Original Article

Progress in Rubber Plastics and

Recycling Technology
The effect of clay 1–18
ª The Author(s) 2021
organophilization on wood Article reuse guidelines:
sagepub.com/journals-permissions
DOI: 10.1177/14777606211019404
plastic composite (WPC) journals.sagepub.com/home/prp

based on recycled high

density polyethylene (HDPE)
and coir fiber

Mário B S Nunes1, Ana Flávia F Farias2,

Eliton S Medeiros3, Juliano E Oliveira4,
Ieda M G Santos2, Laura H Carvalho1
and Amélia S F Santos3

Abstract
One way to optimize composite mechanical properties is through hybridization with small
amounts of reinforcing fillers. Thus, this study investigates the effect of incorporation of 3 wt% of
clay (BT) and organoclay (OBT) on the properties of a recycled wood plastic composite (WPC)
based on HDPE and 20 wt% of coir fiber compounded with 5 wt% of maleic anhydride-grafted
polypropylene (PP-g-MA), as coupling agent, and 5 wt% of Struktol TPW 113, as lubricating agent.
Raw materials were characterized by X-ray fluorescence (XRF), Fourier transform infrared
spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and thermo-
gravimetric analysis (TGA). Coir fiber was characterized by optical microscopy and TGA. Wood
plastic formulations (with clay and organoclay) were prepared in an internal mixer coupled to a
torque rheometer operating at 190 C, 60 rpm for 10 min. Then, the mixtures were compression
molded. Formulations were characterized by SEM, TGA, DSC, tensile and water absorption tests.
FTIR analysis showed the characteristic bands of organophilic clay. XRD showed an increment in
the interplanar distance of the clay, after the incorporation of quaternary ammonium salt (distearyl

1
Department of Materials Engineering—UFCG, Rua Aprı́gio Veloso, Campina Grande, PB, Brazil
2
Chemistry Department, Federal University of Paraiba—UFPB, Paraı́ba, PB, Brazil
3
Department of Materials Engineering, Federal University of Paraiba—UFPB, Paraı́ba, PB, Brazil
4
Engineering Department, Federal University of Lavras—UFLA, Lavras, MG, Brazil

Corresponding author:
Amélia S F Santos, Department of Materials Engineering, Federal University of Paraiba—UFPB, Cidade Universitária,
s/n—Castelo Branco, 58051-900 Paraı́ba, PB, Brazil.
Email: amelia@ct.ufpb.br
2 Progress in Rubber Plastics and Recycling Technology XX(X)

dimethyl ammonium chloride, Praepagen® WB), confirming the organoclay formation. Organo-
philization decreases the clay hydrophilic character and reduces the water uptake of WPC-BT.
Despite the fact that BT incorporation led to WPC nanocomposite with intercalated structure,
this WPC-clay composition did not show a significant increase in tensile strength and elongation at
break. The poor interfacial adhesion between the raw materials and the polymer matrix, the low
aspect ratio provided by coir fibers and also, the partially intercalated structure of composites have
contributed to this behavior.

Keywords
Hybrid nanocomposite, recycling, natural fiber, mineral filler, quaternary ammonium salt

Received 26 April 2020; accepted 3 January 2021

Introduction
Studies of WPC manufactured with recycled plastics are fairly limited, but most of them indicate
that the properties of WPC using a single type of plastic waste have mechanical properties
comparable to, or better than composites using virgin matrices.1-8 Besides this, it is known that
recycled plastics are much more cheaper,9 offering the prospect of lessening waste disposal and
reducing product costs.
HDPE has many attractive characteristics which include low cost, high crystallinity, high
strength (compared to other commodity plastics), ease of processing, excellent electric isolation,
chemical resistance, rigidity and flexibility, even at low temperatures, as well as the absence of
odor and toxicity.10 Lignocellulosic fibers also have a series of advantages, since they are less-
expensive, low density, sustainable, and less abrasive to processing machinery than traditional
glass fiber and mineral fillers.
However, natural fibers are usually polar and hydrophilic, which leads to poor adhesion and
wettability in non-polar matrices, such as polyolefins, and thus, poor mechanical properties of the
final materials. In order to promote filler/matrix interaction, the use of various coupling agents or
compatibilizers has been proposed.11 Among them, maleic anhydride-grafted polyethylene (PE-g-
MA) and polypropylene (PP-g-MA) are the most commonly used due to their ability to effectively
enhance mechanical properties, especially tensile and flexural strengths, of composites based on
PE or PP matrixes.12
The adding of nanoparticles, as clay fillers, to a fiber-based composite, is highly advantageous
since it demonstrates a remarkable enhancement in the thermal, mechanical, physical and thermo-
mechanical properties, due to its high aspect ratio and surface area.13-15 However, in order to
provide a better physical and chemical environment for the polymer, the clay is organically
modified through an ion exchange reaction between organic and inorganic cations, to change the
clay from hydrophilic to organophilic.16
According to Wang et al.,17 the use of surfactants with a number of methylene groups greater
than 16 is important to control the hydrophobicity of organoclay and, thus, obtain exfoliated/
intercalated nanocomposites in non-polar matrices. Another approach that increases the degree
of clay exfoliation in nanocomposites and also favors its interaction with nanocomposite consti-
tuents is the use of coupling agents, like PE-g-MA or PP-g-MA.18,19
Nunes et al. 3

