is constituted by two main macromolecules:
cellulose and lignin. In this study, tucum and malva fibers
[2,9], typically from the Amazon region (purchased in the
municipal market of Manaus), were used as reinforcement of
polyurethane/castor oil polymer [10,11].
Several researchers have studies composites reinforced
with natural fibers [12-15]. The substitution of the synthetic
fibers and matrices by natural products, maintaining their
properties, is relevant to obtaining biomaterials with easy
biodegradation [4]. Mechanical properties are the studies'
principal focus, influenced by other factors, such as tenacity,
tension fibers, interface interactions (between fibers and
matrix), impact resistance, and others [3,16-18].
The rich nature of the hydroxyl groups presents in the

3203
3204 Fibers and Polymers 2021, Vol.22, No.11
vegetal fibers’ structure is a relevant point to interact with
the matrices with different chemical structures [19]. The
matrix used in this study uses isocyanate and polyol from
castor oil, resulting in a polyurethane matrix with high polar
group content. In this case, castor oil is a derivative of
natural and renewable sources [6]. Besides, a vegetable
triglyceride, which has hydroxyl groups in its structure, is
currently used as a try-functional polyol [15]. Both matrix
and fibers have a high content of the polar and compatible
groups, favoring the interaction in the interface region.
This study mainly aggregates the value of the vegetal
products cultivated by the local population of north Brazil
and their contribution to the polyurethane resin’s contribution
to producing biocomposites. Amazonian fibers reinforcing
polyurethane composites based on castor vegetable oil were
studied, varying the fibers type and percentages. Malva and
tucum vegetable fibers, regularly found in the Amazon
region, were used as a substitute for the synthetic products
and reinforce the matrix, to prepare bio polyurethane
composites. In this same proposal, the castor oil was
partially substituted for the synthetic polyurethane polymer.
The fiber’ proportion was variated from 30 to 70 wt.% for
both fibers. Mechanical, thermal, morphological, and
chemical properties characterized the fibers and composites.
In general, the composites exhibited to employ as a
substitute for the total synthetic composite planes.
Experimental
Materials and Methods
For this study, tucum and malva fibers, purchased in the
municipal market of Manaus, were previously collected
from native forests by local communities. Both fibers were
used to reinforce the polyurethane/castor oil polymer (1:2)
(kindly provided by Plural Química Industry, São Carlos, SP,
Brazil).
Fibers Preparation
The fibers were washed in the hot water bath, 70 oC/1 h,
to remove the impurities and sugar. After the extractives
were extracted by the reflux system (balloon reaction and
Soxhlet), directly in a solution of ethylic alcohol (92.6 %)
and acetone (P.A.), 95:5 v/v proportion; enough volume to
cover the fibers. The system was heated at 70 oC/1 h under a
magnetic stir to remove the grace acid and residual sugars.
This pretreatment is relevant to clean the fibers and improve
the interface interaction with the resin. The fibers were
washed with distilled water and dried in an air-circulated
stove (80 oC) until constant weight. Previously to incorporated
in the resin, the fibers were cut at around 30 mm and dried at
105 oC for 4 h.
Composite Preparation
The composites, TPU (tucum polyurethane composite)
Juliana dos Santos Carneiro da Cunha et al.
and MPU (malva polyurethane composite), were prepared
by mixing the PU prepolymer and castor oil (CO) firstly, in
the proportion of 1:2 (MDI:OH - w/w, respectively). Next,
the prepolymer (PU-CO) impregnated the fibers in different
proportions 30, 50, and 70 wt.% dry fibers. The mixture was
made by hand and laboratory tweezers for a few minutes (no
more than 8 minutes), resulting in a homogeneous mixture,
and quickly distributed into the metallic mold (coated with a
Teflon film, 0.2 mm), and it was kept in a hydraulic press at
120 bars/120 oC, during 20 min. Before demolding, the
composite was maintained in the mold at room temperature
for 15 minutes, around 75 oC. After demolding, all composites
were kept 48 h at room temperature before analysis.
