J of Applied Polymer Sci - 2020 - Kalantar Mehrjerdi - Influence of Talc Fillers On Bimodal Polyethylene Composites For

Received: 31 October 2019 Revised: 13 March 2020 Accepted: 16 March 2020
DOI: 10.1002/app.49290
ARTICLE
Influence of talc fillers on bimodal polyethylene composites

for ground heat exchangers
Adib Kalantar Mehrjerdi | Dan Åkesson | Mikael Skrifvars
Swedish Centre for Resource Recovery,

Faculty of Textiles, Engineering and
Abstract
Business, University of Borås, Borås, In this study, a commercial grade of talc is used as filler in a bimodal high-
Sweden
density polyethylene (HDPE) used for the pressure pipe application. The com-
Correspondence posites are characterized by thermogravimetric analysis (TGA), differential
Adib Kalantar, Swedish Centre for scanning calorimetry, dynamic mechanical thermal analysis, and tensile test-
Resource Recovery, Faculty of Textiles,
ing. The results illustrate that the presence of talc has a considerable effect on
Engineering and Business, University of
Borås, 50190 Borås, Sweden. the material properties and the pipe life-length. It is presented that the thermal
Email: [email protected] stability measured by TGA is enhanced, while the oxidation induction time
Funding information
decreases in cooperation of the talc. The nucleation behavior of talc particles
Muovitech AB during crystallization has no obvious effect on melting temperature; however,
an increase in crystallization temperature is evidenced. Storage modulus as
recorded from the dynamic mechanical analysis is also increased in all com-
posites, furthermore, the temperature of the α relaxation is shifted toward
higher temperature and finally the strain hardening modulus for the HDPE/
talc composites is assessed and compared to the neat HDPE as a measure of
environmental stress crack resistance.
KEYWORDS
ageing, degradation, thermal properties, thermogravimetric analysis (TGA)
1 | INTRODUCTION borehole to collect/reject heat from/into the surrounding.

