Professional Documents
Culture Documents
Morphology, thermal,
mechanical, stress
relaxation, water
absorption and
impact properties
Suchart Siengchin1 and Vilai Rungsardthong2
Abstract
Binary and ternary composites composed of high-density polyethylene (HDPE), boehmite
alumina (BA) and different kinds of natural and animal fibers, such as flax, sponge gourd,
palm and pig hair (PH), were produced by hot press technique. Aqueous BA suspensions
were sprayed on the HDPE/flax mat to prepare nanoparticle/natural fiber–reinforced tern-
ary polymer composites followed by drying. The dispersion of the natural and animal fibers
and BA particles in the composites was studied by scanning electron microscopy and dis-
cussed. The thermomechanical and stress relaxation properties of the composites were
determined by the thermogravimetric analysis, dynamic-mechanical thermal analysis and
short-time stress relaxation tests (performed at various temperatures), respectively. The
HDPE-based composites were subjected to water absorption and instrumented falling
weight impact tests. It was found that all the composite systems increased the stiffness and
stress relaxation and reduced the impact toughness. The stress relaxation modulus of nat-
ural and animal fiber composites was higher compared with that of the neat HDPE. This
1
Department of Production Engineering, The Sirindhorn International Thai-German Graduate School of
Engineering (TGGS), King Mongkut’s University of Technology North Bangkok, Bang Sue, Bangkok, Thailand
2
Department of Agro-Industrial Technology, Faculty of Applied Science, King Mongkut’s University of
Technology North Bangkok, Bang Sue, Bangkok, Thailand
Corresponding author:
Suchart Siengchin, Department of Production Engineering, The Sirindhorn International Thai-German Graduate
School of Engineering (TGGS), King Mongkut’s University of Technology North Bangkok, 1518 Pibulsongkram
Road, Bang Sue, Bangkok 10800, Thailand.
Email: suchart.s.pe@tggs-bangkok.org
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1026 Journal of Thermoplastic Composite Materials 26(8)
modulus increased greatly with incorporation of BA. The relaxation master curves were
constructed by applying the time–temperature superposition principle. The inverse of
Findley power law could be fairly applicable to describe the relaxation modulus versus time
traces for all systems studied. Incorporation of BA particles enhanced the thermal
resistance, which started to degrade at higher temperature compared with the HDPE/flax
mat composite. The HDPE/flax mat/BA composite could reduce the water uptake.
Keywords
High-density polyethylene (HDPE), flax, natural and animal fibers, composites and stress
relaxation
Introduction
The use of polymer composites has increased substantially in engineering applications
due to their outstanding properties when compared with pure polymers. Polyethylene
(PE) is one of the most widely used polyolefin polymers. High-density PE (HDPE) was
used as the matrix for nano and natural composite materials and has attracted increasing
interest recently due to its excellent chemical resistance, high impact strength, good ther-
mal and mechanical properties.1–3 The utilization of the good thermal and mechanical
properties of boehmite alumina (BA) nanoparticles in the HDPE composites has been
studied.4,5 BA incorporation increased thermal stability and stiffness of HDPE and
enhanced the elongation at a break obviously at the same time, while impact resistance
of the HDPE/BA systems was reduced with increasing BA content. To achieve a fine
nanoscale dispersion of the fillers is a great challenge. Besides the traditional nanocom-
posite techniques for thermoplastics, the water-mediated dispersion of suitable nanofil-
lers has been recommended.6 It was noticed earlier that this preparation technique of the
nanocomposites has a strong impact on the remarkable property improvements.7
A variety of natural fibers such as rice husk,8 jute,9 flax10 and banana11 fibers have
been tested for use in HDPE/fiber composites. Natural fiber is straightforward not only
from the viewpoint of offering significant cost advantages and benefits associated with
processing compared with synthetic fibers but also with respect to the reduction in the
dependency on foreign and domestic petroleum oil. Several research articles deal with
the optimization of natural fiber-reinforced HDPE composites. Some investigations look