Malva and Tucum Fibers Analysis
Chemical Composition
The chemical characterizations results correspond to the
total composition of the fibers. The three samples’ average
values, humidity free, and the extractives were removed
before characterizations. All TAPPI Standards were adapted
to characterize the lignocellulosic fibers. TAPPI 413 om-02
method was applied to determine the ash content by
considering the calcination at 800 oC for 4 h.
TAPPI T13-m-54, TAPPI T19m-54, and ABNT (Brazilian
Association for Technical Standard, NBR9656) standards
determined the total amount of lignin (soluble and
insoluble), holocellulose and α-cellulose, and moisture
content of the fibers.
Attenuated Total Reflectance Fourier Transform Infrared
(FTIR) Spectroscopy
Powder samples (fibers and composites, 100 mg) were
performed to FTIR spectroscopy using a Shimadzu
spectrometer (IRAffinity-1s) equipped with a prism ZnSe
attachment. Scanning was conducted from 4000 cm-1 to
500 cm-1, with 32 scans on average for each spectrum. All
powder patterns were previously dried at 105 oC for 4 h.
Crystallinity Index
Both fibers were analyzed by XRD (X-ray diffraction)
using Panalytical equipment (model Emperyan), under the
conditions: Cu-kα, 1.54056 Å, 40 kV, 30 mA, 3 o < 2θ <
50 o, 0.015 o and a counting time of 100 s at each 1.05 o. The
crystallinity index (CI %) was calculated by equation (1),
according to Segal method:
 I200  –  Iam 
% CI = ---------------------------
-  100 (1)
I200
where I200 represents the maximum peak intensity
corresponding at (200) plane, and Iam is the value of the
minimum intensity for the amorphous cellulose (valley
between (200) and (110) planes).
Thermal Analysis
Thermogravimetry (TGA) and differential scanning
calorimetry (DSC) were carried out using a TA Instruments,
model SDT Q600 with module DSC-TGA Standard. The
Biocomposites of Amazon Fibers: Malva and Tucum
samples were heated from room temperature to 600 oC with
a heating rate of 10 oC min-1 under a nitrogen atmosphere,
air flowing at 30 ml min-1.
Composite Characterizations
All composites were characterized by thermal analysis
techniques (TGA and DSC) and FTIR, as previously
described for the fibers. Besides this, the composites were
evaluated by Izod impact strength and water absorption,
following ASTM D256 (American Society for Testing and
Materials - Standard test method for unnotched Izod impact
strength) and ASTM D570-98 (Standard Test Method for
Water Absorption of Plastics), respectively. Izod impact
strength was carried out at Tinius Olsen 92T equipment
(kindly carried out by AvanPlas - Polímeros da Amazônia
Ltda, in Manaus - AM, Brazil) with a pendulum (energy
5.6 J), and automatic results calculated. Equation (2)
calculates the water absorption (% WA) test results by the
weight difference.
wfinal – winitial
% WA = ----------------------------
- (2)
winitial
The diffusion mechanism study and kinetics were
performed based on Fick’s law. This model is well-described
by Megiatto et al., firstly apud by Espert et al. [20,21]. The
diffusion behavior in polymers can be classified according to
three different categories, following well described by
Espert et al. [20]. In general, this classification discusses the
relative mobility of the polymer segments, mobility
Figure 1. Malva and tucum fiber characterizations; (a) standard chemical characterizations, (b) SEM surface morphology, and (c) DRX
results (crystallinity index and main peaks).
Fibers and Polymers 2021, Vol.22, No.11 3205
development of a boundary, and penetration mobility of the
water into the polymer. The diffusion cases can be
distinguished by the experimental values fitted using
equation (3):
M
log -------t = log  k  – nlogt (3)
M
where Mt is the moisture content at time t; M∞ is the moisture
content at the equilibrium, and k and n are constants.
The theoretical model performs the diffusion coefficient
(D) analysis, which shows the solvent molecules’ ability (in
this case, water molecules) inside the composite structure.
This coefficient is the most crucial parameter of Fick’s law
inserted in equation (4):
M 0.5
-------t = --4-  D
---- t
0.5
(4)
M L   
where L is the thickness of the samples.