A fluid (e.g., glycol/water mixture) circulating in the
Geothermal energy has a unique position, among the pipes transfers the heat from the ground to the heating
renewable energy resources. Near-surface or shallow gro- system. GSHP systems have an average of 50 years life
und maintains almost constant temperature during the expectancy for the underground infrastructure (GHE).
seasons, so it can be used as a heat source during the Two design parameters, that is, ground thermal conduc-
wintertime and as a heat sink during the summertime. tivity and borehole thermal resistance are required for
A geothermal heat pump system or ground source heat the sizing of GSHP systems. Ground thermal conductivity
pump (GSHP) system consists of a heat pump that is con- is a physical property of the ground surrounding the
nected to the delivery system and a ground heat boreholes, and borehole thermal resistance is defined as
exchanger (GHE). The GHE is a loop or system of pipes the thermal resistance between the heat carrier fluid in
buried horizontally in the ground or vertically inside of a the GHE and the borehole wall and should be kept as
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KALANTAR MEHRJERDI ET AL. 2 of 11
small as possible. It gives temperature difference between extrapolated to a desired lifetime, and the maximum
the fluid in the GHE and temperature at the borehole hoop stress (or MRS) can be extracted. However, recently
wall and is typically shown thermal resistance per unit many investigators have demonstrated the link between
length of the borehole ( K/W m).1,2 Borehole thermal the GCG and the resistance against further deformation
resistance depends on the conductive and convective above the natural draw ratio like <Gp>.6,7 The total fail-
resistance of the fluid, the thermal resistance of the GHE ure time can be divided into three sequential steps:
pipes, and physical properties of the backfilling (a) crack initiation, (b) crack growth step (very slow pro-
material.3,4 gress), and (c) post-yield tensile stretching.
GHE pipes are most often made of a bimodal polyeth- However, this material with its attractive features
ylene (PE) thanks to its versatile properties profile. PE is such as low price, good chemical resistance, good pro-
one of the most widely used plastic commodities with a cessability, toughness and flexibility, weld ability, and so
wide variety of applications. It is available in different forth has unfortunately rather low thermal conductivity.
lengths of the polymer chains, degrees of crystallinity, In the GSHP systems, this parameter has a great influ-
molecular mass distribution, and short- or long-chain ence on the overall borehole thermal resistance.8 In
branches. Due to these characteristics, PE has different recent years, significant research efforts have been made
properties to accommodate specific application needs. to improve the thermal conductivity of the polymers. Sev-
The most important parameter, governing resin eral inorganic materials such as graphite and metallic
properties is the density, which is taken as a measure of powders have frequently been used as thermo-conductive
crystallinity and amount of short-chain branches, that is, fillers in potential applications in the automotive, aero-
high-density polyethylene (HDPE). However, PE used in space, constructions, and electronic industries.9–11 In the
pressure pipe applications is no longer classified by den- geothermal sector, commercial GHE pipes made from
sity; instead, they are now ordered into the minimum HDPE are loaded with inorganic fillers such as talcum
required strength (MRS) classes based on the interna- powder or carbon black in order to modify the thermal
tional standard ISO 9080. PE100 pipes are made from a conductivity of the pipe, which can reduce the borehole
bimodal molecular weight distribution type considered as thermal resistance.12,13 Gosselin et al. and Kalantar et al.
HDPE and have MRS of 10 MPa (i.e., the pipe must with- have shown an increase of thermal conductivity by about
stand a hoop stress of 10 MPa for up to 50 years at 20 C). 75% compared to unfilled grades of HDPE that are used
The aim of using bimodal molecular weight distribution for GHEs. Design calculations indicated that these ther-
PE is to associate low- and high-molecular-weight com- mally enhanced materials can reduce the thermal resis-
ponents in different concentrations. PE100 grade is desir- tance of the boreholes up to 50%, which allows up to 25%
able because it can combine the advantageous reduction of the total drilling length required to fulfill the
mechanical properties such as resistance to slow crack building heating and cooling need.12,13 Most of these
growth (SCG) due to the high-molecular-weight fraction studies have focused on the thermophysical properties of
combined with the improved processing properties of the the composites; however, there has been less work
low-molecular-weight fraction.5 A typical PE100 pipe addressing the effect of fillers on the pipe morphology
compound includes the base HDPE resin, carbon black and long-term impact under loads.
added to around 2.5 wt% as an outdoor stabilizer to pro- Therefore, this study was undertaken to investigate
tect the material against degradation from the UV radia- the influence of talc filling in a bimodal PE100 matrix on
tion, processing stabilizers intended to provide protection the thermal oxidation, morphology, dynamic mechanical
against oxidation during pipe extrusion at high tempera- behavior, and strain hardening. The thermal decomposi-
ture, and other antioxidants to prevent oxidation caused tion, pyrolysis mechanisms, and thermal stability of poly-
by long-term exposure to an oxidative agents such as olefins are well studied by thermogravimetric analysis
water disinfectants and air (oxygen) dissolved to the (TGA),14–16 meanwhile the thermal-oxidative aging prop-
water. erties are investigated by oxidation induction time (OIT)
It is widely recognized that fracture at low stresses is test,17 which is described in ISO 11357-6. This method is
the most common mode of failure for pressure PE pipes, widely recognized to predict the lifetime of plastic
known as SCG or environmental stress crack. Therefore, pipes.18–21 Analysis of melting and crystallization kinetics
it is useless to apply a design stress for the pipes using a of samples is carried out using a differential scanning cal-
tensile test to establish the maximum load that such a orimeter (DSC) method based on the ISO 11357-3. The
pipe can withstand over its lifetime. Typically, a graph dynamic behavior of polymer composites is governed by
showing the logarithm of pipe hoop stress versus loga- the matrix properties and the filler/discrete phase; there-
rithm of failure time is constructed. From the graph, the fore, dynamic mechanical analysis (DMA) is a useful tool
transition from ductile to brittle failure (knee) is for measuring the composite material properties in the
3 of 11 KALANTAR MEHRJERDI ET AL.
solid-state under dynamic conditions as a function of slowly cooling under pressure) to obtain 100 × 100 mm2
temperature or frequency.22–24 Finally, strain hardening plates with a thickness of around 1 mm. After pressing,
modulus obtained from the tensile test is used to evaluate the samples were annealed in a furnace for 1 hr at 120 C
SCG resistance. and then slowly cooled down to room temperature by
switching off the heating of the chamber. Finally, speci-
mens were cut by laser machine (GCC Laser Pro – Spirit
2 | EXPERIMENTAL GLS) to specimens for tensile testing and dynamic
mechanical thermal analysis (DMTA).
2.1 | Material
An HDPE pipe grade P600 BL of strength class PE100 in 2.3 | Characterization

