Nowadays, Carbon Fiber-Reinforced Polymers (CFRPs) have been widely applied in the aerospace and automotive industries. Secondary adhesive bonding, instead of using rivets or bolts in conventional mechanical fastenings, is promising in joining CFRPs because it is simple and applicable for cured parts, widely applied for repairing structures, and of light weight. However, the mechanical performance of secondary bonding is very sensitive to the treatment of CFRP parts. Besides, another concern arises from the fact that secondary bonded specimen often prematurely fails due to delamination and leads to a catastrophic structural collapse. While enhancing the joint strength and toughness is important, limiting the progression of damage is crucial, to ensure confidence in the design and allow enough time for maintenance and repair. Therefore, it is significant to introduce a crack arrest feature into the joints, to slow down (or even stop) the crack growth and achieve progressive failure. In this thesis, we employ advanced surface preparation strategies to enhance the strength, toughness, and safety of adhesively bonded CFRP joints. Globally uniform surface pretreatments, using conventional mechanical abrasion, peel-ply, and pulsed CO2 laser irradiation, are employed at first to improve the mechanical responses of adhesively bonded CFRP joints. Then, to better understand damage mechanisms and guide the joint design, characterizations of surface chemistry, surface energy, and surface morphology are correlated with obtained strength and toughness. Next, trench patterns, ablated by pulsed CO2 laser irradiation, are applied to CFRP substrate to further analyze the role of surface roughness on increased mode I energy release rate. Finally, a novel surface patterning strategy is proposed to achieve superior toughness enhancement in adhesively bonded CFRP joints to improve the joint safety. Such surface preparation strategy is assessed through 2D numerical models and realized experimentally by patterning of pulsed CO2 laser irradiation, illustrating its potential in toughening the joint and successfully delaying the crack propagation.

Le contexte environnemental actuel contraint l’industrie automobile à trouver des solutions pour réduire les émissions de CO2 des véhicules. Une des voies développées consiste à alléger les véhicules en substituant les matériaux à densité élevée comme l’acier par des matériaux plus légers comme les composites. Parmi eux, les SMC (Sheet Molding Compound), généralement employés pour des applications semi-structurales, aspirent à des applications structurales, à condition d’améliorer leurs performances mécaniques (notamment en choc et en fatigue). Les SMC sont composés d’une phase polymère organique (réseau polyester ou vinylester associé à un additif anti-retrait), de charges inorganiques et de fibres de renfort. Cette étude s’est concentrée sur le rôle de la matrice (phase organique + charges) sur les propriétés à la rupture de formulations SMC à fibres de verre et fibres de carbone. Trois axes de recherche ont été développés : i) Analyse de l’existant en évaluant le rôle de l’additif anti-retrait et celui des charges sur les propriétés mécaniques de matrices SMC, ii) Renforcement de matrices SMC par l’utilisation de particules core-shell (CSR), iii) Evaluer le rôle de la matrice sur les SMC à partir des précédents résultats. Dans un premier temps, il a été montré que l’ajout d’un additif de type polystyrène, initialement immiscible dans une résine polyester, conduit à une diminution de la résistance au choc. L’impact de l’augmentation du taux d’un additif initialement miscible (polyester saturé ou polyacétate de vinyle) de faible Tg est gouverné par deux effets antagonistes : la présence de plus en plus importante d’une phase souple renforçante et le développement de microvides qui dégradent les propriétés mécaniques. Puis, l’effet des charges inorganiques a été analysé. Il a été montré que l’ajout de CaCO3 conduisait à une amélioration de la résistance à la propagation de