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Cyanate ester or triazine networks are attaining increasing importance as potential candidates for high temperature adhesives and composite matrices. Low toughness is a major drawback with most crosslinked thermosetting materials, including the cyanate ester networks. Considerable attention has been devoted to the aspect of toughening such brittle networks in our laboratories. Reactive functional thermoplastics not only enhance toughness but also impart highly desirable stability to solvent stress cracking without seriously affecting the moderately high modulus. Various aspects of this technology, have earlier been successfully applied to epoxy and bismaleimide systems. Careful control of the heterophase morphological structure is necessary to achieve significant toughening. This thesis has focused on modifications of a specific cyanate ester network system based on Bisphenol-A with thermoplastic modifiers, which were systematically varied with respect to back-bone molecular weight and chemistry. Hydroxyl or cyanato functional Bisphenol-A based amorphous poly(arylene ether)s have been successfully utilized to toughen the cyanate ester networks. Blends of reactive and non-reactive Bisphenol-A based amorphous poly(arylene ether sulfone)s were also demonstrated to be useful tougheners, apparently by allowing phase size control. The use of Bisphenol-A based amorphous polyarylene ether ketones (which are of lower polarity relative to the Bisphenol-A based polyarylene ether sulfones) resulted in larger, well defined morphologies which in turn resulted in tougher networks. It was demonstrated that either hydroxyl or cyanato reactive end-groups could be effectively utilized. Both were superior to non-reactive systems in terms of mechanical performance as well as solvent stability. One of the major drawbacks of this effort was that 3-4 fold improvements in toughness were attained but this was at the expense of the upper use temperature which dropped to a significant extent. Hydroxyl functional phenolphthalein based amorphous poly(arylene ether)s have also been successfully utilized to toughen the cyanate ester networks. This is significant in that toughened multi phase networks were generated without a sacrifice in either the Tg or the moderately high modulus of the unmodified cyanate ester networks. It has been demonstrated that the heterophase morphological structure which strongly influences mechanical performance is in turn influenced by the back-bone chemistry, molecular weight and end-functionality of the thermoplastic modifier. In addition, the kinetics of network formation also significantly influences the microphase separated morphologies. Generation and control of such microphase separated morphologies employing both thermal and microwave radiation has been investigated. An interdisciplinary investigation was undertaken to explore the feasibility of hydroxy functionalized phenolphthalein based poly(arylene ether sulfone) modified cyanate ester networks as potential candidates for high performance adhesive and composite matrix applications. Investigations into composite matrix applications, involved establishing models for the experimentally determined time and temperature dependent kinetics of cure as well as melt rheology. It is expected that these models will consequently complement efforts in establishing an optimized cure protocol for the fabrication of composite panels. Preliminary studies concerning aspects of fiber-matrix interfacial adhesion and the viability of thermoplastic modified cyanate ester networks as a structural adhesive have been conducted. / Ph. D.