Gu et al.20 investigated the mechanical properties of WPC compositions with different kinds
and content of commercial organoclays. A natural montmorillonite was also tested. Their results
indicated that the use of nanoclay masterbatch was not the best approach to incorporate nanoclay in
WPC, because the direct incorporation of natural clay particles gives more chance of PE-g-MA
molecules to interact with natural clay particles deposited and adhered to fiber surface, giving
strongly physical bonds, than nanoclay masterbatch. The same behavior was not observed, if PE-g-
MA was not added to the formulation, as evaluated by Faruk and Matuana.21
If clay/matrix interface adhesion is properly established and a well exfoliated or intercalated
structure is obtained, the incorporation of clay improves the properties of WPC, including its
thermal properties, modulus of elasticity,19 flexural and tensile strength.22,23 Therefore, WPC
hybridization with small amounts of clay filler is one way to optimize composite properties.
There are many studies in the literature17,19,20,24 involving the use of different kind of organo-
clays, methods of clay incorporation and the effect of clay and coupling agents content in WPC
properties. Nevertheless, there is no study focusing on the comparative evaluation of the incor-
poration natural clay and organoclay on the properties of rWPC nanocomposite with natural fiber.
In this study, the role, and real benefits that clay organophilization with Praepagen® WB
(distearyl dimethyl ammonium chloride) brings to WPC based on HDPE and 20 wt% of coir fiber
compounded with 5 wt% of maleic anhydride-grafted polypropylene (PP-g-MA), as coupling
agent, and 5 wt% of Struktol TPW 113, as lubricating agent were evaluated. As a result, the effect
of clay organophilization in water resistance, thermal, mechanical and morphological properties of
hybrid rHDPE/coir fiber/clay-wood plastic composites was investigated.

Experimental
Materials
Recycled HDPE flakes were donated by Plastex Ind. and Com. of Plastic Materials Ltda. (João
Pessoa, State of Paraı́ba, Brazil). Mature coir fibers up to 5 mm long were supplied by Coco Vivo
Project situated in Porto Seguro (State of Bahia, Brazil) extracted from ripen and dried fruits.
The coupling agent, maleic anhydride-grafted polypropylene (PP-g-MA, Bondyram® 1001), and
the lubricant (Struktol® TPW 113, blend of complex, modified fatty acid ester) were obtained
from Parabor Ltda. (São Paulo, State of São Paulo, Brazil). The PP-g-MA has melt flow index of
100 g by 10 min (190 C, 2.16 kg) and density of 0.90 g.cm3 (23 C). Coir fibers (CF) were
ground in a knife mill (Willey, STAR FT 50 Fortinox) and classified through 16–80 mesh sieves
(0.177 and 1.19 mm).
Bofe bentonite clay (BT) powder was donated by Pegmatec Ldta. (João Pessoa, State of
Paraı́ba, Brazil). It is a natural BT with cationic exchange capacity of 108.36 cmol.kg1. The
clay composition based on X-Ray Fluorescence semi-quantitative analyses (FRX-1800,
Shimadzu) was 76.8–77.2% of Si, 13–13.9% of Al, 5.5–6.1% of Fe, 1.8–1.3% of Mg and
1.5–2.9% of other elements. After organophilization, these results showed only a slight decrease
in the percentage of MgO in the clay, probably, because the Mg2þ cations participate in the
cation exchange process.25
The quaternary ammonium salt used for the organophilization of BT was distearyl dimethyl
ammonium chloride (Praepagen® WB; (C16H33)2Nþ(CH3)2Cl) supplied by Clariant S. A. (São
Paulo, State of São Paulo, Brazil).
4 Progress in Rubber Plastics and Recycling Technology XX(X)

Table 1. Compositions of wood plastic composites.

