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What is This?
Abstract
In the current work, the influence of filler particle size on the performance of the
composites was studied. Some physical parameters were measured for linear low-
density polyethylene (LLDPE) films reinforced with silicon dioxide (SiO2) powder. Sam-
ples filled with SiO2 of different particle sizes and concentrations were prepared. It was
found that fillers with small size caused an increase in mechanical properties of LLDPE at
lower concentration than that of particles with bigger size. This was confirmed experi-
mentally by measuring different physical parameters such as yield strength, coefficient of
thermal expansion, thermal conductivity, melting temperature, and structural morphol-
ogy. Therefore, filler sizes ranged from nano to micro could help in reducing the amount
of the usage of filler, which could overcome the recycling problems of the filled polymers
without affecting the end-use properties of the composite. Illustrations are given using
figures, images, and tables.
Keywords
LLDPE, thermal properties, structural morphology
Introduction
Addition of rigid particles to polymers could result in a number of desirable effects; for
example, an increase in mechanical stiffness, a reduction in coefficient of thermal expansion
Corresponding author:
RM Felfel, Department of Physics, Faculty of Science, Mansoura University, Mansoura 35516, Egypt.
Email: reda_felfel@yahoo.com
(CTE), and improvement in creep resistance and fracture toughness. Youngs modulus for
filled polymers (i.e. composites) results from interaction between the properties of the
composite constituents, such as matrix, reinforcement (fillers), and the interfacial region.
Mechanical properties of particulate composites are dependent on a number of parameters,
such as size, shape, aspect ratio, and dispersion of the reinforcing particles.19
Fu et al.10 investigated the effect of particle size, particle/matrix adhesion and particle
loading on stiffness, strength, and toughness. Range of filler sizes, from micro to nano,
was used and their aspect ratio was fixed at unity. They found that the composite strength
and toughness are strongly affected by all three factors, especially particle/matrix
adhesion. This was expected because strength depends on effective stress transfer
between filler and matrix. They also suggested that stiff particles affect the strength of
composites in two ways: weakening effect due to the stress concentration and the
reinforcing effect since they could act as barriers to crack growth. In some cases, the
weakening effect is predominant and thus the composite strength is lower than the matrix
alone; and in other cases, the reinforcing effect is more significant and the composites
will have strength higher than the matrix.
Cho et al.11 studied the effect of particle size on elastic modulus, tensile strength, and
particle/matrix debonding for vinyl ester resin using two types of particles such as glass
beads and spherical alumina (Al2O3). The mean size of glass beads was 500, 200, 70, and
6 mm in diameter. The mean size of Al2O3 particles was 70, 20, and 3 mm and 50 nm and
15 nm in diameter. The tensile strength of the composites enhanced with decreasing
particle size. They also found that all composites failed by debonding at particle/matrix
interface.
In this study, silicon dioxide (SiO2) powder with different sizes (33, 58, 92, 145, and
199 mm) was used as reinforcement for linear low-density polyethylene (LLDPE). The
influence of filler particle size and the weight fraction on mechanical, thermal, and struc-
tural properties of LLDPE/SiO2 composites were investigated.
Experimental
Materials
The polymer used in this study was LLDPE (LLD3505U; Egyptian European Company
(EEC), Cairo, Egypt). Melting temperature of LLDPE is in the range of 110125 C. Its
ignition temperature and relative density were 350 C and 0.9150.940 g cm3,
respectively. Five sizes of SiO2 were used as filler (Merck KGaA Co., Darmstadt,
Germany, molar mass 60.08 g mol1 and ignition temperature 900 C). The average
diameter of SiO2 particles was 33, 58, 92, 145, and 199 mm (denoted as S33, S58, S92,
S145, and S199, respectively).
Composite constitutes blending. In this stage, the LLDPE powder was mixed with SiO2
of different particle sizes and with different concentrations for each size. SiO2 with
weight fractions of 2, 4, 6, 8, and 10 wt% was added to 5 g of LLDPE using methylene
chloride as the dispersing medium. The mixture was then agitated for 30 min using a
magnetic stirrer to ensure better distribution of the filler and also to prevent the aggre-
gation of filler particles. Afterward, the mixture was casted in Petri dish and left for 6 h to
dry at 60 C in an electrical oven.
Film formation. The purpose of this stage was to convert the above mixture (LLDPE/
SiO2) into a film with a certain thickness (approximately 0.5 mm). The blend composition
was placed between two very smooth iron plates coated with hard chrome. The plates are
inserted into compressor hot press and the temperature was adjusted at 125 C using a
temperature controller. After melting for approximately 15 min, it was pressed to 0.5 mm
thickness. The plates were cooled quickly with cold water bath and then the film was
removed. All specimens were annealed at 60 C for 3 h to remove any frozen internal
stresses before any measurement.
