<div>Sensing of mechanical state is critical in diverse fields including biomedical implants, intelligent robotics, consumer technology interfaces, and integrated structural health monitoring among many others. Recently, materials that are self-sensing via the piezoresistive effect (i.e. having deformation-dependent electrical conductivity) have received much attention due to their potential to enable intrinsic, material-level strain sensing with lesser dependence on external/ad hoc sensor arrays. In order to effectively use piezoresistive materials for strain-sensing, however, it is necessary to understand the deformation-resistivity change relationship. To that end, many studies have been conducted to model the piezoresistive effect, particularly in nanocomposites which have been modified with high aspect-ratio carbonaceous fillers such as carbon nanotubes or carbon nanofibers. However, prevailing piezoresistivity models have important limitations such as being limited to microscales and therefore being computationally prohibitive for macroscale analyses, considering only simple deformations, and having limited accuracy. These are important issues because small errors or delays due to these challenges can substantially mitigate the effectiveness of strain-sensing via piezoresistivity. Therefore, the first objective of this thesis is to develop a conceptual framework for a piezoresistive tensorial relation that is amenable to arbitrary deformation, macroscale analyses, and a wide range of piezoresistive material systems. This was achieved by postulating a general higher-order resistivity-strain relation and fitting the general model to experimental data for carbon nanofiber-modified epoxy (as a representative piezoresistive material with non-linear resistivity-strain relations) through the determination of piezoresistive constants. Lastly, the proposed relation was validated experimentally against discrete resistance changes collected over a complex shape and spatially distributed resistivity changes imaged via electrical impedance tomography (EIT) with very good correspondence. Because of the generality of the proposed higher-order tensorial relation, it can be applied to a wide variety of material systems (e.g. piezoresistive polymers, cementitious, and ceramic composites) thereby lending significant potential for broader impacts to this work. </div><div><br></div><div>Despite the expansive body of work on direct current (DC) transport, DC-based methods have important limitations which can be overcome via alternating current (AC)-based self-sensing. Unfortunately, comparatively little work has been done on AC transport-deformation modeling in self-sensing materials. Therefore, the second objective of this thesis is to establish a conceptual framework for the macroscale modeling of AC conductivity-strain coupling in piezoresistive materials. For this, the universal dielectric response (UDR) as described by Joncsher's power law for AC conductivity was fit to AC conductivity versus strain data for CNF/epoxy (again serving as a representative self-sensing material). It was found that this power law does indeed accurately describe deformation-dependent AC conductivity and power-law fitting constants are non-linear in both normal and shear strain. Curiously, a piezoresistive switching behavior was also observed during this testing. That is, positive piezoresistivity (i.e. decreasing AC conductivity with increasing tensile strain) was observed at low frequencies and negative piezoresistivity (i.e. increasing AC conductivity with increasing tensile strain) was observed at high frequencies. Consequently, there exists a point of zero piezoresistivity (i.e. frequency at which AC conductivity does not change with deformation) between these behaviors. Via microscale computational modeling, it was discovered that changing inter-filler tunneling resistance acting in parallel with inter-filler capacitance is the physical mechanism of this switching behavior.</div>