WPC formulations

Raw materials % Neat WPC WPC-BT WPC-OBT

HDPE flakes 100  Wf* X X X

Coir fiber 20 X X X
PP-g-MA 5 X X X
Strukol TPW 113 5 X X X
BT 3 X
OBT 3 X
*Wf—total sum of the percentages of other constituents than polymer matrix (fiber, additives and fillers).

Preparation of organophilic bt (OBT)

Organophilic clay (OBT) was prepared in order to facilitate intercalation of polymer into clay
galleries. With this goal, about 20.0 g of quaternary ammonium salt (Praepagen® WB) was added
to a 2000 mL glass flask containing 768 mL of distilled water and 32 g of natural BT, passed
through a 200 mesh sieve. The mixture was mechanically stirred for 20 min at room temperature.
The resulting organobentonite (OBT) was rinsed with distilled water for several times to remove
excess salt, dried at 60 C for 48 h and finally ground in order to pass through a 200 mesh sieve,
according to the procedure described by Araújo et al.26,27

Preparation of wood plastic composite formulations

Recycled HDPE formulations were prepared with 20 wt% of coir fiber, without any pretreatment,
and 3 wt% of (a) natural clay (BT), or (b) organophilic clay (OBT). These formulations also
contained 5 wt% of maleic anhydride-grafted polypropylene (PP-g-MA), and 5 wt% of Struktol
TPW 113. Additionally, one wood plastic composite formulation, without clay, was prepared,
keeping the other components and conditions constant.
All components were previously mixed and added simultaneously into a Thermo Scientific
Haake torque rheometer, model Rheomix PolyLab OS, with internal chamber of 69 cm3 using
roller type rotors. The mixtures were processed for 10 min at 190 C and 60 rpm. Before mixing, the
coir fiber was dried in an oven at 100 C for 3 h. Table 1 shows the nomenclature and composition
of each formulation prepared in the melt state.
Composite mixtures were dried in an air circulation oven for 12 h at 60 C, and then compression
molded in a 15 kgf hydraulic press (Marconi, model MA098/A) operating at 200 C for 8 minutes,
according to the following pressurization ramp: unpressurized for 3 minutes, 3 kgf for 3 minutes
and 9 kgf for 2 minutes. The approximately (200x200x2) mm manufactured sheets were removed
from the press and quenched in an ice bath. All characterizations were carried out on samples cut
out from the sheets according to the dimensions of respective test standards.

Characterizations
Morphological, structural and thermal properties. An optical microscope Olympus BX41M-LED
operating with 50X magnification was used to observe the length and diameter of ground coir
fibers used in WPC formulations, previously classified through 16–80 mesh sieves, as described in
Nunes et al. 5

subitem 2.1. About 50 measurements were taken and analyzed by using the ImageJ software. After
measuring the length and diameter of the fibers, the average aspect ratio was calculated. The data
obtained was organized according to their average aspect ratio as: 2 < L/D < 8.5 - short fibers;
8.5 < L/D < 20 - medium fibers; and 20 < L/D < 60 - long fibers.
Fourier transform infrared spectroscopy analysis (FTIR) was performed in order to detect the
presence of specific chemical groups in natural clay (BT) and organoclay (OBT). The presence of
characteristic groups of the quaternary ammonium salt was investigated, as a way to confirm clay
organophilization. The spectra were recorded at ambient temperature, using an IRPrestig-21 Shi-
madzu spectrometer, operating with KBr disks in the range 4000–400 cm1 with 32 scans and
resolution of 4 cm1.
X-ray diffraction (XRD) analyzes were performed at room temperature in a Shimadzu LabX
XRD-6000 diffractometer, using 30 kV CuK radiation (l ¼ 1.5418 Å), potency of 2 kVA, and
current of 30 mA. The starting materials were examined in a 3–10 range of 2y at a scan rate of
1 .min1 and 0.0016 .min1, for the clay samples and WPC formulations, respectively. This
technique was used to confirm that organoclay was obtained and the kind of hybrid rHDPE/coir
fiber/clay-wood plastic nanocomposite formed. The interlayer spacing (d001) of the clays was
calculated using Bragg’s law (equation (1)).28

