This work investigates processing-microstructure-property relationships of a model cryogenically mechanically alloyed polymer-polymer system: polycarbonate (PC) and poly (ether ether ketone) (PEEK). Mechanically milled and alloyed powders were characterized using a variety of techniques including microscopy and thermal analysis. Cryogenically mechanically alloyed powders processed for 10 hours were shown to have a sub-micron level two-phase microstructure. These powders were processed into testable coupons using a mini ram-injection molder; microstructure and bulk mechanical properties of the coupons were investigated as a function of mechanical alloying and injection molding parameters. Atomic force microscopy, transmission electron microscopy, and scanning transmission X-ray microscopy revealed that the intimate blending achieved during the mechanical alloying process is not retained upon post-processing using a conventional polymer processing technique. Injection molded coupons were tested in 3-point bend mode via dynamic mechanical and quasi-static mechanical testing. Results demonstrated that no improvement in energy to break, strain at failure, or failure strength was achieved in coupons made from cryogenically mechanically alloyed powders compared to those of coupons made from non-mechanically alloyed samples. / Ph. D.

Résumé non communiqué / Résumé non communiqué

There has been a great interest in preparing polymeric reflective surfaces in the last few years. The application of supercritical fluid technology in this area is beginning to receive a great deal of attention. Poly ether ether ketone (PEEK) is well known for its excellent thermal, chemical, mechanical and electrical properties. These properties make it ideal for use in aerospace, electrical, fluid handling and coating industries. Supercritical infusion of a silver-containing additive (1,5-cyclooctadiene- 1,1,1,5,5,5-hexafluoroacetylacetonato)silver(I) into a PEEK film was achieved with moderately high density CO2 at various temperatures, pressures, and times. During the infusion process: 1) polymer sample was exposed to both supercritical CO2 and the additive under pressure for a brief time, 2) depressurization of the system caused the CO2 to rapidly diffuse out of the polymer; while the remaining additive in the polymer desorbed at a much slower rate governed by its diffusivity in the CO2-free polymer. Following this process the infused film was heated for a short time period to thermally reduce the infused metal and to form a reflective surface. In this research the effect of different additive concentrations, infusion conditions (e.g. temperature, pressure, time), and curing conditions (e.g. air flow rate, temperature, time) on the nature of the PEEK surface will be presented. / Master of Science

Sulfonated polyaromatic hydrocarbon membranes have emerged as desirable candidates for proton exchange membranes (PEMs) due to their excellent mechanical properties, high thermal and chemical stability, and low cost. Specifically, sulfonated multiblock copolymers are attractive because their phase-separated morphologies aide in facile proton transport. In this work, the functionalization of semicrystalline gels of poly(ether ether ketone) (PEEK) is explored as a novel post-polymerization method to prepared blocky copolymers, and the effect of copolymer architecture on membrane physical properties, structure, and performance is extensively investigated. First, the blocky sulfonation of PEEK was explored to prepare blocky copolymers (SPEEK) with densely sulfonated domains and unfunctionalized, crystallizable domains. Compared to random SPEEK ionomers at similar ion content, blocky SPEEK exhibited enhanced crystallizability, decreased melting point depression, and faster crystallization kinetics. Phase separation between the hydrophilic sulfonated blocks and hydrophobic PEEK blocks, aided by polymer crystallization, resulted in enhanced water uptake, superior proton conductivity, and more closely associated ionic domains than random SPEEK. Furthermore, the random and blocky bromination of PEEK was investigated to prepare PEEK derivatives (BrPEEK) with reactive aryl-bromides. Spectroscopic evidence revealed long domains of unfunctionalized homopolymer for blocky BrPEEK, and this translated to an increased degree of crystallinity, higher melting temperature, and more rapid crystallization kinetics than random BrPEEK at similar degrees of bromination. The subsequent sulfonation of blocky BrPEEK resulted in a hydrophilic-hydrophobic blocky copolymer with clear multi-phase behavior. The phase-separated morphology contributed to decreased water uptake and areal swelling compared to random SPEEK and resulted in considerably higher proton conductivity at much lower hydration levels. Moreover, Ullmann coupling introduced superacidic perfluorosulfonic acid side chains to the BrPEEK backbone, which yielded membranes with less water content and less dimensional swelling than random SPEEK. Superior proton transport than random SPEEK was observed due to the superacid side chain and wider hydrophilic channels within the membranes, resulting in more continuous pathways for proton transport. Overall, this work provided a novel platform for the preparation of functionalized PEEK membranes