for ways to improve the interactions between polymer matrix and natural fibers. The use
of HDPE-based maleated coupling agents was helpful to increase the strength properties
of HDPE–wood-flour composites, due to the increased interaction between the wood
flour and the HDPE matrix.12 Choudhury13 demonstrated that the tensile and flexural
properties of ionomer-treated sisal/HDPE composites were strongly improved compared
with neat HDPE. Mulinari et al.14 studied the effect of modification of sugarcane bagasse
cellulose with zirconium oxychloride/HDPE composites. The modified bagasse reduced
the composites elongation. The increase in stiffness is associated with fibers reinforce-
ment at the cost of the tensile strength and ductility. This reduction is associated
with defects generated in the material after cellulose fibers insertion. The plant- and
animal-based fibers attracted much attention in the engineering and bioengineering
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Siengchin and Rungsardthong 1027
industries such as automotive and medical applications and have undergone comprehen-
sive researches for new composites. The goal of this study was to explore the potential of
the water-mediated technique using nanospraying to disperse suitable fillers on nanos-
cale and investigate the potential of flax, sponge gourd (SG), palm and pig hair (PH)
fibers produced reinforced HDPE composites. A further aim of this work was to demon-
strate the feasibility of the production of HDPE/flax mat/BA composites. Accordingly,
binary and ternary composites composed of HDPE, BA and different kinds of natural and
animal fibers were produced by hot press technique and the structure–property relation-
ships of the resulting compounds were evaluated.
Experimental
Materials and preparation of composites
Nonwoven flax fibers (flax mat; 220 g/m2) were supplied by Dittrich Vliesstoffe GmbH
(Ramstein-Miesenbach, Germany). The flax fibers in the nonwoven textile are randomly
orientated. The nonwoven textile is made of individual fibers. PH and oil palm empty
fruit bunch fiber are the byproducts obtained from two food processing plants in Thai-
land (Betagro safety Meat Packing Co., Ltd and Asian Palm Oil Co., Ltd) SG fibers are
commercially available in Thailand. The natural and animal fibers were used as reinfor-
cing fillers. The water dispersible BA (AlO(OH); Dispal111N7-80 of Sasol GmbH,
Hamburg, Germany) served as filler for all composite systems. The nominal particle size
of alumina in water was 220 nm, although that of the alumina powder as delivered was
40 mm. Alumina has Al2O3 content of 80 wt% and specific surface area is 100 m2/g.
HDPE (Finck&Co, Krefeld, Germany) was used as a polymeric matrix for all composite
systems and its density was 0.95 g/cm3.
The HDPE binary and ternary composites were prepared by nanospraying and/or hot
press methods, respectively. First, the HDPE/flax mat/BA ternary composites were
produced by a hot press using nanospraying technique. The BA particles were dispersed
in water at ambient temperature under continuous mechanical stirring for 30 min to
obtain aqueous BA slurry. The BA slurry was sprayed into the nonwoven flax fibers by a
hand spraying-up and dried for 48 h at room temperature (RT) and then for 24 h at 80 C
in oven. The flax mat contents in the binary composites were set for 20 and 40 wt%. The
flax mat and alumina or PH, SG, palm fibers contents in the ternary composites were set
for 20 and 10 wt%, respectively. The composites produced are listed in Table 1. The
HDPE ternary composites followed by hand lay-up process of natural or animal fibers
and then a layer of HDPE sheet. The binary and ternary composites based on HDPE,
after the BA particles spraying on the flax mat and dried, were compression molded into
1-mm-thick sheets at T ¼ 190 C using the hot press (P/O/Weber, Maschienen und Appa-
ratebau, Remschalden, Germany).
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1028 Journal of Thermoplastic Composite Materials 26(8)
Sample designation Flax mat (wt%) BA (wt%) PH (wt%) Palm (wt%) SG (wt%)
HDPE – – – – –
HDPE/flax mat(l) 20 – – – –
HDPE/flax mat(h) 40 – – – –
HDPE/flax mat/BA 20 10 – – –
HDPE/flax mat/PH 20 – 10 – –
HDPE/flax mat/palm 20 – – 10 –
HDPE/flax mat/SG 20 – – – 10
BA: boehmite alumina; HDPE: high-density polyethylene; PH: pig hair; SG: sponge gourd.
