Abstract

The polymer industry is continually researching new materials that offer increased performance at
lower costs, often necessitating the introduction of fillers. Nanoparticles offer significant
advantages over macro- or micro-sized fillers, including a greater surface area to mass ratio, low
percolation threshold and often very high aspect ratios, and consequently there has been significant
research and investment into the production of polymer-based nanocomposites. Much of this
research has focussed on carbon nanotubes (CNT) in this role, although few studies have
demonstrated their significant potential. In this thesis a range of techniques, including ball milling
and covalent functionalisation, were employed to create several varieties of carbon nanotubes. The
effect of these well characterised CNT samples on the mechanical properties of thermoplastic
polyurethanes (TPUs) was investigated.

The effectiveness of shortening CNT by ultrasonication, chemical treatment and high-energy ball
milling was investigated in a preliminary study. High-energy ball milling was chosen as the
preferred option due to its high throughput and effectiveness at shortening CNT samples. An
increase in ball milling time corresponded to a reduction in CNT median length; however, fine
control of sample length distribution was not possible. Ball milling was also found to qualitatively
increase amorphous carbon content, whilst a slight increase in side wall oxidation with increased
ball milling time was also observed.

The impact of CNT morphology and length distribution on the properties of TPU-based
nanocomposites was investigated through the production of a series of solution processed
nanocomposites. CNT length distribution and morphology was found to have minimal impact on
nanoscale dispersion, microphase morphology and mechanical behaviour of the resultant
nanocomposites. Tensile testing did reveal a small increase in tensile strength with decreasing CNT
length, which was accomplished without the traditional loss of the host TPU’s ‘rubbery’ behaviour.
However, the improvements were minimal and ultimately not statistically significant. In contrast,
the TPU / purified multi-walled carbon nanotube (pMWNT) nanocomposite, demonstrated
acceptable dispersion, a much higher interfacial shear strength compared to the other
nanocomposites and consequently demonstrated enhanced mechanical properties, even under cyclic
loading.

In conjunction with the investigation into the effects of CNT morphology, this study also explored a
variety of processing methodologies in an attempt to optimise CNT dispersion and mechanical

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behaviour of the nanocomposites. Ultimately, processing methodology had minimal impact on CNT
dispersion. However, the mechanical properties of all materials, including the host TPU, were
decreased with increased melt processing time, and this behaviour was significantly worse in the
CNT-based nanocomposites. It was concluded that the poor performance of the melt processed
samples was primarily caused by TPU degradation, exacerbated by the addition of CNT.

Based on these findings, the functionalisation of the carbon nanotube materials, to improve both
dispersion and CNT interactions with the host TPU, was investigated. Specifically, the effect of
functional group length and conformation was studied through several iterations to select an optimal
functionality. Tensile testing of rudimentary nanocomposites formed from these functionalised
CNT materials, showed that an increase in hydrophobic tail length resulted in an increase in tensile
strength and a reduction in Young’s modulus. As a result, octadecylamine with a toluene 2,4-
diisocyanate linker was chosen as the optimal functionality for use in TPU-based nanocomposites.
Several varieties of CNT materials were later modified with the optimal functionality, although
conversion rates were lower than expected due to poor CNT dispersion during the reaction process.
The impact of this functionalisation on the properties of the resultant nanocomposites was
investigated. Contrary to expectation, dispersion was slightly reduced for all nanocomposites, whilst
the mechanical properties remained largely unchanged. It was thought that reduced dispersion and
apparent preferential functionalisation of CNT end caps over sidewalls were major contributing
factors in the failure of the functionalised CNT nanofillers to improve tensile behaviour.

Finally, to investigate the effects of CNT loading on the properties of TPU-based nanocomposites,
the pMWNT sample was chosen as the optimal nanofiller. Scanning electron microscopy
demonstrated that dispersion, specifically the ratio of aggregates to individual nanotubes, was
unaffected. As expected, Young’s modulus increased with pMWNT loading; however, the trend
observed did not follow any established predictive models. In contrast, tensile strength peaked at
3wt% implying that the sheer number of aggregates present overwhelmed any additional
reinforcement provided by the increased loading. It was concluded that the optimal nanocomposite
was the TPU / pMWNT (1%) sample based on the significant increase in tensile strength obtained
without compromising its ‘rubbery’ behaviour.

This work has contributed to the understanding of TPU / CNT nanocomposites and to the greater
field of CNT-based polymeric nanocomposites. Furthermore, this thesis continued the development
of a novel microwave-assisted functionalisation procedure. The failure of the functionalisation to
greatly enhance CNT dispersion and mechanical behaviour in the nanocomposite, despite

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acceptable functional group loadings is significant for the field. It highlights not only the need for
improved dispersion during functionalisation but also the need for preferential functionalisation of
the sidewalls, over the CNT end caps.

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