LLDPE/SiO2 composites were prepared with different weight factions (2, 4, 6, 8,
and 10 wt%) and particle sizes (i.e. S33, S58, S92, S145, and S199). Table 1 sum-
marizes the codes, compositions, and weight fractions of the prepared composites in
the current study.
Characterization methods
Tensile test. The tensile measurements were carried out at room temperature (approx-
imately Tr 25 C) using a locally designed stressstrain testing machine. A load cell of
1 kN was used and the crosshead speed was 0.144 mm s1. The test was carried out for
four independent replicates in this study and the average was determined. Yield strength
was determined as the maximum tensile stress before the start of plastic deformation (see
Figure 1).
Thermal expansion. Linear expansion coefficients () of the samples were measured
using a technique designed by El-Tonsy.12,13 This technique has been previously dis-
cussed and used for thin films of polymeric and metallic materials.
In dilatometry, the linear expansion coefficient T is given by the well-known
formula:
L 1 L 1 thermal strain
T ;
L T Tr L T T
where L is the original length of the samples at Tr, T is the running temperature, and L
is the change in the sample length corresponding to a T in temperature. El-Tonsy12
reported that the maximum error obtained from this setup will not surpass +5.6%.
Melting properties. Melting temperatures of the samples were measured using differ-
ential thermal analyzer that was locally designed, manufactured, and calibrated using
1. LLDPE 2% S33 LLDPE/SiO2 composites of average grain size 33 m and filler content
2. LLDPE 4% S33 of 2, 4, 6, 8, and 10 wt%, respectively.
3. LLDPE 6% S33
4. LLDPE 8% S33
5. LLDPE 10% S33
1. LLDPE 2% S58 LLDPE/SiO2 composites of average grain size 58 m and filler content
2. LLDPE 4% S58 of 2, 4, 6, 8, and 10 wt%, respectively.
3. LLDPE 6% S58
4. LLDPE 8% S58
5. LLDPE 10% S58
1. LLDPE 2% S92 LLDPE/SiO2 composites of average grain size 92 m and filler content
2. LLDPE 4% S92 of 2, 4, 6, 8, and 10 wt%, respectively.
3. LLDPE 6% S92
4. LLDPE 8% S92
5. LLDPE 10% S92
1. LLDPE 2% S145 LLDPE/SiO2 composites of average grain size 145 m and filler content
2. LLDPE 4% S145 of 2, 4, 6, 8, and 10 wt%, respectively.
3. LLDPE 6% S145
4. LLDPE 8% S145
5. LLDPE 10% S145
1. LLDPE 2% S199 LLDPE/SiO2 composites of average grain size 199 m and filler content
2. LLDPE 4% S199 of 2, 4, 6, 8, and 10 wt%, respectively.
3. LLDPE 6% S199
4. LLDPE 8% S199
5. LLDPE 10% S199
standard materials such as benzoic acid (Tm 123 C) and tin (Tm 231.9 C).14 The
accuracy of this technique was estimated to be about +1%. The differential thermal
analysis (DTA) trace will be presented as the difference in temperature between the
specimen and empty pan against the sample temperature.
Figure 1. Stressstrain curve obtained from the tensile tester for pure LLDPE sample.
LLDPE: linear low-density polyethylene.
Qd
K ;
AT1 T2 t
where Q is the amount of heat passing in time t through the specimen with surface
temperatures T1 and T2, d is the thickness of the specimen, and A is the surface area of the
specimen through which the heat flow takes place. At least triplicates of specimens were
used for all tests and the error bars represent the standard deviation from the average.
Figure 2. A schematic diagram of the system used for the measurement of thermal conductivity
coefficient (K).
polymers such as polyethylene and polypropylene have weaker interface with inorganic
fillers such as glass and ceramic particles.16
The increase in the mechanical properties of LLDPE/SiO2 composites was sug-
gested to be due to the filler interaction between the polymer chains (i.e. cross linking
effect), providing localized regions of enhanced strength, which in turn can retard the
growth of cracks or cavities. The decrease in yield strength for the composites after
tipping point was attributed to agglomeration of the particles, which would weaken the
interfacial adhesion and reduce the number of debonding/voiding sites within the
composites.17
Polymer composites are usually composed of two or more distinctive phases that
exhibit an interface. The possible interactions between inorganic components and
polymer matrices are hydrogen bonds, interactions, van der Waals, or electrostatic
forces.18 A chemical bonding between the filler particles and the polymer matrix could
be achieved using a dual functional compound, which is able to react with the filler
surface and also cross-link into the polymer matrix (i.e. coupling agents).16,19 In this
study, no coupling agents were used and consequently the chemical bonding at filler
polymer interfaces is not expected. The bonding between SiO2 particles and LLDPE was
suggested to be only attributed to physical entanglement and mechanical adhesion.20
Local stress maxima developed around heterogeneities may initiate various
micro-mechanical deformation processes in polymers and polymer composites. The
basic deformation mechanisms of neat polymers are shear yielding and crazing,
while polymerfiller debonding is the dominating deformation process in
particulate-filled polymers. Number of debonded particles and the size of the formed
voids have direct influence on the macroscopic properties of composites.