A systematic study was conducted to examine the influence of fiber surface treatment and sizing on the formation of fiber-matrix interphase and its effects n the mechanical properties of composite laminates. Three material systems having the same Apollo graphite fibers and HC 9106-3 toughened epoxy matrix, but with different fiber surface treatments and sizings were used in this study. The fibers used in the 810A and 820 A systems received 100% and 200% industry standard surface treatments respectively and were sized with Bisphenol-A unreacted epoxy material. The 810 O system was manufactured with 100% surface treated fibers that were sized with pvp (polyvinylpyrrolidone), a thermoplastic material. The presence of different interphase in these materials was confirmed using a permanganic etching technique. Results indicate that the interphase is discontinuous and made of linear chain polymeric material in the 810 A system. The interphase in the 810 O system has a gradient morphology while the 820 A system does not possess a well defined interphase. Mechanical test results indicate that the 810 O system significantly greater longitudinal tensile strength and failure strain compared to the 810 A system. The 810 A and 820 A systems have similar longitudinal tensile properties. Transverse tensile test results indicate that the 820 A system has the highest strength while the 810 O system has the lowest strength. The (0,90₃), cross-ply laminates from the three material systems exhibit different damage mechanisms and failure modes under monotonic tensile loading. Fatigue test results indicate that the 810 O laminates have longer fatigue lives at higher load levels and shorter fatigue lives at lower load levels compared to the 810 A laminates. The 820 A laminates have longer life compared to the other two materials systems, at all three load levels. The 810 O material exhibits greater damage and stiffness reduction than the other two materials. The 810 A and 820 A systems exhibit a brittle stress concentration controlled failure, while the pvp sized 810 O system exhibits a global strain conuolled failure. A micromechanics model was developed to investigate the role of the interphase on the tensile strength of unidirectional laminates. A new parameter called the ‘efficiency of the interface’, is introduced in the model. A simple scheme that uses the experimentally determined tensile modulus of unidirectional laminates in a concentric cylinders model, is described to estimate the interfacial efficiency. The tensile fatigue performance of cross-ply laminates is predicted using this micromechanics model in a cumulative damage scheme. The predicted fatigue lives and failure modes agree well with experimental results. / Ph. D.

Poly(arylene ether phosphine oxide)s (PEPO) are a recently identified subset of an important macromolecular series which includes industrially important high performance thermoplastics, such as the polysulfones, e.g. UDEL@ and polyether ketones, e.g. PEEK@, PEKK@, etc. The PEPO materials show an elevated glass transition temperature, high thermal and oxidative stability, improved solubility, and increased flame resistance. It has been demonstrated that a variety of metal salts including metals such as iron, zinc, cobalt, and copper, can be complexed at a molecular level with the phosphoryl group in films of these polymers producing novel transparent metal/polymer "composites". A procedure for obtaining homogeneous films from solutions of the metal halide complexed polymers has been developed. FTIR experiments as well as Tl phosphorus (31 P) NMR measurements were conducted to demonstrate the existance of metal complexation in the solid state. The effect of the chemical composition of the chain, type of metal salt, molar concentration of the metal salt, and heating cycle were investigated and found to influence properties of the films such as solubility, glass transition temperature, thermal stability, and storage mexiulus. Additionally, linear poly(arylene ether phosphine oxide)s were reduced to different extents to the corresponding phosphine containing polymers. Properties such as intrinsic One of these phosphine polymers was subsequently used in the generation of a rhodium catalyst for the hydroformylation of octene-l. The utilization of polymer-supported catalysts has important advantages such as catalyst recovery and the ease of separation of the product. The catalyst activity of the polymeric rhodium complex was studied as a function of reaction time as well as ligand to rhodium ratio. For a phosphorus/rhodium ratio of two these heterogeneous catalysts suffer in tenns of reaction rate in relation to their homogeneous counterparts. However, at phosphorus/rhodium ratios of approximately eight the reaction is almost quantitative after three hours, and the selectivity is greatly improved over that of monomeric homogeneous catalysts for the same P/Rh ratio. / Master of Science

