Dissertations / Theses on the topic 'Electrically conductive polymer'

The growing demand in portable and compact consumer devices and appliances has resulted in the need for the miniaturisation of electronic components. These miniaturised electronic components are sensitive and susceptible to damage by voltages as low as 20V. Electrically conductive styrenic thermoplastics are widely used in electronic packaging applications to protect these sensitive electronic components against electro-static discharge (ESD) during manufacturing, assembly, storage and shipping. Such ESD applications often require the optimal volume resistance range of ≥ 1.0x105 to < 1.0x108 Ω. The best known method to render styrenic thermoplastics conductive is by the incorporation of conductive fillers, such as carbon black but the main limitation is the difficulty in controlling the conductivity level due to the steep percolation curve. Thus the aim of this research is to develop electrically conductive styrenic thermoplastics by blending several styrenic resins with polymeric conductive additives to achieve optimal volume resistance range for ESD applications with the ease in controlling the conductivity level.

Electrically conductive polymer composites, i.e. polymers filled with conductive fillers, may display a broad range of electrical properties. A rational design of fillers, filler surface chemistry and filler loading can tune the electrical properties of the composites to meet the requirements of specific applications. In this dissertation, two studies were discussed. In the first study, highly conductive composites with electrical conductivity close to that of pure metals were developed as environmentally-friendly alternatives to tin/lead solder in electronic packaging. Conventional conductive composites with silver fillers have an electrical conductivity 1~2 orders of magnitude lower than that of pure, even at filler loadings as high as 80-90 wt.%. It is found that the low conductivity of the polymer composites mainly results from the thin layer of insulating lubricant on commercial silver flakes. In this work, by modifying the functional groups in polymer backbones, the lubricant layer on silver could be chemically reduced in-situ to generate silver nanoparticles. Furthermore, these nanoparticles could sinter to form metallurgical bonds during the curing of the polymer matrix. This resulted in a significant electrical conductivity enhancement up to 10 times, without sacrificing the processability of the composite or adding extraneous steps. This method was also applied to develop highly flexible/stretchable conductors as building block for flexible/stretchable electronics. In the second study, a moderately conductive carbon/polymer composite was developed for use in sensors to monitor the thermal aging of insulation components in nuclear power plants. During thermal aging, the polymer matrix of this composite shrank while the carbon fillers remained intact, leading to a slight increase in filler loading and a substantial decrease in the resistivity of the sensors. The resistivity change was used to correlate with the aging time and to predict the need for maintenance of the insulation component according to Arrhenius’ equation. This aging sensor realized real-time, non-destructive monitoring capability for the aging of the target insulation component for the first time.

Layer-by-layer (LbL) assembly was used to produce highly conductive thin films with carbon black (CB) and polyelectrolytes. The effects of sonication and pHadjustment of the deposition mixtures on the conductivity and transparency of deposited films were studied. Drying temperature was also evaluated with regard to thin film resistance. Sonication and oven drying at 70oC produced films with the lowest sheet resistance (~ 1500 Ω/sq), which corresponds to a bulk resistivity of 0.2 Ω⋠cm for a 14- bilayer film that is 1.3 μm thick. Increasing the pH of the PAA-stabilized mixture and decreasing the pH of the PEI-stabilized mixture resulted in films with 70% transparency due to thinner deposition from increased polymer charge density. Varying the number of bilayers allows both sheet resistance and optical transparency to be tailored over a broad range. Variation of deposition mixture composition led to further reduction of sheet resistance per bilayer. A 14 bilayer film, made from mixtures of 0.25wt% carbon black in 0.05wt% PAA and plain 0.1wt% PEI, was found to have a sheet resistance of approximately 325 Ω/sq. Bulk resistivity was not improved due to the film being 8 μm thick, but this combination of small thickness and low resistance is an order of magnitude better than carbon black filled composites made via traditional melt or solution processing. Applications for this technology lie in the areas of flexible electronics, electrostatic charge dissipation, and electromagnetic interference shielding.

Polymers and polymer-based composite materials with electro-conductive properties, respectively, are materials with several potential applications. New materials are being offered in every area and novel products are constantly being introduced. Among these new materials, composites made of electro-conductive monofilaments and insulating polymers are nowadays being used as antistatic materials in the carpets and textiles industries. One promising approach for the manufacture of this kind of material is to generate the electrically conductive fibres in-situ, that is, during the actual forming process of the component. The main objective of this project was to establish the feasibility of producing electrically conductive polyaniline (PANI) fibres within a suitable polymer matrix by means of the development of a suitable processing strategy, which allows the fabrication of an anisotropically conducting composite. It is remarkable, however, that layered structures of the conducting filler were also formed within the matrix material. The latter morphology, particularly observed in compression moulded specimens of a specific polymer system, was also in good agreement with that inferred by means of a mathematical model. Experimentation was carried out with three different PANI conductive complexes (PANIPOLTM). They were initially characterised, which assisted in the identification of the most suitable material to be deformed into fibres. Preliminary processing was carried out with the selected PANIPOLTM complex, which was blended with polystyrene-polybutadiene-polystyrene (SBS), low density polyethylene (LDPE) and polypropylene (PP), respectively. The resultant blends were formed by ram extrusion, using a capillary die, to induce the deformation of the conducting phase into fibres. The morphological analysis performed on the extrudates suggested that the most suitable polymer matrix was SBS. Further experimentation was carried out with the polymer system selected. The relationships between the content of conductive complex in the composites and their electrical conductivity and microstructure were established. The blends were compression moulded and they displayed a morphology of layered domains of the conducting phase within the SBS matrix. The behaviour of the conductivity with respect to the PANIPOLTM complex in the compression moulded blends was found to be characteristic of a percolating system with a threshold as low as 5 weight percent of the conducting filler in the blends. The morphological analysis performed on the extruded blends suggested that the conducting phase was deformed into elongated domains, aligned parallel to the extrusion direction, which in some cases displayed a considerable degree of continuity and uniformity. The level of electrical conductivity in the extrudates was considerably lower than that of their corresponding non-extruded blends. This was attributed to a lack of continuity in the conducting elongated domains produced in-situ within the SBS matrix. Percolation theory and a generalisation of effective media theories were used to model the behaviour of the conductivity with respect to the content of PANIPOLTM in the compression moulded blends. Both approaches yielded similar values for the critical parameters, which were also in good agreement with the percolation threshold experimentally observed. The results of the modelling suggested that, at the percolation threshold, the morphology of the composite may consists of aggregates of flattened polyaniline particles forming very long layered structures within the SBS matrix, which is in agreement with the results of the morphological analysis.