(Carl Zeiss GmbH, Oberkochen, Germany). The surface was gold coated prior to SEM
inspection, which was performed at low acceleration voltage.
Stress relaxation response. Short-time (duration 30 min) stress relaxation tests were
made in single cantilever mode at different temperatures, ranging from 5 to 45 C, using
the above-mentioned DMA apparatus. The strain applied was 0.5%. Isothermal tests
were run on the same specimen in the temperature range of 5–45 C by increasing its tem-
perature stepwise by 5 C. Prior to the stress relaxation measurement, the specimen was
equilibrated for 3 min at each temperature step. The specimen dimensions were
30 10 1 mm3 (length width thickness).
Water absorption. Water absorption of the composites was investigated over a period
of 30 days. The composites were cut into specimens (20 20 mm2) and then they were
immersed in water in a bath at RT. Weight gains were recorded by periodic removal of
the specimens from the water bath and weighing on a balance. The percentage gain at
any time t (Mt) as a result of moisture absorption was calculated from the following
equation
Ww Wd
Mt ¼ 100% ð1Þ
Ww
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Siengchin and Rungsardthong 1029
where Wd and Ww denote the weight of dry material (initial weight of materials) and
weight of materials after exposure to water absorption, respectively.
Instrumented falling dart impact. Instrumented falling weight impact (IFWI) tests were
performed on a Fractovis 6785 (Ceast, Pianezza, Italy) using the following settings:
incident impact energy, 20 J; diameter of the dart, 20 mm; diameter of the support rig,
40 mm; weight of the dart, 10.357 kg; drop velocity, 1.97 m/s. IFWI tests were
performed on quadratic specimens of 60 60 mm2 at RT.
Thermogravimetric analysis
The effects of BA particles and natural and animal fibers on the thermal stability of
HDPE systems are displayed in Figure 2. One can be recognized that thermal degra-
dation of HDPE was a one-step procedure representing depolymerization. The binary
and ternary composite systems exhibited two-step–like transitions. Due to the dehydra-
tion from cellulose unit and thermal cleavage of glycosidic, the decomposition tempera-
ture of HDPE/fibers composites was comparatively lower than that of the HDPE as
reported for jute/HDPE composites.9 One can recognize that the thermal stability
decreased remarkably with increasing of flax mat content in the HDPE at whole tempera-
ture range. For the composites containing 20 wt% flax mat, the weight loss as reaching
370 C, was enhanced by approximately 15% compared with the HDPE/flax mat 40 wt%.
The incorporation of BA particles strongly improved the thermal degradation of the
HDPE/flax mat composite. In addition, it has to be mentioned that BA for improving the
thermooxidative stability has been reported for PEs and Polyoxymethylene (POM).4,15
The HDPE/flax mat/BA composite started to degrade at higher temperature compared
with the HDPE/flax mat composite. Note that the resistance to thermal degradation of
the HDPE/flax mat/PH composite was slightly higher than those of composites contain-
ing palm and SG. One possible explanation is that the high moisture content of natural
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1030 Journal of Thermoplastic Composite Materials 26(8)
Figure 1. SEM image from the fracture surfaces of HDPE/flax mat (a), HDPE/flax mat/BA (b),
HDPE/flax mat/PH (c), HDPE/flax mat/palm (d) and HDPE/flax mat/SG (e) composites. BA: boeh-
mite alumina; HDPE: high-density polyethylene; PH: pig hair; SEM: scanning electron microscopy;
SG: sponge gourd.