l
d001 ¼ ð1Þ
2seny
where: d001, it is the basal reflection plane (001) of layered silicate in nm; l it is the wavelength of
the CuKalfa radiation at 0.15418 nm; and y it is the angle in degrees of the basal reflection peak
(001) of montmorillonite.
SEM analysis was performed in Zeiss LEO 1430, a scanning electron microscope operating at
an accelerating voltage of 15 kV in secondary electron (SEM-SE) mode for the clay samples and in
backscattered electrons (BSE/SEM) mode for the composite samples. The clays were fixated with
double side carbon tape and gold sputtered prior to analysis whereas for the composites, SEM
analysis was performed on the cryogenically fractured surface of gold sputtered samples. The
surface and morphology of clays, fiber and clay dispersion, as well as the fiber/matrix and clay/
matrix interfaces of the composites were evaluated.
Thermogravimetric analysis of the raw materials and of wood plastic composite formulations
were performed on a Shimadzu apparatus TG S1HA, using an alumina pan and approximately
12 mg of material. The samples were heated at 10 C.min1 under nitrogen atmosphere with a gas
flow of 50 mL.min1. TGA curves and their derivatives (DTG) were recorded in the 30–700 C
range in order to evaluate the thermal stability of the samples.
Differential scanning calorimetry (DSC) analyzes of the wood plastic composite formulations
(11 mg) were conducted on a DSC-60 Shimadzu calorimeter, operating with heating and cooling
rates of 10 C.min1 and nitrogen flow of 50 mL.min1 on aluminum pans. A three stages
heating/cooling/heating protocol was employed, i.e. samples were heated from 30 to 200 C,
maintained for 2 min at 200 C, cooled to room temperature, and then heated until 200 C again.
The degree of crystallinity (Xc) of the samples, obtained during 2nd heating stage, was calculated
using equation (2):
DHf
Xc ¼ ð2Þ
ðw:DH  Þ
6 Progress in Rubber Plastics and Recycling Technology XX(X)

Figure 1. Test specimen type 5A. I2—overall length,  75 mm; b2—width at ends (12.5 + 1) mm; l1—Length
of narrow parallel-sided portion (25 + 1) mm; b1—width of narrow parallel-sided portion (4 + 0.1) mm;
r1—Small radius (8 + 0,5) mm; r2—Large radius, (12.5 + 1) mm; L—initial distance between grips (50 + 2)
mm; L0—gauge length (20 + 1) mm; h—thickness, 2 mm. Extracted from ISO 527-2. Plastics—Determi-
nation of tensile properties—Part 2: Test conditions for moulding and extrusion plastics.

where, DHf ¼ enthalpy of fusion obtained from the analysis of samples; DH ¼ standard enthalpy
of fusion for a 100% crystalline HDPE, which is assumed to be 293.6 J.g129; and w ¼ weight
fraction of polymer matrix in the composite.

Mechanical and physical properties. Tensile testing was conducted on a Shimadzu, AG-X 10 kN
universal testing machine, at room temperature and a crosshead speed of 5 mm/min. Type 5A
specimens were prepared by machining the pressed sheets, according to ISO 527-2 (Figure 1). At
least eight test specimens of each composite formulation were tested and average values of tensile
strength (MPa) and elongation at break (%) were determined. All the compositions were statisti-
cally evaluated through Turkey-Kramer test.
Water absorption testing was conducted according to ASTM D 570. Specimens measuring
(75  25  2.5) mm were machined from the pressed composite sheets, dried for 24 h at 50 C
and then, weighed. The specimens were placed in a container with distilled water at 23 C sup-
ported on edge and entirely immersed. The weight of each specimen was determined within 24 h
intervals during 21 days. After each of these intervals, the test specimens were removed from the
water, pat-dried with absorbing paper, weighed and returned to the container. Three samples of
each composition were tested and average values of percentage of water absorption (WA), as a
function of time interval, was calculated according to the equation (3):
 
W2  W1
WAð %Þ ¼ x 100 ð3Þ
W1
where: W1 is the weight of oven-dried composite sample before immersion, and W2 is the weight of
the composite sample after immersion at a given time interval.

Results and discussion

Morphological, structural and thermal properties
Optical micrographs indicate that coir fibers are predominantly short and medium in length, which
have a mean aspect ratio (L/D) of 5 and 13, respectively (Figure 2). The average length and
diameter observed were 1094 mm and 112 mm, respectively, which results in an aspect ratio of
Nunes et al. 7

Figure 2. Coir fibers micrograph and fiber aspect ratio distribution (inset).

