A polymer-based composite reinforced with a mixture of Ni and Al powders was investigated as an example of a multifunctional structural energetic material. Micron-sized Ni powder, nano/micron-sized Al powders, and Teflon or epoxy were fabricated as bulk materials by pressing or casting. The thermally initiated reaction response of these materials was evaluated using differential thermal analysis coupled with x-ray diffraction. The analyses showed evidence of thermally initiated reactions between Ni and Al powders, as well as between Ni+Al and Teflon. Nano-sized Al powder showed a preference for reaction with Teflon over Ni, while micron-sized Al reacted strongly with Ni regardless of the presence of a binder. Teflon was shown to be very reactive with the Ni+Al/nano Al mixture, whereas epoxy was not reactive with the metallic powders, and also inhibited reaction between Ni and nano Al. The structural/mechanical behavior of these materials was evaluated using elastic and plastic property measurements via static and dynamic compression tests. Dynamic mechanical testing using reverse Taylor anvil-on-rod impact tests combined with velocity interferometry gave qualitative and quantitative information about the transient deformation and failure response of the composites. The material containing 20wt% epoxy and nano-sized Al powder showed the most superior mechanical properties in terms of elastic modulus and static and dynamic compressive strength. The addition of Ni and Al powders to the epoxy matrix increased the strength of the composites, and their tendency toward brittle fracture, as evidenced by Ni particle pullout in SEM analysis. The results illustrate that nano-sized Al particles provide significant enhancement to strength of epoxy composites, but at the expense of reactivity. The nano-Al particles get dissociated from the Ni and Al mixture and swept into the epoxy, generating a nano-Al containing epoxy matrix with embedded Ni particles. The chemical reactivity of the system is thus sacrificed as contacts between Ni and Al powders are minimized. A mixture of nano-sized Ni and Al particles may however provide the best combination of high strength and reactivity.

This study is an industrial project commissioned by British Gas plc. (UK) to investigate the state of in-service naturally aged polyethylene (PE) buried pipes and to define procedures or techniques available to facilitate the condition assessment programme of PE pipelines systems. The primary goal of this study was to establish a better understanding of the ageing process in commercial piping materials and to understand its effect on long term integrity of PE pipeline systems. Eltex, Rigidex and Aldyl A are trade names of the PE gas grade resins used in this study and they represent the range of pipe materials used in the transport of potable water and gas in the UK. Sections of pipes used in this project were supplied by British Gas plc. in the form of unaged pipes and pipes which were aged in-service. Laboratory based accelerated ageing of the pipe resin samples was also carried out. The ageing regimes considered were water ageing at 23°C, air-oven ageing at 80°C, water ageing at 80 C, vacuum ageing at 80°C and in-service aged samples. Compression moulded plaques were produced as reference material. By utilising specific instrumentation and designs, several reliable procedures were developed to produce specimens directly from pipes. The feasibility of using micro-samples instead of large samples was demonstrated. A methodology was developed to retrieve disk samples using electrofusion "tapping-tee" saddles. Appropriate test specimens were designed for chemical and physical evaluations. This sampling method negates the need for excavating large sections of pipe material for the purpose of condition assessment. Reliable micro and macro-sampling test methods were developed and established as techniques for the condition assessment programme. Characterisation techniques included: (i) differential scanning calorimetry (DSC) to measure (from the same specimen) both the degree of crystallinity and the oxidation induction time (OIT), (ii) HPLC analysis was used to quantify additives concentrations, (iii) Fourier transform infrared spectroscopy was used to monitor the carbonyl index and to identify a pipe resin type from site, (iv) micro- and macro-tensile and fatigue tests to assess the changes in the mechanical properties as function of ageing. The fatigue test procedure was developed to produce brittle fracture at laboratory scale within a shorter period of time as compared to existing procedures such as the hydrostatic test. A reference data-base was created using the above identified tools and the criteria and methodology for carrying out site condition assessment inspection was compiled. The fundamental mechanisms of chemical and physical ageing were studied along with the possibility of their effect on the mechanical properties of PE pipes.

