IOSR Journal of Polymer and Textile Engineering (IOSR-JPTE)

e-ISSN: 2348-019X, p-ISSN: 2348-0181, Volume 2, Issue 3 (May - Jun. 2015), PP 06-11
www.iosrjournals.org

Effect of Nanoclay on the Structure and Properties of High

Density Polyethylene Composites
Vineesh Vishnu1, R.S.Rajeev2, M.A.Joseph1
1. Department of Mechanical Engineering, National Institute of Technology Calicut, India
2. Department of Space, Vikram Sarabhai Space Centre, Trivandrum, India.

Abstract: In this study we prepared high density polyethylene (HDPE)/ clay nanocomposites by melt
compounding in a twin screw extruder with rotational speed of 50rpm and the temperatures of the zones are set
to 180-210C.Different screw configuration have been used to study the effect of screw elements on the
properties of nanocomposites. screw configuration changed from dispersive to distributive type. Cloisite 15A
was used as the filler and weight percent of clay was fixed to 3wt%. Maleated polyethylene grafted polyolefins
supplied from Reliance ltd. A new combination of maleic anhydride grafted polyethylene prepared in our lab
through grafting also taken as compatibilizer.the samples were then characterized by XRD,FTIR and DSC. The
results showed that PE/clay nanocomposites provide better exfoliation with high dispersive screw
configuration. The addition of clay also increased the dispersion and crystallinity of the composite. The clay
particles helped the nanocomposites to develop toruos path that prevent the leakage of gas through it.
Rheological results indicated an increase in the viscosity with the addition of nano clay to PE. wide angle x-ray
diffraction shows the better exfoliation of nano particle clays in the polymer matrix. The mechanical, thermal
and rheological characteristics were measured by using differential scanning calorimetry (DSC), X-ray
diffraction (XRD). XRD indicates that Compatibilizer nanoclay ratio plays an important role in the exfoliation
of clay in the polyethylene.
Keywords nanocomposites, Cloisite 15A, Maleated polyethylene grafted polyolefins, HDPE.

I. Introduction
Nanocomposites of polyolefin (PO) with nanoscale layered silicates have been studied by many researchers,
scientifically and technologically, because these materials offer markedly improved properties as compared to
the conventional polymer composites(1-7). Polymerclay nanocomposites are emerging as a class of advanced
engineering materials. Several key properties, such as strength and permeation, can be improved by adding a
small amount of clay into the polymeric matrix [8,9]. The properties of polymerclay nanocomposites depend
on the degree of clay dispersion or on the extent of delamination of the individual clay layers in the polymeric
matrix [10]. The clay layer is hydrophilic in nature and can be converted to organoclay to promote the wetting
of the polymermolecule onto the clay surface [11,12]. By properly controlling the surface properties of the
organoclay, various degrees of organoclay dispersion can be achieved to give: (a) conventional composites, (b)
intercalated nanocomposites, (c) intercalated-exfoliated nanocomposites and (d) exfoliated nanocomposites [12].
The clays surface properties can be modified in various ways. One can use clay with a different layer charge
density, control the surfactant surface coverage or vary the kind of intercalated surfactant [1315].
The packaging industry plays a significant role in a nation economic development; thus, its improvement can
help the economic growth by increasing the efficiency of food marketing and other products, and by adding
value to exports, for example. In this context, nanocomposites, a new class of materials, have a fundamental role
in this improvement, because they have better mechanical, thermal and barrier properties than the pure polymer.
The nanocomposites are characterized by the use of a reinforcement agent with nano dimensions, which is
added in small quantities compared to the traditional composites.

II. Materials and Methods

2.1 Screw Elements and Configuration
The screw configuration used for the extrusion of nanoclay reinforced HDPE composites are shown in
figure1. Two types of screw configurations were used one was dispersive and changed to distributive.

DOI: 10.9790/019X-0230511

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Effect Of Nanoclay On The Structure And Properties Of High Density Polyethylene Composites

