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Reinforcement of poly ether sulphones (PES) with exfoliated graphene oxide for aerospace

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2012 IOP Conf. Ser.: Mater. Sci. Eng. 40 012022

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International Conference on Structural Nano Composites (NANOSTRUC 2012) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 40 (2012) 012022 doi:10.1088/1757-899X/40/1/012022

Reinforcement of poly ether sulphones (PES) with exfoliated

graphene oxide for aerospace applications

K Balasubramanian
Head: Materials Engineering, DIAT(DU), Girinagar, Pune- 411025, Maharashtra,
India

E-mail: balask@diat.ac.in, meetkbs@gmail.com

Abstract. Composite materials have been used for aerospace for some time now and have
gained virtually 100% acceptance as the materials of choice. Speciality polymers like poly
ether sulphones (PES), poly ether ether ketones(PEEK) , poly ether imides (PEI) are highly
preferred materials as plastic matrix due to their superior temperature performance, excellent
wear & friction resistance, excellent dimensional accuracy, high tensile strength, high modulus,
precise machinability and chemical resistance. In recent years nanoadditives like single and
multiwall carbon nanotubes, graphenes and graphene oxides(GO) are finding huge market
potential in aerospace and automobile industries. But manufacture related factors such as
particle/ matrix interphases, surface activation, mixing process, particle agglomeration, particle
size and shape may lead to different property effects. In this research GO/PES composites were
prepared by high shear melt blending technique. GO monolayers were exfoliated from natural
graphite flake and dispersed homogeneously in PES matrix for the GO content ranging
between 0.5 to 2.0 volume percentage with a high shear twin screw batch mixer. These melt
blended nanocomposites were injection moulded for mechanical property validation of tensile
strength, flexural modulus and impact resistance. Addition of 0.5 volume percentage of GO
enhanced the tensile strength and flexural modulus by 40% and 90% respectively. The results
show that addition of GO to PES increase mechanical properties due to the formation of
continuous network, good dispersion and strong interfacial interactions. The strong interfacial
interactions were accounted for the increase in glass transition temperature. Also there was a
significant improvement in the impact resistance of the PES/ GO nanocomposite. The injection
moulded samples were tested for stealth performance by measuring the electromagnetic
shielding property.

1. Introduction
The excellent mechanical, thermal and electrical property, combining with its ultrahigh surface area
and economical sources (graphite), makes graphene a promising nanoscale filler for the fabrication of
polymer composites. However, since graphene sheets are intrinsically stacked in graphite due to the
high van der Waals forces of attraction between the adjacent layers, the exfoliation and incorporation
of it into polymer matrix to synthesise single layer graphene reinforced polymer, which has been
considered as the best utilization of the excellent in plane properties of graphene is rather difficult [1].
In the past several years, various methods for producing graphene have been developed, such as
micromechanical exfoliation, chemical vapour deposition, epitaxial growth and chemical synthesis [2].
Recently there are several reports related to graphene/ polymer composites [3-8]. When incorporated,
graphene improved significantly the electrical, thermal and mechanical properties of the host polymer

Published under licence by IOP Publishing Ltd 1

International Conference on Structural Nano Composites (NANOSTRUC 2012) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 40 (2012) 012022 doi:10.1088/1757-899X/40/1/012022

at a low concentration. Presence of functional groups like hydroxyl, carbonyl and carboxyl groups are
found to make graphene oxide sheets strongly hydrophilic, which allows graphene oxide to readily
swell and disperse in water.
In addition, the oxygen functionality allows the improvement in interactions with the polar polymer
matrices. But surface modification is required to disperse graphene oxide in nonpolar polymer [9, 10].
Carbon nanotube reinforced polymer composite have been widely investigated in recent years while
application of graphene or graphene oxide as a reinforcing phase has been mainly focussed on
thermoplastics or thermoset polymers in which the strength and modulus increased but flexibility
decreases. In the previous work, it was found that addition of multiwall carbon nanotubes enhanced
the conducting properties of EPDM [11]. Extensive literature is not available on the polymer
nanocomposites of graphene and graphene oxides of speciality and engineering polymers like poly
ether ether ketones, liquid crystal polymers and polysulphones. In this work a modified Hummers
method was used to produce chemical exfoliated graphene oxide nanosheets. These nanosheets were
melt blended with a high shear twin screw compounder and injection moulded to validate the
mechanical and electromagnetic properties.
2.Experimental is
2.1. Materials
Flake graphite with average particle size of 20µm was purchased from Research Lab Mumbai. Powder
grade PES was procured from Solvay speciality Chemical. Sodium nitrate and potassium
permanganate was procured from Ranchem, India. Concentrated hydrochloric acid and concentrated
nitric acid were procured from Merck, India. Hydrogen peroxide was purchased from Fischer
Scientific.

2.2.Preparation of Graphene Oxide (GO)

3g of flake graphite, 3 g of sodium nitrate and 150ml of concentrated sulphuric acid were taken in a
beaker and ultrasonicated in an ice water bath for a period of 1 hour. 25g of potassium permanganate
was added slowly to the mixture over two hours. 500ml of aqueous sulphuric acid solution was added
and ultrasonicated for 2 hours. To the ultrasonicated mixture 20 ml of H202 was added and stirred at
temperature of 700C. The product was washed distilled water for several times. This solution was then
freeze dried.