Scanning Electron Microscopy (SEM)
All samples, fibers, and composites were surface-
metalized by a sputter coating (BAL-TEC, SCD 050 Sputter
Coater) with a thin gold thickness (10 nm) and analyzed by
SEM (ZEISS, model Leo 435 VP) at an acceleration voltage
of 15 kV.
Results and Discussion
Both fiber composition results, malva and tucum, are
3206 Fibers and Polymers 2021, Vol.22, No.11
according to lignocellulosic fibers results showed in the
literature, as reported by Fonseca et al. [22]. The fibers
showed results corresponding to the majority components,
as listed in Figure 1a. Both fibers presented a high value
concerning the cellulose content 58.80 % (±2.90) and
68.23 % (±0.04), respectively, an excellent result than the
values reported in the natural fibers’ literature. Fibers with
high cellulose content are desirable properties to the
extraction and production of nanofibers and nanocrystals.
Moreover, the cellulose content provides high tensile and
flexural strength to lignocellulosic fibers, which is excellent
for reinforcement in composite materials, as demonstrated in
the literature [3,16,23].
Tucum is a fiber well used in the Amazon region by local
producers and regularly applied as handicrafts, the reason
why it is still rarely mentioned in scientific studies. Malva
fibers are commonly applied as a reinforcement in composite
materials than tucum. Their chemical and mechanical
characterization is poorly described in the literature because
the malva plant has a relevant pharmacological property
[24,25]. Several countries commonly use malva plants in
traditional medicine, as Turkey, Iran, Italy, Bulgaria, Albanian,
and others. Their relevant properties are antimicrobial,
antioxidants, antidiabetic, anti-inflammatory activities, and
others. The malva types M. parviflora and M. sylvestris are
commonly used to obtain the extractives against anti-
inflammatory and wound healing activity [26,27].
Fonseca et al. [22] report scientific studies about tucum
fibers; the results showed that this fiber presents 75.5 wt.%
of the cellulose and only 3.8 wt.% insoluble lignin. The
difference observed between fibers and their chemical
compositions can be mainly related to the species, weather
conditions, soil type, and other fibers’ characteristics (age or
extractives). All fibers cultivated in the Amazon region are
considered seasonal plants; the clime is very intense and
defined, alternating between rain and intense drought periods.
Morphological studies of the fiber surfaces have been
available by SEM. The images displayed in Figure 1b are
revealing the arrangement and medium fiber’s thickness
118.9±3.5 µm and 82.3±2.3 µm, malva and tucum fibers,
respectively. Following Fonseca et al. [22], microfibrils
diameter measured was 19.8±4.3 µm, which presents a high
mechanical performance in concerning tension strength
360±146 MPa, elongation of break 11.0±3.6 %, and modulus
elongation 4.3±2.7 GPa. Similar properties about the malva
fibers are listed in the literature by Branco et al. [28],
concerning tension strength 297±89 MPa, elongation 5±2 %,
diameter 45±15 µm, specific gravity 1.48±0.01 g/cm3, and
moisture 11.0±0.5 % [28]. All results are relevant to
compare and complement this study proposed.
Images show similar superficial morphology, smoothly,
and a longitudinal section with slots. The relevant properties
that favor their application as a reinforcement in composites,
due to the easy interaction with pre-polymers matrix, during
Juliana dos Santos Carneiro da Cunha et al.
the impregnation process, as seen in the studies with other
fibers described in the literature [29,30]. The interface
region's condition is relevant in the composite material,
which occurs the physical and chemical interactions that will
support the mechanical solicitations.
Crystallinity index patterns were determined by DRX
analysis (Figure 1c), exhibiting mainly intensities at
2θ=18.5 o and 22.6 o, minimum and maximum reflection
planes, respectively, corresponding to the crystal region of
the fibers. From the spectra results, the crystallinity index
calculated was 68.56 % and 79.34 %, malva and tucum
fibers, respectively. The DRX curves were observed subtle
peaks at 15 o and 35 o relative to amorphous regions of the
lignocellulosic fibers [31-33]. The literature showed the
different parts of the tucum plant, with a crystalline fraction
of 39 to 56 %.
