The influence of voids on the moisture uptake of epoxy has been studied. Specimens with void contents from 0 to about 50% were prepared. Void geometry and content were analyzed using microscopy and density methods. Void containing dry samples were characterized by Differential Scanning Calorimetry and Dynamic-Mechanical Analysis which verified consistency of chemistry of the epoxy network. The moisture uptake of specimens immersed in distilled water at 40 °C was monitored. The rate of absorption and saturation moisture content increased with increasing void content. The moisture uptake of void-free and void containing specimens was non-Fickian. The Langmuir model provided good fits to the experimental results for specimens with low to medium void content, although the moisture uptake of the high void content specimens showed substantial deviations from the Langmuir diffusion model. The moisture diffusivity agreed reasonably with predications from the Maxwell inclusion model over a range of void contents from 0 to 50%. The state of sorbed water was examined using mass balance calculations and DSC analysis. Only 6-8% of the void volume is occupied by water at saturation. Absorbed water may be classified as free and bound water. For void-free specimens, only bound water was found. The medium and high void content specimens contained water in three states: free water, freezable bound water, and non-freezable bound water. The DSC results show that the proportions of free water and freezable bound water increase with increasing void content, while the content of non-freezable bound water decreased. Moisture induced swelling decreased with increasing void content. The swelling is attributed to the content of non-freezable bound water. / Includes bibliography. / Dissertation (Ph.D.)--Florida Atlantic University, 2018. / FAU Electronic Theses and Dissertations Collection

The aim of this study is to investigate a novel toughening approach for liquid mouldable carbon fibre/epoxy composites. The toughening mechanism is based on the use of thermoplastics for the toughening of epoxy resins in which polymer blends are formed, leading to phase separated morphologies which allows for various toughening mechanisms to take place. Instead of standard melt or solution blending, the thermoplastic in this study is introduced as solid phenoxy fibres, which are combined with dry carbon fabric preforms. These phenoxy fibres remain solid during resin infusion and dissolve when the laminates are heated and phase separation takes place before curing completed. The main benefits of this approach are that the viscosity of matrix resin remains low, which makes liquid moulding of these laminates possible. Localised and selective toughening of particular regions within a structure can also be achieved. Process time and cost can also be reduced by eliminating the polymer blending process. It was found that modification with phenoxy improved composite Mode-I interlaminar toughness significantly, with an increase of up to 10-folds for bifunctional epoxy composite and 100% for tetrafunctional epoxy composite, while tensile properties were not adversely affected. It was found that it is possible to combine the dissolvable phenoxy fibres with an undissolved aramid interleaf to improve toughness and damage properties. However, the phenoxy-epoxy systems had lowered environmental stability and degraded after hot-wet and solvent conditioning.

Epoxy coatings are currently the most popular corrosion protection mechanism for steel reinforcement in structural concrete. However, these coatings are easily damaged on worksites, negating their intended purpose. This study investigates self-healing coatings for steel reinforcement to introduce an autonomous healing mechanism for damaged coatings. Coatings were applied to steel coupons, intentionally damaged, and introduced to a corrosive environment via aerated salt-water tanks. Performance of the experimental coatings was evaluated qualitatively and quantitatively. Adhesion strength and effects of coating thickness were also studied. Results from coated steel coupons subjected to damage and submerged in salt-water aeration tanks exhibited improved corrosion resistance performance with self-healing coatings. However, self-healing coatings have comparable poor adhesion to the substrate as do conventional coatings. This paper shows preliminary results demonstrating the potential benefits of self-healing coatings for steel reinforcement and identifies numerous avenues for future research.