Thesis (MScEng (Mechanical and Mechatronic Engineering))--University of Stellenbosch, 2009. / ENGLISH ABSTRACT: Thermoplastic composites (TPCs) have shown significant advantages over thermosetting composites. They have only been put into use recently and global knowledge in TPCs is often proprietary, therefore a study into the application, processing and properties is of importance. The aim of the study is to contribute knowledge in TPCs for South African industry and academic institutions. This thesis studies continuous fibre reinforced thermoplastics (CFRTPs), focussing on the autoclave processing of commingled CFRTPs. A literature study provided background knowledge to CFRTPs regarding processing techniques and mechanics. Flexural testing and impact testing were performed on a variety of CFRTPs and thermosetting composites (TSCs). These tests were performed to further understand CFRTPs as well as to compare CFRTPs and TSCs. The flexural testing revealed that CFRTPs have comparable strength and stiffness to the TSCs that were tested. They also revealed that pre-consolidated sheets showed better and more consistent properties than sheets made from commingled fabric. The impact testing revealed that the tested CFRTPs and TSCs had similar impact resistance even though thermoplastic composites are supposed to be more impact resistant. The tests also showed that thick unreinforced thermoplastics had much higher impact resistance than the reinforced materials. Manufacturing experiments were performed to establish sound processing methods of CFRTPs. It was realised here that the high temperatures required to process the materials require specific processing consumables and tooling. The experiments began by processing flat panels in a convection oven with vacuum bagging techniques. They then progressed to autoclave processing of parts with complex geometry. An airline seat backrest was chosen as the case study in the application of CFRTPs. This application requires structural strength and stiffness and also has strict fire, smoke, toxicity and heat release (FSTH) requirements. Its geometry was sufficiently complex to demonstrate the use of commingled CFRTP material. Backrests were made from both CFRTPs and TSCs so that a comparison could be made between the two types. The backrest was modelled using finite element methods (FEM) to determine an adequate lay-up. This lay-up was then used for both the CFRTP and TSC backrests to ensure similarity between the backrests of both materials. LPET (modified polyethylene terephthalate) was the chosen thermoplastic matrix as it was more attainable than PPS (polyphenylene sulphide) CFRTPs. The backrests of both materials were manufactured in an autoclave with a vacuum bag method and then assembled using adhesives and bonding jigs. Testing revealed that the stiffness and mass of the CFRTP backrests were very similar to the epoxy backrests. This implies that commingled CFRTPs can replace the use of TSCs in similar applications. A basic cost comparison was also performed to compare the manufacture of CFRTP backrests to TSC backrests. Further work is needed to optimise processing time of these materials to make them more competitive with TSCs. The processing time of commingled materials will probably never be as quick as that of press formed pre-consolidated sheets. Their ability to be formed into more complex parts does however make their use advantageous. / AFRIKAANSE OPSOMMING: Termoplastiese saamgestelde materiale (Engels: thermoplastic composites (TPCs)) toon beduidende voordele bo termoverhardbare saamgestelde materiale. Hulle word eers sedert onlangs benut en algemene kennis in TPCs is dikwels patentregtelik, dus is ’n studie van die aanwending, prosessering en eienskappe daarvan van belang. Die doel van hierdie studie is om ’n bydrae te lewer tot die kennis van TPCs vir die Suid-Afrikaanse industrie en akademiese instellings. Hierdie tesis ondersoek kontinue veselversterkte termoplastieke (Engels: continuous fibre reinforced thermoplastics (CFRTPs)) en fokus op die outoklaafprosessering van vermengde (Engels: commingled) CFRTPs. ’n Literatuurstudie het die agtergrondkennis rakende die prosesseringstegnieke en meganika van CFRTPs verskaf. Buigtoetsing en impaktoetsing is op ’n verskeidenheid CFRTPs en termoverhardbare saamgestelde materiale (Engels: thermosetting composites (TSCs)) uitgevoer. Hierdie toetse is uitgevoer om CFRTPs beter te verstaan asook om CFRTPs en TSCs te vergelyk. Die buigtoetsing het onthul dat CFRTPs ooreenstemmende sterkte en styfheid het as die TSCs wat getoets is. Dit het ook getoon dat vooraf-gekonsolideerde plate beter en meer konsekwente eienskappe getoon het as plate wat van vermengde materiaal gemaak is. Die impaktoetsing het onthul dat die CFRTPs en TSCs wat getoets is soortgelyke impakweerstand gehad het, selfs al is termoplastiese saamgestelde materiale veronderstel om meer impakweerstand te toon. Die toetse het ook getoon dat dik onversterkte termoplastieke veel hoër impakweerstand gehad het as die versterkte