Fumed silica filler has long been used to structurally reinforce silicone elastomers. Unfortunately, the combination of as little as a few weight percent of untreated fumed silica nanoparticles [uFSN] with a siloxane polymer, such as PDMS, forms a difficult to process waxy solid admixture that even long periods of high shear mixing will not thin. In the course of the current work it was noted that after a period of storage certain solid admixtures would become viscous liquids when subjected to additional high shear mixing. It was further found that the required aging period could be decreased if the admixture storage temperature were increased. The only known interaction of PDMS and uFSN at moderate conditions is the adsorption of polymer on filler, and this interaction is also known to occur more quickly at higher temperature. This study examines the relationship between polymer adsorption and admixture liquefaction. Further, the mechanical properties of cured elastomers containing liquefied admixtures are examined to assess the degree of reinforcement that these materials afford.

Doctor of Philosophy / Department of Chemical Engineering / Peter H. Pfromm / One area of considerable importance in modern biotechnology is the preparation of highly active and selective enzyme based biocatalysts for applications in organic solvents. A major challenge is posed by the tendency of enzymes to cluster when suspended in organic solvents. Because the clusters obstruct the transport of substrates to the active site of the enzyme, the observed activity is often severely reduced. Over the past two decades, many strategies have been proposed to mitigate this problem. We have tackled this major hurdle by devising an immobilization strategy that utilizes fumed silica as carrier for the enzyme molecules. Fumed silica is a non-porous nanoparticulated fractal aggregate with unique absorptive properties. The enzyme/fumed silica preparation is formed in two steps. The buffered enzyme molecules are physically adsorbed on the fumed silica and then lyophilized. This protocol was shown to be successful with two enzymes of industrial relevance, Candida antarctica Lipase B (CALB) and subtilisin Carlsberg. The maximum observed catalytic activity in hexane reached or even exceeded commercial immobilizates and nonbuffer salt based preparations. The results demonstrated that catalytic activity has an intricate relationship with the nominal surface coverage (%SC) of the support by the enzyme molecules. s. Carlsberg exhibited an ever increasing activity as more surface area was provided per enzyme molecule. The activity leveled off when a sparse surface population was reached. CALB showed a maximum in catalytic activity at an intermediate surface coverage with steep decreases at both lower and higher surface coverage. It was shown that this maximum results from the presence of three distinct surface loading regimes after lyophilization: 1. a low surface coverage where opportunities for multi-attachment to the surface likely lead to detrimental conformational changes, 2. an intermediate surface coverage where interactions with neighboring proteins and the surface help to maintain a higher population of catalytically competent enzyme molecules, and 3. a multi-layer coverage where mass transfer limitations lead to a decrease in the apparent catalytic activity. Conformational stability analyses with both fluorescence and CD spectroscopy showed evidence that these regimes are most likely formed during the adsorption step of our protocol. A low conformational stability region was detected at low surface coverage while adsorbates with highly stable enzyme ensembles were observed at high surface coverage. Secondary structural analysis of the lyophilized nanobiocatalysts with FTIR confirmed a substantial decrease in the alpha-helical components at low surface coverage. In summary, the work presented here traces the phenomenological observation of the catalytic behavior of a nanobiocatalyst to molecular-level: enzyme-enzyme and enzyme-support interactions, which are specific to the intricate properties of the enzyme molecules.