Fig.1.Screw Configuration
2.1 Materials
A HDPE (film blowing grade), L60075 from Reliance pvt.ltd. with melt flow index of 8 g/10 min (190 C,
2.16 kg), weight average molecular weight, Mw, of 420,907 g/mol and molecular weight distribution of 20.89
was chosen as matrix. Two grade of HDPE grafted with maleic anhydride (1%), PEMA, trade name Polybond
3009,Optim,and Fusabond Dupont from Reliance, with melt flow index of 2 g/10 min and 1.5g/10min (190 C,
2.16 kg) and melting temperature of 127C was used as compatibility agent. The nanoclay was montmorillonite,
MMT, trade name Cloisite15A from Southern Clay, with less than 2% of moisture.
2.2 Mixing Of Materials
The polymer with compatibilizer and nanoclay in the powder form were mixed according to the
combination as follows. Nanoclay in each combination was fixed as 3wt%. the blends were mixed with 5kg
each in an internal mixer with rotational speed of 1500rpm for 10min.all the batches were preheated @100C
for 8hrs under vacuum condition.
2.3 Grafting of Maleic Anhydride onto Polyethylene
The grafting reaction was carried out in a twin-screw extruder. Before extruding, MAH and DCP were
dissolved in acetone and then mixed with HDPE granules. After volatilizing the acetone, MAH and DCP
adhered onto the granules homogeneously. The temperature profile of the extruder was 140 C, 160 C, 180 C
and 200 C, and the rotation speed of the screws was 60 rpm. The strips from the extruder were cut into granules
about 4 mm long after cooling in a water bath.
III. Melt Compounding
For each type of nanocomposite, as well as for the neat polymer, the same processing procedure was
applied so that the thermomechanical history of the nanocomposites and that of neat polymers remain similar.
The powders were dry blended and fed in a co-rotating twin-screw extruder, Brabender,Germany.The mixing
was carried out at a temperature distribution of 180 200 C, and speed of 100 rpm. The extruded
nanocomposites were pelletized at the die exit. Nanocomposites containing 3wt% clay and different
combination compatibilizer have been prepared.
Table.1 Combination of composites
No

Designation

Combination

Clay (wt%)

HDPE

100/0/0

HDPE-CLAY

97/3

HDPE-FB-CLAY

94/3/3,82/15/3,88/9/3

HDPE-OPT-CLAY

94/3/3,82/15/3,88/9/3

HDPE-FB

1:1,1:5

HDPE-OPT

1:1,1:5

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Effect Of Nanoclay On The Structure And Properties Of High Density Polyethylene Composites
IV. Characterization
4.1 FTIR Analysis of Maleic Anhydride

Fig.2 FTIR Peaks of Maleic Anhydride

4.2 XRD Analysis.
Fig.3 shows the XRD patterns (in the range <10) of neat 15A and the 15A-included composites. The
primary (001) diffraction of neat 15A was evident, indicating an interlayer spacing of 3.15 nm For the
PENC1:3 and PENC1:5 composites, the (001) diffraction position of 15A hardly changed, while the PENC1:1
exhibited a weaker diffraction. These results suggest that, PNC1:1 gives better exfoliation. The 15As (001)
diffraction was still discernible but became much weaker with the inclusion of the two maleated polyolefins.

Fig.3 XRD Pattern

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Effect Of Nanoclay On The Structure And Properties Of High Density Polyethylene Composites
4.3 Crystallization Behaviour of Nanocomposites
Sample: HDPE-NC/FB, 1:1
Size: 4.3000 mg
Method: H-C-Hl
Comment: TACS /31343, N2 atm

File: C:\TA\Data\DSC\HDPE-31343-1-1 FB.001

Operator: PBS/PVA
Run Date: 04-Dec-2013 13:36
Instrument: DSC Q20 V24.9 Build 121

DSC

Heat Flow (W/g)

126.14C
154.6J/g

-2
133.22C

-4
20

40

60

80

100

120

140

Temperature (C)

Exo Up

160
Universal V4.7A TA Instruments

Fig.4.DSC Curves
Sample: HDPE-NC/FB, 1:1
Size: 4.3000 mg
Method: H-C-Hl
Comment: TACS /31343, N2 atm

File: C:\TA\Data\DSC\HDPE-31343-1-1 FB.001

Operator: PBS/PVA
Run Date: 04-Dec-2013 13:36
Instrument: DSC Q20 V24.9 Build 121

DSC

Heat Flow (W/g)

126.14C
154.6J/g

-2
133.22C

-4
20

40

Exo Up

60

80

100

Temperature (C)

120

140

160
Universal V4.7A TA Instruments

Fig.5. DSC Curves

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Effect Of Nanoclay On The Structure And Properties Of High Density Polyethylene Composites
DSC measures the crystallinity of the sample and melting point.

Degree of Crystallinity Xc =
H=melting enthalpy of the sample
Hm= melting enthalpy of 100% crystalline form of PE, value is 293J/g.
X= weight fraction of HDPE in the sample.
For 1:1, Xc=52.7%
For 1:5, Xc= 49%
Increase in crystalinity increases the gas barrier properties.

V. Torque During The Extrusion of Polymer Nanocomposites

Torque developed during the extrusion increased first and decreased with improvement of exfoliation. The
torque remains constant when the clays are sterted to disperse in the polymer matrix.

VI. Conclusion
The XRD analysis ensures the dispersion of clay in the polymer composites. The effect of compatibilizers
and clay ratio is clear from the chart.1:1 ratio gives the most improvement in exfoliation.Crystallinity increses
with addition of nanclay into HDPE DSC curves validates the result. Intercalation or dispersion of HDPE
between the gallery improves the thermal stability and mechanical strength with compatibilizers.

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Effect Of Nanoclay On The Structure And Properties Of High Density Polyethylene Composites
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