materiale. Vervaardigingseksperimente is uitgevoer om betroubare prosesseringsmetodes vir CFRTPs vas te stel. Daar is besef dat die hoër temperature wat vereis word om die materiale te prosesseer ook spesifieke prosesseringsverbruiksware en -gereedskap benodig. Die eksperimente het begin met die prosessering van reguit panele in ’n konveksie-oond met vakuumsaktegnieke. Daar is toe aanbeweeg na die outoklaafprosessering van onderdele met komplekse geometrie. Die rugleuning van ’n vliegtuigsitplek is gekies as die gevallestudie in die gebruik van CFRTPs. Hierdie toepassing vereis strukturele sterkte en styfheid en is ook onderhewig aan streng vereistes t.o.v. brand, rook, toksisiteit en hittevrystellimg (Engels FSTH). Die geometrie daarvan was kompleks genoeg om die gebruik van vermengde CFRTP-materiaal te demonstreer. Rugleunings is gemaak van beide CFRTPs en TSCs sodat ’n vergelyking tussen die twee tipes gemaak kon word. Die rugleuning is gemodelleer deur eindige element metodes (EEM) te gebruik om ’n aanvaarbare oplegging te bepaal. Hierdie oplegging is toe gebruik vir beide die CFRTP en TSC rugleunings om die gelykvormigheid tussen die rugleunings van beide materiale te verseker. LPET (Engels: modified polyethylene terephthalate) was die gekose termoplastiese matriks aangesien dit meer verkrygbaar was as PPS (Engels: polyphenylene sulphide) CFRTPs. Die rugleunings van beide materiale is vervaardig in ’n outoklaaf met ’n vakuumsakmetode en toe geintegreer deur die gebruik van kleefstowwe en setmate. Toetsing het getoon dat die styfheid en massa van die CFRTP rugleunings baie soortgelyk was aan die epoksie rugleunings. Dit impliseer dat vermengde CFRTP die plek van TSCs in soortgelyke gebruike kan inneem. ’n Basiese kostevergelyking is ook gedoen om die vervaardiging van CFRTP-rugleunings teenoor TSC-rugleunings te vergelyk.

Les composites thermoplastiques sont de plus en plus privilégiées dans les structures aérospatiales au vue de leur tolérance aux dommages améliorée par rapport aux résines thermodurcissables. Néanmoins, ils restent sensibles à l’impact car il produit des endommagements complexes au sein du matériau, dont le délaminage est le plus critique. La propagation de ces endommagements en compression après impact (CAI) entraîne une réduction de la tenue résiduelle. D’abord, des essais ENF ont été menés afin de déterminer la ténacité interfaciale par le biais de la méthode de la complaisance et de la technique de thermographie infrarouge. Ensuite, l’essai « Short Beam Shear » est proposé afin d’investiguer le couplage entre la fissuration matricielle et le délaminage. L’effet de la vitesse de sollicitation a été également étudié. La valeur de ténacité mesurée semble indépendante à la vitesse de sollicitation car, lors des essais réalisés, la propagation est instable. Ensuite, le comportement d’une éprouvette académique été étudié à l’aide du « Discrete Ply Model » (DPM) permettant d’enchaîner la simulation d’impact et de CAI. Ce modèle est basé sur une approche semi-discrète modélisant le délaminage et la fissuration matricielle par des éléments cohésifs, permettant de prendre en compte le couplage entre ces deux endommagements. Une vaste campagne d'essais expérimentaux d’impact et de CAI a été mise en place sur quatre empilements différents impactés à trois niveaux d’énergie. Le modèle DPM a prouvé sa capacité à prédire correctement les endommagements d’impact et de CAI. Finalement, afin de se rapprocher des conditions de structures réelles, le comportement en compression après impact d’une plaque trouée a été investigué. / High-performance thermoplastic composite have been increasingly used in aerospace applications because of their advantageous mechanical properties. Nevertheless, impact damage leads to significant reduction in structure compressive strength although damage may remain unnoticed. Delamination is the most critical damage. Short Beam Shear (SBS) test has been proposed to reproduce impact damage chronology and characterize delamination toughness. Infrared thermography is used for local measuring of fracture toughness in this unclassical test showing unstable fracture growth. Mode II fracture toughness (GIIC) values are comprised between 0.9 and 1.7 N/mm and there was no influence of the loading rate in GIIC values. Discrete Ply Model (DPM) is therefore used to model impact and compression after impact tests on laminated composite structures. Tests have been conducted in order to validate DPM capacity to capture the effects of progressive damage and failure. Impact damage and specimen’s compressive strength is well predicted by DPM. CAI damage propagation is driven by the buckling of the structure. DPM is finally employed to study impact on an industrial sample with a large diameter hole. Impact damage correlates with tests but buckling is difficult to estimate, meaning that rupture of the specimen does not correlate to tests. Nevertheless, DPM shows a good ability to predict damage in thermoplastic composite.