using a simple post-polymerization functionalization procedure. The established methods produced blocky-type copolymers with properties reminiscent of multiblock copolymers prepared by direct polymerization from monomers/oligomers. / PHD / Block copolymers are an important class of polymers that are composed of two or more blocks of distinct polymeric segments covalently tethered to one another. Dissimilarity in the chemical nature of the blocks leads to self-organization into well-defined structures, and this unique structural order imparts material properties that are different from (and often superior to) the properties of the individual blocks alone. Thus, block copolymers are advantageous for a diverse array of applications including membranes, gas separation, water purification, medical devices, etc. Although considerable synthetic progress has been made towards discovering novel methods to prepare block copolymers, their widespread use is somewhat limited by the complex, energy-intensive procedures necessary to precisely control the block sequencing during polymerization. In this dissertation, a straightforward, inexpensive physical procedure is explored to synthesize blocky copolymers with controlled sequencing from commercially available polymers. This process relies on performing reactions in the gel state, whereby segments of the polymer chain are effectively shielded from the functionalizing chemistry. In particular, the gel state sulfonation and bromination of poly(ether ether ketone), a high performance polymer, is investigated to develop novel, blocky materials for membrane applications. This work not only expands the methodology towards the synthesis of block copolymers, but alaso provides critical insight into the effect of copolymer architecture on membrane physical properties, structure, and performance. Furthermore, this work provides an economically feasible method to prepare blocky copolymers from commercially derived materials, thereby providing a means to progress the widespread use of block copolymers in industry.

The phase diagrams for the thermoreversible gelation of poly(ether ether ketone) (PEEK) in dichloroacetic acid (DCA) and 4-chlorophenol (4CP) were constructed over broad temperature and concentration ranges, revealing that PEEK is capable of dissolving and forming gels in DCA and 4CP up to a weight fraction of 25 wt.%. Highly porous aerogels of PEEK were prepared through simple solvent exchange and solvent removal of the PEEK/DCA or PEEK/4CP gels. Solvent removal utilized freeze-drying (sublimation) methods or supercritical CO2 drying methods. Varying the weight fraction of PEEK dissolved in solution determined PEEK aerogel density. Mechanical properties (in compression) were shown to improve with increasing density, resulting in equivalent compressive moduli at comparable density regardless of preparation method (concentration variation, gelation solvent, solvent removal method, or annealing parameters). Additionally, density-matched aerogels from various MW PEEK showed a correlation between increasing MW and increasing compressive modulus. Contact angle and contact angle hysteresis revealed that PEEK aerogels have a high contact angle, exceeding the conditions necessary to be classified as superhydrophobic materials. PEEK aerogel contact angle decreases with increasing density and a very low contact angle hysteresis that increases with increasing density, regardless of gelation solvent or drying method. Small angle neutron scattering (SANS) contrast-matching experiments were used to elucidate the morphological origin of scattering features, wherein it was determined that the origin of the scattering feature present in the small angle scattering region was stacked crystalline lamella. Ultra-small angle X-ray scattering (USAXS)/SAXS/Wide angle X-ray scattering (WAXS) was then used to probe the hierarchical nanostructure of PEEK aerogels across a broad range of length scales. The Unified Fit Model was used to extract structural information, which was then used to determine the specific surface areas of PEEK aerogels. Regardless of gelation solvent, gel concentration, or solvent removal method, all PEEK aerogels display high surface areas as determined by SAXS and high surface areas as determined by nitrogen adsorption methods. Surface area values determined from SAXS data were consistently higher than that measured directly using nitrogen adsorption, suggesting that pore densification diminishes the accessible aerogel surface area. / Ph. D. / Poly(ether ether ketone) (PEEK) is a semicrystalline polymer with high temperature thermal transitions and excellent mechanical strength, making it an ideal candidate for many high-performance polymer applications. When PEEK is dissolved in particular solvents, it will form a 3-dimensional network where crystalline polymer is the cross-linking unit of the network. Careful solvent removal does not significantly perturb the gel network structure and produces a low-density aerogel. This work details the first reported instance of the monolithic gelation of PEEK and the first examples of PEEK aerogels. The nanostructure of these gels and aerogels is fully characterized to relate structural features to physical properties such as mechanical stiffness and wettability.