Malva fibers show only one peak at 15.6 o, which possibly
is corresponding to the two overlapping diffraction peaks as
observed in the tucum curve, at 14.8 o related to (010) or
(1-10) planes (probably corresponding to cellulose Iα and
Iβ, respectively). The second peak in this region, at 16.3 o
related to (001) or (110) planes is probably corresponding to
cellulose Iα and Iβ, respectively. This behavior is directly
related to the amorphous region contribution of cellulose.
Besides the difference, both results exhibited a sharp peak
at 2θ=22.6 o, with an interatomic distance of 4.835 Å
(following Bragg Law), corresponding to the (011) or (200)
lattice plane if the cellulose is the type Iα or the type Iβ,
respectively, indicating higher crystallinity [33].
TGA analysis (Figure 2) for both lignocellulosic fibers
started with a loss mass at around 45-60 oC, due to moisture
content corresponding to superficial and intermolecular
water. Intra or structural-molecular water evaporates above
200 oC, which are present between the molecular chains,
strongly bound to the structure chains. TGA and DSC
analysis indicated the thermal stability of all fibers around
250 oC. From 270 oC, the onset temperature of thermal
decomposition of the holocellulose (both hemicellulose and
cellulose) until around 370 oC, approximately. From 400 oC,
the last peak was observed, above 500 oC, corresponding to
the protolignin decomposition (lignin present in the natural
fibers); DSC confirms these events already well described in
the literature Silva et al. [12,13,34,35].
In general, the fibers’ thermal characterization incorporated
into the polymer matrix presents the events that correspond
to the fibers superposed by the matrix’s events. This result
occurs because structures are present at both materials,
matrix and fibers, carbon long chains, hydrogens, and
oxygens, besides the different structures. When the
polymeric resin well involves the fibers, the fusion of both
structures simultaneously occurs, according to the temperature
increases.
Generally, a polyurethane structure is composed of
hydrogen bonds and the chain extension with NH, CO
Biocomposites of Amazon Fibers: Malva and Tucum Fibers and Polymers 2021, Vol.22, No.11 3207

Figure 2. TGA/DTG and DSC curves of the results; (a) malva fiber and (b) tucum fiber (N2 atmosphere rate: 20 ml min-1; heating rate: 10 oC
min-1).

Figure 3. Thermal analysis (TGA/DTG and DSC) of the composites, PU-CO (polyurethane with castor oil) reinforced with (a) malva and
(b) tucum fibers (50 wt.%); from room temperature to 800 oC; the rate of 10 oC min-1; N2 atmosphere: 30 ml min-1.

groups of the urethane bond or oxygen present in another
flexible segment [29]. Figure 3 presents the thermal analysis
(TGA/DTG and DSC) curves of the composites. The results
showed that the degradation temperature occurred at 342 oC
(TPU 50 wt.%) and 352 oC (MPU 50 wt.%). In comparison,
the onset temperature for both biocomposites is around
264 oC, a few degrees below the fibers’ onset temperature.
This result is indicative that the process does not degrade the
fiber structure considerably when in the polymeric matrix.
All events were detected by the DSC analysis, as observed in
the curves of both graphs in Figure 3.
Following the literature, the results described by Oliveira
et al. [29] corresponding to the PU-OM matrix show the
peak of the thermal degradation between 320-350 oC. These
results confirmed that until around 300 oC the composite
stability was maintained due to the natural fibers were well-
covered by the polymer matrix preserving the materials, do
not decrease the temperature.
Besides, the events above 400 oC correspond to flexible
segments and polyol residual from the degradation step and
the partial lignin degradation. After 600 oC, the total thermal
degradation occurs, corresponds to amines, phenol groups,
and aromatic ring structures from both fibers and matrix.
All composites reinforced with tucum and malva fibers
were characterized by Izod impact strength, presenting a
gradual increase in the values, according to the increase of
percentage fibers, as presented in Figure 4.
Composites reinforced with tucum presented the best
results for all compositions concerning the composites with
malva. Impact strength values were 21, 26, and 18 % higher
for TPU than MPU, between the composites 30, 50, and
70 wt.%, respectively.