Figure 3. Infrared spectra of BT and OBT at 4000–2768 cm1 (A) and at 1900–400 cm1 (B).

about 10. According to Stark and Rowlands,30 wood plastic composite elastic modulus increases
with increasing L/D ratio of fibers. However, an increase in tensile strength of composite relative
to neat polymeric matrix only occurs if: there is good adhesion between fiber and polymer matrix;
fibers are well dispersed within the matrix; and fibers are oriented in a preferential direction.30-32
On the other hand, low aspect ratio values may cause stress concentrations, which leads to a
decrease in the material tensile strength.30
The transmittance infrared spectra for BT and OBT are shown in Figure 3. FTIR spectrum for
BT reveals the presence of a band at 3640 cm1, attributed to OH stretching of the montmorillo-
nite. The bands at 3438 cm1 are attributed to stretching of silanol groups (Si-OH) and to the
8 Progress in Rubber Plastics and Recycling Technology XX(X)

Figure 4. Diffractograms for BT and OBT (A) and for WPC-BT and WPC-OBT (B).

stretching vibration of the -OH group of adsorbed water. The band at 1639 cm1 is assigned to the
vibrational deformation of H–O–H grouping. The bands at 1069, 475 and 420 cm1 refer to the
stretching vibrations of the Si–O–Si group and the bands at 793 and 522 cm1 correspond to
octahedral layers of aluminosilicate, Si–O–Al.33-36
The spectrum of the organoclay modified with Praepagen® WB shows the appearance of two
bands around 2918 and 2851 cm1, associated to the C–H stretching of CH2 and CH3 saturated
hydrocarbon groups, and the presence of a band in the region of 1469 cm1 is attributable to bending
vibrations of methylene groups. Furthermore, there are shifts of the 3640 cm1, 1069 cm1 and
475 cm1 absorption bands characteristic of the BT to lower wavenumbers, i.e. to values around
3624 cm1, 1041 cm1 and 468 cm1, respectively. These new peaks and shifts indicate that the
quaternary ammonium salt did intercalate in the interlayer spaces of the clay, suggesting that the
organoclay was obtained.35,37 Due to long alkyl chain of Praepagen® WB the compatibility between
clay and HDPE should be favored, probably, resulting in improved mechanical properties.
The BT diffractogram (Figure 4(A)) shows a peak around 2y ¼ 5.84 corresponding to a basal
interplanar distance (d001) of 1.51 nm, calculated by the Bragg equation, of montmorillonite.
The XRD pattern of OBT (Figure 4(A)) shows 2y ¼ 4.79 for organophilic montmorillonite,
which corresponds to a basal interplanar distance (d001) of 1.84 nm. This increase in the basal
interplanar spacing after organophilization confirms the intercalation of organic cations into the
clay interlayer space.38 A basal reflection (002) around 2y ¼ 7.06 was also observed, indicating
that a small part of clay layers was not intercalated by surfactant.39-41 This can be attributed to
steric effects of the organic salt, as well as its molecular volume, preventing complete exchange of
exchangeable cations of molecules of the organic salt inside the basal spacing of clay, giving
indications of possible adsorption of this salt on the outer surface of clay.33,40 The surfactant excess
could further act as coupling agent in composite formulation, since it is a low molecular weight
organic component.
The WPC-BT diffractogram shows an increase in the clay interplanar distance from 1.51 to
1.87 nm (Figure 4), indicating clay partial intercalation, as basal reflection d(001) around 2y * 4.6
was observed (Figure 4(B)). Nevertheless, a basal reflection d(002) around 6.4 was still observed,
indicating no change in interplanar distance for a fraction of clay content. According to the
Nunes et al. 9