granular form was supplied by KPIC, Korea. This HDPE
is commercially used for extruded pipes and is classified The thermal stabilities of HDPE composites were studied
as an MRS 10 according to ISO 9080. It has a melt flow by using a TGA apparatus supplied by TA instruments Q
rate (190/5) of 0.21 g/10 min and a density of 500, USA. Samples of 7 ± 3 mg were heated at 10 C/min
0.960 g/cm3. Talc powder supplied by Ubersicht Talkum, in an air purge stream from 30 to 750 C. The flow rate
Germany was used as filler. The density of the material was 50 mL/min. The weight change as a function of tem-
was 2.77 g/cm3, and the particle size distribution is pres- perature was recorded and analyzed. The relative thermal
ented in Table 1. stability of the samples is evaluated by T5, T50, and Toffset
from the thermogravimetric (TG) and derivative ther-
mogravimetric (DTG) curves. The onset temperature of
2.2 | Compounding and sample decomposition (T5) and maximum decomposition peak
preparation (T50) can be considered as the temperature at the 5 and
50% weight loss, respectively, and finally the Toffset,
Both the PE100 and the talc were dried overnight to expel which is extrapolated offset temperature of the DTG cur-
any moisture prior to the blending, in a vacuum oven at ves, represents the end of decomposition.
70 C. The weighed materials (0, 10, 15, and 25 wt% talc Analysis of melting and crystallization kinetics of var-
concentration) were loaded into a 15 cm3 twin-screw ious HDPE samples was carried out using DSC type TA
micro-compounder (DSM Xplore, The Netherlands). The instruments Q 2000, USA. The conditions applied to
compounding was done at 200 C and 50 rpm for 5 min. determine the melting and crystallization behaviors
Argon gas was used to maintain an inert environment in together with calculation of characteristic parameters:
the compounder. The extruded strand was cooled in air, Samples were heated up in aluminum pans under a
pelletized by cutting, and kept in a glass desiccator before nitrogen flow (50 mL/min) from 30 to 180 C at 10 C/min
further analysis or making specimens. The compositions and maintained at 180 C for 5 min to erase any previous
of each sample are presented in Table 2. Plates were then thermal history. Then, the samples were cooled down to
made by compression molding of the blended material. 30 C at 10 C/min, maintained at isothermal conditions
Compression molding was adapted from ISO 18488:2015 for 1 min and finally heated up to 180 C at 10 C/min.
(by increasing pressure to 40 kN in 13 min at 160 C and The determination of the OIT was performed on the
same DSC instrument. Samples were heated up to 200 C
at 20 C/min and then the gas was switched from nitro-
TABLE 1 Size distribution of talc (data from the supplier) gen to oxygen. The samples were then maintained at
Talc grade D100 (μm) D98 (μm) D50 (μm) 200 C until the maximum exotherm peak was reached.
The induction time is taken as the time between the gas
HB-M45B 45 38 7.6
switching and the onset of the heat flow peak.
The time–temperature dependency of the mechanical
properties was determined by DMTA using a TA instru-
TABLE 2 Composition of PE100/talc blends
ments Q800 supplied by Walters LLC, USA. In this study,
Sample HDPE wt% Carbon black wt% Talc wt% the specimens were deformed under flexure using a sin-
PK 97.5 2.5 0 gle cantilever clamp arrangement, at a frequency of 1 Hz.
10PK 87.75 2.25 10 The specimen dimensions were 17.5 × 4.9 × 1.1 mm.
Transitions are studied from a thermal sweeping, from
15PK 82.87 2.13 15
−65 to 110 C at a rate of 3 C/min. The viscoelastic prop-
25PK 73.13 1.87 25
erties, such as the storage modulus (E0 ), loss modulus
(E00 ), and tan δ (E00 /E0 ) were recorded as a function of thermal decomposition temperature (T5) of PE100 is
temperature. noticeably increased with the addition of talc. For exam-
Tensile test was carried out to calculate the strain ple, the T5 for sample 25PK is 406 C, about 70 C higher
hardening modulus using a universal testing machine than for pure PE100, which indicates that the presence of
(Tinius Olsen H10KT) on dumbbell-shaped specimens in talc slows down the thermal decomposition of PE100
accordance with the ISO 18488:2015 standard.25 The remarkably. With increasing talc content, the onset tem-
strain hardening modulus was determined from the slope perature for HDPE/talc composites changes slightly.