Buildings consume around half of the UK's total energy consumption and are responsible for almost 50% of UK's total carbon dioxide (CO2) emissions. Use of high thermal resistance insulation in buildings is critical to save the substantial amounts of space heating energy lost through building fabric. Conventional building insulation materials have higher thermal conductivity values ranging from 40 mWm-1K-1 (Glass fibre) - 26 mWm-1K-1 (Polyurethane foam) and require larger thicknesses to achieve stringent building regulation requirements which may not be feasible due to techno-economic constraints. Vacuum Insulation Panel (VIP) is a relatively new insulation for building applications that offers 5-8 times higher thermal resistance and can achieve significant space savings in buildings. VIPs are produced as a rigid panel comprising inner core board laminated in an outer high barrier envelope under evacuated conditions (< 5mbar). However, the main challenge for large scale acceptance of VIPs in building applications is their higher cost. VIPs have been shown to have an approximately 10 times longer payback compared to conventional EPS insulation due to their high initial cost. Expensive materials currently being used for VIP manufacturing such as fumed silica contribute to high cost of VIPs and it is critical to identify alternative low cost materials for VIP components to overcome the challenge of high cost. The aim of this thesis was to develop an alternative low cost material and investigate its suitability for use as VIP core. Expanded perlite, a low cost material was identified as a replacement of expensive fumed silica in a VIP core. Composite samples containing expanded perlite, fumed silica, silicon carbide (SiC) and polyester fibres were developed by dry mixing of the constituents in different mass ratios and their different properties were experimentally measured to identify optimum composition of composite. Gaseous thermal conductivity at different pressures was calculated from the pore size data obtained using Mercury Intrusion Porosimetry (MIP), gas adsorption and electron microscopy. Radiative conductivity of composite samples was measured using Fourier Transform Infrared (FTIR) to ascertain the opacifying effect of expanded perlite and opacifier (SiC). Centre of panel thermal conductivity of core boards of size 100mm x 100mm made of composite material at atmospheric pressure was measured by using a small guarded hot plate device. Average pore diameter values of expanded perlite decreased with the partial filling of fumed silica aggregates and was found to be in the range of 150-300 nm yielding lower gaseous conductivity values of 1.2-2.1 mWm-1K-1 at 100mbar and became negligible upon further decreasing pressures below 10 mbar. Core boards made of optimised composite containing 30% expanded perlite and 50% fumed silica along with SiC and polyester fibres was found to achieve centre of panel thermal conductivity of 28 mWm-1K-1 at atmospheric pressure and the average radiative conductivity of 0.67 mWm-1K-1 at 300K with its gaseous thermal conductivity at 1 mbar being 0.016 mWm-1K-1. According to the results of the thesis VIP prototypes consisting of core made with optimised composite consisting (50 mass% of fumed silica, 30 mass% of expanded perlite along with 8 mass% of fibre and 12 mass% of SiC) yielded centre of panel thermal conductivity of 7.4-7.6 mWm-1K-1 at pressure of 0.53-0.64 mbar. Opacifying properties of expanded perlite were observed and quantified. Expanded perlite reduced the radiative conductivity of the composite requiring smaller quantities of high density opacifiers such as SiC. For sample containing no expanded perlite, average radiative conductivity was calculated to be 1.37 mWm-1K-1 and radiative conductivity values decreased to 1.12 mWm-1K-1, 0.67 mWm-1K-1, 0.63 mWm-1K-1 and 0.50 mWm-1K-1 with mass ratio of expanded perlite 20%, 30%, 40% and 60% respectively. It was concluded that the solid conductivity of prototypes VIPs was 1.8-2 times higher compared to those of commercially available VIPs and is the main reason for higher centre of panel thermal conductivity.

The aim of this study is to investigate the effects of compatibilizers, fumed silica and mixing order of components on morphological, thermal, mechanical and flow properties of LDPE/Fumed silica nanocomposites. As compatibilizer(Co) / ethylene/n-butyl acrylate/maleic anhydride (E-nBA-MAH), ethylene/glycidyl methacrylate (E-GMA) and ethylene/methyl acrylate/glycidyl methacrylate (E-MA-GMA) Lotader&reg / resins / as silica Cab-o-sil&reg / M5 fumed silica were used. All samples were prepared by means of a lab scale co-rotating twin screw extruder and injection molded into standard samples. In the first step, individual effects of filler and compatibilizers were studied in binary systems with LDPE. Then, keeping the amount of compatibilizer constant at 5%, ternary nanocomposites were prepared by adding 2 or 5% of fumed silica using different component mixing orders. Among investigated mixing orders, mechanical test results showed that the best sequences of component addition are FO1 [(LDPE+Co)+M5] and FO2 [(LDPE+M5)+Co] mixing orders. Considering the compatibilizers, E-nBA-MAH terpolymer showed the highest performance in improving the mechanical properties, E-GMA copolymer also gave satisfactory results. According to the DSC analysis, since addition of fumed silica and compatibilizer does not influence the crystallization behavior of the compositions, it is concluded that, neither fumed silica nor any of the compatibilizers have nucleation activity on LDPE. MFI test results showed that, addition of fumed silica increases the melt viscosity, decreasing MFI values of samples. This change seems to be directly proportional to fumed silica amount.