In der vorliegenden Arbeit wurden neue Nanopartikel/Polymer-Kompositmaterialien und Methoden zur ihrer Herstellung entwickelt. Durch die Verwendung lumineszierender, anorganischer Nanopartikel und transparenter Polymere konnte für verschiedene Systeme die Lumineszenz als Funktion auf die Nanokomposite übertragen werden. Zunächst wurden in allen Fällen stabile Partikeldispersionen in Monomeren oder Polymerlösungen erzeugt, die in einem zweiten Schritt durch in-situ-Polymerisation oder Filmgießen in Komposite verarbeitet wurden. So konnten orangelumineszierende ZnS:Mn-Nanopartikel durch eine Cofällungsreaktion dargestellt und in eine stabile Dispersion in Acrylsäure überführt werden. Diese Dispersion konnte mit dem Tintenstrahldrucker als transparente Schicht gedruckt und durch Strahlungshärtung polymerisiert werden. Durch die Beimengung von MMA gelang erstmals die Herstellung transparenter ZnS:Mn-Nanokomposite durch die thermische Copolymerisation in Masse. Eine weitere Modifizierung mit Oleylamin ermöglichte die Stabilisierung der Partikel in Laurylacrylat und die Herstellung von ZnS:Mn/PLA-Nanokompositen durch Photopolymerisation der Dispersion. ZnS:Mn/PMMA-Nanokomposite und die isolierten Partikel weisen eine Fluoreszenzquantenausbeute von ca. 30 % auf. Dieser Wert übertrifft bisher publizierte Werte für ZnS:Mn-Nanopartikel deutlich. Blau-grün lumineszierende, kupferdotierte ZnS-Nanopartikel wurden in Wasser synthetisiert und durch einen Phasentransfer mit Octylamin hydrophob modifiziert. Mit den modifizierten ZnS:Cu-Nanopartikeln wurden PLA-Nanokomposite durch Redispergierung und in-situ-Polymerisation hergestellt. Des Weiteren konnten ZnS/PMMA-Filme durch ein Gießverfahren mit den hydrophobisierten ZnS:Mn- und ZnS:Cu-Partikeln hergestellt werden. Zinkoxid-Nanopartikel wurden in Ethanol synthetisiert. Die Partikel konnten als stabile Dispersion in BDMA überführt werden. Die Methode erlaubt die Kontrolle über Partikelgrößen im Bereich von 6-10 nm (DLS) und über die Partikelkonzentration bis zu 10 Gew%. Wachstumsprozesse, die für ZnO in Ethanol nur schwer zu kontrollieren sind, sind in BDMA vollständig eingestellt. Alternativ konnten die Zinkoxid-Nanopartikel durch die Zugabe von Oleylamin aus der ethanolischen Dispersion isoliert und gleichzeitig modifiziert werden. Die hydrophobisierten Partikel sind redispergierbar in unpolaren Monomeren. Mit dieser Methode wurden ZnO-Dispersionen in Laurylacrylat hergestellt. Dispersionen in BDMA und LA konnten photopolymerisiert werden. Die stabilen ZnO-Dispersionen in Acrylatmonomeren mit Konzentrationen bis 10 Gew% und daraus herstellbare, transparente Polymernanokomposite durch UV-Härtung sind als Neuheit zu bewerten. Zur Herstellung von YVO4:Eu/Polymer-Nanokompositen wurde eine Methode für die in-situ-Generierung der Nanopartikel in Methylmethacrylat entwickelt. Dazu wurden neuartige, inverse Mikroemulsionen mit MMA als Ölphase erzeugt. In den Mizellen entstanden durch eine Fällungsreaktion rot-emittierende YVO4:Eu- Nanopartikel. Die resultierende Partikeldispersion in MMA wurde polymerisert und so in Nanokomposite umgewandelt. Eine alternative Herstellungsmethode basiert auf der Synthese von citratstabilisierten YVO4:Eu-Nanopartikeln in Wasser und anschließendem Phasentransfer mit Octylamin. Man erhält ein hydrophobes Pulver, das in Laurylacrylat zu einer stabilen Mischung redispergiert werden kann. Die resultierenden Dispersionen sind photopolymerisierbar [169]. YVO4:Eu enthaltende Polymernanokomposite wurden bisher nicht beschrieben. Der Phasentransfer mit Alkylaminen wurde bereits für Gold-Nanopartikel demonstriert. Die Anwendung auf ZnS:Cu- und YVO4:Eu-Nanopartikel ist als Weiterentwicklung zu betrachten. Zur Partikelgrößenbestimmung an den Monomerdispersionen und Pulvern wurden dynamische Lichtstreuung, Kleinwinkelröntgenstreuung, Transmissionselektronenmikroskopie und Röntgendiffraktometrie eingesetzt. Alle genannten Nanokompositmaterialien konnten mit hoher Transparenz und geringer Trübung hergestellt werden, wie mit Transmissionsmessungen und Trübungsmessungen gezeigt wurde. Mit Transmissionselektronenmikroskopie an Ultramikrotomdünnschnitten konnte für ZnS/PMMA- und ZnO/PBDMA-Nanokomposite eine homogene Partikelverteilung im Polymer nachgewiesen werden. Durch die Variation des Partikelanteils wurden für die verschiedenen Systeme Konzentrationsgrenzen im Bereich von 3-10 Gew% zur Herstellung transparenter Komposite ermittelt. Die Nanokomposite weisen eine intensive Photolumineszenz auf. Blau- (ZnS:Cu), grün- (ZnO), orange- (ZnS:Mn) und rot- (YVO4:Eu) emittierende Nanokomposite wurden erhalten (Abbildung 75). Mit Fluoreszenzspektroskopie wurden die charakteristischen Anregungs- und Emissionsspektren der Kompositproben aufgenommen. Neben der Lumineszenz können die intensive UV-Absorption des ZnO, bzw. der hohe Brechungsindex des ZnS in Nanokompositen nutzbar gemacht werden. Die entwickelten Methoden beruhen auf einfachen, aufskalierbaren Prozessen und die verwendeten Edukte sind kommerziell erhältlich und ungiftig. Die entwickelten stabilen, druckbaren und strahlungshärtbaren Nanopartikeldispersionen in Acrylatund Methacrylatmonomeren sind daher auch für industrielle Anwendungen geeignet.