of the true stress–true strain curves. The modulus <Gp> The observed values obtained for T5 in this study are
was calculated from Neo-Hookean Strain Measure model lower than our previously reported data,26 where a
between a true strain of 8 and up to the point of maxi- unimodal HDPE and talc were used. This can be
mum stress, but less than a strain of 12.6 Tests were per- explained by two clarifications: First, since air was used
formed in two different conditions: (a) at room in the current study as a purge gas, consequently it can
temperature at a drawing speed of 0.5 mm/min and (b) at accelerate the degradation process of the HDPE via reac-
80 C with complete accordance with the ISO 18488:2015. tion with oxygen, therefore, the onset thermal decompo-
The elongation was determined with a laser extensome- sition temperature can shift toward higher temperature
ter; therefore, two reflecting and self-adhesive gauge in the nitrogen environment. In fact, the degradation
marks were attached to the test specimens. The initial mechanism of PE includes probably a series of several
distance between these marks (gauge length) was set to complex reactions, as it was suggested by Peterson,27
12.5 mm. The reported results are based on measure- although the primary degradation is through the random
ments of five specimens from each batch. scission chain branching can occur simultaneously. Sec-
ond, PE100 has a bimodal molecular weight distribution,
due to the presence of more short branching in the high-
3 | R ES U L T S A N D D I S C U S S I O N molecular-weight part and therefore greater probability
of chain scission in the larger molecules, the high-molec-
3.1 | Thermal properties ular-weight part may degrade prior to the low-molecular-
weight part.28 A practical implication that can be drawn
3.1.1 | Thermogravimetric analysis from this conclusion is that enhancing the thermal stabil-
ity by adding talc may have a positive effect on the pro-
The thermal stability of PE100 and PE/talc composites cess conditions related to the allowable welding
was tested by TGA, and their TG and DTG curves in the temperatures during the electrofusion process.29 During
air atmosphere are shown in Figures 1 and 2, with the electrofusion welding process, excessive welding time
detailed data listed in Table 3. Neat PE100 starts to can result in high temperatures in the area of fusion
decompose at around 336 C and at the decomposition joints, where thermal degradation of PE may occur.
proceeds until 488 C. According to the TG plots, the It is deduced from Figure 1 that the mass loss for pure
shape of the TG curves is almost the same for all the talc in the interval from room temperature up to 800 C
PE/talc composites, indicating that they have the same was about 2.5% and this small decomposition started just
pyrolysis behavior and a change in the filler content may below 650 C. In addition, nearly 100% of the PE in all
not lead to a significant change in the mechanism of the samples degraded up to 500 C, and the remaining residue
reaction; however, differences can be recognized when contained carbon black and talc. Since the analysis was
comparing with the plot for neat PE100. The onset done in the air, almost all carbon black and small
amount of talc degraded. The amount of final residue
increased correspondingly with the proportion of filler,
and the percentage of residue for talc was in accordance
with the compounding values given in Table 2.
A derivative plot of mass loss versus time for the TGA
data in the air indicates numerous degradation steps, as
very irregular sharp points and peaks arise for all sam-
ples. In addition, the thermal degradation of PK mainly
occurs under a narrow temperature range indicating the
temperature sensitivity of the thermal degradation of
F I G U R E 1 Thermogravimetric plots showing the mass loss PE100. However, due to the addition of talc particles, the
(%) versus temperature with a heat rate of 10 C/min in air number of decomposition steps decreased, and the begin-
atmosphere [Color figure can be viewed at wileyonlinelibrary.com] ning of the decomposition is shifted to a higher
F I G U R E 2 Derivative mass loss (DTG) versus temperature for all studied samples shown on the temperature range of 300–550 C for
ease of comparison [Color figure can be viewed at wileyonlinelibrary.com]
TABLE 3 Characteristics of the