Evaluating all results previously showed, the tucum fibers
reported a difference in their chemical composition about the
malva fibers. The relevant difference showed cellulose
percentage and their crystallinity index, 12.6 and 13.2 %
higher for tucum than malva fiber (Figure 1). When
combined, both properties confer more resistance to natural
fibers, consequently improving the transference energy
mechanism between fiber/matrix, and hence the mechanical
properties, as seen in this case (Figure 4).
It is essential to highlight some points about composites
3208 Fibers and Polymers 2021, Vol.22, No.11 Juliana dos Santos Carneiro da Cunha et al.

Figure 4. Izod impact strength and SEM images (interface of the composites) results of the PU composites reinforced with tucum and malva
fibers (30, 50, and 70 wt.%, 30 mm). Malva: the lowest standard deviation was ±27 Jm-1 (at 50 wt.%) and the highest was ±39 Jm-1 (at
70 wt.%), tucum: the lowest standard deviation was ±23 Jm-1 (at 30 wt.%) and the highest was ±2.0 Jm-1 (at 50 wt.%).

reinforced with natural fibers, that in general, the composites
do not present homogenous results. Comparatively, the
impact strength results increased and showed excellent
values to composites with 50 and 70 wt.%. This quantity of
the natural fibers reinforcing a polymeric matrix is relevant
to substitute the synthetic material, maintain or improve
mechanical properties. Also, the polymeric matrix,
polyurethane, used in this study, has around 66 wt.% of the
castor oil from a renewable source. They turn this composite,
almost a green material, having less than 20 wt.% of the
synthetic material, into the composite with 70 wt.% fibers.
All samples showed a fiber bridge after the Izod impact
test, then the fibers were carefully separated, prepared for
SEM analysis, and this region performs the images. Figure 4
shows the SEM images of this fractured region. Images
show the covering of the resins’ fibers, and the interface
region was easily seen in the composites with fibers 30 and
50 wt.% (TPU and MPU). The composites prepared with
Biocomposites of Amazon Fibers: Malva and Tucum
more fibers, 70 wt.%, it was not easy to observe the interface
region between matrix and fibers. Arrows indicated the
central regions in the SEM images. When the percentage of
the fibers increases, consequently, the resin’s presence
decreases, and the interaction fiber-fiber increases.
In this case, fibers’ increase did not negatively influence
the mechanical properties’ results, as observed in the Izod
impact results (Figure 4). The fibers’ thickness is probably
relevant in this result, facilitating the fibers’ wettability
during the impregnation process and promoting the
minimum resin between the fibers.
The literature presents that the composite materials’
results improve due to increased fibers percentage or length.
This increase leads to a maximum point in the mechanical
properties of the composites. After this point, the properties
decrease considerably, depending on the matrix or the fibers
used. This effect is due to fiber-fiber interaction and poor
adhesion in the interface region (fiber-matrix), caused by the
decrease in the amount of resin [36,37].
Applying Fick’s law for diffusion (equation (3) and
equation (4)) in the data obtained in the water absorption
test, enabling the assessment of the water diffusion process
in the biocomposites, Figure 5 reports the D values
(diffusion coefficient). The parameter k is related to the
interaction behavior between the composites’ components
and the water molecules, and Table 1 lists the values.
In this case, the composite compositions did not change,
only the fibers’ proportion as reinforcement, therefore not
Figure 5. Water absorption results of the composites: TPU and
MPU (30, 50, 70 wt.%) in function of the D (diffusion coefficient,
mm2 h-1).
Table 1. Water absorption results of the composites with malva and
tucum fibers. Diffusion coefficients D (mm2 h-1)×10-8 and k values
Composites D (mm2·h-1)×10-8 k percentage of the fibers increase. It is relevant to highlight
(wt. %) TPU MPU TPU MPU
30 20.8 1.4 0.38 1.47
50 13.0 5.7 0.13 1.34
70 8.3 1.3 0.36 1.80
Fibers and Polymers 2021, Vol.22, No.11 3209
strongly influencing the k values, as seen in Table 1. The
variation in the proportion of sisal fibers in the composites
did not influence their water molecules’ affinity. The
chemical nature of the composite components reflects in the
material affinity for water. As in this study, the components’
chemical nature was not modified, then the value of k
remained unchanged.