literature,42,43 the displacement of the peak (001) to lower angles (2y) of the clay indicates that
intercalation occurred.
The XRD spectrum of WPC-OBT showed a reduction in the value of the interplanar spacing
(001) of the clay from 1.84 to 1.71 nm, indicating the formation of a microcomposite and a
partial salt loss, due to thermal degradation during processing (Figure 4). On the other hand, no
double peak for WPC-OBT was observed (Figure 4(B)) and the basal reflection d(002) around
7.06 for OBT (Figure 4(A)) was suppressed, which could indicate partial intercalation of this
fraction of clay.
These results indicate that for polyethylene based WPC with coir fiber, the partial intercalation
of polymer chains between the clay layers can be achieved without organophilization, as demon-
strated by Faruk and Matuana,21 and Devi and Maji.44 Probably, the processing aids played an
important hole in this process, since polyethylene/clay composites usually display no change in the
basal spacing of the clay.29,31
SEM micrographs for BT and OBT (Figure 5(A) and (B)) suggest that both clays have an irregular
shape and the smooth surface of OBT indicates the presence of surfactant on its outer surface.
Figure 5(C) to (F) shows SEM micrographs of the fracture surface of wood plastic composite
formulations. The micrographs indicate the crushing (Figure 5(D)), and presence (Figure 5(C) and
(D)) of coir fibers. Cavities between clay agglomerates and the matrix can also be observed (Figure
5(E) and (F)), indicating a poor adhesion between clay/matrix and fiber/matrix phases and, prob-
ably, inefficient stress transfer from the matrix to clay and coir fibers.
The influence of the amount of coupling agent on the dispersion of clay particles in the HDPE
matrix was evaluated by Lee et al.19 They showed that to achieve a higher degree of dispersion for
the nanosized clay particle and consequently, an increase in tensile and flexural modulus, it is
necessary to use a high aspect ratio particle, and have a good interface between polymer and clay
and finally, a high exfoliation level.
Besides that, Lee et al.19 also achieved better results of clay dispersion and intercalation with an
increase of maleic anhydride-grafted polyethylene (PE-g-MA) content. In this study, fibers and
clay particles arrangements appear with bad adhesion between the reinforcing fillers and the
polymer matrix (Figure 5(C) to (F)). These images suggest that either the amount of the coupling
agent was not high enough or its effectiveness to compatibilize reinforcing fillers with polymer
matrix was not good, thereby reducing the mechanical properties1.
Aiming to evaluate differences in the thermal stability of WPC as a function of clay addition and
clay organophilization, thermogravimetric analysis was carried out. Figure 6(A) shows the TGA
curves for different types of clay. The first mass loss stage occurs from room temperature to about
106 C. This decomposition stage is attributed to free water elimination, i.e. clay dehydration. At
this stage the mass loss of raw materials: BT and OBT is approximately 12.31% and 1.97%,
respectively. It evidences that the water percentage in the organoclay was lower than that of the
neat clay, indicating that the hydrophilic character of the clay was significantly reduced with the
organic modification. According Madejová et al.,34 there are at least two reasons why the orga-
nophilic clays contain less free water than the pure inorganic mineral: the large size of the organic
cation occupies physically space that could hold water in an inorganic system, and the lower
hydration energy of organic cations.
A second stage of mass loss between 230 C and 464 C is observed for OBT . This decomposition
stage is associated to degradation of the organic salt and its mass loss is approximately 30.6%. The
second decomposition stage for BT (418–530 C) and third for OBT (500–800 C) are attributed to
10 Progress in Rubber Plastics and Recycling Technology XX(X)

Figure 5. SEM micrographs of raw materials (A) BT and (B) OBT, and of fracture surfaces of neat-WPC (C),
WPC-BT (D and E) and WPC-OBT (F).

dehydroxylation of clay and, in the case of OBT, also to final decomposition of organic salt.41,45 The
mass loss of BT and OBT in this stage is about 3.21% and 5.25%, respectively.
TGA curve profiles of neat-WPC, WPC-BT and WPC-OBT are similar, with neat-WPC having
a lower thermal stability than the other WPC samples (Figure 6(B)). The curves exhibit a weight
loss stage in the 223–350 C temperature attributed to the degradation of coir fiber components
(cellulose, hemicellulose and lignin) (Figure 6(C)). Another weight loss between 360 C and 504 C
is associated with the degradation of HDPE matrix.46-47
Table 2 shows the values of the initial thermal decomposition temperature (Tonset) for wood
plastic composites, which indicates the order of thermal stability, and the temperature at the
Nunes et al. 11

Figure 6. TGA curves of the raw materials (A), and of wood plastic composite formulations (B), and their
respective DTG curves (C).

Table 2. Initial thermal decomposition temperature (Tonset), temperature at the maximum rate of weight loss
(Tmax) for HDPE matrix and residue content for WPC formulations.