The natural hip joint in healthy people has a very low friction with very little (or no) wear. It works as a dynamically loaded bearing and is subjected to about 1-2 million cycles of loading per year. The applied load is the body weight which is tripled when walking and even higher during other activities such as running and jumping. Unfortunately these joints are not always healthy due to various causes such as fractures or disease leading to severe pain which necessitates joint replacement. Currently, the orthopaedic industries are working towards developing an ideal artificial hip joint with low wear, low friction, good lubrication, better fixation/stability and biocompatibility. Many different designs and materials have been investigated with some promising new implants which can be used depending on patients' individual need (large or small joint), activity and age. In this work, two types of artificial hip joints were tested for friction and lubrication studies: Metal-on-Metal (MoM) Biomet hip resurfacing ReCaps with large diameters (>35-60 mm) and different diametral clearances (~ 60-350 µm), and Zirconia Toughened Alumina (ZTA) heads against carbon-fibre-reinforced poly-ether-ether ketone (CFR PEEK) cups with different diameters (>35-60 mm) and diametral clearances (60-1860 µm). Seven serum-based lubricants with different viscosities were used with and without carboxy methyl cellulose (CMC) additions as gelling agent to increase viscosity depending on the CMC content. The maximum load applied was 2000 N for the stance phase with a minimum load of 100 N for the swing phase. A Pro-Sim friction hip simulator was used to investigate the frictional torque generated between the articulating surfaces so as the friction factor can be calculated. Stribeck analysis was then employed to assess the mode of lubrication. For the metal-on-metal hip resurfacing joints, the friction factors were in the range 0.03-0.151 and those for the ZTA ceramic heads versus CFR PEEK cups were in the range 0.006-0.32. Stribeck analyses showed mainly mixed lubrication for both MoM and ZTA ceramic-on-CFR PEEK joints. The experimental results were in agreement with most of the theoretical calculations suggesting mixed lubricating regimes at low viscosities and moving on to fluid film lubrication at higher viscosities. Joints with larger-diameters, lower clearances and lower surface roughness exhibited a higher lambda ratio suggesting improved lubrication. Viscosity flow curves for the serum-based lubricants having viscosity ≤ 0.00524 Pas showed non-linear relationship between viscosity and shear rate indicating non-Newtonian flow with pseudoplastic or shear-thinning characteristic, i.e. viscosity decreased as shear rate increased up to shear rates of ~ 1000 s⁻¹. However, at shear rates greater than 1000 s⁻¹ Newtonian flow became dominant with almost constant viscosity, i.e. a linear relationship between shear stress and shear rate. On the other hand, viscosity flow curves for the lubricants with viscosity ≥ 0.0128 Pas showed non-Newtonian behaviour up to a shear rate of 3000 s⁻¹ with shear-thinning characteristic.