Values of k are indicative of the affinity between the
polymeric matrix and water molecules [38]. The higher
values of the k to composites reinforced with malva fibers
(MPU) than tucum (TPU) indicate more water affinity. In
this case, the matrix applied is the same, changing the
reinforcement only. The results show an indication of the
character of both fibers when used as reinforcement of the
composites. Malva fibers have more strong interaction, or
hygroscopicity, with water molecular than tucum fibers. The
presence of the polar groups exposed in the MPU is more
than TPU, promoting interactions between the materials and
water molecules efficiently. The relative values of k that
refer to the interaction between the materials consequently
influenced the mobility speed results (diffusion coefficient,
D) of the composite’s water molecules. The higher k values
indicate a higher affinity of the composite for water
molecules; therefore, the relative mobility speed (D) will be
lower. Table 1 lists the correlations, where the D values for
TPU composites are higher than MPU; consequently, the k
values are lower for TPU than MPU.
Water absorption tests indicated that the composites
reinforced with 70 wt% fibers (both tucum and malva fibers)
presented a low diffusion coefficient of the water compared
to all the composites in this study, 8.3×10-8 mm2·h-1 (TPU)
and 1.3×10-8 mm2·h-1 (MPU). Despite the many fibers
(70 wt.%) reinforcing the polymeric matrix, the water
diffusion coefficient was lower than the other composites,
indicating the interaction intensified of the interface region
(fiber/matrix). This increase, regardless of the fiber type, has
relative importance to replacing synthetic materials with
natural products and renewable sources, lignocellulosic
fibers and castor oil, and maintaining or improving the final
materials’ thermal stability properties. Additionally, the
water absorption test presented consistent results than Izod
impact strength values, indicating that the composite with
70 wt.% fibers had a better adhesion at the fiber/matrix
interface than the others.
The results reported in the literature correlated to
thermoset composites reinforced with lignocellulosic fibers
show a profile similar to the one observed in this study. The
k values are constant, and D values increase according to the
that the D values increase is correlated to the excellent
adhesion and covered of the fibers by polymeric matrix.
When the fibers, hydrophilic, are well covered by the
resin, with few voids present, the water molecules’ diffusion
will probably occur through the matrix. In the interface
3210 Fibers and Polymers 2021, Vol.22, No.11
region, the intensity of fiber-matrix interaction determines
the speed of diffusion of water molecules. The higher the
interaction in the interface region, the smaller the number of
free polar groups to interact with water molecules, justifying
the diffusion coefficient’s increase. On the other hand, the
increase in free polar groups provides interaction with water
molecules, decreasing their diffusion through the material.
This behavior can be correlated with the impact results due
to increased or decreased resistance values, better resistance
to impact, better interaction, and less diffusion of water
molecules.
Conclusion
This work turned possible to elucidate the properties and
potential applications of the new fibers from the Amazon
region, as malva and tucum fiber. Besides, the tucum fibers'
chemical characterizations still are fewer used in the
materials area. The fibers presented similar properties to
other fibers studied in the literature, such as their lignin (9-
11 %) and cellulose (59-69 %) contents and thermal stability.
Beyond the bio-polyurethane polymer reinforced by these
typical fibers prepared with castor oil, composite materials
exhibited promissory results. The progressive substitution of
the matrix by natural fibers, from 30 to 70 wt.%, maintained
or improved the composite properties’ thermal stability and
the impact Izod results. The synthetic material’s replacement
by natural products and renewable source, lignocellulosic
fibers and castor oil, maintaining or improving both
composites’ thermal stability, was around 300 oC. Composites
with a high percentage of the fibers, 50 and 70 wt.%,
presented the best Izod Impact results carried out in this
study, up to 450 J m-1. These results are probably due to
good interaction between fibers and polymeric matrix, as
seen in the SEM morphological images, suggested that the
interaction matrix and fibers were promoted by polar groups
in their surfaces, improving all properties.