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Siengchin and Rungsardthong 1031
Figure 2. Weight loss versus temperature for the HDPE systems studied. HDPE: high-density
polyethylene.
fibers also caused a great problem for thermal properties. The change in the TGA values
shows the moisture difference between PG and natural composites. This finding is in
agreement with that reported by Cheung et al. who observed that the composite with ani-
mal fiber provided better thermal properties also.16
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1032 Journal of Thermoplastic Composite Materials 26(8)
Figure 3. E0 (a) and tan (b) versus T traces for the HDPE systems studied. HDPE: high-density
polyethylene.
processes in pure HDPE describe three transitions, namely, a-, b- and g-relaxations from
higher to lower temperature.17,18 The relaxation transition (g) located at 110 C was
assigned to the glass transition temperature. The b transition of HDPE was invisible due
to the absence of the chain branches. The latter peak in HDPE (a-relaxation at
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Siengchin and Rungsardthong 1033
approximately 80 C) was usually attributed to the chain segment mobility in the
crystalline phases and reoriented defect in crystalline phases. One can notice that the
g-relaxation peak of HDPE also exhibited a shift to high temperature regions with
the incorporation of BA particles. The shift of this peak toward higher temperatures due
to alumina indicates for the reinforcing effect. On the other hand, the effect of natural
and animal fibers on the relaxation transitions was marginal.
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1034 Journal of Thermoplastic Composite Materials 26(8)
Figure 4. Characteristic relaxation modulus–time curves registered for the HDPE systems stud-
ied at testing temperature of 5 C (a) and 45 C (b). HDPE: high-density polyethylene.
Figure 4(a) to (b) display the stress relaxation modulus (Er) as a function of time for
the binary and ternary composites systems containing different amounts of flax mat at
temperature of 5 C and 45 C, respectively. The solid lines appearing in each curve
represents the calculated data using the inverse of the Findley power law model. It is
clear from Figure 4 that the relaxation modulus decreased with increasing temperature.
The Er values of the all composites systems were higher when compared with the HDPE.
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Siengchin and Rungsardthong 1035
For the relaxation modulus of HDPE/flax mat/BA ternary composite after the relaxation
time of 1800 s was increased by 25% and 40% at T ¼ 5 and 45 C, respectively, compared
with the HDPE/flax mat binary composite. This relaxation modulus increased greatly
with incorporation of BA particles due to the development of a restricted molecular
mobility. This phenomenon, observed also in DMA test and reported in Polystyrene
(PS),21 is associated with a pronounced increase in the stiffness. One can also recognize
that the HDPE/flax mat/SG composite exhibited higher relaxation modulus value than
the composites containing PH and palm. The DMA corroborated this fact by indicating
that the storage modulus of roughness surface SG was shifted toward higher values
(compare Figure 3(a)). However, the difference in the relaxation modulus between
natural and animal fibers diminishes with increasing temperature. Figure 5 demonstrates
the effect of increased temperature on the relaxation modulus response of HDPE/flax
mat composite. One can recognize that the shape of relaxation curves of the composites
was similar at all test temperature. The time-independent relaxation modulus (ErF0)
increased remarkably with increasing temperature.
Master curves of the relaxation modulus were produced by superimposing the
relaxation modulus versus time traces using the time–temperature superposition (TTS)
principle. A reference temperature (Tref ¼ 25 C) was used for this superposition
(shifting) process. The related shift factor (aT) used for the generation of relaxation
modulus master curve is aT ¼ Er(T)/(Er(Tref)). Master curves of the relaxation modulus
against time created and simulated fits according to the inverse of the Findley power law
at a reference temperature of 25 C are shown in Figure 6 for the HDPE, HDPE/flax mat
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1036 Journal of Thermoplastic Composite Materials 26(8)
Figure 6. Relaxation modulus master curves constructed by considering the TTS and selecting
Tref ¼ 25 C and their fitting by the Findley power law equation (inverse). TTS: time–temperature
superposition.
and HDPE/flax mat/BA composite. The shift factors are linked with TTS via the
Arrhenius function. From the shift factors for the relaxation modulus of the HDPE, the
activation energy of 200 kJ/mol can be calculated. The activation energy of the HDPE/
flax mat and HDPE/flax mat/BA binary and ternary composites was calculated as 157
and 153 kJ/mol, respectively. One can notice that the relaxation modulus increased with
decreasing activation energy and addition of flax and BA reinforcements. On other hand,
the related curves show a good fit between the experimental and the simulated results
according to the Findley power law. This power law fits very well to the relaxation
modulus data for all systems up to approximately 1333 min.