Sample T5 ( C) T50 ( C) Toffset ( C) Residue @ 700 C (%)
TG and DTG measurements of PE100/
talc composites PK 336 437 488 0.6
10PK 366 445 500.5 10.28
15PK 396 461 501 15.11
25PK 406 458 475 25.88
Talc – – – 97.46
temperature as can be observed in Figure 2. The

retarding effect by the addition of talc might be attributed
to increase of the activation energy of thermal oxidation,
and thus, this enhances the thermal stability of PE100 as
it was also observed in another research study.30
3.1.2 | Oxidation induction time
The effective antioxidant content of the test samples was

determined using the oxidative induction time (OIT) test.
F I G U R E 3 Schematic diagram for the determination of
Figure 3 illustrates a schematic diagram of a typical OIT oxidation induction time (OIT) as the onset of oxidation
thermogram. The OIT values represent a sensitive mea- decomposition [Color figure can be viewed at wileyonlinelibrary.com]
sure of stabilizer consumption and residual stabilization
effectiveness. The more resistant to oxidative degradation
the sample is, the higher the OIT value is. Figure 4 shows
the effect of talc on the OIT for PE100. Surprisingly, it Similar behavior has also been reported in other stud-
was observed that the OIT values decreased continuously ies.17,31,32 This phenomenon may be explained that the
with increasing talc content. Contrary to 93.5 min of OIT increase of hydroxyl groups ( OH) in composite material
of PE100, it was 4.8 min for the PE100 specimen with provided by talc can lead to side reactions during decom-
25 wt% talc loading. positions and accelerates thermal oxidation.17,33
The above result is, however, not consistent with the the heat of fusion (ΔHm), the initial crystallization tem-
TGA test result. The surprising disagreement between perature (Tc onset), and the maximum crystallinity tem-
OIT and TGA results could be explained that these two perature (Tc peak) are extracted from the DSC curves and
tests represent different aspects of the thermal degrada- given in Table 4. Degree of crystallinity (Xc) is calculated
tion process of the HDPE composites. In the former, the using the following equation:
focus is on thermal oxidation, while in the later, the ther-
mal decomposition due to chain rupture is determined. ΔH m
X c% = × 100
In other words, only when a chain ruptures and volatile ΔH o o × w
fragments are formed, the weight loss may occur and can
be detected in a TGA measurement. where, ΔHo is the assumed heat of fusion of 100% crystal-
An important practical implication of these findings line HDPE (293 J/g) and w is the mass fraction of resin
is that talc might reduce the efficiency of stabilizers by (HDPE) in the composites.
adsorbing them on their surface, which as a result In the DSC tests, each PE and PE/talc blend sample
reduces the expected service lifetime of the stabilizers. showed a single melting peak in the heating scan and
This adverse effect might be reduced or prevented by there was no visible difference in the melting tempera-
adding more stabilizers to compensate for the adsorbed ture of HDPE among all the samples, meanwhile, the
part, or by adding modifiers with higher affinity for talc heat of fusion decreased continuously with increasing
to coat the talc surface. However, there is a need for more talc content. Nevertheless, reduction in the heat of fusion
intense investigation to test the robustness of this has not substantially changed the crystallinity of the
phenomenon. PE100/talc composites compared with neat HDPE. The
obtained DSC cooling scans can be seen in Figure 5. One
of the most noteworthy trends extracted from Figure 5 is
3.1.3 | Differential scanning calorimetry that both the onset and the peak crystallization tempera-
tures increased by close to 3 C when adding talc, which
The influence of talc filler on the crystallization and melt- implies that the introduction of the talc even in the low-
ing of PE100 was studied by DSC measurements. Some est concentration could promote crystallization capability
useful kinetic parameters such as the melting tempera- of the PE100 resin, whereas talc concentration has a simi-
ture (Tm onset), the melting peak temperature (Tm peak), lar marked effect on the crystallization temperature. The
increasing of Tc onset in presence talc particles might be
attributed to heterogeneous nucleation caused by
fillers.34
This means that the crystallization kinetics is
enhanced with the addition of nucleation seeds. The
maximum crystallization rate is not significantly
increased for the composites (179 J/g for the neat PE100
vs. 183 J/g with 25 wt% talc). It can be noticed that the
talc also has another effect by inducing pre-starting of the
crystallization (small crystallization peck) at around
129 C for all the composites, as seen in the upper-left cor-
F I G U R E 4 Comparing oxidation induction values of the ner of the Figure 5.
PE100 and PE100/talc composites (mean value of at least three Therefore, it can be concluded that the introduction
measurements, error bar shows calculated SD) of talc provides a strong nucleating effect that can
TABLE 4 Thermal properties of neat PE100 and PE100/talc composites by a standard heating–cooling–heating procedure at a rate of
10 C/min (Mean value of three measurements are listed)
Sample Tm onset ( C) Tm peak ( C) ΔHm (J/g) Tc onset ( C) Tc peak ( C) Xc (%) ± SDa