Samples Tonset ( C) Tmax ( C) Residue (%)

Neat-WPC 360 461 1.66

WPC–BT 380 478 9.42
WPC–OBT 390 473 5.96

maximum rate of weight loss (Tmax) of the HDPE matrix. The data indicate that WPC-BT and WPC-
OBT have higher Tonset and Tmax values than neat-WPC and that WPC-OBT shows an increase in
thermal stability of about 30 C compared to neat-WPC. The improvement in thermal stability (at
least of 20 C for Tonset and 12 C for Tmax) of hybrid WPC samples relative to neat-WPC can be
attributed to clay layers acting as barriers to the transport of volatiles generated during decomposi-
tion, thus favoring the increase in thermal stability of composite.48 The slight decrease of WPC-OBT
thermal stability relative to WPC-BT should be attributed to degradation of the organic salt (Figure
6(B)). Any difference related to clay intercallation extent in the polymer matrix (Figure 4(B)) did not
result in large thermal stability difference between WPC-OBT and WPC-BT.
12 Progress in Rubber Plastics and Recycling Technology XX(X)

Table 3. Thermal transitions and crystallinity degree of WPC formulations determined under cooling
and 2nd heating.

2nd heating 1st cooling

Samples Tm ( C) ΔHf (J/g) Xc (%) Tc ( C)

Neat-WPC 132.62 102.8 50.02 115.03

WPC–BT 131.96 93.69 47.62 114.43
WPC–OBT 132.21 93.48 47.52 115.61
DHf: melting enthalpy; Tm: melting temperature; Xc: cristallinity index; Tc: crystallization temperature.

At 600 C, the neat-WPC sample contained a small amount of carbonaceous residues, which
were associated with coir fiber in inert atmosphere at that temperature. The mass loss associated to
decomposition of carbonaceous residues at 480–550 C was not observed for hybrid composites.
This behavior can be attributed to strong interactions between the different components, keeping
these compounds connected to the structure of material, and resulting in no occurrence of this
decomposition stage. Therefore, the amount of carbonaceous residues at 600 C for the hybrid
composites was higher than that of neat WPC due to the presence of clay. The residue content for
WPC-OBT was smaller than WPC-BT (Table 2) due to differences in the organic content of clays
(Figure 6(A)).
Wood plastic composite formulations have an exothermic peak around 115 C in the cooling
stage, which corresponds to the HDPE crystallization temperature (Tc), and in the subsequent
heating stage an endothermic peak around 132 C, which corresponds to its melting temperature
(Tm) (Table 3). Thus, the addition of BT and OBT to wood plastic composite essentially does not
change its thermal transitions, such as melting temperature (Tm) and crystallization temperature
(Tc). This behavior can be attributed to the high crystallinity of HDPE chains and its fast crystal-
lization rate.
On the other hand, there is a slight reduction in the degree of crystallinity for the hybrid (with
clay) WPC samples, regardless of the kind of clay (natural or organophilic) used, confirming
absence of any nucleating effect of clay particles in HDPE matrix. This may be caused by the
presence of clay particles with different orientations and their poor dispersion in the polymer
matrix, hindering the packing of HDPE chains in the crystalline regions.49

Mechanical and physical properties

Contrary to what expected, the tensile strength of WPC-OBT was somewhat lower (8.18 + 0.52)
MPa than that of WPC-BT (10.22 + 0.89) MPa (Figure 7(A)). It is believed that this behavior can
be associated with XRD data which indicated that the clay basal spacing in WPC-BT was higher
than in WPC-OBT (Figure 4(B)). Both hybrids have similar mechanical properties to neat-WPC,
indicating that clay incorporation did not lead to reinforcement or to stress concentration points in
the composite, as already observed in other works.18,24,28 The DSC data (Table 3) supports the
assessment that neither clay nor organoclay acted as nucleating agents. Similar results were
reported by Lee et al.19 in wood fiber/polyethylene/organoclay nanocomposites with Cloisite
20A (C20A) organoclay. This indicates that, for these systems, the performance of a natural
regional clay (BT) and its derivative (OBT) was similar to that of the imported organoclay (C20A).
Nunes et al. 13

Figure 7. Tensile strength (A) and elongation at break (B) of WPC compositions. Values with the same
superscript letters are not statistically significantly different (p < 0.05), using the Turkey-Kramer test.