2.3. Preparation of graphene oxide/PES nanocomposite

PES was dried in an dehumidifying chamber for a period of 8 hours at 1600C. The surface treated
graphene oxides were tumble blended with the resins. Compounding was done using a twin screw
mixer ( screw speed 40 rpm) with zonal temperatures ranging between 2400C to 2800C.
The compounded samples were injection moulded for testing the mechanical and shielding properties.

3. Testing and Characterisation

3.1. Mechanical Testing

Tensile properties were determined for samples according to BS 903: Part A: 1971 using Lloyd
Tensile testing machine, type 200R fitted with a 500N load cell. The grip separation speed was
10mm/min at room temperature. The average of five results was reported. Flexural testing was carried
out, according to ISO 178 with the test spped of 10mm/min using Lloyd tensile test machine. The
Dapmat computer programme software calculated all flexural properties automatically. The average of
five samples per formulation was reported.

3.2. Shielding Efficiency

The sample geometry as shown in figure 1 washers were electrically connected between the inner
and outer conductor of a specially designed coaxial fixture, which is placed between the signal source
and the detector. The ratio of the power of the signal received with the sample present to the power

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International Conference on Structural Nano Composites (NANOSTRUC 2012) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 40 (2012) 012022 doi:10.1088/1757-899X/40/1/012022

received with no sample is the shielding effectiveness of the sample. The sample must make good
electrical contact at both the inner and outer surfaces, or the measured shielding effectiveness will be
lower than the sample is capable of providing. The microwave transmission losses of the filled plastic
materials within the range of 0.1-20 GHz, were measured at room temperature. A major drawback of
this test is that it would not identify any property anisotropy which is common in filled polymer
nanocomposite.

3 mm

21 mm

9.2 mm

Figure 1. Sample Dimensions for EMI test.

4. Results and Discussion

4.1. Properties
Table 1 presents the FTIR spectroscopy of graphene oxide. Peaks corresponding to the presence of
hydroxyl and carboxyl were observed at 3458 and 1727 cm-1respectively. These peaks indicate the
oxidation of graphite by concentrated acid. The functional groups allow the graphene oxide to disperse
in the polymer system during high shear mixing. X ray diffraction peak as in figure 2 in the result of
surface treated graphene. This clearly indicates that the interlayer spacing of graphite is expanded after
the chemical modification.
Table 1. FTIR peaks of Graphene oxide.
Wave number Group
cm-1
3458 Hydroxyl
1727 Carboxyl

Figure 2. XRD peek of Graphene oxide.

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International Conference on Structural Nano Composites (NANOSTRUC 2012) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 40 (2012) 012022 doi:10.1088/1757-899X/40/1/012022

Table 2. Comparison of Mechanical Properties of

GO/PES nanocomposite.
Composition Tensile Flexural
Strength Modulus
(MPa) (MPa)
PES 102 5918

PES+ 0.5 138 8216

Vol% GO

PES+1.0 142 8354

Vol% GO

PES+1.5 147 8693

Vol% GO

PES+2.0 148 8742

Vol% GO

Table 3. Comparison of Shielding effectiveness of

GO/PES nanocomposite.
Composition Shielding
Effectiveness( dB)
PES -
PES+ 0.5 Vol% GO 9.1
PES+1.0 Vol% GO 26
PES+1.5 Vol% GO 38
PES+2.0 Vol% GO 42

0.5µm

Figure 3. SEM of GO in PES.

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International Conference on Structural Nano Composites (NANOSTRUC 2012) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 40 (2012) 012022 doi:10.1088/1757-899X/40/1/012022

Tensile and flexural data for the composite produced are shown in Table 2. Mechanical properties
increases which proved that high shear mixing and surface functionalisation of graphenes help in
molecular level adhesion. The test samples are assumed to be isotropic and homogeneous. The
shielding effectiveness of 0.5 vol % was found to be 9 dB for the frequency range of 750-2000MHz.
The value was found to be consistent for all the five samples. The shielding effectiveness of 1 vol%
and 1.5vol%of graphene was found to be 26dB and 38dB respectively for the frequency range of 750-
2000MHz. With 2 vol% the values were found to be 42dB between the frequency range of 750-
2000MHz.
Figure 3 shows the scanning electron microscopy of graphene oxide dispersed in PPS. From the
SEM no obvious graphene oxide aggregates were observed from the cross section of the composite.

4. Conclusions
Dispersion of graphene oxide was possible with different volume percentage loading in PES.
Graphene oxide sheets containing abundant carboxylic and hydroxylic groups can form strong
interactions with PES matrix. Use of graphene oxide help in improving the mechanical and
electromagnetic shielding properties. From scanning electron microscopy it is clear that graphene
oxides have good adhesion with PES. It can also be inferred that at low concentration of graphene
oxide percolation threshold can be easily achieved. High shear mixing of graphene oxide with PES
increased the interfacial interactions between the functional groups of graphene oxide and poly ether
sulphones. Such high performance composite can be explored for automotive and aerospace
applications since they are light weight, corrosion resistance and such systems can be used to develop
self repairing components.

5. Acknowledgments
Author wish to acknowledge encouragement from Dr Prahlada, Vice Chancellor, DIAT (DU), Pune,
India.

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