Total hip joint prostheses made of CoCrMo heads versus ultra high molecular weight polyethylene (UHMWPE) cups have a limited lifetime, mainly due to the wear of the UHMWPE cups as a result of high friction between the articulating surfaces leading to osteolysis and implant loosening with revision surgery becoming inevitable in more active patients. Tribology plays an important role in developing the design, minimizing wear and reducing friction of hip joint prostheses in order to improve their long-term performance, with good lubricating properties. Metal-on-metal hip resurfacing prostheses have shown significantly lower wear rates compared with conventional metal-on-polyethylene implants and thus osteolysis is potentially reduced leading to increased lifetime of the prosthesis. Nevertheless, excessive wear of metal-on-metal joints leads to metal ion release, causing pseudo-tumours and osteolysis. An alternative approach to such bearings is the use of newly developed carbon fiber-reinforced poly-ether-ether-ketone (CFR PEEK) acetabular cups articulating against ceramic femoral heads due to their better wear resistance compared to UHMWPE. In this study, therefore, friction and lubrication properties of large diameter, as cast, Co-Cr-Mo metal-on-metal hip resurfacing implants with various diameters and clearances have been investigated and compared to those of the newly developed zirconia toughened alumina (ZTA) ceramic femoral heads articulating against carbon fiber reinforced poly-ether-ether-ketone (CFR PEEK) acetabular cups with different diameters and clearances. Friction hip simulator was used to measure frictional torque and then friction factors were calculated along with Sommerfeld numbers leading to Stribeck analysis and hence the lubricating mode was also investigated. This involved using lubricants based on pure bovine serum (BS) and diluted bovine serum (25 vol. %BS+75 vol. %distilled water) with and without carboxymethyl cellulose (CMC) (as gelling agent). Standard Rheometer was used to measure lubricant viscosity ranged from 0.0014 to 0.236 Pas at a shear rate of 3000 . Pure bovine serum, diluted bovine serum without CMC and with CMC (25BS+75DW+0.5gCMC and +1gCMC) showed pseudoplastic flow behaviour up to shear rate of ~139 s⁻¹ above which a Newtonian flow with significant increase in shear stress was observed. The viscosity flow curves for the 25BS+75DW+2gCMC, +3.5gCMC and +5gCMC showed only shear thinning up to a shear rate of 3000 . The shear rate application modified the flow behaviour of bovine serum from a pseudoplastic to a Newtonian flow depending on its purity and CMC content. This will cause a different frictional behaviour depending on joint diameter and clearance, as seen in this work. The experimental data were compared with theoretical iv predictions of the lubricating regimes by calculating theoretical film thickness and lambda ratio. The metal-on-metal Biomet ReCaps showed similar trends of Stribeck curves, i.e. friction factors decreased from ~0.12 to ~0.05 as Sommerfeld numbers increased in the range of viscosities ~0.001-0.04Pas indicating mixed lubrication regimes above which the friction factor increased to ~0.13 at a viscosity of 0.236Pas. The Stribeck analyses suggested mixed lubrication as the dominant mode with the lowest friction factor in the range ~0.09 - ~0.05 at the physiological viscosities of ~0.01 to ~0.04 Pas and that such joints can be used for more active patients as compared to the conventional total hip replacement joints with 28mm diameter. The Stribeck curves for all ZTA ceramic-on-CFR PEEK components illustrated a similar trend with BS fluids showing higher friction factors (in the range 0.22-0.13) than the diluted BS+CMC fluids (in the range 0.24-0.05). The friction tests revealed boundary-mixed lubrication regimes for the ZTA ceramic-on-CFR-PEEK joints. The results, so far, are promising and suggest clearly that the newly developed ZTA ceramic femoral heads articulating against CFR PEEK cups have similar friction and lubrication behaviour at optimum clearances to those of currently used metal-onmetal hip resurfacing implants at the range of viscosities 0.00612 to 0.155Pas. These results clearly suggest that the ZTA ceramic-on-CFR-PEEK joints showed low friction at the physiological viscosities of ~0.01Pas in the range ~0.1-0.05, suggesting that these novel joints may be used as an alternative material choice for the reduction of osteolysis. The result of this investigation has suggested that the optimum clearance for the 52mm diameter MOM Biomet ReCaps could be ~170μm. However, 48 and 54mm joints showed lower friction due to clearances to be >200μm. For the 52mm ZTA ceramic-on-CFR-PEEK joints the optimum clearance seems to be ≥ 630μm radial clearance. These results suggested that increased clearance bearings have the potential to generate low friction and hence no risk of micro- or even macro-motion for the ceramic-on-CFR-PEEK joints. This study found no correlation between theoretical predictions and experimental data for all metal-onmetal and ZTA ceramic-on-CFR PEEK bearings at the physiological viscosity (0.0127Pas). However, at lubricant viscosity of 0.00157Pas, the theoretical prediction of lubrication regime correlated well with the experimental data, both illustrating boundary lubrication. As expected, a decrease in viscosity resulted decrease in the film thickness.