With excellent electrical, thermal and mechanical properties as well as large specific surface area, graphene has been applied in next-generation nano-electronics, gas sensors, transparent electrical conductors, thermally conductive materials, and superior energy capacitors etc. Convenient and productive preparation of graphene is thereby especially important and strongly desired for its manifold applications. Chemically developed functionalized graphene from graphene oxide (GO) has significantly high productivity and low cost, however, toxic chemical reduction agents (e.g. hydrazine hydrate) and raised temperature (400-1100°C) are usually necessary in GO reduction yet not preferred in current technologies. Here, microwaves (MW) are applied to reduce the amount of graphene oxide (GO) at a relatively low temperature (~165°C). Experimental results indicate that resurgence of interconnected graphene-like domains contributes to a low sheet resistance with a high optical transparency after MW reduction, indicating the very high efficiency of MW in GO's reduction. Moreover, graphene is usually recumbent on solid substrates, while vertically aligned graphene architecture on solid substrate is rarely available and less studied. For TIMs, electrodes of ultracapacitors, etc, efficient heat dissipation and electrical conductance in normal direction of solid surfaces is strongly desired. In addition, large-volume heat dissipation requires a joint contribution of a large number of graphene sheets. Graphene sheets must be aligned in a large scale array in order to meet the requirements for TIM application. Here, thermally conductive fuctionalized multilayer graphene sheets (fMGs) are efficiently aligned in a large scale by vacuum filtration method at room temperature, as evidenced by SEM images and polarized Raman spectroscopy. A remarkably strong anisotropy in properties of aligned fMGs is observed. Moreover, VA-fMG TIMs are prepared by constructing a three-dimensional vertically aligned functionalized multilayer graphene architecture between contact Silicon/Silicon surfaces with pure Indium as a metallic medium. Compared with their counterpart from recumbent A-fMGs, VA-fMG TIMs have significantly higher equivalent thermal conductivity and lower contact thermal resistance. Electrical and thermal conductivities of polymer composite are also greatly interested here. Previous researches indicated that filler loading, morphology of fillers, and chemical bonding across filler/polymer interfaces have significant influence on electrical/thermal conductivity of polymer composite. Therefore, the research also pays substantial attention to these issues. First, electrical resistivity of CPCs is highly sensitive on volume or weight ratio (filler loading) of conductive fillers in polymer matrix, especially when filler loading is close to percolation threshold (pc). Thermal oxidation aging usually can cause a significant weight loss of polymer matrix in a CPC system, resulting in a filler loading change which can be exhibited by a prompt alteration in electrical resistivity of CPCs. Here, the phenomena are applied as approach for in-situ monitoring thermal oxidation status of polymeric materials is developed based on an electrical sensors based on conductive polymeric composites (CPCs). The study developed a model for electrical resistivity of sensors from the CPCs as a function of aging time at constant aging temperature, which is in a good agreement with a Boltzmann-Sigmoidal equation. Based on the finding, the sensors show their capability of in-situ in-situ monitor and estimate aging status of polymeric components by a fast and convenient electrical resistance measurement. Second, interfacial issues related to these thermal conductive fillers are systemically studied. On the one hand, the study focuses on relationship between morphology of h-BN particles and thermal conductivity of their epoxy composites. It is found that spherical-agglomeration of h-BN particles can significantly enhance thermal conductivity of epoxy resin, compared with dispersed h-BN plates, by substantially reducing specific interfacial area between h-BN and epoxy resin. On the other hand, surface of high thermal conductive fillers such as SiC particles and MWNTs are successfully functionalized, which makes their surface reactive with bisphenol A diglycidyl ether and able to form chemical bonding between fillers and epoxy resin. By this means, thermal conductivity of polymer composites is found to be significantly enhanced compared with control samples, indicating the interfacial chemical bonding across interface between thermal conductive fillers and polymer matrix can promote heat dissipation in polymeric composites. The finding can benefit a development of high thermal conductive polymer composites by interfacial chemical bonding enhancement to meet the demanding requirements in current fine pitch and Cu/low k technology.

Optically reflective polyimide films have been prepared by the incorporation of silver(I) acetate and a {dollar}\beta{dollar}-diketone solubilizing agent, hexafluoroacetylacetone (HFAH), into a dimethylacetamide solution of the poly(amic acid) formed from {dollar}3,3\sp\prime,4,4\sp\prime{dollar}-benzophenonetetracarboxylic acid dianhydride (BTDA) and {dollar}4,4\sp\prime{dollar}-oxydianiline {dollar}(4,4\sp\prime{dollar}-ODA). Optically reflective and conductive polyimide films have been prepared by replacing the {dollar}\beta{dollar}-diketone (HFAH), with the less substituted {dollar}\beta{dollar}-diketone, trifluoroacetylacetone (TFAH). The former system has been both cast directly from the poly(amic acid) resin and cast from the poly(amic acid) resin onto a fully imidized {dollar}\rm BTDA/4,4\sp\prime{dollar}-ODA base (forming a metallized topcoat). Thermal curing of the silver(I)-containing poly(amic acid) leads to imidization with concomitant silver(I) reduction, yielding a reflective silver surface, when HFAH is the solubilizing agent, and a reflective and surface-conductive silver surface, when TFAH is the solubilizing agent. The metallized {dollar}\rm BTDA/4,4\sp\prime{dollar}-ODA films retain the essential mechanical properties of undoped films and have good thermal stability particularly in nitrogen atmospheres. The system which forms a metallized topcoat also exhibits the essential mechanical and thermal properties of the parent polymer while minimizing the silver required to form the reflective surface, and has outstanding metal-polymer and polymer-polymer adhesion attributed to mechanical interlocking. Films were characterized by X-ray, DSC, TGA, XPS, TEM, SEM, AFM.