PK 117.25 132.59 172.00 117.78 110.92 59.93 ± 1.03
10PK 117.18 131.02 156.30 120.33 113.08 60.91 ± 1,65
15PK 117.28 132.8 143,23 120.49 113.13 59.23 ± 0.24
25PK 117.66 131.9 131.77 120.87 114.31 62.30 ± 1.32
a
Calculated SD of three measurements.
F I G U R E 5 Differential scanning calorimetry (DSC) cooling scans for PE100 and PE100/talc composites. The upper-left corner shows
the effect of talc on the crystallization for PE100 with 25 wt% talc [Color figure can be viewed at wileyonlinelibrary.com]
accelerate the process of crystalline nuclei formation by compression stress along the outer wall and as tension
multiplying the number of crystalline units in the matrix, stress along the inner wall thickness of the pipe. It is rea-
thus a greater number of small but more regular crystal- sonable to expect that these residual stresses accelerate
line units are generated. Similar experimental results the failure in the pipes under pressure.40 Hence, it can be
have been obtained previously and are reported in the deduced that talc can obviously promote the nucleation
literature.35,36 rate and crystallization behaviors of PE100; therefore, the
Further calculation of the density of the neat PE gravity-induced sag and residual stress in pipe production
100 gave a value of 0.95 g/cm3, which agrees with the is expected to be effectively avoided due to fast hardening
results of the overall crystallinity. These values are in the of the molten material. Besides, systematic improvement
low range for a typical HDPE polymer, which is attrib- in pressure performance of PE pipes may be enhanced by
uted to the bimodal nature of PE100 resins. The incorpo- the reduction of residual stresses. This could be an addi-
ration of short-chain branches and high molecular tional benefit when adding talc to the material.
weight can reduce the degree of crystallinity, and hence
the resin density.
In the pipe industry, it has been widely accepted that 3.2 | Mechanical properties
the production of large diameter and thick wall pipes is
problematic. Due to the large wall thickness, the cooling 3.2.1 | Dynamic mechanical thermal
process of the pipe after leaving the extruder die head is analysis
very slow and therefore, the gravity of the resin leads to
sagging of melted polymer,37,38 resulting in very inhomo- The storage modulus, E0 and the loss modulus, E00 were
geneous wall thickness distribution. Thus, the wall thick- measured from the DMTA tests. The variations of storage
ness at the upper part of the pipe becomes smaller than modulus and the loss modulus, with temperature for dif-
at the lower part of the pipe. Another problem is the for- ferent formulated PE100/talc composites, are graphically
mation of a thermal gradient across the pipe wall during presented in Figure 6 with detailed data listed in Table 5.
the cooling process. The outside and inside surfaces are The storage modulus (E0 ) shows a continuously decreas-
cooled down by a water spray and solidified quickly. The ing trend with increasing temperature for the composites.
crystallization and shrinkage of the core region will, This behavior is typical of polymeric materials since the
therefore, be much slower, which causes formation resid- chain movement and relaxation times of the polymer are
ual stress within a pipe.39,40 These residual stresses act as increased at higher temperatures. There is a notable
FIGURE 6 Variation of storage modulus (E0 ) and loss modulus (E00 ) with a temperature of PE100 and talc composites at 1HZ [Color
figure can be viewed at wileyonlinelibrary.com]
TABLE 5 Dynamic mechanical properties of neat PE100 and PE100/talc composites at 1HZ (Mean value of three measurements are
listed)
Sample E0 at 23 C (MPa) T E00 max ( C) E00 max (MPa) T tan δ max ( C) Ring stiffness Sr (kPa)a
PK 1,345 44.19 130.77 73.89 27.4
10PK 1,886 44.66 183.6 84.23 38.4
15PK 2,448 45.13 217.87 97.50 49.8
25PK 3,301 46.89 287.8 90.90 67.2
a
Ring stiffness is calculated based on the modulus at 23 C and a pipe with a standard dimension ratio (SDR) of 17.
increase in the storage modulus (E0 ) of composites with enough for many engineering applications. For example,
the incorporation of talc particles compared to the ring stiffness is an important design factor in the pipe
corresponding modules of neat PE10, which indicates industry and particularly when extruding pipes for GSHP
increased stiffness of these composites. Since the crystal- systems. Ring stiffness (Sr) is a measure of the pipe resis-
linity of the samples was in the same range, it can be tance acting against ring deflection (buckling stress) cau-
inferred that talc particles impose restrictions against the sed by the presence of external force like soil, traffic
molecular motion of polymer chains, resulting in more loads, or negative internal pressure (vacuum). Usually, a
elastic response of the material, which reduces the flexi- borehole is sealed by grouting and backfilling material
bility and enhances the stiffness. just after inserting the GHE into the borehole. Since the