Organic-inorganic polymer hybrids containing butyl stannoxane dodecamer cages (Sn_POSS) as nano-building blocks were prepared and investigated. Sn_POSS was employed as a linear, crosslinking or non-bonding molecularly blended unit. For this purpose, it was synthesized with two acrylamido, primary- or secondary amino, or with two additional non- functional groups, which were attached via ionic-bonded sulfonate substituents. The nano- building block was then incorporated in matrices such as PS, PAOS, PETA, PEMA, PHEMA and PPO-based epoxies (the latter with different mesh sizes). Sn_POSS reinforces the studied matrixes by filler-filler interactions (self-assembly to nano-domains). Specific interactions of the ionic bonds of Sn_POSS with suitable pendant groups of the matrixes also can generate reinforcement and suppress filler aggregation. Moreover, the Sn_POSS can undergo several types of chemical reactions like heat-induced oligomerization, dissociation of the ionic substituents, acidolysis of the Sn-butyl bonds, as well as radical reactions of the latter. The influence of ionically bonded cages on the hybrids' morphology, as well as their ability of dissociation and short-distance migration in the polymer network at elevated temperature, was evaluated by TEM, IR and NMR analyses. The mechanical...

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Improvement properties of building materials are essential. In this dissertation thesis, the main concern had been on synthesizing a new resin to improve the properties of concrete and brick. Solvent-based polymers have been used for many years to improve the quality of building materials. In contrast to solvent-based polymers, water-based emulsion polymers are one of the available solutions that have been used to improve the quality of building materials. Several advantages can be enumerated for water-based emulsion polymers such as lower volatile organic compounds (VOC), easier application, lower carbon dioxide emissions in the production, and fossil resource preservation. Water-based emulsion polymers are synthesized from simple homopolymers to copolymers with various monomers and additives. In this research, the synthesis and characterization of water-based acrylic styrene emulsion copolymer had been the main concern. Acrylic monomers could develop the qualities such as thermoplasticity, water solubility, and a longer lifespan of the polymer, while styrene monomers will impart water resistance and stiffness properties. In this research, the first step had been the synthesis of a water-based emulsion copolymer. Furthermore, considering the importance of biodegradability of the synthesized copolymer, the research followed by the replacement of ingredients such as emulsifiers with higher biodegradability characteristics with eco-friendly by-products, i.e. reducing the microplastic hazards. As a result, the copolymer could be decomposed better, and consequently, problems with the release of microplastics will be reduced. The synthesized water-based acrylic styrene emulsion copolymer was characterized by FTIR, DSC, and TGA. The FTIR results confirmed successful emulsion polymerization of acrylic styrene copolymer. DSC results confirmed the formation of an amorphous thermoplastic type of copolymer with a single glass transition temperature. The TGA result also confirms a single decomposition temperature. The film formation was carried out using a film applicator to evaluate the film formation properties. The substitution of the superseded emulsifiers (both anionic and nonionic) did not alter the characteristics of the synthesized copolymer, while some of the qualities such as water absorbance of the dried copolymer are improved (a water absorption test was carried out). To improve the quality of both synthesized emulsion copolymers (with conventional and superseded emulsifiers), the nanocomposite of the emulsion copolymer was prepared (Cloisite 30B at a concentration of 0.2 to 1 %). The synthesized nanocomposite showed better water resistance in the coating application in contrast with emulsion copolymer. The next stage of the research has been concentrated on the application of the synthesized water-based emulsion copolymer to building materials (concrete and brick). The synthesis copolymer has been applied as a coating on the surface of the concrete and bricks. Moreover, the synthesis copolymer was used as one of the ingredients in the mixture of the concrete. The promising results for the coating improved when the synthesis polymer was modified with nanoparticles (Cloisite 30B at a concentration of 1 % weight of the latex). Incorporating the synthesized copolymer in the mixture of concrete caused decreasing in the density of concrete by 4 % ( via air voids formation mechanism). However, water absorption was improved when synthesized copolymer was mixed with the concrete. The synthesized copolymer and the nanocomposite is a suitable coating for the concrete and brick. Furthermore, this copolymer is a suitable water-based coating with improved properties in building materials.