O objetivo deste estudo foi o desenvolvimento de compósitos poliméricos flexíveis e altamente condutores elétricos preparados por moldagem por compressão e por fabricação de filamentos fundidos (FFF) para possíveis aplicações como materiais piezoresistivos ou piezoelétricos para sensores de compressão. Compósitos baseados em misturas de poli(fluoreto de vinilideno)/poliuretano termoplástico (PVDF/TPU) como matriz e contendo várias frações de negro de fumo-polipirrol (CB-PPy) como aditivo condutor foram preparados. Diversas técnicas de caracterização foram realizadas para avaliar as propriedades mecânicas, térmicas, químicas e elétricas, morfologia e printabilidade dos materiais investigados. Primeiro, blendas de PVDF/TPU com diferentes composições foram produzidas por mistura por fusão seguida de moldagem por compressão. Os resultados mostraram que a flexibilidade desejada para os materiais foi melhorada com a adição de TPU aos compósitos de PVDF. As imagens SEM evidenciaram a obtenção de uma blenda co-contínua com 50/50 vol% de PVDF/TPU. As blendas compostas de PVDF/TPU 38/62 vol% e a blenda co-contínua de PVDF/TPU 50/50 vol% foram selecionadas como matrizes para a preparação de compósitos moldados por compressão e impressos em 3D a fim de alcançar uma ótima combinação entre condutividade, propriedades mecânicas e printabilidade. Várias quantidades de negro de fumo-polipirrol, de 0 a 15%, foram adicionadas às blendas selecionadas para aumentar a condutividade elétrica dos compósitos e possivelmente atuar como agente nucleante para a fase cristalina do PVDF a fim de aumentar sua resposta piezoelétrica. A adição de CB-PPy aumentou a condutividade elétrica de todos os compósitos. No entanto, a condutividade elétrica dos compósitos baseados em blendas co-contínuas PVDF/TPU 50/50 vol% foi maior do que as encontradas para os compósitos de PVDF/TPU 38/62 vol% com mesma concentração de aditivo. De fato, o limiar de percolação elétrico dos compósitos com blenda co-contínua foi de 2%, enquanto o limiar de percolação elétrico dos compósitos compostos da blenda não contínua foi de 5%. Com relação às propriedades mecânicas, a incorporação do aditivo condutor nas blendas resultou em materiais mais rígidos com maior módulo de elasticidade, menor alongamento na ruptura e maior módulo de armazenamento. O módulo de armazenamento (G') e a viscosidade complexa (η*) dos compósitos aumentaram com a adição de CB-PPy. O limiar de percolação reológico foi de 3% para PVDF/TPU/CB-PPy 38/62 vol% e 1% para PVDF/TPU/CB-PPy 50/50 vol%, indicando que uma quantidade maior de carga poderia comprometer a processabilidade dos compósitos. A adição de CB-PPy também resultou na redução dos valores de Tg e Tm dos compósitos devido à redução da mobilidade das cadeias poliméricas. Com base na condutividade elétrica e no comportamento mecânico dos compósitos, três composições diferentes foram selecionadas para a extrusão de filamentos para serem posteriormente utilizados no processo de impressão 3D. No geral, as peças impressas em 3D apresentaram propriedades mecânicas e elétricas inferiores devido à presença de vazios, defeitos e camadas sobrepostas que podem dificultar o fluxo de elétrons. Os valores de condutividade elétrica dos compósitos impressos em 3D de PVDF/TPU/CB-PPy 38/62 vol% contendo 5% e 6% de CB-PPy são de uma a sete ordens de grandeza menores do que os encontrados para os compósitos com a mesma composição moldados por compressão. Mesmo que o valor da condutividade elétrica para o compósito PVDF/TPU 38/62 vol% com 6% de CB-PPy moldado por compressão foi de 1,94x10-1 S•m-1, o compósito impresso em 3D com a mesma composição mostrou um valor muito baixo de condutividade elétrica de 6,01x10-8 S•m-1. Por outro lado, o compósito co-contínuo de PVDF/TPU 50/50 vol% com 10% de aditivo impresso em 3D apresentou um alto valor de condutividade elétrica de 4,14×100 S•m-1 mesmo após o processo de impressão. Além disso, as respostas piezoresistivas dos compósitos foram investigadas. Para os compósitos PVDF/TPU/CB-PPy 38/62 vol%, as amostras moldadas por compressão e impressas em 3D com 5% e 6% de CB-PPy exibiram boa resposta piezoresistiva. No entanto, apenas os compósitos com 6% de aditivo apresentaram valores elevados de sensibilidade e gauge factor, atuação em ampla faixa de pressão e respostas piezoresistivas reprodutíveis durante a aplicação de 100 ciclos de compressão/descompressão para ambos os métodos de fabricação. Por outro lado, para os compósitos co-contínuos de PVDF/TPU/CB-PPy apenas a amostra moldada por compressão com 5% de CB-PPy apresentou respostas piezorresistivas boas e reprodutíveis. A cristalinidade e o teor de fase β do PVDF foram investigados para os compósitos. Embora o grau de cristalinidade das amostras tenha diminuído com a adição de CB-PPy, a porcentagem de fase β no PVDF aumentou. O coeficiente piezoelétrico d33 das amostras aumentou com a porcentagem de fase β. A adição de 6% ou mais de CB-PPy foi necessária para aumentar significativamente o coeficiente piezoelétrico (d33) dos compósitos. O conteúdo de fase β e as respostas piezoelétricas do PVDF foram menores para as amostras preparadas por FFF. Por fim, como pesquisa colateral, a eficiência de blindagem contra interferência eletromagnética (EMI-SE) foi medida para todos os compósitos. Compósitos com maior condutividade elétrica apresentaram melhor blindagem da radiação eletromagnética. Além disso, os compósitos baseados na blenda co-contínua apresentaram maior eficiência de blindagem contra EMI do que os compósitos de PVDF/TPU 38/62 vol%. O principal mecanismo de blindagem foi a absorção para todos os compósitos. As amostras preparadas por FFF apresentaram respostas de EMI-SE menores quando comparadas às amostras moldadas por compressão.
The aim of this study was the development of flexible and highly electrically conductive polymer composites via compression molding and fused filament fabrication for possible applications as piezoresistive or piezoelectric materials for pressure sensors. Composites based on blends of poly(vinylidene fluoride)/thermoplastic polyurethane (PVDF/TPU) as matrix and containing various fractions of carbon black-polypyrrole (CB-PPy) as conductive filler were prepared. Several characterization techniques were performed in order to evaluate the mechanical, thermal, chemical and electrical properties, morphology and printability of the investigated materials. First, PVDF/TPU blends with different compositions were prepared by melt compounding followed by compression molding. The results showed that the flexibility aimed for the final materials was improved with the addition of TPU to PVDF composites. SEM images evidenced the achievement of a co-continuous blend comprising 50/50 vol% of PVDF/TPU. The blends composed of PVDF/TPU 38/62 vol% and the co-continuous blend of PVDF/TPU 50/50 vol% were selected as matrices for the preparation of compression molded and 3D printed composites in order to achieve an optimal compromise between electrical conductivity, mechanical properties and printability. Various amounts of carbon black-polypyrrole, from 0 up to 15%, were added to the selected blends in order to rise the electrical conductivity of the composites and to possible act as nucleating filler for the β crystalline phase of PVDF in order to increase its piezoelectric response. The addition of CB-PPy increased the electrical conductivity of all composites. However, the electrical conductivity of composites based on PVDF/TPU 50/50 vol% co-continuous blends was higher than those found for PVDF/TPU 38/62 vol% composites at the same filler content. Indeed, the electrical percolation threshold of the conductive co-continuous composite blends was 2%, while the electrical percolation threshold of the composites with the nonco-continuous composite blends was 5%. With respect to the mechanical properties, the incorporation of the filler into the blends leaded to more rigid materials with higher elastic modulus, lower elongation at break and higher storage modulus. The storage modulus (G’) and complex viscosity (η*) of the composites increased with the addition of CB-PPy. The rheological percolation threshold was found to be 3% for PVDF/TPU/CB-PPy 38/62 vol% and 1% for PVDF/TPU/CB-PPy 50/50 vol%, indicating that higher amount of filler could compromise the processability of the composites. The addition of CB-PPy also resulted in a reduction on the Tg and Tm values of the composites due to the reduction of the mobility of the polymeric chains. Based on the electrical conductivity and mechanical behavior of the composites, three different