The aggregation tendency of fillers usually increases with decreasing particle size,
and extensive aggregation would lead to insufficient homogeneity and lower mechanical
characteristics compared to polymers alone. Aggregated filler particles act as crack
initiation sites (i.e. crack tip).21 This could be the reason for decreased yield strength
after a certain concentration of SiO2.
Generally, recalling Figure 3, it is found that fillers with smaller size cause increase in
mechanical properties of LLDPE at lower concentration than particle of bigger sizes.
This behavior of composites is conventionally attributed to the enhanced energy
absorption as a result of the longer path, which the crack has to go through because it has
to bypass the numerous tiny particles; whereas larger particles act as stress con-
centrators.22 Furthermore, size of the voids created within the composites decreases with
decreasing filler size. Therefore, it was expected that the composites with smaller filler
size would have higher tensile properties in comparison to composites with bigger
sizes.23 It was also reported that large particles could easily debond from the matrix and
lead to the premature failure of the part under loading.21
Figure 3. Change in yield strength against SiO2 content of LLDPE/SiO2 composites. The tensile
test was conducted at Tr.
SiO2: silicon dioxide; LLDPE: linear low-density polyethylene; Tr: room temperature.
particle sizes S58 and S92, respectively, and no turning points were seen for bigger filler
sizes, S145 and S199.
Figure 5 shows the measured thermal strain of LLDPE reinforced with SiO2 of
average size 92 mm (S92).
From Figure 4, it can be concluded that the filler particle size and content play
important roles in controlling thermal expansion of composites. In addition, a good
correlation was observed between thermal expansion and mechanical properties. Linear
thermal expansion coefficient of the composites reached the minimum values at filler
content equivalent to maximum values of yield strength.
Most of the polymers have coefficients of thermal expansion at least an order of
magnitude greater than mineral fillers. Thus, mineral-filled composites have lower
coefficients of expansion than unfilled polymers and rule of mixtures could be applied
unless strong bonding occurs between filler and polymer.16 This might explain the
reduction in thermal expansion of composites with increasing filler content up to a cer-
tain limit.
As can be seen from Figure 4, after the thermal expansion coefficient of LLDPE/
SiO2 composites reached its lowest value, it started to increase with increasing filler
content. This increase in thermal expansion might be ascribed to an increase in the
amount of microscopic voids with increasing filler content and size. During the test,
the applied thermal stress inside the voids due to an increase in temperature (i.e. the
thermal expansion of voids) might be another reason for the increase in thermal
expansion of the composites.26
Figure 4. Change in linear thermal expansion coefficient of LLDPE/SiO2 composites versus filler
weight fractions and sizes.
LLDPE: linear low-density polyethylene; SiO2: silicon dioxide.
Figure 5. Thermal strain of LLDPE reinforced with SiO2 of average size for S92.
LLDPE: linear low-density polyethylene; SiO2: silicon dioxide.
10
Figure 6. Change in melting temperature of LLDPE/SiO2 composites having different filler sizes
and concentrations.
LLDPE: linear low-density polyethylene; SiO2: silicon dioxide.
Figure 7. Thermal conductivity coefficient (K) against concentration of SiO2 filler in LLDPE.
SiO2: silicon dioxide; LLDPE: linear low-density polyethylene.
11
Figure 8. Optical polarizing microscopic images of LLDPE/SiO2 composites after tensile testing.
LLDPE: linear low-density polyethylene; SiO2: silicon dioxide.
12
Figure 9. Optical microscopic image of the failure process via crack growth.
Conclusions
The mechanical properties (yield strength) and thermal properties of LLDPE/SiO2
composites with SiO2 filler of different size ranging from 33 mm to 199 mm were
investigated. The major findings can be drawn as follow:
From the above results and considerations, we conclude that the practical importance
of these values provides acceptable evaluations of structural morphology parameter
changes for LLDPE.
Funding
This research received no specific grant from any funding agency in the public, commercial,
or not-for-profit sectors.
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