Table 5 gives values for the storage modulus at room density of the backfilling material is much higher than
temperature, which was extracted from the DMA analy- the density of the fluid inside of the GHE, the buckling
sis. The values are slightly higher than the flexural modu- strength is crucial. Although in some Scandinavian coun-
lus reported by the supplier meanwhile, Starck and tries grouting is not mandatory, however, again since the
others41,42 have reported that E0 is approximately equal to density of the fluid (with a mixture of antifreeze) is lower
the Young's modulus or stiffness. It might be argued that than the density of the groundwater, therefore in deep
the storage modulus measured by DMA is, however, not boreholes, the buckling stress is an issue for the practi-
exactly the same as the Young's modulus of the classic tioners. Ring stiffness of the GHEs is also a key factor for
stress–strain curves, because Young's modulus is nor- the horizontal installation as mentioned earlier due to
mally calculated from the slope of the initial liner part of the static and dynamic loads that occur. As it can be seen
a stress–strain curve, while the E0 can be viewed just as a in Table 5, the calculated ring stiffness of PE100 and
point on the line, meanwhile this approximation is good PE100/talc composites for a pipe is compared and the Sr
exhibited an increasing trend with increased filler PE100 and low talc concentration and PE/talc with high
content. content.
Plots of loss modulus E00 against the temperature for The yield stress is greatly affected by the degree of
PE and the PE100/talc composites show the loss peak crystallinity and, considering the above result from DSC
seen at around 45 C, which corresponds to the α transi- that the overall crystallinity (density) of the samples is
tion regions, while there was no β transition peak per- similar, therefore, at low draw ratios (up to their yield
haps due to absence or the negligible number of side- point) the curves follow the same trend. This is because
chain branches. The α transition process is attributed to the load is mainly carried by rigid crystalline lamellae in
the gradual motion of main chain units within the crys- the PE. However, the main differences between the stud-
tallites before the onset of melting. The peak intensity ied samples are found in their post-yield and strain hard-
and broadness increase with the talc concentration in the ening development. The behavior of the neat PK and
PE100/talc composites (see Table 5). The α transition 10PK is common for a bimodal PE resin, these show sig-
temperature (T tan δ) has been shifted toward a higher nificant cold drawing, good deformability, and undergoes
temperature with an increase in the filler content. The strain hardening, which results in a high strength at
maximum temperature in the tan δ and the loss modulus break. A small slope difference between the curves for
(E00 ) curves also give valuable information, that is, the α PK and 10PK can be recognized above the natural draw
relaxation peak temperature may relate to the highest ratio, indicating differences in strain hardening moduli of
service temperature for the composites applications.24 these composites. At higher particle concentrations
Shifting the T tan δ for the composites to the higher tem- (15PK and 25PK), a pronounced decrease in the draw
perature have some advantages, that is, in a GSHP sys- ratio and vanished strain hardening without a trace were
tems with cooling systems, where the temperature of observed.
GHE is increasing during the service life of the project. It is worthwhile to address that none of the studied
The determined temperatures for the α transition samples showed draw ratio well below 8 and due to this
from E00 plots are somewhat lower than the limitation, it was impossible to calculate the strain hardi-
corresponding values obtained from the tan δ plots. ness modulus although the test was performed at a very
These differences in the E00 and tan δ plots have been low strain rate.7,43 Therefore, a similar test has been con-
observed previously.41 ducted at 80 C and the results of the strain hardening
modulus are obtained from the slope of the true stress–
true strain curves and compared in Figure 8.
3.2.2 | Strain hardening modulus As it can be seen from the figure that the <Gp> of
the PE 100 was deteriorated to some extent by adding
Stress–strain curves of studied samples, expressed in the talc. The absolute value for strain hardening modulus of
form of true stress–draw ratio curves, obtained at the neat PE100 was slightly lower than what was reported in
strain rates of 0.5 mm/min at room temperature are the literature.44 All of the <Gp> values for the PE100/
shown in Figure 7. Clearly, the specimens with various talc composites were in the range of values for the
talc concentrations display completely different strain unimodal PE80 and bimodal PE100, which are 25 and
hardening behavior at room temperature. In general, 45 MPa, respectively.44
these behaviors can be divided into two groups: the neat
F I G U R E 8 Effects of the filler concentration on the strain