compositions were selected for the extrusion of filaments to be used in a 3D printing process. Overall, the 3D printed parts presented lower mechanical and electrical properties because of the presence of voids, defects and overlapping layers that can hinder the flow of electrons. The electrical conductivity values of PVDF/TPU/CB-PPy 38/62 vol% composites containing 5% and 6 wt% of CB-PPy 3D printed samples are one to seven orders of magnitude lower than those found for compression molded composites with the same composition. Even if the electrical conductivity value for PVDF/TPU 38/62 vol% compression molded composite with 6% of CB-PPy was as high as 1.94x10-1 S•m-1, the 3D printed composite with same composition showed a very low electrical conductivity of 6.01x10-8 S•m-1. On the other hand, the 3D printed co-continuous composite PVDF/TPU 50/50 vol% with 10% of filler displayed a high value of electrical conductivity of 4.14×100 S•m-1 even after the printing process. Moreover, the piezoresistive responses of the composites were investigated. For PVDF/TPU/CB-PPy 38/62 vol% composites, the compression molded and 3D printed samples with 5% and 6% of CB-PPy exhibited good piezoresistive response. However, only the composites with 6% displayed high sensitivity and gauge factor values, large pressure range and reproducible piezoresistive responses under 100 cycles for both methods. On the other hand, for PVDF/TPU/CB-PPy co-continuous composites only the compression molded sample with 5% of CB-PPy presented good and reproducible piezoresistive responses. The crystallinity and β phase content of PVDF were investigated for the composites. Althought the degree of crystallinity of the samples decreased with the addition of CB-PPy, the percentage of β phase in PVDF was increased. The piezoelectric coefficient d33 of the samples increased with the percentage of β phase. The addition of 6% or more of CB-PPy was necessary to increase significatively the piezoelectric coefficient (d33) of the composites. The β phase content and piezoelectric responses of PVDF were lower for samples prepared by FFF. Finally, as a collateral research, the electromagnetic interference shielding effectiveness (EMI-SE) were measured for all composites. Composites with higher electrical conductivity showed better shielding of the electromagnetic radiation. In addition, composites based on the co-continuous blend displayed higher EMI shielding efficiency than 38/62 vol% composites. The main mechanism of shielding was absorption for all composites. Specimens prepared by FFF displayed diminished EMI-SE responses when compared to compression molded samples.
Lo scopo di questo studio è lo sviluppo di compositi polimerici flessibili e ad elevata conducibilità elettrica tramite stampaggio a compressione e manifattura additiva (fused filament fabrication) per possibili applicazioni come materiali piezoresistivi o piezoelettrici in sensori di pressione. In particolare, sono stati preparati compositi a base di miscele di poli(vinilidene fluoruro)/poliuretano termoplastico (PVDF/TPU) come matrice e contenenti varie frazioni di nerofumo-polipirrolo (CB-PPy) come riempitivo conduttivo. Sono state utilizzate diverse tecniche di caratterizzazione al fine di valutare le proprietà meccaniche, termiche, chimiche ed elettriche, la morfologia e la stampabilità dei materiali ottenuti. In primo luogo, miscele PVDF/TPU con diverse composizioni sono state preparate mediante mescolatura allo stato fuso seguita da stampaggio a compressione. I risultati hanno mostrato che la flessibilità del PVDF viene notevolemente migliorata dall’aggiunta di TPU. Le immagini SEM hanno evidenziato il raggiungimento di una miscela co-continua per una composizione 50/50% in volume di PVDF/TPU. Le miscele composte da PVDF/TPU 38/62 vol% e la miscela co-continua di PVDF/TPU 50/50 vol% sono state selezionate come matrici per la preparazione di compositi per stampaggio a compressione e manifattura additiva al fine di ottenere un compromesso ottimale tra conducibilità, proprietà meccaniche e stampabilità. Alle miscele selezionate sono state aggiunte varie quantità di nerofumo-polipirrolo, dallo 0 al 15%, per aumentare la conducibilità elettrica dei compositi ed eventualmente fungere da additivo nucleante per la fase β cristallina del PVDF al fine di aumentarne la risposta piezoelettrica. L'aggiunta di CB-PPy ha aumentato la conduttività elettrica di tutti i compositi. Tuttavia, la conduttività elettrica dei compositi basati su miscele co-continue di PVDF/TPU 50/50% in volume era superiore a quella trovata per compositi PVDF/TPU 38/62% in volume con lo stesso contenuto di riempitivo. Infatti, la soglia di percolazione elettrica delle miscele conduttive era del 2%, mentre la soglia di percolazione elettrica dei compositi con miscele composite non continue era del 5%. Per quanto riguarda le proprietà meccaniche, l'incorporazione del riempitivo nelle mescole ha portato a materiali più rigidi con modulo elastico più elevato, allungamento a rottura inferiore e modulo conservativo più elevato. Il modulo conservativo (G') e la viscosità complessa (η*) dei compositi sono aumentate con l'aggiunta di CB-PPy. La soglia di percolazione reologica è risultata essere del 3% per PVDF/TPU/CB-PPy 38/62 vol% e dell'1% per PVDF/TPU/CB-PPy 50/50 vol%, indicando che una maggiore quantità di riempitivo potrebbe compromettere la processabilità dei compositi. L'aggiunta di CB-PPy ha comportato anche una riduzione dei valori di Tg e Tm dei compositi a causa della riduzione della mobilità delle catene polimeriche. Sulla base della conduttività elettrica e del comportamento meccanico dei compositi, sono state selezionate tre diverse composizioni per l'estrusione di filamenti da utilizzare in un processo di stampa 3D. Nel complesso, le parti stampate in 3D presentavano proprietà meccaniche ed elettriche inferiori a causa della presenza di vuoti, difetti e strati sovrapposti che possono ostacolare il flusso di elettroni. I valori di conducibilità elettrica dei compositi PVDF/TPU/CB-PPy 38/62 vol% contenenti il 5% e il 6% di CB-PPy di campioni stampati in 3D sono da uno a sette ordini di grandezza inferiori a quelli trovati per i compositi stampati a compressione con la stessa composizione. Anche se il valore di conducibilità elettrica per il composito stampato a compressione PVDF/TPU 38/62 vol% con il 6% di CB-PPy era pari a 1,94x10-1 S•m-1, il composito stampato in 3D con la stessa composizione ha mostrato un valore molto basso di conducibilità elettrica, pari a 6,01x10-8 S•m-1. D'altra parte, il composito PVDF/TPU 50/50 vol% stampato in 3D con il 10% di riempitivo ha mostrato un elevato valore di conducibilità elettrica, pari a 4,14 × 100 S•m-1, anche dopo il processo di stampa. Inoltre, sono state studiate le risposte piezoresistive dei compositi. Per i compositi PVDF/TPU/CB-PPy 38/62 vol%, i campioni stampati a compressione e stampati in 3D con il 5% e il 6% di CB-PPy hanno mostrato una buona risposta piezoresistiva. Tuttavia, solo i compositi con il 6% hanno mostrato valori di sensibilità e gauge factor elevati, ampio intervallo di pressione e risposte piezoresistive riproducibili in 100 cicli per entrambi i metodi. D'altra parte, per i compositi co-continui PVDF/TPU/CB-PPy solo il campione stampato a compressione con il 5% di CB-PPy ha presentato risposte piezoresistive adeguate e riproducibili. La cristallinità e il contenuto di fase β del PVDF sono stati studiati per i compositi. Sebbene il grado di cristallinità dei campioni diminuisca con l'aggiunta di CB-PPy, la percentuale di fase β in PVDF risulta aumentata. Il coefficiente piezoelettrico d33 dei campioni aumenta anch’esso con la percentuale di fase β. L'aggiunta del 6% o più di CB-PPy è stata necessaria per aumentare significativamente il coefficiente piezoelettrico (d33) dei compositi. Il contenuto di fase β e le risposte piezoelettriche del PVDF sono inferiori per i campioni ottenuti mediante stampa 3D. Infine, come ricerca collaterale, è stata misurata l'efficacia della schermatura contro le interferenze elettromagnetiche (EMI-SE) per tutti i compositi. I compositi con una maggiore conduttività elettrica hanno mostrato una migliore schermatura della radiazione elettromagnetica. Inoltre, i compositi basati sulla miscela co-continua hanno mostrato un'efficienza di schermatura EMI maggiore rispetto ai compositi a 38/62% in volume. Per tutti i compositi, il principale meccanismo di schermatura è l'assorbimento. I campioni preparati mediante manifattura additiva hanno mostrato risposte EMI-SE inferiori rispetto ai campioni stampati a compressione.