Water absorption. Figure 7 depicts the water uptake as a function of time for the
binary and ternary composites systems containing different amounts of flax mat. The
water uptake was 0.93% after subjected to water absorption. This was due to the light
interaction with water. A rapid water uptake was observed for all binary and ternary
composites within the first 7 days of immersion. The water absorption of composite
systems was reached quasi-equilibrium state after 18 days. One can also recognize that
the penetration of water increased markedly with increasing flax mat content in HDPE
matrix. Note that the incorporation of BA particles in the HDPE/flax mat composite
could reduce the water uptake. The HDPE/flax mat/BA composite recorded water
absorption value at 4.87% upon 30 days. This is in accordance with recent reports claim-
ing that the water absorption was reduced by adding nanofillers. For polyester and poly-
esterimide with silicon dioxide, titanium dioxide and zinc oxide composites when
compared with standard compounds, showed better water resistance.22 On the other
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Siengchin and Rungsardthong 1037
Figure 7. Water uptake on the binary and ternary composites systems containing different
amounts of flax mat. Fick’s law was used to calculate the diffusion coefficient of water absorption
(D) after 30 days immersed in water, that is D ¼ (kb/40)2.
hand, the water sorption behavior was slightly considered to depend on the types of rein-
forcing fibers. The water uptake of HDPE/flax mat/PH composite was reduced by
approximately 33% and 14% as reaching 30 days compared with the composites contain-
ing SG and palm, respectively. Fick’s law was adopted to calculate the diffusion coeffi-
cient (D) of water absorption values. It is well resolved that there is a fair agreement
between the water uptake and those calculated by the Fick’s law. By comparing the dif-
fusion coefficient (compare Figure 7), one may conclude that the D of HDPE/flax mat
composite decreased with incorporation of BA. This result suggests that D may be sen-
sitive to the nanoparticles barrier effect. It has also been observed that these nanofillers
reacted with water lead to decrease the rate of diffusion.23,24 Addition of SG and palm
fibers into the HDPE/flax mat also yielded an increase in diffusion coefficient of water
absorption.
Falling dart impact response. The reinforcing effects of the BA particles and natural and
animal fibers on the force versus time curves are demonstrated on the HDPE systems in
Figure 8. Observation of impact energy indicates that the natural and animal fibers
enhanced the stiffness and reduced the toughness of the related composites at the same
time. Addition of the BA in HDPE/flax mat composite was accompanied with a shift of
the force peak toward higher force and longer time. This is due to the nanoparticle
character of the reinforcing effects. Note that the BA reinforcing the matrix in HDPE/
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1038 Journal of Thermoplastic Composite Materials 26(8)
Figure 8. Characteristic force–time curves for the HDPE systems studied. HDPE: high-density
polyethylene.
flax mat system leads to increased stiffness and accompanied with reduced ductility.
This is in qualitative agreement in accordance with the DMA results (compare Figure 3(a))
and the reduction in impact toughness of HDPE by BA particles was also discussed in Ref.
[5]. The presence of SG fibers was associated with a reduction in the maximum force peak
compared with the PH and palm reinforcements. Accordingly, the observed impact
resistance is likely less due to the BA particles themselves, but more due to their amount of
flax fibers.
Conclusion
This work devoted to study the morphology, thermal, mechanical, stress relaxation,
water absorption and falling weight impact properties of a HDPE and its PH, palm, SG
fibers and BA reinforced binary and ternary composites. The BA was introduced in the
HDPE/flax mat in 10 wt% via spraying method. Based on this work, the following
conclusions can be drawn:
1038
Siengchin and Rungsardthong 1039
The stress relaxation values of the all composites systems were higher compared with
the HDPE. This relaxation modulus increased greatly with incorporation of BA parti-
cles due to the development of a restricted the molecular mobility. With addition SG
exhibited higher relaxation modulus value than the composites containing PH and
palm. Based on isothermal short-term stress relaxation experiments master curves in
form of stress relaxation modulus versus time were constructed by TTS principle. The
related master curves could be well described by the inverse of the Findley power law.
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