La faible densité et les propriétés mécaniques remarquables des composites polymères en font des matériaux de choix pour remplacer les métaux. Cependant, leurs propriétés physicochimiques rendent leurs surfaces peu adhésives pour divers types de revêtements. Pour améliorer l’adhérence de revêtements métalliques sur des substrats de PEEK, et pour mieux comprendre les mécanismes de l’adhésion, les propriétés de surface du matériau ont été modifiées par des procédés physiques en voie sèche.D’une part, cette étude montre que les traitements par plasma oxydants (à basse pression, ou à pression atmosphérique) permettent d’améliorer la mouillabilité de la surface et l’adhérence de revêtements métalliques, par l’augmentation de la polarité de la surface, quantifiée par XPS. D’autre part, cette étude montre que l’ablation laser infrarouge à impulsion femtoseconde permet la gravure d’un motif dense, induisant de meilleures tenues mécaniques de l’assemblage. Enfin, cette étude montre que la modification de la chimie et de la topographie combinées améliore davantage ce potentiel d’adhérence.Le but de cette étude est d’ouvrir une voie vers un modèle décrivant les mécanismes de l’adhésion, influencés par la chimie de surface et la géométrie d’un motif, en s’appuyant sur un modèle mécanique permettant de décrire la dynamique des contraintes se propageant au travers de l’interface, en tenant compte des propriétés mécaniques des matériaux. / Thanks to their low densities and good mechanical properties, polymer composites are good candidates for metal alloys substitutes. However, their physicochemical properties limit their adhesion potential towards several types of coatings. In order to improve metallic thin films adhesion on PEEK substrates, and to better comprehend adhesion mechanisms, dry-phase methods have been used to alter the surface properties of the material.First, this study shows that oxidative plasma treatments (at low or at atmospheric pressure) improve the wettability and the practical adhesion of metallic coatings, by an increase of the polar component of the surface, as measured by XPS. Second, this study shows that dense patterns etched by an infrared femtosecond laser allow good practical adhesion of the metallic thin films on the substrate. Finally, this study shows that the modification of both surface chemistry and the surface topography at the same time further improves the practical adhesion of the metallic thin films.The goal of this study is to propose a route towards a model describing the combined influence of surface texture and chemistry, with the support of a mechanical model describing the dynamics of the stress dissipation through the interface while taking into account the mechanicals properties of the interfacial materials.

Membrane technology has great potential to complement traditional energy-intensive molecular separation processes such as distillation, with the advantage of low footprint generation. However, this would only be achieved with the development of better membranes able to operate in challenging conditions, including combinations of organic solvents, high temperatures, extreme pHs, and oxidative environments. This dissertation aims to use high-performance polymeric materials that can withstand temperatures of 120 °C in polar aprotic solvents like N,N-dimethylformamide as separation membranes, using different crosslinking strategies and alternative routes for commercially available material processing. The thesis will be divided into two main approaches. The first approach will start from soluble polyimides as precursors, with designed functionalities that allow post-membrane modifications, such as chemical crosslinking, thermal crosslinking, and thermal rearrangement to enhance the material's chemical resistance. The focus will be on the polyimide synthesis by an alternative one-step room-temperature polyhydroxyalkylation reaction. The chemical and thermal crosslinking take place without involving the imide bond, by incorporating a highly tunable functional group (isatin) in the synthesis of the materials. Propargyl as a pendant group will be used for the thermal crosslinking, and hydroxyl group for the thermal rearrangement. In all cases, the obtained membranes were stable in common organic solvents at 120 °C. The second approach will start from intrinsically solvent-resistant and commercially available poly(aryl ether ketone)s, turned into membranes by a closed-loop modification-regeneration strategy, to address long-term separations in organic solvents at high temperatures. We present for the first time porous poly(aryl ether ketone) flat-sheet and hollow fiber membranes prepared without the use of strong acids or high temperatures. Two methodologies are proposed. The developed strategies shall contribute toward avoiding the regular consumption of new materials and waste generation since the polymer used does not require crosslinking for its stability under organic solvents.