All basic characterizations correlated to lignocellulosic
fibers were applied in this study, possibly by applying these
fibers in a different matrix, probably resulting in composites
with excellent properties. The water absorption results are
relevant to complementary available about the interface
between fibers and matrix, in addition to verifying the
degree of affinity of the composite for water. As predicted in
the literature, composites with a higher number of active
polar sites on the fibers’ surface lead to an increase in D
values and, consequently, in the percentage of water
absorbed. In this study, D values varieties according to the
fiber types and the fiber percentages into de matrix, as
discussed. Because of the set of results presented, the
prepared composites presented promising results as
substitutes for slabs produced with synthetic materials still
industrially commercialized.
Juliana dos Santos Carneiro da Cunha et al.
Acknowledgments
The authors gratefully acknowledge UFAM (Universidade
Federal do Amazonas) and IFAM (Instituto Federal do
Amazonas) for the infrastructure and CNPq for the financial
support (# 426530/2016-0) and fellowship to J.S.C.C. The
authors gratefully acknowledge the LAMAC (Amazon
Materials and Composites Laboratory) facilities.
References
1. N. García, G. Galeano, L. Mesa, N. Castaño, H. Balslev,
and R. Bernal, Acta Bot. Brasilica., 29, 45 (2015).
2. B. H. Ramirez, A. Parrado-Rosselli, and P. Stevenson,
Colombia Forestal, 12, 7 (2009).
3. A. S. Monteiro and J. Baruque-Ramos in “Natural Fibres:
Advances in Science and Technology Towards Industrial
Applications” (R. Fangueiro and S. Rana Eds.), Vol. 12,
pp.127-137, Springer Netherlands, Portugal, 2016.
4. M. S. Oliveira, F. S. da Luz, A. T. Souza, L. C. da C.
Demosthenes, A. C. Pereira, F. da C. G. Filho, F. de O.
Braga, A. B. H. da S. Figueiredo, and S. N. Monteiro,
Polymers, 12, 2259 (2020).
5. S. N. Monteiro, F. M. Margem, J. I. Margem, L. B. de
Souza Martins, C. G. Oliveira, and M. P. Oliveira, Mater.
Sci. Forum., 775, 255 (2014).
6. L. F. C. Nascimento, F. S. da Luz, U. O. Costa, F. de O.
Braga, E. P. Lima Júnior, and S. N. Monteiro, Materials,
12, 3939 (2019).
7. Z. Zhang, S. Cai, Y. Li, Z. Wang, Y. Long, T. Yu, and Y.
Shen, Compos. Sci. Technol., 194, 108151 (2020).
8. K. M. Faridul Hasan, P. G. Horváth, and T. Alpár, Polymers,
12, 1072 (2020).
9. F. Kahn, Rev. Peru. Biol., 15, 31 (2008).
10. E. C. Ramires, F. Oliveira, and E. Frollini, J. Appl. Polym.
Sci., 129, 2224 (2013).
11. A. Arshanitsa, L. Krumina, G. Telysheva, and T. Dizhbite,
Ind. Crops Prod., 92, 1 (2016).
12. C. G. Silva, F. De Oliveira, and E. Frollini, Waste Biomass
Valorization, 10, 3515 (2019).
13. F. Oliveira, E. C. Ramires, E. Frollini, and M. N. Belgacem,
Ind. Crops Prod., 72, 77 (2015).
14. J. D. Megiatto, C. G. Silva, D. S. Rosa, and E. Frollini,
Polym. Degrad. Stab., 93, 1109 (2008).
15. D. O. Castro, A. Ruvolo-Filho, and E. Frollini, Polym.
Test., 31, 880 (2012).
16. M. S. Zainol Abidin, L. Y. Fei, P. C. Wee, A. Anjang, and I.
L. Daungkil, IOP Conf. Ser. Mater. Sci. Eng., 370, 012046
(2018).
17. S. Diestel and A. Krause, J. Appl. Polym. Sci., 135, 1 (2018).
18. I. M. Cattani and J. Baruque-Ramos in “Natural Fibres:
Advances in Science and Technology Towards Industrial
Applications” (R. Fangueiro and S. Rana Eds.), Vol. 12,
pp.89-98, Springer Netherlands, Portugal, 2016.
