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An understanding of the fundamental mechanism behind the relief of shear stress in single-crystal silicon subject to loading by shock-waves has to this day remained elusive. What is known is that this material undergoes a first-order pressure-induced polymorphic phase transition from its ambient pressure cubic-diamond (cd) crystal structure to its first stable high-pressure phase, known as β-Sn, at a pressure of about 120 kbar under hydrostatic compression. By investigating the evolution of the transition parameters for this phase transition as a function of increasing uniaxial shear stress representative of the effects of shock-compression via ab-initio Density Functional Theory computational techniques, we predict a significant lowering of the stress at which the phase transition occurs. This raises the question as to whether the onset of plastic response at the material's Hugoniot Elastic Limit (HEL) reported in experiments corresponds in fact to the phase transition itself, a very plausible possibility which has never been considered before. Furthermore, we present molecular dynamics simulations using a Tersoff-like potential of shock-compressed single crystals of silicon. We find an elastic response up to a critical stress, above which the shear stress is relieved by an inelastic response associated with a partial transformation to a new high-pressure phase, where both the new phase (Imma) and the original cubic diamond phase are under close to hydrostatic conditions. We note that these simulations are also consistent with shear stress relief provided directly by the shock-induced phase transition itself, without an intermediate state of plastic deformation of the cubic diamond phase.

Polymer-based piezoelectric and triboelectric generators form the basis of well-known energy harvesting methods that are capable of transforming ambient vibrational energy into electrical energy via electrical polarization changes in a material and contact electrification, respectively. However, the low energy conversion efficiency and limited thermal stability of polymeric materials hinder practical application. While nanostructured polymers and polymer-based nanocomposites have been widely studied to overcome these limitations, the performance improvement has not been satisfactory due to limitations pertaining to long-standing problems associated with polymeric materials; such as low crystallinity of nanostructured polymers, and in the case of nanocomposites, poor dispersion and distribution of nanoparticles in the polymer matrix. In this thesis, novel functional polymeric nanomaterials, for stable and physically robust energy harvesting applications, are proposed by developing advanced nanofabrication methods. The focus is on ferroelectric polymeric nanomaterials, as this class of materials is particularly well-suited for both piezoelectric and triboelectric energy harvesting. The thesis is broadly divided into two parts. The first part focuses on Nylon-11 nanowires grown by a template-wetting method. Nylon-11 was chosen due to its reasonably good ferroelectric properties and high thermal stability, relative to more commonly studied ferroelectric polymers such as polyvinylidene fluoride (PVDF) and polyvinylidene fluoride-trifluoroethylene (P(VDF-TrFE)). However, limitations in thin-film fabrication of Nylon-11 have led to poor control over crystallinity, and thus investigation of this material for practical applications had been mostly discontinued, and its energy harvesting potential never fully realised. The work in this thesis shows that these problems can be overcome by adopting nanoporous template-wetting as a versatile tool to grow Nylon-11 nanowires with controlled crystallinity. Since the template-grown Nylon-11 nanowires exhibit a polarisation without any additional electrical poling process by exploiting the nanoconfinement effect, they have been directly incorporated into nano-piezoelectric generators, exhibiting high temperature stability and excellent fatigue performance. To further enhance the energy harvesting capability of Nylon-11 nanowires, a gas -flow assisted nano-template (GANT) infiltration method has been developed, whereby rapid crystallisation induced by gas-flow leads to the formation of the ferroelectric δʹ-phase. The well-defined crystallisation conditions resulting from the GANT method not only lead to self-polarization but also increases average crystallinity from 29 % to 38 %. δʹ-phase Nylon-11 nanowires introduced into a prototype triboelectric generator are shown to give rise to a six-fold increase in output power density as observed relative to the δʹ-phase film-based device. Interestingly, based on the accumulated understanding of the template-wetting method, Nylon-11, and energy harvesting devices, it was found that thermodynamically stable α-phase Nylon-11 nanowires are most suitable for triboelectric energy generators, but not piezoelectric generators. Notably, definitive dipole alignment of α-phase nanowires is shown to have been achieved for the first time via a novel thermally assisted nano-template infiltration (TANI) method, resulting in exceptionally strong and thermally stable spontaneous polarization, as confirmed by molecular structure simulations. The output power density of a triboelectric generator based on α-phase nanowires is shown to be enhanced by 328 % compared to a δʹ-phase nanowire-based device under the same mechanical excitation. The second part of the thesis presents recent progress on polymer-based multi-layered nanocomposites for energy harvesting applications. To solve the existing issues related to poor dispersion and distribution of nanoparticles in the polymer matrix, a dual aerosol-jet printing method has been developed and applied. As a result, outstanding dispersion and distribution. Furthermore, this method allows precise control of the various physical properties of interest, including the dielectric permittivity. The resulting nanocomposite contributes to an overall enhancement of the device capacitance, which also leads to high-performance triboelectric generators. This thesis therefore presents advances in novel functional polymeric nanomaterials for energy harvesting applications, with improved performance and thermal stability. It further offers insight regarding the long-standing issues in the field of Nylon-11, template-wetting, and polymer-based nanocomposites.