A constante evolução dos Materiais Poliméricos e seus compostos, a procura por um melhor desempenho e redução de peso em peças técnicas, têm levado a busca de soluções inovadoras em materiais termoplásticos para peças tradicionalmente produzidas em materiais metálicos. Nestes casos, a fase inicial de um projeto deve ser realizada com muito cuidado e é onde as metodologias de Seleção de Materiais e Processos de Fabricação (SMPF) mais podem contribuir para o sucesso de um produto. Existem muitas ferramentas para seleção de materiais, algumas delas até mesmo voltadas especificamente aos polímeros, mas nota-se que uma metodologia adequada - e talvez específica - ainda seja necessária. O objetivo deste trabalho foi analisar os métodos utilizados na academia e na indústria para a seleção de materiais termoplásticos, bem como os bancos de dados e programas de computador disponíveis, na busca de subsídios para auxiliar profissionais de projeto de produtos, sejam eles engenheiros ou não. Assim, tratou-se inicialmente de aspectos de Engenharia de Materiais e de SMPF e especificamente de Materiais Poliméricos termoplásticos, na busca de oferecer uma base comum por meio de definições e premissas utilizadas. Como é de interesse entender a inserção da filosofia de SMPF na indústria de transformação de materiais termoplásticos, investigou-se os processos de SMPF na academia e na indústria. A partir desta investigação, é apresentada uma discussão entre as semelhanças e uma possível intersecção entre estas duas realidades, analisando-se os sistemas existentes de maneira a apontar caminhos para estas duas áreas e culminando com uma proposta de modificações nas metodologias atuais para adequá-las as necessidades dos projetistas que trabalham com materiais poliméricos. / The constant evolution of polymers and its compounds, the search for better performance and weight reduction in parts have been leading to innovative solutions in thermoplastic replacing metals in parts traditionally made of the later. In such cases, the initial stages of a project needs a special care and are where the Material and Process Selection (MPS) tools can really shine. If the designer chooses wisely and take advantage of the design freedom made possible by the use of plastics, a part can not only be made more economically but also with a better performance. Many tools are available in the marketplace, some even designed to deal specifically with polymers, but it is becoming clear that a more adequate and specific polymer selection methodology is needed. The objective of this work is to analyze the methodologies used in the academy and in the industry in the area of thermoplastic materials selection, together with the databases and software available, in search for subsidies to help product designers in their work. In this way, this work deals initially with materials engineering, materials and process selection (MPS) and thermoplastic materials basic knowledge, in a way to offer a basis for discussion. As it tries to understand the MPS in the industry, these processes are investigated in the academy first, leading to a discussion on the similarities and possible intersection between both worlds, an analysis of the existing tools, and finally pointing towards modifications on the actual methodologies to bring the theory of MPS to the real world of designers.