Three-dimensional nanocomposite networks consisting of percolated Si nanowires in a SiOx matrix, Si:SiO2, were studied. The structures were obtained by reactive ion beam sputter deposition of SiOx (x~0.6) thin films at 450 °C and subsequent crystallization using conventional oven as well as millisecond line focus laser annealing. Rutherford backscattering spectrometry, Raman spectroscopy, X-ray diffraction, cross-sectional and energy-filtered transmission electron microscopy were applied for sample characterization. While oven annealing resulted in a mean Si wire diameter of 10 nm and a crystallinity of 72 % within the Si volume, almost single-domain Si structures with 30 nm in diameter and almost free of amorphous Si were obtained by millisecond laser application. The structural differences are attributed to the different crystallization processes: Conventional oven tempering proceeds via solid state, millisecond laser application via liquid phase crystallization of Si. The 5 orders of magnitude larger diffusion constant in the liquid phase is responsible for the three times larger Si nanostructure diameter. In conclusion, laser annealing offers not only significantly shorter process times but moreover a superior structural order of nano-Si compared to conventional heating.

Piezoelectric materials have had widespread application since their discovery both in bulk crystal and thin film applications, but thin film piezoelectrics have unlocked key applications like acoustic filtering and energy harvesting. [1] This work investigates a small subset including energy harvesting, multifunctional nanocomposites, acoustic wave resonators, and gravimetric and infrared sensing. Electroactive polymers such as PVDF-TrFE have a unique combination of characteristics including a high dielectric constant, piezoelectricity, pyroelectricity, biocompatibility, and mechanical flexibility. [2, 3, 4, 5, 6] This unique combination gives them a wide potential application space including energy harvesting, biomedical devices, drug delivery, flexible electronics, and tactile sensing. [7] In recent years, there has been significant work investigating potential composite materials based on electroactive polymers and nanoparticles. [8] This interest has been primarily driven by the increased commercial availability, tunability, and available functionalities of nanoparticles. In this work, nanocomposites of PVDF-TrFE, barium titanate (BTO), and europium barium titanate (EBTO) are investigated. EBTO is an optically active material which can add optical functionality to these active polymer composites. [9] Acoustic wave resonators including bulk acoustic wave resonators and surface acoutstic wave resonators are widely used for front end filtering technologies, but their high quality factor, small size, and low power makes them good candidates for sensing technologies. [10, 11, 12] In this work, FBARs are applied to VOC sensing and infrared sensing sucessfully.

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A thesis submitted to the Faculty of Engineering and the Built Environment, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Master of Science in Engineering. Johannesburg, May 2016 / In this study, hybrid multiscale epoxy composites were developed from woven glass fabrics and PAN nanofibers embedded with short ECNFs (diameters of ~200nm) produced via electrospinning. Unlike VGCNFs or CNTs which are prepared through bottom-up methods, ECNFs were produced through a top-down approach; hence, ECNFs are much more cost-effective than VGCNFs or CNTs. Impact absorption energy, tensile strength, and flexural strength of the hybrid multiscale reinforced GFRP composites were investigated. The control sample was the conventional GFRP composite prepared from the neat epoxy resin. With the increase of ECNFs fiber volume fraction up to 1.0%, the impact absorption energy, tensile strength, and flexural strength increased. The incorporation of ECNFs embedded in the PAN nanofibers resulted in improvements on impact absorption energy, tensile strength, and flexural properties (strength and modulus) of the GFPC. Compared to the PAN reinforced GRPC, the incorporation of 1.0% ECNFs resulted in the improvements of impact absorption energy by roughly 9%, tensile strength by 37% and flexural strength by 29%, respectively. Interfacial debonding of matrix from the fiber was shown to be the dominant mechanism for shear failure of composites without ECNFs. PAN/ECNFs networks acted as microcrack arresters enhancing the composites toughness through the bridging mechanism in matrix rich zones. More energy absorption of the laminate specimens subjected to shear failure was attributed to the fracture and fiber pull out of more ECNFs from the epoxy matrix. This study suggests that, the developed hybrid multiscale ECNF/PAN epoxy composite could replace conventional GRPC as low-cost and high-performance structural composites with improved out of plane as well as in plane mechanical properties. The strengthening/ toughening strategy formulated in this study indicates the feasibility of using the nano-scale reinforcements to further improve the mechanical properties of currently structured high-performance composites in the coming years. In addition, the present study will significantly stimulate the long-term development of high-strength high-toughness bulk structural nanocomposites for broad applications. / MT2016