fissure. La résistance à l’amorçage de fissure semble être liée au retrait de polymérisation. La diminution des propriétés à la rupture en présence de microsphères de verre a été démontrée. L’utilisation de charges alternatives a également été explorée. Dans un second temps, des matrices vinylester ont été renforcées par des particules core-shell, qui ont démontré leur efficacité en augmentant considérablement la résistance au choc et la ténacité des systèmes. Des analyses microscopiques ont permis d’identifier des mécanismes de renforcement. Enfin, le rôle de la matrice sur les SMC a été évalué. Ainsi, une augmentation du taux d’additif dans les SMC renforce la matrice et modifie probablement la résistance de l’interface fibre-matrice, entraînant une augmentation de la résistance au choc. L’ajout CaCO3 dégrade cette propriété. De plus, celui-ci masque l’effet renforçant des particules core-shell. Enfin, sur composites à fibres de carbone sans CaCO3, l’ajout de particules CSR permet d’augmenter jusqu’à 20% leur résistance au choc et d’améliorer leur tenue en fatigue. / Because of the current environmental context, automotive industry has to find solutions to reduce CO2 emissions of vehicles. In order to address this issue, one of the possible ways concerns the reduction of the overall weight of cars by substituting heavy steel parts by lightweight composite materials. Among composite materials, Sheet Molding Compounds (SMCs) are used in cars (semi-structural parts) thanks to their low cost and low weight. Their use in structural applications is relevant, provided that their mechanical properties are improved (especially in impact and fatigue). These composites are generally constituted of a polymer matrix (unsaturated polyester or vinylester resin blended with an anti-shrinkage additive) reinforced by short fibers and mineral fillers. The aim of this work was to evaluate the role of the matrix on the mechanical properties of carbon fibers (FC-SMC) and glass fibers-based SMC composite (FV-SMC). Three points were developed : i) a study of existing SMC formulations by assessing the influence of low-profile additive and inorganic fillers on the matrices mechanical properties, ii) a study of the toughening of SMC matrices by adding core-shell rubbers particles (CSR), iii), from the previous results, a last part to assess the impact of the matrix on SMC mechanical properties. First, it was shown that adding a polystyrene (PS) low-shrinkage additive, initially immiscible with a polyester resin (before polymerization), leads to a reduction of Charpy impact resistance, because of PS domains which act as defects. When an initially miscible low-Tg additive is used (PVAc or saturated polyester SP), two antagonist effects were found. When the amount of PVAc or SP was increased, a competition between composition (the presence of a soft phase is more important) and morphology (larger microvoids are created, which lead to a drop of fracture toughness) controlled the evolution of mechanical properties. Then, it was shown that CaCO3 improved fracture toughness of materials. Crack initiation resistance seemed to be lied to polymerization shrinkage. Adding glass microspheres led to a drop of mechanical properties. Other types of fillers were also investigated. In a second part, vinylester matrices were blended with CSR particles. An important toughening was obtained in comparison to a standard SMC matrix. Toughening mechanisms like CSR cavitation, plastic deformation of the matrix or crack-bridging were identified with electronic microscopic observations. Finally, the role of the matrix on SMC was studied. Increasing the rate of saturated polyester (low-profile additive) in FC- SMC formulations led to a better Charpy impact resistance, because of the higher matrix toughness and a probable modification of the fiber/matrix adhesion. With CSR particles in FV-SMC, the presence of CaCO3 limited the toughening. On FC-SMC without fillers, CSR particles led to a better Charpy impact resistance and a better fatigue behavior.