Total hip joint prostheses made of CoCrMo heads versus ultra high molecular weight polyethylene (UHMWPE) cups have a limited lifetime, mainly due to the wear of the UHMWPE cups as a result of high friction between the articulating surfaces leading to osteolysis and implant loosening with revision surgery becoming inevitable in more active patients. Tribology plays an important role in developing the design, minimizing wear and reducing friction of hip joint prostheses in order to improve their long-term performance, with good lubricating properties. Metal-on-metal hip resurfacing prostheses have shown significantly lower wear rates compared with conventional metal-on-polyethylene implants and thus osteolysis is potentially reduced leading to increased lifetime of the prosthesis. Nevertheless, excessive wear of metal-on-metal joints leads to metal ion release, causing pseudo-tumours and osteolysis. An alternative approach to such bearings is the use of newly developed carbon fiber-reinforced poly-ether-ether-ketone (CFR PEEK) acetabular cups articulating against ceramic femoral heads due to their better wear resistance compared to UHMWPE. In this study, therefore, friction and lubrication properties of large diameter, as cast, Co-Cr-Mo metal-on-metal hip resurfacing implants with various diameters and clearances have been investigated and compared to those of the newly developed zirconia toughened alumina (ZTA) ceramic femoral heads articulating against carbon fiber reinforced poly-ether-ether-ketone (CFR PEEK) acetabular cups with different diameters and clearances. Friction hip simulator was used to measure frictional torque and then friction factors were calculated along with Sommerfeld numbers leading to Stribeck analysis and hence the lubricating mode was also investigated. This involved using lubricants based on pure bovine serum (BS) and diluted bovine serum (25 vol. %BS+75 vol. %distilled water) with and without carboxymethyl cellulose (CMC) (as gelling agent). Standard Rheometer was used to measure lubricant viscosity ranged from 0.0014 to 0.236 Pas at a shear rate of 3000 . Pure bovine serum, diluted bovine serum without CMC and with CMC (25BS+75DW+0.5gCMC and +1gCMC) showed pseudoplastic flow behaviour up to shear rate of ¿139 above which a Newtonian flow with significant increase in shear stress was observed. The viscosity flow curves for the 25BS+75DW+2gCMC, +3.5gCMC and +5gCMC showed only shear thinning up to a shear rate of 3000 . The shear rate application modified the flow behaviour of bovine serum from a pseudoplastic to a Newtonian flow depending on its purity and CMC content. This will cause a different frictional behaviour depending on joint diameter and clearance, as seen in this work. The experimental data were compared with theoretical iv predictions of the lubricating regimes by calculating theoretical film thickness and lambda ratio. The metal-on-metal Biomet ReCaps showed similar trends of Stribeck curves, i.e. friction factors decreased from ~0.12 to ~0.05 as Sommerfeld numbers increased in the range of viscosities ~0.001-0.04Pas indicating mixed lubrication regimes above which the friction factor increased to ~0.13 at a viscosity of 0.236Pas. The Stribeck analyses suggested mixed lubrication as the dominant mode with the lowest friction factor in the range ~0.09 - ~0.05 at the physiological viscosities of ~0.01 to ~0.04 Pas and that such joints can be used for more active patients as compared to the conventional total hip replacement joints with 28mm diameter. The Stribeck curves for all ZTA ceramic-on-CFR PEEK components illustrated a similar trend with BS fluids showing higher friction factors (in the range 0.22-0.13) than the diluted BS+CMC fluids (in the range 0.24-0.05). The friction tests revealed boundary-mixed lubrication regimes for the ZTA ceramic-on-CFR-PEEK joints. The results, so far, are promising and suggest clearly that the newly developed ZTA ceramic femoral heads articulating against CFR PEEK cups have similar friction and lubrication behaviour at optimum clearances to those of currently used metal-onmetal hip resurfacing implants at the range of viscosities 0.00612 to 0.155Pas. These results clearly suggest that the ZTA ceramic-on-CFR-PEEK joints showed low friction at the physiological viscosities of ~0.01Pas in the range ~0.1-0.05, suggesting that these novel joints may be used as an alternative material choice for the reduction of osteolysis. The result of this investigation has suggested that the optimum clearance for the 52mm diameter MOM Biomet ReCaps could be ~170¿m. However, 48 and 54mm joints showed lower friction due to clearances to be >200¿m. For the 52mm ZTA ceramic-on-CFR-PEEK joints the optimum clearance seems to be ¿ 630¿m radial clearance. These results suggested that increased clearance bearings have the potential to generate low friction and hence no risk of micro- or even macro-motion for the ceramic-on-CFR-PEEK joints. This study found no correlation between theoretical predictions and experimental data for all metal-onmetal and ZTA ceramic-on-CFR PEEK bearings at the physiological viscosity (0.0127Pas). However, at lubricant viscosity of 0.00157Pas, the theoretical prediction of lubrication regime correlated well with the experimental data, both illustrating boundary lubrication. As expected, a decrease in viscosity resulted decrease in the film thickness.