Hydrocarbon chains are a basic component in a number of systems as diverse as biological membranes, phospholipids and polymers. A better understanding of the physical properties of n-alkane chains should provide a better understanding of these more complex systems. With this aim, vibrational spectroscopy has been extensively used. This technique, sensitive to molecular details, is the only one able to both identify and quantify conformational disorder present in paraffinic systems. To achieve this, methyl deformations have been widely used as "internal standards" for the normalisation of peak areas. However, in the case of n-alkanes with short chain length, such as n-C[44]H[90] for example, the infrared spectra recorded at liquid nitrogen temperature and reported here show the sensitivity of these latter peaks to the various crystal structures formed. Indeed, the main frequencies of the symmetric methyl bending mode were found between 1384 cm[-1] and 1368 cm[-1] as a function of the crystal form. Changes in the frequency of the first order of the L.A.M. present in the Raman spectra were also observed. At higher temperatures, non all-trans conformers, inferred from different infrared bands present in the wagging mode region, were found to be essentially placed at the end of the n-alkane chains. At the monoclinic phase transition, the concentration of end-gauche conformers, proportional to the area of the infrared band at 1342 cm[-1], increases abruptly. On the contrary, in the spectra recorded at liquid nitrogen temperature no such band is observed. We also studied the degree of disorder in two purely monodisperse long chain n-alkanes, namely n-C[198]H[398] and n-C[246]H[494]. The chain conformation as well as the tilt angle of the chains from the crystal surfaces were determined by means of low frequency Raman spectroscopy and S.A.X.S. measurements on solution-crystallised samples. The increase in the number of end-gauche conformers which was expected to occur with the increase of the tilt angle as a function of the temperature was not detected due to a perfecting of the crystals. Indeed, due to successive heating and cooling to -173°C, the concentration of non all-trans conformers was found to decrease within the crystals. Their numbers were found to be up to six times higher in n-C[198]H[398] crystallised in once folded form than when crystallised in extended form. The C-C stretching mode region of the spectra was used to identify the chain conformation and to estimate the length of the all-trans stem passing through the crystal layers at -173°C. The transition between once folded and extended form crystals was indicated by the presence of additional bands in this region at 1089 cm[-1], 1078 cm[-1] and 1064 cm[-1]. Some of those bands may be related to the fold itself. At the same time, a strong decrease of the intensity of the infrared bands present in the wagging mode region was observed. Finally, the triple layered structure proposed on the basis of X-ray measurements obtained from the crystals of a binary mixture of long chain n-alkanes, namely n-C[162]H[326] and n-C[246]H[494], was confirmed from the study of the C-C stretching mode region of the infrared spectra.

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