Thick composites (~ 3 mm in thickness) of polypyrrole with electrically insulating porous (polystyrene) and nonporous (polymethyl methacrylate) substrates were prepared using a two-step batch method. In the two-step method, impregnation of volatile (iodine) or nonvolatile (ferric chloride) oxidant in the substrate is followed by in-situ polymerization of pyrrole. Conductivities as high as 10-1 S/cm were obtained in this work in the case of composites of polypyrrole and porous, crosslinked polystyre. Use of the nonvolatile oxidant (ferric chloride) resulted in higher conducting polymer yield, as well as composites having a higher conductivity, thermal stability, and mechanical strength. However, the volatile oxidant (iodine) could be transported to the substrate using supercritical carbon dioxide as the solvent. As a result, partitioning of the oxidant between the solvent phase and the polymer substrate, and hence the distribution of the oxidant in the substrate, could be controlled by manipulation of the pressure. The two-step batch method in which supercritical carbon dioxide is used to facilitate transport and as a solvent for the oxidant was found to be an effective method for the production of thick composites with uniform conductivity, thermal stability, and mechanical strength. Such composites are desired in important practical applications such as rechargeable battery electrodes and electromagnetic interference shielding materials.

Measurements on free standing films of the conductive polymer polyaniline (PANi) have revealed that charge transport within this material depends upon the level of intermolecular order. This factor is found to depend upon the method of sample preparation. PANi protonated by immersion of solid emeraldine base in aqueous methane sulphonic acid has low conductivity, 30-40 Scm(^-1). This can be enhanced, up to 250 Scm(^-1) if films are stretch oriented prior to protonation. Stretched samples have an electrical conductivity anisotropy factor of order 7 at 300 K, also revealed in their thermopower over the range 100 - 300 K. The behaviour of electrical conductivity with temperature is commensurate with charge transport in a disordered system. Protonation of PANi dissolved in meta cresol by addition of camphor sulphonic acid (CSA) yields material with conductivity of 250-300 Scm(^-1) Variation of the acid concentration has revealed a transition to a metallic response in conductivity (near 300 K) when 20-30% of polymer nitrogen sites are protonated. This character extends to progressively lower temperatures as protonation is increased to 60%. The metallic nature of this material is evident in the linear temperature dependence of thermopower and is ascribed to the presence of crystalhne regions within the polymer fihn, as revealed by an independent x-ray analysis The role of molecular order upon the properties of thin films of 3[2(S2-methylbutoxy)ethyl]-polythiophene has been investigated. Starting with polymer dissolved in 'good' solvent, quantities of nonsolvent lead to reorganisation of the sidechain groups when added. This promotes an increase in effective conjugation length which can be transferred to the solid state by the spin coating process as indicated by spectroscopic studies. With these films acting as the active layer in a field effect transistor the charge carrier mobility can be measured. It is found that as molecular order increases, mobility decreases from 10(^-5) cm(^2)V(^-1)s(^-1) to 710(^-8) cm(^2)V(^-1)s(^-1). This is ascribed to increased interchain separation and effects due to macroscopic aggregate grain boundaries.

In smart textiles, electrical conductivity is often required for several functions, especially contacting (electroding) and interconnecting. This thesis explores electrically conductive textile surfaces made by combining conventional textile coating methods with the intrinsically conductive polymer complex poly(3,4-ethylene dioxythiophene)-poly(styrene sulfonate) (PEDOT:PSS). PEDOT:PSS was used in textile coating formulations including polymer binder, ethylene glycol (EG) and rheology modifier. Shear viscometry was used to identify suitable viscosities of the formulations for each coating method. The coating methods were knife coating, pad coating and screen printing. The first part of the work studied the influence of composition of the coating formulation, the amount of coating and the film formation process on the surface resistivity and the surface appearance of knife-coated textiles. The electrical resistivity was largely affected by the amount of PEDOT:PSS in the coating and indicated percolation behaviour within the system. Addition of a high-boiling solvent, i.e. EG, decreased the surface resistivity with more than four orders of magnitude. Studies of tear strength and bending rigidity showed that textiles coated with formulations containing larger amounts of PEDOT:PSS and EG were softer, more ductile and stronger than those coated with formulations containing more binder. The coated textiles were found to be durable to abrasion and cyclic strain, as well as quite resilient to the harsh treatment of shear flexing. Washing increased the surface resistivity, but the samples remained conductive after five wash cycles. The second part of the work focused on using the coatings to transfer the voltage signal from piezoelectric textile fibres; the coatings were first applied using pad coating as the outer electrode on a woven sensor and then as screen-printed interconnections in a sensing glove based on stretchy, warp-knitted fabric. Sensor data from the glove was successfully used as input to a microcontroller running a robot gripper. These applications showed the viability of the concept and that the coatings could be made very flexible and integrated into the textile garment without substantial loss of the textile characteristics. The industrial feasibility of the approach was also verified through the variations of coating methods.

Thesis (M. S.)--Materials Science and Engineering, Georgia Institute of Technology, 2009.
Committee Chair: Rosario Gerhardt; Committee Member: Gleb Yushin; Committee Member: Hamid Garmestani. Part of the SMARTech Electronic Thesis and Dissertation Collection.

