The 9th International Chemical Engineering Congress & Exhibition (IChEC 2015)

Shiraz, Iran, 26-28 December, 2015

FTIR Spectra and Mechanical Properties of Nano-Sized Calcium

Carbonate Reinforced Cross-linked High Density Polyethylene
Hamid Garmabia*, Javad Dastjerdia
a

Department of Polymer Engineering and Color Technology, Amirkabir University of Technology, No. 424,
Hafez Ave., Tehran, Iran
E-mail address: garmabi@aut.ac.ir (H. Garmabi).

Abstract
In this work, novel nanocomposites of silane cross-linked high density polyethylene (PEX)
reinforced by various contents of calcium carbonate nanofillers (NCC) were prepared using a corotating twin screw extruder. FTIR observations showed a good interaction between PEX and
NCC particles. This good interaction makes tensile modulus of neat PEX increases up to 21% by
addition of 10 wt% NCCs which is attributed to good matrix/filler adhesion, whereas an inverse
trend occurred about the strength at yield because of debonding.
Keywords: Cross-linked polyethylene, Calcium carbonate, FTIR, Mechanical analysis,
Nanocomposites

Introduction
One of the main weaknesses of polyethylene (PE) is falling of critical physical properties at
the elevated temperature which limits its applications. Cross-linking of PE is among the
methods developed to prevent this depression where three-dimensional network is formed and
limit infinite deformation under load but the segments between cross-link points remain
flexible [1]. Increasing temperature leads to elimination of crystals and PEX tends to show
rubber-like behavior. The main utilizations of PEX is making hot water pipes, foams for
thermal insulation, wires, cables , etc. [2]. Cross-linking of polyethylene is performed by
physical manner such as radiation cross-linking or chemical methods, i.e. peroxide and silane
cross-linking. In general, confined researches have been carried out about PEX
nanocomposites. For example in the recent years, Roumeli et al. have been worked on
developing PEX nanocomposites based on carbon nanotubes and nanodiamonds and achieved
valuable results. According to the above items, development of PEX/ CaCO3 nanocomposites
with respect to their low cost and good processability is valuable. Therefore the aim of the
current work was evaluation of the nanocomposites through mechanical testing and finding
the mechanism of deformation in this new composite.
Experimental
Silane based cross-linkable high density polyethylene (g-HDPE) according to Sioplas system,
XP650, along with catalyst masterbatch based on dibutyltin dilaurate (DBTDL) purchased
from Hyundai Engineering Plastics Co., Ltd. (South Korea). Nano-CaCO3 powder,

The 9th International Chemical Engineering Congress & Exhibition (IChEC 2015)
Shiraz, Iran, 26-28 December, 2015

SOCAL312, supplied from Solvay with 45-90 nm size and stearic acid (SA) coated. For the
preparation of samples, mixture of 95 parts of g-HDPE and 5 parts of catalyst masterbatch
were used. PEX pellets and 0, 1, 5, and 10 wt% nano-CaCO3 were compounded by a twin
screw corotating extruder. The extruded mixture was grinded and injection molded at 190 C

and finally in order to completion of cross-linking process, was kept in water bath at 85 C for
24h. The nomenclature of the samples used in this study is shown in Table 1. Tensile tests
were performed through dumb-bell-shaped specimens at room temperature (22 2C) with a
cross-head speed of 50 mm/min using an lnstron (Galdabini, Italy) according to ASTM D638.
In order to enhancement of results accuracy, the test repeated at least five times for each
sample and the average values were reported.
Table 1. Nomenclature of the samples used in this work
NCC content
composition
(wt%)
PEX
0
PEX1
1
PEX5
5
PEX10
10

Results and discussion

FTIR spectra of PEX and PEX5 are shown in Figure 1. The Peaks at 800 and 1090 cm-1 are
allocated to Si-OCH3 bonds and the weak shoulder close to 1030 cm-1 is assigned to Si-O-Si
groups which are cross-link agents that are affected by larger peak of SiOCH3 in 1090 cm-1.
The peaks which appears at 875 and 2523 cm-1 in PEX5 relate to nano-sized calcium
carbonate and shifting of the peak at 1465 cm-1 in PEX to 1453 cm-1 in PEX5 is attributed to
interaction between PEX and NCC [3]. Table 2 presents the tensile parameters which have
been obtained from stress-strain curves of all the samples. Improving tensile modulus by
addition of NCC could be attributed to presence of SA as coupling agent between matrix and
filler which causes promotion of load transfer between the filler and the matrix. Reduction of
strength at yield, specifies that debonding is predominant deformation mechanism [4]. Due to
entity of agglomerates in PEX10, this structures act like big particle which leads to stress
concentration and facilitation of crack propagation and as a result, debonding occurs at lower
stress than the smaller particles accordingly strength at yield is lowered.

The 9th International Chemical Engineering Congress & Exhibition (IChEC 2015)
Shiraz, Iran, 26-28 December, 2015
Figure 1. FTIR spectra of PEX and PEX5
Table 2. Mechanical Properties of neat PEX and its nanocomposites
composition

Youngs
modulus (MPa)

Strength at yield
(MPa)

PEX

800.92

27.58

PEX1

805.06

27.73

PEX5

890.76

26.19

PEX10

967.42

25.52

Conclusions
In the current study, the new derivative of PEX was prepared and performed structural and
mechanical analyzes on them. The obtained results can be summarized as follows:
The presence of stearic acid makes good interaction between PEX and NCC.
The existence of good adhesion led to promotion of load transfer between PEX and
NCC, accordingly the Youngs modulus of neat PEX has been increased.
The presence of NCC led to promotion of debonding mechanism and reduction of the
strength at yield.
References
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