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Published Content: Jeedimalla, N.; Jacquet, C.; Bahneva, D.; Youte Tendoung, J.-J.; Roche, S. P. J. Org. Chem. 2018, 83, 12357. The present thesis will be focused on the study of House-Meinwald Rearrangement (HMR) reactions for the congested trisubstituted spiro-epoxide molecules. Including their regio-selective, chemo-selective, enantio- selective selective and stereo-selectivity’s will be discussed in detailed by the mechanistic study approach of HMR reaction of trisubstituted spiro-epoxides. Chapter 1 will present the efforts towards the biomimetic total synthesis of meroterpenoid natural product (+)-liphagal, which possess a recognizable biological activity. The shortcomings associated with its stereochemical assignment, and also the revision of stereochemical assignment of siphonodictyal B, through which the biosynthesis of (+)-liphagal was proposed were discussed. Chapter 2 will focus on the study of regio and chemoselective HMR reaction. In addition, a three-step sequence for the synthesis of α-arylated cyclohexanones and the most challenging cycloheptanones is reported. First, an efficient one-pot synthesis of β, β’-disubstituted benzylidene cycloalkanes using the palladium-catalyzed Barluenga reaction from readily available feedstock chemicals is described. Second, an epoxidation followed by the HMR of spiro-epoxides is reported to produce a number of α -arylated cycloalkanones upon the ring expansion. Reactions catalyzed by bismuth triflate underwent quasi-exclusively ring expansion for all substrates (electronically poor and rich), demonstrating the difficulty to achieve the ring enlargement for electron deficient spiro-epoxides. On the other hand, via catalysis with aluminium trichloride the rearrangement proceeded typically in high yields and with remarkable regioselectivity. In this case, a switch of regioselectivity was achieved for spiro-epoxides with electron-withdrawing substituents which enabled this method to be successfully extended to some chemo specific arene shifts and it can also synthesize aldehydes derivatives bearing a α-quaternary carbon. / Includes bibliography. / Dissertation (Ph.D.)--Florida Atlantic University, 2019. / FAU Electronic Theses and Dissertations Collection