With the push to more environmentally friendly materials to solve some of the biggest challenges in the coatings industry, electrically conductive polymers (ECPs) are seen as a flexible solution due to their unique properties. ECPs are seen as an attractive substitute to the current metallic materials used in applications such as printable electronics, anti-static protection, and corrosion mitigation. Polypyrrole (PPy) is seen as a popular class of ECPs due to its inherent high electrical conductivity, resistance to environmental degradation, and ease of synthesis. The first part of this work was to study the ability of polypyrrole to be synthesized through a novel photochemical process. This method eliminated the need to stabilize particles in a suspension and deposit an electrically conductive film onto a variety of substrates. The second part of this work was to synthesize functional versions of PPy that could further be crosslinked into the coating matrix to improve bulk physical properties through better interaction between the functional filler and the organic coating matrix. The last part of this work is based off prior work at NDSU on AL-flake/PPy composites. This study took the development of these pigments further by incorporating organic anions known to inhibit corrosion and study their efficacy. Advanced analytical methods such as Conductive Atomic Force Microscopy was used to study the electrical properties of PPy. In addition, advanced electrochemical tests such as Electrical Impedance Spectroscopy (EIS), Scanning Vibrating Electrode Technique (SVET), Linear Polarization (LP), and Galvanic Coupling (GP) were conducted alongside traditional accelerated weathering techniques such as ASTM B117 and GM 9540 to determine the corrosion resistance of the synthesized coatings.
Army Research Laboratory

In this thesis, low direct currents (DC) have been shown to successfully reduce bacterial adherence to conducting polymers in unique electrically modified flow devices without the aid of an antimicrobial agent. However, alternating currents (AC) and radio-frequency currents (RF) were not found to be effective. The design and manufacture of these new DC and RF flow devices has been comprehensively documented within, accompanied by relevant standard operating procedures and experimental designs. Additionally, the thesis includes a review of seminal bioelectric literature and discusses the potential for exciting future developments in this multidisciplinary field of research. These findings are ultimately intended to facilitate the design of new indwelling medical devices (IMDs) as well as electrically sterilized polymer surfaces for a wide range of far-reaching applications in industries where bacterial biofilms proliferate

The world’s increased energy storage demand, as well as the environmental concerns related to the combustion of fossil fuels, has triggered a transition to intermittent renewable energy sources as well as to electrical and hybrid vehicles. Current day rechargeable batteries are, due to the invention and development of lithium ion batteries, technologically well positioned to answer to some of these demands. Conventional batteries, however, utilize inorganic materials of limited supply that require large amounts of energy during refining and processing. The materials also add a significant cost to the final product, making the rechargeable batteries less attractive for large scale applications. During the last decade, significant efforts have been made to find suitable organic matter based electrode materials that can replace the inorganic materials. One class of organic materials that can be used for electrical energy storage, or be included as components in organic matter based energy storage systems, is conducting polymers. The aim of this thesis was to investigate the possibilities and limitations of using the conducting polymer polypyrrole in energy storage applications. The polymer was synthesized onto cellulose extracted from the Cladophora sp. algae, and the result was a flexible composite material. Symmetrical energy storage devices constructed with the composite material were shown to exhibit a pseudocapacitive behavior. The resistance in the cells was investigated and was found to scale linearly with the separator thickness. Cells could be cycled for 4,000 cycles without significant capacitance loss and cells that were overcharged to 1.8 V cell potential, were found to be protected by a resistive potential drop. Devices were constructed as proof-of-concept and were used to power a remote control and a digital thermometer. The self-discharge in polypyrrole was studied extensively. It was found that oxygen was responsible for the oxidation of the reduced electrode, while the positive electrode self-discharged due to a faradaic reaction. Through spectroscopy and the temperature dependence of the self-discharge, it was suggested that the self-discharge of oxidized polypyrrole is linked to the degradation at high potentials, commonly referred to as overoxidation.

In this study, electrically conductive coating materials composed of epoxy resin and carbon black (CB) were prepared by applying two different mixing techniques (Grinding and Mechanical Mixing). The effect of carbon black addition, ultrasonication, mixing type and surface modification of carbon black on the morphologies, electrical and mechanical properties of the composites were investigated. According to test results, Grinding Method is much more efficient and for this method, percolation concentration was found as 2 vol %. The electrical resistivity value obtained at this composition is around 107 ohm.cm. Also, for the samples prepared by Grinding Method, the hardness increased by adding conductive filler, but the impact energy and adhesive strength decreased with increasing carbon black content. Ultrasonication was applied to the samples containing 2 vol % CB obtained by Grinding Method to reduce the electrical resistivity further. Three different ultrasonic mixing times were tried, however, no positive effect was observed on electrical and mechanical properties. Since the addition of carbon black has a negative effect on the processability of the mixture, it was aimed to obtain desired conductivity value at lower percolation concentration by modifying carbon black surface with different silane coupling agents and formamide. The best result in terms of electrical conductivity was obtained for the materials produced with formamide treated carbon black by Grinding Method. At 1 vol % concentration, the electrical resistivity was found as approximately 106 ohm.cm which is three orders smaller than the resistivity of materials prepared with untreated carbon black.

The aim of this study was to improve electrical properties of conductive polymer composites. For this purpose, various studies were performed using different materials in this dissertation. In order to investigate the effect of alternative composite preparation methods on electrical conductivity, nylon 6/carbon black systems were prepared by both in-situ polymerization and melt-compounding techniques. When compared with melt compounding, in-situ polymerization method provided enhancement in electrical conductivity of nylon 6 composites. Furthermore, it was aimed to improve electrical conductivity of polymer composites by modifying surface chemistry of carbon black. 1 wt. % solutions of 3-Aminopropyltriethoxysilane and formamide were tried as chemical modifier, and treated carbon black was melt mixed with low-density polyethylene (LDPE) and nylon 6. According to electron spectroscopy for chemical analysis (ESCA), chemicals used for surface treatment may have acted as doping agent and improved electrical conductivity of polymer composites more than untreated carbon black did. Formamide was more effective as dopant compared to the silane coupling agent. In order to investigate electromagnetic interference (EMI) shielding effectiveness and dielectric properties of conductive polymer composites, 1, 2 and 3 wt. % solutions of formamide were tried as chemical modifier and treated carbon black was melt mixed with poly(ethylene terephthalate) (PET). Composites containing formamide treated carbon black exhibited enhancement in electrical conductivity, EMI shielding effectiveness and dielectric constant values compared to composites with untreated carbon black. In order to enhance electrical conductivity of polymer composites, the selective localization of conductive particles in multiphase polymeric materials was aimed. For this purpose, carbon nanotubes (CNT) were melt mixed with polypropylene (PP)/PET. Grinding, a type of solid state processing technique, was applied to PP/PET/CNT systems to reduce the average domain size of blend phases and to improve interfacial adhesion between these phases. Grinding technique exhibited improvement in electrical conductivity and mechanical properties of PP/PET/CNT systems at low PET compositions. To investigate application potential of conductive polymer composites, polyaniline (Pani)/carbon nanotubes (CNT) composites were synthesized and electrochemical capacitance performances of these systems, as electrode material in electrochemical capacitors, were studied. Polyaniline/carbon nanotubes composites resulted in a higher specific capacitance than that of the composite constituents. Pseudocapacitance behavior of Pani might contribute to the double layer capacitance behavior of nanotubes. Additionally, as an alternative to Pani/CNT systems, polyaniline films were deposited on treated current collectors and electrochemical capacitance performances of these electrode systems were investigated. The highest specific capacitance of polyaniline/carbon nanotubes composites was 20 F/g and this value increased to 35.5 F/g with polyaniline film deposited on treated current collector.