FIGURE 7 Stress–strain curves expressed as true stress–true hardening modulus <Gp> at 80 C. Values show the mean value of
strain performed at room temperature at 0.5 mm/min [Color figure three measurements and the error bars indicate one SD up and
can be viewed at wileyonlinelibrary.com] one down
It has been shown that the SCG is controlled by the ACKNOWLEDGMENTS

rate of craze initiation and as soon as a fracture is We are thankful to the Muovitech AB for financial sup-
formed,45 its growth depends on the rate of fibrils' entan- port for this research study. The authors also acknowl-
glement and tie molecules. It is assumed that the crack edge the support provided by Dr. Britta Gerets
resistance is mainly governed by the intercrystalline tie from SKZ.
molecules: the greater the tie molecules, the higher the
stress crack resistance will be. Therefore, it can be ORCID
inferred that the response of a PE material after natural Adib Kalantar Mehrjerdi https://orcid.org/0000-0002-
draw ratio like strain hardening modulus <Gp> is an 5725-586X
intrinsic material property, which is the same condition
that governs the SCG. After the yield point and before RE FER EN CES
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Received: 31 October 2019 Revised: 13 March 2020 Accepted: 16 March 2020

Influence of talc fillers on bimodal polyethylene composites

Adib Kalantar Mehrjerdi | Dan Åkesson | Mikael Skrifvars

Swedish Centre for Resource Recovery,

1 | INTRODUCTION borehole to collect/reject heat from/into the surrounding.

1 of 11 wileyonlinelibrary.com/journal/app J Appl Polym Sci. 2020;137:e49290.

An HDPE pipe grade P600 BL of strength class PE100 in 2.3 | Characterization

TABLE 3 Characteristics of the

temperature as can be observed in Figure 2. The

3.1.2 | Oxidation induction time

The effective antioxidant content of the test samples was

Sample Tm onset ( C) Tm peak ( C) ΔHm (J/g) Tc onset ( C) Tc peak ( C) Xc (%) ± SDa

F I G U R E 8 Effects of the filler concentration on the strain

It has been shown that the SCG is controlled by the ACKNOWLEDGMENTS

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