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<p dir="ltr">The natural honeycomb made from beeswax is an engineering marvel. Modern-day engineering has taken several inspirations from it in the form of hexagonal panels and cells made of various materials such as polymers, ceramics, and metals for light-weighting without compromising on its mechanical properties. Previously, characterizing this structure has relied on two-dimensional (2D) surface observations on the macroscale which have an inherently limited scope in understanding complex three-dimensional (3D) structures. As a result, several seminal features of the honeycomb that would have shed light on how it is constructed and what makes it so mechanically robust are left out of reach and overlooked. X-ray microscopy (XRM) is a powerful tool to characterize these complex structures non-destructively, yielding insights that are not possible without three-dimensional (3D) datasets. Further, when a time-resolved approach is adopted, where an external stimulus is interrupted for an XRM scan, one can obtain four-dimensional (4D) datasets. This provides unrivaled information on how complex 3D structures evolve over time when a stimulus is applied.</p><p dir="ltr">In this work, a time-resolved approach towards understanding how bees build out their hexagonal cells, both under normal and abnormal conditions was developed. Several previously unreported, but seminal features of the honeycomb such as the “coping” and porosity at well-defined locations yielded insights into how the comb is constructed. The corrugated spine is seen to be the foundation on which all hexagonal cells are built on. Additionally, this work also explores how bees accommodate distortions within the ordered lattice during the merger of two combs. Behaviorally they are seen to reduce the distortion within cells to minimize the wastage of wax and to keep the cells usable. A 3D parameter using automated image processing was developed to quantify how distortions are accommodated in an ordered lattice.</p><p dir="ltr">This work will further shed light on the mechanical behavior of the natural honeycomb arising from the corrugated nature of the spine and the gradient in its wall thickness which plays a role in crack deflection when the honeycomb is loaded under tension. When loaded under compression, the honeycomb lattice crumples in a manner to limit the damage to very local regions thereby forming a damage-tolerant crumple zone.</p>

Part I: This part of the dissertation describes a new approach to high molecular weight aromatic polyketones via soluble precursors derived from bis(a-aminonitrile)s. Bis(a-aminonitrile)s were easily synthesized from dialdehydes and secondary amines in very high yield by the Strecker reaction. Polymerization of bis(a-aminonitrile)s with activated dihalides using NaH as base in DMF yielded soluble, high molecular weight polyaminonitriles, which were hydrolyzed in acidic conditions to produce the corresponding polyketones. A novel approach to the synthesis of high molecular weight wholly aromatic polyketones without ether linkages or alkyl substituents in the polymeric backbones was demonstrated. These polyketones displayed excellent thermal properties and solvent resistance. A very efficient synthesis for diphenol and activated dihalide monomers containing keto groups was also developed based on a-aminonitrile chemistry. Novel activated dihalide monomers were obtained in quantitative yields. This method is suitable for any activated dihalide by reaction with 2 equivalents of 4-fluorobenzylaminonitrile and NaH, followed by hydrolysis to produce a new monomer with two more p-fluorobenzoyl units. For the synthesis of polyaminonitriles containing ether linkages in the polymeric backbone, only low to medium molecular weight polymers were obtained. The model studies proved that the carbanions of the aminonitriles can react with ether linkages to form more stable phenoxide anions and cause the termination of the polymerization. Part II: Functional hyperbranched poly(arylene ester)s were synthesized by thermal polymerization of 5-acetoxyisophthalic acid or 3,5-diacetoxybenzoic acid. Carboxylic terminated hyperbranched copolyesters were also synthesized by copolymerization of 5-acetoxyisophthalic acid and 3-hydroxybenzoic acid using different molar ratios of these two monomers. Both carboxylic acid and phenolic terminated hyperbranched polyesters were functionalized with different reactive groups. The carboxyl terminated hyperbranched poly(arylene ester)s were successfully used to modify inherently brittle epoxy resins. The hyperbranched polymers were chemically incorporated into the epoxy networks using triphenylphosphine (TPP) as a catalyst and 4,4'-diaminodiphenyl sulfone (DDS) as a curing agent. The chemistry and the proper formation of crosslinked networks were confirmed by solution 1H NMR, solid state CPMAS 13C NMR, kinetic FTIR spectroscopes and gel fraction analysis. Fracture toughness was improved without sacrificing thermal properties. The fracture toughness K1C values of the modified epoxies were found to be a function of the percentage loading, the molecular weights and the proportion of linear units of hyperbranched polyesters. Because the carboxylic acid terminated hyperbranched poly(arylene ester)s were immiscible with the commercially available epoxy EPON 828, the percentage loadings of hyperbranched modifiers were limited and the processibility of epoxy resins was difficult, especially at high percentage loadings of hyperbranched modifiers. These problems could be solved using phenolic terminated hyperbranched poly(arylene ester)s, which are more soluble in epoxy resins. / Ph. D.