One of the aim of this study is to prepare conductive polymer nanocomposites of polypropylene to obtain better mechanical and electrical properties. Composite materials based on conductive fillers dispersed within insulating thermoplastic matrices have wide range of application. For this purpose, conductive polymer nanocomposites of polypropylene with nano dimentional conductive fillers like carbon black, carbon nanotube and fullerene were prepared. Their mechanical, electrical and thermal properties were investigated. Polypropylene (PP)/carbon black (CB) composites at different compositions were prepared via melt blending of PP with CB. The effect of CB content on mechanical and electrical properties was studied. Test samples were prepared by injection molding and compression molding techniques. Also, the effect of processing type on mechanical and electrical properties was investigated. Composites become semiconductive with the addition of 2 wt% CB. Polypropylene (PP) / Carbon Nanotube (CNT) and Polypropylene / Fullerene composites were prepared by melt mixing. CNT&rsquo
s and fullerenes were surface functionalized with HNO3 : H2SO4 before composite preparation. The CNT and fullerene content in the composites were varied as 0.5, 1.0, 2.0 and 3.0 % by weight. For the composites which contain surface modified CNT and fullerene four different compatibilizers were used. These were selected as TritonX-100, Poly(ethylene-block-polyethylene glycol), Maleic anhydride grafted Polypropylene and Cetramium Bromide. The effect of surface functionalization and different compatibilizer on mechanical, thermal and electrical properties were investigated. Best value of these properties were observed for the composites which were prepared with maleic anhydride grafted polypropylene and cetramium bromide. Another aim of this study is to built and characterize transistors which have polyethylene as dielectric layers. While doing this, polyethylene layer was deposited on gate electrode using vacuum evaporation system. Fullerene , Pentacene ve Indigo were used as semiconductor layer. Transistors work with low voltage and high on/off ratio were built with Aluminum oxide - PE and PE dielectrics.

Electrically conductive or electro-active fibers are the key components of smart and interactive textiles, which could be used in medical, sports, energy, and military applications in the near future. The functionalization of high-performance textile yarns/fibers with conjugated polymers can produce conductive fibers with better electro-mechanical properties, which is difficult with commonly used spinning techniques. In this thesis work, textile-based conductive yarns/fibers were prepared by coating viscose and polyester (PET) yarns with the conjugated polymer PEDOT. For coating purposes, an efficient technique called chemical vapor deposition (CVD) was used, which is a solventless technique and can produce PEDOT polymer layers with high conductivity values. The polymerization of EDOT monomer vapors and coating of oxidant (FeCl3 or FepTS) enriched viscose and PET yarns took place simultaneously. The PEDOT-coated viscose and polyester yarns showed relatively high conductivity values, which could be sufficient for many electronic applications. The polymerization process and the quality of PEDOT polymer strongly depends on different reaction conditions. In this research work, the impact of most of these reaction parameters on the electrical, mechanical, and thermal properties of PEDOT-coated conductive yarns was considered separately. Under specific reaction conditions, it was found that viscose fibers were successfully coated with PEDOT polymer and showed rather high electrical conductivity (≥ 15 S/cm). However, due to the acid hydrolysis of viscose fibers in FeCl3 solutions, the mechanical properties were drastically reduced. In order to improve the mechanical properties of conductive yarns, a relatively stable and chemical-resistant substrate (PET) was coated with PEDOT polymer. Comparative studies between PEDOT-coated viscose and PET conductive yarns showed that the electrical and mechanical properties were enhanced by changing the substrate material. Later on, PEDOT-coated conductive fibers were treated with silicone elastomer solution and due to the thin silicone layers, the hydrophobic properties, flexibility, and durability of coated yarns was improved. Furthermore, a novel electrical resistance-measuring setup was developed, which can be used not only for fibers but also for fabric structures. The electrical characterization of PEDOT-coated conductive yarns showed that it can be used effectively for sensitive fibers without damaging their surface morphology. Finally, the use of conductive yarns as stretch sensors was evaluated. For this purpose, small rectangular knitted patches of conductive yarns were prepared and then the change in electrical resistance values at different extension percentages (5–50%) was investigated. The constant variations in electrical resistance values at different extension and relaxation cycles for longer periods of time revealed that the conductive yarns produced have the potential to be used as stretch sensors for monitoring of vital signs in medical and sports applications.

Thesis for the Degree of Doctor of Philosophy to be presented on March 08, 2013, 10.00 in KA-salen, Kemigården 4, Chalmers University of Technology, Gothenburg

The aim of this study was to improve the mechanical and electrical properties of conductive polymer composites. For this purpose, different studies were performed in this dissertation. In order to investigate the effects of the carbon nanotube (CNT) surface treatment on the morphology, electrical and mechanical properties of the composites, poly(ethylene terephthalate) (PET) based conductive polymer composites were prepared by using as-received, purified and modified carbon nanotubes in a twin screw extruder. During the purification of carbon nanotubes, surface properties of carbon nanotubes were altered by purifying them with nitric acid (HNO3), sulfuric acid (H2SO4), ammonium hydroxide (NH4OH) and hydrogen peroxide (H2O2) mixtures. Electron Spectroscopy for Chemical Analysis (ESCA) results indicated the removal of metallic catalyst residues from the structure of carbon nanotubes and increase in the oxygen content of carbon nanotube surface as a result of purification procedure. Surface structure of the purified carbon nanotubes was also modified by treatment with sodium dodecyl sulfate (SDS), poly(ethylene glycol) (PEG) and diglycidyl ether of Bisphenol A (DGEBA). Fourier Transformed Infrared Spectroscopy (FTIR) spectra of the carbon nanotube samples indicated the existence of functional groups on the surfaces of carbon nanotubes after modification. All composites prepared with purified and modified carbon nanotubes had higher electrical resistivities, tensile and impact strength values than those of the composite based on as-received carbon nanotubes, due to the functional groups formed on the surfaces of carbon nanotubes during surface treatment. In order to investigate the effects of alternative composite preparation methods on the electrical and mechanical properties of the composites, in-situ microfiber reinforced conductive polymer composites consisting of high density polyethylene (HDPE), poly(ethylene terephthalate) and carbon nanotubes were prepared in a twin screw extruder followed by hot stretching of PET/CNT phase in HDPE matrix. Composites were produced by using as-received, purified and PEG treated carbon nanotubes. SEM micrographs of the hot stretched composites pointed out the existence of in-situ PET/CNT microfibers dispersed in HDPE matrix up to 1 wt. % carbon nanotube loadings. Electrical conductivity values of the microfibrillar composites were higher than that of the composites prepared without microfiber reinforcement due to the presence of continuous PET/CNT microfibers with high electrical conductivity in the structure. To investigate the potential application of conductive polymer composites, the effects of surfactant usage and carbon nanotube surface modification
on the damage sensing capability of the epoxy/carbon nanotube/glass fiber composite panels during mechanical loadings were studied. Surface modification of the carbon nanotubes was performed by using hexamethylene diamine (HMDA). 4-octylphenol polyethoxylate (nonionic) (Triton X-100) and cetyl pyridinium chloride (cationic) (CPC) were used as surfactants during composite preparation. Electrical resistivity measurements which were performed during the impact, tensile and fatigue tests of the composite panels showed the changes in damage sensing capabilities of the composites. Surface treatment of carbon nanotubes and the use of surfactants decreased the carbon nanotube particle size and improved the dispersion in the composites which increased the damage sensitivity of the panels.