Ce manuscrit rassemble les recherches effectuées dans le cadre du développement d’une résine thermoplastique photopolymérisable pour une application composite. Ce travail a été effectué dans le cadre du projet COMPOFAST, lancé par ARKEMA à la fin de l’année 2012. Ce projet, accompagné par l’ADEME, a pour but, la mise au point d’une nouvelle génération de composites thermoplastiques à haute cadence de production pour la conception de pièces pour l’automobile. L’intérêt de ces matériaux, et donc du projet, est l’allégement des véhicules par réduction de la masse des pièces utilisées et la recyclabilité des matrices choisies. A travers ce projet, plusieurs techniques ont été envisagées. Dans le cadre de cette thèse c’est le procédé QCM, pour Quick Composite Molding, qui a été étudié au sein du LPIM. L’utilisation de la lumière pour assurer la polymérisation de la matrice rend novateur ce procédé. Cette étape dite de photopolymérisation est connue pour être l’un des moyens les plus rapides pour former une résine solide à partir d’une formulation liquide. Le procédé repose également sur la dépose automatisée de bandes de préimprégnés sur un moule ouvert afin d’augmenter la vitesse de production des pièces de composites. Techniquement, deux étapes ont été prévues : la première consiste en la réalisation des bandes de préimprégnés de manière automatique. La deuxième étape est la conception du composite par dépose automatique sur un moule des bandes de renforts préirradiés à laquelle succède une étape finale d’irradiation pour obtenir le composite requis. / This manuscript brings together research in the development of a light-curing thermoplastic resin for a composite application. This work was performed under the COMPOFAST project launched by Arkema at the end of 2012. This project, along with the ADEME, aims at the development of a new generation of thermoplastic composites with high production rates for designing automobile parts. The advantages of these materials, and therefore of the project, is making vehicles lighter by reducing the mass of the parts used and the recyclability of the selected matrices. Through this project, several techniques were considered. As part of this thesis, it's the QCM method for Quick Composite Molding, which has been studied within the LPIM. The use of light to ensure the polymerization of the matrix makes this method innovative. This step called photopolymerization is known to be one of the fastest ways to form a solid resin from a liquid formulation. The method also relies on the automated removal prepreg bands on an open mold in order to increase the rate of production of composite parts. Technically, two stages were planned: the first involves the automatically construction of prepreg tapes. The second step is the design of the composite by automatically depositing prepregs on the mold which is followed by a final step of irradiation to give the desired photocomposite.

Neuartige Hybridgarn-Textil-Thermoplaste (HGTT) ermöglichen die automatisierte Fertigung von Faserverbundbauteilen in serienfähigen Taktzeiten. Im Rahmen des Produktionstechnischen Zentrums der TU Dresden (ProZeD) und mit Mitteln des Bundesministeriums für Bildung und Forschung wurde ein solcher Fertigungsprozess entwickelt und gestaltet. In diesem wird das Bauteil in zwei wesentlichen Schritten aus textiler Rollenware durch einmaliges Erwärmen und Konsolidieren bei gleichzeitiger Formgebung hergestellt. Im ersten Schritt erfolgt der endkonturnahe Zuschnitt, sowie für dickwandigere Bauteile das Übereinanderlegen mehrerer textiler Preforms und deren Fixierung gegen Verrutschen. Für diesen Prozessschritt wurden das Plasmaschneiden als Trennverfahren von HGTT untersucht und ein Abwicklungsmechanismus für die Rollenware sowie ein Greifersystem für das verzugsfreie Handling der Preform entwickelt. Kernstück der technischen Umsetzung ist dabei eine Parallelkinematik, die a) den Plasmabrenner zum Ausschneiden der Preform führt, b) das Handling der Lagen übernimmt und c) durch optische Überwachung der Faserlage die Qualität sichert. Im zweiten Prozessschritt wird in einem angetriebenen Werkzeug das Material durch Heißpressen konsolidiert. Zur Sicherung einer effektiven Temperierung wird beim Werkzeug auf das MELATO-Prinzip zurückgegriffen und dessen mögliche Einsatzbedingungen untersucht. Ziel von EFFEKT ist es, den Prozess zur Serienreife weiter zu entwickeln, d. h. durch Optimierung der Prozessparameter die Taktzeiten zu minimieren, die gleichbleibende Qualität des Fertigteils sicherzustellen sowie ohne Verschnitt und Ausschuss ressourcenschonend zu fertigen.