Ce travail de thèse décrit la préparation de deux types de films de polymères : i) des films nanocomposites à base de silice pyrogénée aux propriétés superhydrophobes et ii) des films LbL auto-assemblés, incluant tous deux des dérivés de poly(2,3,4,5,6-pentaflurostyrene) (PPFS), utilisés comme briques élémentaires. La stratégie utilisée ici consiste à exploiter les nombreux avantages que présente la réaction de substitution du fluor en position para du PPFS avec un thiol, pour générer de nouveaux dérivés aux propriétés ajustables. Ainsi, le premier volet de la thèse a consisté à introduire des chaînes de PPFS de façon covalente à la surface de silice pyrogénée par une stratégie dite de «grafting through» en utilisant la polymérisation radicalaire contrôlée par le voir nitroxydes, en présence de PS-DEPN comme macroamorceur. La cinétique de polymérisation du PFS avec et sans particules silice a été étudiée dans divers solvants, différentes particules hybrides de silices modifiées en surface par une couronne de PPFS ont été préparé. Ensuite, un thiol perfluoré (perfluorodecanethiol:PFDT) a été utilisé pour modifier le PPFS, considéré dans ce cadre comme matrice hôte pour la préparation des nanocomposites et pour modifier le PPFS présent à la surface des particules de silice. A partir de là, un large panel de films nanocomposite a été préparé à partir des différentes combinaisons possibles de polymère hôte (PPFS ou PPFS-PFDT) et de charges inorganiques de silice (modifiées par le PPFS ou par le PPFS-PFDT). Les propriétés de mouillabilité ainsi que la morphologie de surface de chaque film ont été analysées et il en résulte que certains films présentent un caractère superhydrophobe. Le deuxième volet de la thèse a porté sur la modification du PPFS par des thiols porteurs de fonctions acide carboxylique, toujours par la réaction de substitution décrite précédemment. Différents dérivés de PPFS carboxylés de DS variés ont été synthétisés. Leur habilité à développer des liaisons hydrogène avec un polymère modèle accepteur de liaison H (la poly(4-vinyl pyridine) (P4VP)) a été étudiée. Il en ressort que dépendamment de la nature du solvant, des mélanges miscibles ou des complexes interpolymères ont ensuite été formés. Des solutions de complexes préformés ont été successivement déposées par spin-coating pour construire des films. De plus, des films multicouches LbL stabilisés par des liaisons H entre le PPFS carboxylé et la P4VP ont été élaborés and il a été démontré que la nature du solvant de dépôt, ainsi que le taux de modification du PPFS, impactent fortement le mécanisme de croissance, l’épaisseur du film et les caractéristiques de surface, en termes de topologie et de mouillabilité. / This work describes the preparation of two kinds of thin polymer films : i) self-cleaning silica-based (nano)composites films and ii) LbL self-assembling films, both including poly(2,3,4,5,6-pentaflurostyrene) (PPFS) derivatives, as building blocks. The cornerstone of the approach is to exploit the thiol-para fluoro substitution reaction to PPFS chains in order to generate derivatives with tailored properties. In this frame, PPFS chains were anchored onto the surface of vinyl-functionalized fumed silica nanoparticles by nitroxide-mediated polymerization (NMP) in presence of PS-DEPN as macro-initiator via a “grafting through” strategy. The kinetics of NMP of PFS were investigated in presence and without silica in various solvents and well-characterized hybrid silica particles containing different polymer grafting weight were declined. Then, perfluorodecanethiol (PFDT) was employed to modify PPFS, considered as the host polymer matrix, and to functionalize PPFS chains tethered to silica particles. A large panel of (nano)composite films from the different possible host matrix/silica particles combinations was prepared. The wettability and the surface morphology of each film were discussed, as a function of the host structure (PPFS or PPFS-PFDT with different DS) and silica (modified with PPFS or PPFS-PFDT), as well as the silica content. It results that superhydrophobic features can be reached. Subsequently, PPFS was modified by using carboxylic acid mercapto modifier via the thiol-para fluoro coupling. Various carboxylated PPFS derivatives differing in the degree of substitution (DS) were prepared and their ability to develop H-bonds in solution with a model strong H-bond acceptor partner (poly(4-vinyl pyridine) (P4VP)) was investigated. Dependently on the nature of the solvent, a miscible blend or interpolymer complexes (IPC) were achieved. IPC-containing solutions were used to successfully fabricate spin-assisted films. Furthermore, H-bonds mediated LbL self-assembly multilayer films involving carboxylated PPFS and P4VP were prepared and it was evidenced that the nature of the deposition solvent as well as the extent of the modification (quantified by the DS), impact the growth mechanism, the thickness and the surface features, in terms of topology and wettability.