This thesis focuses on the electrical output of polyaniline films subjected to uniaxial strain in hydrochloric acid solutions. Polyaniline belongs to novel class of materials known as conducting polymers. Alternating single and double bonds in the backbone of conducting polymers allow them to transmit electric charge when they are doped with negatively charged ions. Modifying the degree of doping and other electrical/chemical treatments allow conducting polymers to exhibit conducting, semi-conducting, or insulating electrical properties. Resilient mechanical properties, good processability, and low cost make conducting polymers good candidates for applications traditionally held by metals and semi-conductors. When tensile strain is applied to polyaniline in an electrolyte solution, the material selectively absorbs negatively charged ions. This charge imbalance produces a measurable electrical output. Theoretical models based on Fick’s second law of diffusion were compared against experimental results to determine fundamental material properties such as diffusivity and ion solubility in polyaniline. These properties were used to quantify polyaniline as a sensor material based on characteristics including sensitivity, accuracy, precision, range, linearity, and error. Films were cast from solutions of polyaniline powder (Mn = 65,000) in N-methyl-2-pyrrolidinone solvent, with thicknesses ranging from 2.72 to 158 µm.

A novel metal-polymer composite is presented, comprised of a micron-sized nickel powder dispersed within a silicone polymer matrix. The composite is intrinsically electrically insulating, but displays a dramatic increase in conductivity under compression, tension and torsion. The electrical response to applied compression is characterised. Combined with electron microscopy, the large sensitivity to compression is shown to be due to the uniquely spiky morphology of the filler particles. Low mechanical energy mixing techniques are essential for retaining these sharp tips. In addition, wetting of the nickel particles by the silicone polymer is highly effective, resulting in negligible inter-particle contact between metallic grains even at very high loadings and compressions. Current-voltage characteristics are highly non-linear, displaying peaks, hysteresis, negative differential resistance, trap-filling and radio frequency emission. Evidence points towards an inter-particle conduction mechanism dominated by field emission and Fowler-Nordheim tunnelling, made possible by localised field enhancements at the sharp tips. A novel mechanism of grain charging and the 'pinching-off of conduction pathways is also suggested. Granular forms of the composite display dramatic increases in resistance when exposed to organic solvent vapours, transduced by a polymer swelling mechanism. Responses are dependent upon vapour concentration, and differential responses are obtained with other polymers, indicating excellent potential for applications in artificial olfactory devices (electronic noses). Polymer-solvent interactions follow both Fickian and anomalous diffusion characteristics, and follow basic trends predicted by solubility parameters.

This research project was concerned with the establishment and characterisation of a quartz crystal microbalance (QCM) - conductimetric interdigitated electrode hybrid "second generation" Electronic Nose system. Research objectives covered a number of technical limitations and analytical difficulties existed in the "first generation" Electronic Nose system. A wide variety of work was carried out, including the design and fabrication of the electronic nose system, the optimisation of sensors response, the device modelling, the studies of vapour-polymer interaction mechanisms and the application of the electronic nose in multi-component analysis. A QCM-interdigitated electrode hybrid sensor odour measurement system was established, and sensor fabrication techniques developed. Some important parameters corresponding to sensor characteristics were investigated such as the conditions for polymer film polymerisation. By studying 16 different coatings, "optimal" individual initial resistances were proposed, which minimise long-term baseline resistance drift, whilst maintaining good sensitivity. A set of sensors was made with low initial resistance variation. Sensor detection dynamic range was found to be dependent on the type of the coating material and the film thickness. The response of a combined hybrid sensor pair remained stable during a test period of 45 days, which showed an improved stability. The principle of the sensor's response and device modelling were addressed. The vapour-polymer interactions and sensor pair's response were linked by a sensitivity coefficient (S), which was defined as the relative resistivity change by a single molecule absorbed into the polymer film. A pair of sensors showing concentration independence over a wide concentration range can be formed on separate QCM and interdigitated electrodes with the same polymer. The combined response (Srf) can be used to identify a particular vapour. Based on the concentration independence, the proposed "odour maps" showed the feasibility of distinguishing odourants using a significantly lower number of different types of sensor coatings. This demonstrated the improved selectivity of a hybrid system compared with the single property system.

The increasing demand for energy and the pressure to reduce reliance on fossil fuels encourages the development of devices to harness clean and renewable energy. Solar energy is a large enough source to fulfill these demands, however, in order to overcome its daily and seasonal variability, it has been proposed that sunlight be harvested and stored in the form of chemical fuels. One potential approach is the photosynthetic splitting of water to store solar energy in the simplest chemical bond, H–H, using a device that includes: semiconducting microwire arrays as light harvesting components, redox catalysts, and a membrane barrier for separating the products of water redox reactions.. However, the harvested solar energy can be lost across the system and it is critical to characterize the electrical properties of each component within the system to quantify how much of this energy will ultimately be coupled to the water splitting reactions. The aim of this research is to develop approaches for characterization of a proposed system of this kind, incorporating individual semiconductor microwires as photoelectrodes (with no redox catalysts) embedded into a candidate conducting polymer membrane to form a single functional unit. Semiconductor microwires were isolated and using a novel contact formation approach with tungsten probes in a standard probe station, and their current versus voltage properties were characterized. This approach is of particular interest when ii considering the limitations of conventional contact formation approaches (e.g. thermal evaporation of contact metals), arising from the small dimensions of the microwires and also the incompatibility of these techniques with many microwire/polymer structures due to the unwanted interactions between polymers, photoresists, etchants and the high temperature lithographic processes. The electrical properties of different microwires and also the junctions between microwires and two candidate polymers were studied. Specifically, the combination of methyl-terminated silicon microwires and PEDOT:PSS:Nafion demonstrated promising behavior, with a total DC resistance of approximately 720 kΩ (i.e. losses < 16 mV at maximum available photocurrent), making it a suitable candidate for the use in the proposed system. The outcome of these research may be applied to many applications including semiconducting microstructures and conducting polymers.