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This thesis systematically investigates the properties of the aluminium adherend which influence the fracture toughness of aluminium-epoxy adhesive joints in humid environments. The fracture energy of the adhesive joint exposed to a humid environment in comparison with the fracture energy in a dry environment provides a measure of the joint durability. A 500C and 95% relative humidity environment is used to simulate aging of an adhesive joint over several years under normal service conditions. Initially, surface roughness is found to have a significant influence on the fracture toughness of the adhesive joint in humid conditions. A direct correlation between the bond durability and the angle of deliberately machined micro-roughness in the aluminium surface is determined. Consequently a model is developed which initially has the capacity to describe the bond durability performance. The preparation of aluminium surfaces involves the use of a novel ultramilling tool to produce well defined and controlled surface topography. This work represents the first time surface angles of features in the 1????m to 10????m range have been systematically varied and a direct relationship with bond durability has been determined. The use of surface analytical tools aids in elucidating mechanisms involved in the failure of the adhesive joint and contributes to the development of the stress based diffusion model. Examination of the aluminium oxide hydration level reveals this property has a negligible effect on the fracture toughness of the aluminium-epoxy joints exposed to humid environments. This information confirms the dominant role of the physical properties of the aluminium surface in determining the adhesive joint durability. This is the first occasion that planer oxide films grown in an RF plasma have had their hydration state adjusted in a controlled manner and their properties subsequently assessed in terms of bond durability properties. Further alteration of the aluminium surface chemistry is achieved through the application of an organo-silane coupling agent and a series of novel organo-phosphonate compounds. This work further develops the stress based diffusion model developed in conjunction with the micro-machining studies. The components of surface roughness and the ability of interfacial bonds to co-operatively share load are essential for the maintenance of fracture toughness of adhesive joints exposed to humid conditions. The ability of the silane coupling agent to share load through a chemically cross-linked film is a significant property which provides the superior fracture toughness in comparison with the phosphonate treated joints. Although the organo-phosphonate treated aluminium provides hydrolytically more stable bonds than the silane coupling agent, the film is not cross-linked via primary chemical bonds and the reduced load sharing capacity of interfacial bonds increases the bond degradation rate. The stress based diffusion model evolving from the initial work in the thesis can be used to predict the performance of more complex systems based on a thorough characterisation of the aluminium surface chemistry and topography. The stress based diffusion model essentially describes the concept of the production of micro-cavities at the epoxy-aluminium interface under mode 1 load, as a result of the distribution of strong and weak adhesive bonds. Alternatively, micro-cavities may result from an inhomogeneous stress distribution. In areas where the adhesive bonds are weak, or the local stresses are high, the interfacial load produces larger micro-cavities which provide a path of low resistance for water to diffuse along the bond-line. The water then degrades the adhesive bond either through the displacement of interfacial epoxy bonds or the hydration of the oxide to form a weak barrier layer through which fracture can occur. Alternatively, the water can hydrolyse the adhesive in the interfacial region, leading to cohesive failure of the epoxy resin. The bond durability performance of a series of complex hydrated oxide films used to pre-treat the aluminium adherend provides support for the stress based diffusion model. Whilst surface area is an important property of the aluminium adherend in producing durable bonding, the best durability achievable, between an epoxy adhesive and aluminium substrate, requires a component of surface roughness which enhances the load sharing capability in the interfacial bonding region. This component of durability performance is predicted by the model. In more specific terms, a boiling water treatment of the aluminium adherend indicates a direct correlation between bond durability, surface area and topography. The characterisation of film properties indicates that the film chemistry does not change as a function of treatment conditions, however, the film topography and surface area does. The overall bond durability performance is linked to both of these properties. The detailed examination of the hydrated oxide film, produced by the boiling water treatment of aluminium, is the first time the bond durability performance has been related to the film topography. It is also the first occasion that the mechanism of film growth has been examined over such a large treatment time. The combination of surface analysis and bond durability measurements is invaluable in confirming the properties, predicted by the stress based diffusion model, which are responsible in forming fracture resistant adhesive bonds in humid conditions. The bond durability of high surface area and low surface area hydrated oxide films indicates that surface area is an important property. However, this study confirms that the absence of the preferred surface topography limits the ultimate bond durability performance attainable. The fracture toughness measurements performed on aluminium adherends pre-treated with a low surface area film also supports the mechanism of load sharing of interfacial adhesive bonds and its contribution to the overall bond durability. The role performed by the individual molecules and particles in an oxide film is similar to the load sharing performed by the silane coupling agent molecules. Further support for the stress based diffusion model is provided by films produced on aluminium immersed in nickel salt solutions. The topography of these film alters as a function of treatment time and this is directly related to fracture toughness in humid environments. This work provides the first instance where such films have been characterised in detail and their properties related to bond durability performance. The study is also the first time that the growth mechanism of the film produced on the aluminium substrate has been examined in detail. The film growth mechanism supports the film growth model proposed for the hydrated oxide film produced by the boiling water treatment. The major findings presented in this thesis are summarised as the direct correlation between surface profile angle, the importance of co-operative load sharing of interfacial adhesive bonds and the relative insignificance of surface oxide hydration in the formation of durable aluminium-epoxy adhesion. This information is used to develop a stress based diffusion model which has the capacity to describe the fracture toughness of a range of aluminium-epoxy adhesive joint systems in humid environments. The stress based diffusion model is also capable of predicting the relative performance of the bond systems examined in the final chapters of the thesis, where complex interfacial oxide films are involved in the formation of adhesive bonds.

The epoxide deoxygenation reaction is formally the reverse of the epoxidation reaction. Compared to epoxidation, which has reached its full maturity, epoxide deoxygenation has not been as intensively developed. Among the few deoxygenation reagents, a handful are catalytic in a metal complex, show high stereospecificity and operate under mild conditions. A common feature of all present deoxygenation reagents is that they do not perform asymmetric deoxygenation of racemic epoxides. Rhenium (VII) trioxo complexes are emerging as pliable catalysts for epoxide deoxygenation. Designing a chiral rhenium (VII) trioxo complex was our goal. Guided by the mechanism of rhenium (VII) trioxo catalyzed epoxide deoxygenation and the mechanism of the stereogenic information transfer, we have designed and prepared a chiral rhenium(VII) trioxo complex. This complex is void of stereogenic centers and the source of asymmetry is the restricted rotation around a carbon-carbon bond. Detailed conformational analysis of the new chiral complex was done by extensive NMR measurements and molecular modeling. The rotation barrier for the diolate was experimentally and computationally estimated to be 9.72 kcal/mol and 8.06 kcal/mol, respectively. Unsuccessful attempts were made to prepare a camphor based scorpionate because of the extreme steric congestion. A menthone based scorpionate was successfully prepared. The related rhenium (TII) trioxo complex with this scorpionate revealed contradicting chemical and spectroscopic features. / Graduation date: 2005