Thermosetting polymers can cure at a gradient of cure temperatures due to a variety of factors, including heat transfer in the thermoset during heating and the exotherm due to the chemical reaction occurring during the cure. A new method for assessing the effect of cure conditions on mechanical behavior of toughened thermosets has been developed. Modeling of the phase separation process of a model thermoset system provided detailed understanding of the mechanism of property variation with cure temperature for this material. Subsequent characterization of gradient temperature cured samples has shown important variations, illustrating not only the importance of cure conditions, but the possibility of producing materials with new and useful properties. A special mold was developed to cure samples in a controlled gradient of temperature. Example systems known to show pronounced variations in microstructure cured in this gradient mold showed large variations of microstructure as a function of position within the sample, corresponding to the cure temperature at that point. A model toughened thermoset system was developed to demonstrate gradients of properties following cure in the gradient temperature mold. Cyanate ester materials were modified with hydroxyl-terminated butadiene-acrylonitrile copolymers as well as low Tg amorphous polyesters. The polyesters showed very desirable properties for a toughener, including relatively good thermo-oxidative stability in comparison with the butadiene-acrylonitrile toughener. However, the variation of properties of the cured materials with temperature was small, and to better understand the property variation possible using a gradient cure temperature technique, the butadiene-acrylonitrile toughened cyanate ester system was chosen for further study. This system showed a significant variation of glass transition temperature of the cyanate-rich phase as a function of cure temperature. Modeling of the phase separation process of this material was varied out employing a modeling procedure developed for epoxy materials. Various characteristics of the system were determined in order to apply the model to the chosen toughened thermoset. These included viscosity, surface, and thermodynamic parameters in addition to a careful characterization of the morphological parameters developed during cure at the chosen temperatures. Results show excellent predictive capability of the model for microstructure. Prediction of phase composition as a function of cure temperature is also possible, again with good agreement with experiment results. Higher cure temperatures result in a non-equilibrium phase composition, depressing the glass transition temperature of the continuous cyanate ester rich phase. This provides a mechanism by which properties of the system change as a function of position within a gradient temperature cured sample. Dynamic mechanical analysis was employed to characterize the relaxation properties of gradient and isothermally cured samples. The Havriliak Negami equation was chosen to describe the relaxation behavior of these samples. Comparison of the fitting of isotherms over the small, experimentally accessible range of frequencies showed that the use of time-temperature superpositioning could more reliably discern relatively small differences. The breadth of the relaxation corresponding to the glass transition of the polycyanurate phase was increased with a gradient cure temperature relative to isothermally cured samples. This increased broadness was expressed in an alternative way through the use of an autocorrelation function, which allows direct comparison of the time-dependent transition from a fully unrelaxed condition to a fully relaxed one. / Ph. D.