There were also no significant changes in elongation at break values (Figure 7(B)), regardless
of the type of clay incorporated into WPC. Nevertheless, the WPC-BT, which had the slightly
higher tensile stress of 10.22 MPa, showed a slightly lower elongation at break than the other
samples. These results confirm a mild reinforcing effect of the intercalated nanocomposite and
the adverse effect of poor interfacial adhesion of the clays with the polymeric matrix (Figure
5(E) and (F)).27,50
According to Araujo et al.34 and Xu et al,27,50 the partial intercalation/exfoliation of the polymer
into organoclay is not enough to overcome the weak interactions between polymer and clay,
attributed to the non-polar nature of the polymer matrix. Similar tensile test results was found
by Araujo et al.27,51 by comparing polyethylene nanocomposite with natural and organophilic clay
modified with Praepagen® WB. Therefore, the incorporation of coir fiber together with other
processing aids added to WPC formulations based on polyethylene nanocomposites with natural
and organophilic clay modified with Praepagen® WB did not change the previous mechanical
behavior observed by Araujo et al.27,51
The water uptake was measured by comparing the specimen’s weight to its initial weight. As
expected, the water uptake increased linearly with immersion time and then, leveled off (Figure 8).
The leveling off is considered as the saturation state of absorption process.52 Time to reach the
saturation point was not the same for all formulations. Neat-WPC and WPC-BT samples showed
minimum (7.32%) and maximum (16.18%) water absorptions, respectively.
The hydrophilic nature of coir fiber promotes the water absorption in manufactured WPCs.
Because of constant coir fiber content (20%) in all formulations, the different water absorptions
among all manufactured composites can be attributed to the role of coupling agent, nanoclay, the
degree of exfoliation of clay layers, the quality of adhesion between fiber and matrix and the
different degrees of crystallinity of the composites.53
The agglomeration of the clay (Figure 5(E) and (F)), which cause weak interface bonding in
composites, may be responsible for the increase in water uptake of WPC-BT and WPC-OBT
samples, in comparison with neat-WPC.54 Furthermore, the degree of crystallinity of the WPC
slightly decreased with the incorporation of BT and OBT (Table 3). As a result, there is more free
volume for the water to diffuse into the WPC, and thus to increase water uptake of hybrid
composites.55
14 Progress in Rubber Plastics and Recycling Technology XX(X)

Figure 8. Water uptake of WPC samples as a function of immersion time.

In the case of WPC-OBT, the increment in water uptake for neat-WPC from 7.32% to 12.54%
with addition of the organoclay after 21 days of experiment might also be due to the octadecylo-
nium ion on clay surface, which could react with water. The N–Hþ groups of alkylammonium ions
are hydrogen-bonded to water molecules by donating protons to the water-oxygen atoms and may
form up to three hydrogen bonds with water molecules.56 Nevertheless, the relative hydrophobic
character of OBT compared with BT (Figure 8) prevailed, and WPC-OBT displayed smaller water
uptake than WPC-BT, which is consistent with previous investigations.23,53,57 Also, the poor
adhesion and the presence of pores in the hybrid systems may also be responsible for the higher
water uptake of these systems compared to neat-WPC.

Conclusions
Results indicate that hybrid HDPE/coir fiber WPC using clay nanoparticles is an alternative to
improve thermal stability of WPC composites without unduly increasing its costs, since best
composite performance was achieved with natural clay incorporation. Therefore, clay organo-
philization with Praepagen® WB (distearyl dimethyl ammonium chloride) did not bring any
further improvement to mechanical, thermal and morphological properties of hybrid rHDPE/coir
fiber/clay-wood plastic composites. Only a slight tendence to improve its water resistance has
been observed.
Despite the fact that BT produced WPC composite with partial intercalated structure, this WPC-
clay composition did not show a significant increase in tensile strength and elongation at break.
The poor interfacial adhesion of raw materials with polymeric matrix, the low aspect ratio provided
by coir fibers and also, the partially intercalated structure of composites have contributed to this
behavior.
Nunes et al. 15

Acknowledgements
The authors gratefully acknowledge Prof. Dr. Amanda Melissa Damião Leite of Federal University of Rio
Grande do Norte (UFRN) for her suggestions about kind of surfactant chosen; National Foundation for
Science and Technology Development, CNPq (Proc. No. 476549/2012-4 and 564913/2010), for the financial
support of this study; and also, Laboratory of Rapid Solidification (LSR) and Laboratory of Fuels and
Materials (LACOM) of Federal University of Paraı́ba (UFPB) for characterizations.

Declaration of conflicting interests

The author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or
publication of this article.

Funding
The author(s) disclosed receipt of the following financial support for the research, authorship, and/or publi-
cation of this article: The authors received financial support from National Foundation for Science and
Technology Development, CNPq (Proc. No. 476549/2012-4 and 564913/2010).

ORCID iD
Amélia S F Santos https://orcid.org/0000-0002-7655-120X

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