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Materials Chemistry
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1. Introduction
Polyhedral oligomeric silsesquioxanes (POSS) are organicinorganic molecules, approximately 1 to 3 nm in diameter, with the
general formula (RSiO1.5)n where R is hydrogen or an organic
group, such as alkyl, aryl or any of their derivatives.13 The
incorporation of POSS molecules into polymeric materials leads
to significant improvements in the polymeric mechanical properties, thermal behavior and flame retardancy.46
Graphene oxide (GO) has created a lot of attention as it
provides a pathway to produce large quantities of graphene
sheets in solution at low cost.79 The easy processibility of GO
and its compatibility with various substrates, including plastics,
makes it an attractive candidate for the high yield manufacturing
of graphene based flexible electronics.
The structure of graphene oxide sheets consists of a basal plane
of the sheet, decorated with hydroxyl and epoxy functional
groups. Carbonyl groups are present as carboxylic acids along
the sheet edge but also as organic carbonyl defects within the
sheet.10,11
These functional groups provide a variety of surface-modification reactions, which can be used to develop functionalized
GO-based materials. For example graphene oxide is intrinsically
hydrophilic and its dispersion in water is easily achieved.1215
The chemical interaction between amino groups and functional groups of graphene oxide has also been extensively
debated in the literature.1619 For example, the treatment of GO
a
2. Experimental
Graphene oxide was purchased from Cheaptubes (GO; thickness
0.71.2 nm estimated by AFM, see supporting information).
Aminopropyl heptaisobutyl POSS (referred to as POSS-NH2
from now on) was purchased from Hybrid Plastics (USA) as
crystalline powder and used as received.
GO water solution (1 mg ml 1) was prepared and sonicated
(750 W, 60% amplitude) for 1 h to yield a yellow suspension.
After this mixing process, the solution was transferred to a vial
and it was centrifuged for 30 min at 9000 rpm. The supernatant
of the dispersion was carefully extracted and separated from the
residual visible at the bottom of the vial.
J. Mater. Chem., 2012, 22, 62136217 | 6213
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Commercially available silicon with an electrical sheet resistivity of 14 Ohms/square has been used as substrate. The Si
surface was cleaned with ethanol and acetone, rinsed with water,
dried under nitrogen and taken inside a dry Ar glovebox.
Afterwards, the Si surface was treated in oxygen plasma for
10 min. The plasma was generated by a radio frequency power
supply (13.56 MHz) and carried out at room temperature with
the gas pressure fixed at 4.5 10 2 Torr. The power employed
was fixed at 20 W (substrate bias 300 V). The plasma-treated Si
surface was then immersed into a 1% (3-aminopropyl)triethoxysilane (APTES, purchased from Aldrich) solution in toluene for 1
h at room temperature. Following this treatment, the APTES
modified Si substrate was rinsed in toluene and dried in nitrogen.
The characterization of the APTES self-assembled monolayer
has already been reported in our previous study.20 The thickness
of the prepared films was about 58 nm as estimated by atomic
force microscopy.20
Subsequently, the APTES modified Si substrate was kept in
the prepared GO aqueous solution and rinsed at 80 C for 1 h.
This sample, referred to hereafter as APTES-GO, was immersed
into a POSS-NH2 solution of hexane at room temperature for
1 h. The prepared sample was washed with hexane to remove the
excess of POSS-NH2. After that, this sample, referred to as
APTES-GPOSS, was dried in a nitrogen stream.
Infrared spectroscopy in the 5004000 cm 1 range, was used to
confirm the chemical composition. The surface morphology of
the films was investigated by optical and field emission scanning
electron microscopy (FE-SEM).
The wettability of these films was investigated by contact
angle measurements. Contact angles were measured with a FTA
1000 Series instrument equipped with a CCD camera. Deionized water droplets were dropped carefully onto the surfaces
and the contact angle was monitored statically as a function of
time.
Tribological properties were investigated through instrumented indentation tests by using a Micro-Materials nanoindenter (Nanotest 600). A Berkovich tip was used, providing
a load of 0.1 mN. The friction coefficient versus scanning length
was recorded for each test. Five valid tests were performed on
each sample. Si samples coated with different films were mounted
onto the flat base and the friction coefficients were recorded
automatically.
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Fig. 2 Optical micrographs (450 mm 600 mm) of (a) neat SiGO and
(b) APTES-GO samples, respectively.
Scheme 1 Proposed schematic view for the construction of APTESGPOSS trilayer film.
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Fig. 5 Friction coefficient for: (a) APTES modified Si, (b) APTES-GO
and (c) APTES-GPOSS samples, respectively. The average friction
coefficient is reported above the corresponding curve.
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4. Conclusions
Acknowledgements
We are grateful to the Italian Ministry of Education and
University through the 2008 PRIN project (Grant No.
20089B75ML_001).
Dedication: In memoriam of Daniela Tabuani.
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