This thesis focuses on designing thermoplastic composites with high mechanical properties and a low processing temperature. Thermoplastic composites, which are used in this work, are composed of thermoplastic polyurethane (TPU) matrices and plain woven E-glass fabrics (GFs). TPUs were synthesised with large quantities of hard segments (HS), including 70% and 90%wt HS. The GF-TPU composites manufactured in this study have a melting point of around 175oC. As such, 180oC represents the processing temperature, which was used to produce GF-TPU composites. The influences of HS content and annealing treatment at 80oC on the thermal, dynamic mechanical and mechanical properties of TPU samples and GF-TPU composites with 25% fibre volume fraction (Vf) have been investigated. The highest crystallinity, storage modulus, Tg, yield strength, tensile strength and tensile modulus of all the TPU samples are seen in the TPU/90 samples annealed for 4 days. The TPU/90 samples display higher tensile properties than the TPU/70 and polypropylene (PP) samples, while the PP samples show the greatest elongation at break point. Furthermore, the tensile properties of the TPU/70 and TPU/90 samples are much higher than those of commercial TPUs. As such, annealed GF-TPU/90 composites with 25% Vf present the greatest dynamic mechanical, flexural, and tensile properties. GF-TPU/90 composites with 25% Vf show higher flexural strength than GF-PP composites or GF-polyamide 6 (PA6) composites with the same Vf. The effects of fibre surface treatments on the mechanical properties of GF and GF-TPU/70 composites with 25% Vf have also been studied in this investigation. GF treated with burn-off treatment is found to exhibit the lowest tensile properties. The interfacial adhesion between GF treated by NaOH for 0.5hrs and a TPU/70 matrix is greater than between GF treated by acetone for 5hrs and a TPU/70 matrix. Silanised GF presents greater tensile properties than desized GF. Thus, enhanced interfacial adhesion and tensile, flexural, ILSS and GIC properties are observed in the silanised GF-TPU/70 composites than in the desized GF-TPU/70 composites. GF-TPU/70 composites based on GFs treated by NaOH for 0.5hrs then sized with 0.15%wt. aminosilane display the greatest interfacial adhesion, flexural properties, ILSS and GIC, damage tolerance and impact-damage resistance. Conversely, the lowest interfacial adhesion, GIC, damage tolerance and impact-damage resistance are seen in the GF-PP composites based on 25% Vf as-received GF. There is a significant increase in the tensile and flexural properties of GF-TPU/90 composites with increasing the Vf from 25% to 50%. Moreover, the flexural strength of GF-TPU/90 composites with 50% Vf is not only higher than that of GF-EP composites or GF-vinyl ester composites with normalised 50% Vf, but is also much higher than that of GF-PP composites with 50% Vf. Despite this result, GF-TPU/90 composites with 50% Vf show the lowest fracture toughness, impact-damage resistance and damage tolerance, which are improved by adding 25% and 50%wt. of TPU/70 to the TPU/90 matrix. GF-TPU/90 composites based on a modified matrix have higher GIC, GIIC, impact-damage resistance and damage tolerance than GF-TPU/90 composites based on an unmodified matrix. The GIC, GIIC, impact-damage resistance and damage tolerance of GF-TPU/90 composites based on a modified matrix increase with increasing the percentage of TPU/70. Hence, the highest GIC, GIIC, impact-damage resistance and damage tolerance are seen in the GF-TPU/90 composites based on a modified matrix with 50%wt. of TPU/70.

The goal of this work is to understand how the wear and deformation mechanisms of hardmetalinserts change when the cobalt binder phase is replaced with a dierent metal or analloy. The focus is on inserts for steel turning. The work presented in this licentiate thesisconsists of the rst steps.Cobalt is the most common binder phase in hardmetal tools based on tungsten carbide asthe hard phase. Metallic cobalt powder, present during the manufacturing, has been associatedwith lung diseases and an increased risk for lung cancer if inhaled. Therefore it is importantto investigate alternative binders as one possible solution.This work studies binder phase alloys from the iron-nickel-cobalt system. These alloyscan be either austenitic, martensitic or a mixture of the two phases. By changing the binderphase composition to change the crystal structure it is possible to tailor the macroscopic mechanicalproperties of the material. It is also possible to tailor the composition in such a waythat the binder is transformation toughening, forming martensite as a response to mechanicaldeformation.The majority of inserts for steel turning are coated, and it is important to investigate if thehardmetals with alternative binder can be coated and if the coating adhesion is sucient forsteel turning.Four dierent alternative binder alloys and one reference with cobalt binder coated bychemical vapour deposition were investigated by scratch testing to determine the adhesion.The scratch test adhesion was sucient on all samples, but signicant variations in coatingadhesion were found.One alternative binder with 86wt%Ni and 14wt%Fe and a reference with cobalt binder manufacturedto mimic state of the art turning inserts were tested in steel turning. The alternativebinder grades had a lower resistance to plastic deformation and this was attributed to earlyaking of the coating due to a lower coating adhesion. Focused ion beam and scanning electronmicroscopy were used to study the deformation of the hard metal in the used cuttinginserts.

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