Biocomposites of Amazon Fibers: Malva and Tucum
19. Z. Zhang, S. Cai, Y. Li, Z. Wang, Y. Long, T. Yu, and Y.
Shen, Compos. Sci. Technol., 194, 108151 (2020).
20. A. Espert, F. Vilaplana, and S. Karlsson, Compos. Part A,
35, 1267 (2004).
21. J. D. Megiatto, C. G. Silva, E. C. Ramires, and E. Frollini,
Polym. Test., 28, 793 (2009).
22. A. S. Fonseca, J. Raabe, L. M. Dias, A. E. R. Baliza, T. G.
Costa, L. E. Silva, R. P. Vasconcelos, J. M. Marconcini, H.
Savastano, L. M. Mendes, A. Yu, W. J. Orts, and G. H. D.
Tonoli, Waste Biomass Valorization., 10, 3125 (2019).
23. M. R. Silva, R. V. Pinheiro, A. L. Christoforo, T. H.
Panzera, and F. Rocco Lahr, Mater. Res., 21, 1 (2018).
24. L. F. C. Nascimento, L. H. L. Louro, S. N. Monteiro, A. V.
Gomes, R. L. S. B. Marçal, É. P. Lima, and J. I. Margem,
Mater. Res., 20, 399 (2017).
25. J. I. Margem, V. A. Gomes, F. M. Margem, C. G. D.
Ribeiro, F. O. Braga, and S. N. Monteiro, Mater. Res., 18,
114 (2015).
26. J. Sharifi-Rad, G. Melgar-Lalanne, A. J. Hernández-
Álvarez, Y. Taheri, S. Shaheen, D. Kregiel, H. Antolak, E.
Pawlikowska, M. Brdar-Jokanović, J. Rajkovic, T.
Hosseinabadi, B. Ljevnaić-Mašić, N. Baghalpour, M.
Mohajeri, P. V. T. Fokou, and N. Martins, Phyther. Res.,
34, 546 (2020).
27. K. Chandran, S. Song, and S. I. Yun, Arab. J. Chem., 12,
1994 (2019).
28. C. T. N. M. Branco, D. S. aa Costa, R. T. Fujiyama, W. R.
Fibers and Polymers 2021, Vol.22, No.11 3211
El Banna, and M. Kuwahara, “Particulate Fibers Adding
Wood Waste”, pp.255-259, 25th SAE Bras. Int. Congr.
Disp., 2016.
29. F. Oliveira, E. C. Ramires, E. Frollini, and M. N. Belgacem,
Ind. Crop. Prod., 72, 77 (2015).
30. L. F. C. Nascimento, S. N. Monteiro, F. M. Margem, A.
Camposo Pereira, N. Simonassi, and M. P. Oliveira, J.
Mater. Res. Technol., 7, 520 (2018).
31. N. Sgriccia, M. C. Hawley, and M. Misra, Compos. Part A,
39, 1632 (2008).
32. K. G. Satyanarayana, J. L. Guimara, and F. Wypych, Compos.
Part A, 38, 1694 (2007).
33. L. Manzato, L. C. A. Rabelo, S. M. de Souza, C. G. da
Silva, E. A. Sanches, D. Rabelo, L. A. M. Mariuba, and J.
Simonsen, J. Mol. Struct., 1143, 229 (2017).
34. C. G. da Silva, S. Grelier, F. Pichavant, E. Frollini, and A.
Castellan, Ind. Crops Prod., 42, 87 (2013).
35. C. G. Silva, F. S. Kano, and D. S. Rosa, J. Therm. Anal.
Calorim., 138, 2375 (2019).
36. G. B. Carvalho, S. V. Canevarolo-Jr., and J. A. Sousa,
Polym. Test., 85, 106418 (2020).
37. E. N. Amini and M. Tajvidi, J. Compos. Mater., 52, 3159
(2020).
38. J. D. Megiatto, F. B. Oliveira, D. S. Rosa, C. Gardrat, A.
Castellan, and E. Frollini, Macromol. Biosci., 7, 1121
(2007).