Orientadores: Chang Tien Kiang, Elias Hage Junior / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-07-20T05:26:20Z (GMT). No. of bitstreams: 1 Cardoso_Giselia_M.pdf: 2679256 bytes, checksum: 20c2cfedadeeb83bd8a03e60f9c2c1a4 (MD5) Previous issue date: 1994 / Resumo: Misturas poliméricas binárias de poliamida 6,6 com aditivo macromolecular ¿ poliamida 6 modificada, policarbonato e poli(metacrilato de metila) ¿ em quantidades de 1 a 10% em massa, foram preparados por fusão e moldadas por injeção através do Mini Max Molder de fabricação da Custom Scientific Instruments. Os produtos obtidos foram caracterizados por microscopia ótica (MO), calorimetria diferencial de varredura (DSC) e análise dinâmico-mecânica (DMA). A análise em microscopia ótica foi realizada de forma qualitativa na observação da influência da natureza química e da quantidade de aditivo macromolecular na modificação da microestrutura da poliamida 6,6. as análises de DSC foram realizadas de duas maneiras: varredura de temperatura, na verificação de existência de miscibilidade nas e determinação. Pela equação de Nishi ¿ Wang, do parâmetro de interação de Flory ('X IND. 12¿); e isotérmica, na avaliação do efeito da presença dos aditivos macromoleculares na velocidade de cristalização da poliamida 6,6. A existência de separação de fase no estado sólido das misturas foi verificada através da análise do comportamento dinâmico-mecânico. O estudo conclui que a adição de pequena quantidade de macromoléculas retarda o aparecimento e reduz a taxa de crescimento dos esferulitos na poliamida 6,6 / Abstract: Binary polymeric blends of polyamide 6,6 with macromolecular additive ¿ modified polyamide 6, polycarbonate and poly(methyl methacrylate) ¿ in amounts varying from 1% to 10% in mass, were prepared by melting and injection ¿ molded a Mini Max Molder ¿ Custom Scientific Instruments. The obtained products were characterized by optical microscopy (OM), differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The optical microscopy analysis was performed as a qualitative observation of the influence of chemical nature and quantity of macromolecular additive in the modification of microstructure of polyamide 6,6. the DSC analysis were done in two ways: temperature scanning, where it was verified the miscibility of mixtures and the Flory¿s interaction parameter 'X IND. 12¿ was determined by Nishi ¿ Wang equation; and isothermally, where the presence of macromolecular additives in the rate of crystallization of polyamide 6,6 was evaluated. DMA of rod samples were performed to evaluate the presence of phase separation in the solid state. It is concluded that blending small amounts of macromolecular additives can delay and reduce the spherulitic crystallization growth in the polyamide 6,6 / Mestrado / Ciencia e Tecnologia de Materiais / Mestre em Engenharia Química

Τα συμπολυμερή κατά συστάδες (block copolymers) έχουν κεντρίσει το ενδιαφέρον αρκετών ερευνητών όχι μόνο για το γεγονός ότι τα τμήματα από τα οποία αποτελούνται βρίσκονται στην νάνο-κλίμακα, αλλά και λόγω των ποικίλων φυσικών και μηχανικών ιδιοτήτων που εμφανίζουν, εξαιτίας της ικανότητας τους να αυτό-οργανώνονται (self assembly materials) σε διάφορες μορφολογίες. Η όχι και τόσο εύκολη διαδικασία παρασκευής συμπολυμερών κατά συστάδες πραγματοποιείται εμπλέκοντας σε αυτή παράγοντες, ανάλογα με το επιθυμητό αποτέλεσμα, όπως το μοριακό βάρος, τη νανοδομή και τη σύσταση. Στην παρούσα εργασία μελετήθηκαν και συγκρίθηκαν οι δυναμικές και στατικές ιδιότητες πρωτότυπων συμπολυμερών δύο και τριών συστάδων, γραμμικής και ετεροκλαδικής αστεροειδούς αρχιτεκτονικής ΑΒ, ΑΒC, AnBn και An(B-C)n, καθώς και η επίδραση διαφόρων παραγόντων στις παραπάνω ιδιότητες. Τα συμπολυμερή παρασκευάστηκαν μέσω «ζωντανού» ανιονικού πολυμερισμού, όπου οι κλάδοι των αστεροειδών συμπολυμερών ήταν συνδεδεμένοι σε ένα πυρήνα. Η Α φάση ήταν πολυστυρόλιο (PS), η Β φάση ήταν ανάλογα την περίπτωση πολυμεθακρυλικός εξυλεστέρας (ΡΗΜΑ) ή πολυμεθακρυλικός αιθυλεστέρας (ΡΕΜΑ) και η C φάση ήταν πολυμεθακρυλικός μεθυλεστέρας (PMMA). Με την ολοκλήρωση της παρούσας διπλωματικής εργασίας, συμπεραίνουμε ότι ο προσεκτικός έλεγχος της μακρο-μοριακής χημείας και ο συνδυασμός της με την μακρο-μηχανική δοκιμή επιτρέπει τον προσδιορισμό όλων των σημαντικών παραμέτρων που επηρεάζουν τη μηχανική συμπεριφορά. Η κατανόηση της επίδρασης των μοριακών παραμέτρων, όπως η επιλογή των κατάλληλων πολυμερών - φάσεων, το ποσοστό συμμετοχής τους καθώς και η αρχιτεκτονική, γραμμική και αστεροειδής διαμόρφωση, στη μηχανική συμπεριφορά είναι δυνατή. Η αστεροειδής αρχιτεκτονική εμφανίζει καλύτερη μηχανική συμπεριφορά από τη γραμμική. Έπειτα, η παρουσία δύο ψαθυρών φάσεων στο ΑnDn, προσδίδουν υψηλό μέτρο ελαστικότητας και αντοχή καθώς και ικανοποιητική ολκιμότητα. Ακόμα, η προσθήκη του PHMA, ως φάση Β επέφερε αυξημένη ολκιμότητα και ικανοποιητική αντοχή / μέτρο ελαστικότητας, ενώ η εισαγωγή του PMMA, ως φάση C στα αστεροειδή συμπολυμερή δεν επέφερε σημαντικές αλλαγές στις μηχανικές ιδιότητες. Τέλος ο αριθμός των κλάδων είχε θετική επίδραση στη μηχανική συμπεριφορά των αστεροειδών. / Block copolymers have recently received much attention not only for the fact that their components are in nano-scale size but also for the various natural and mechanical properties that they present because of their self-organization ability in various morphologies (self–assembly materials). The production process of block copolymers is realized easily, involving factors as the molecular weight, the nanostructure and the composition. In present work were studied and compared the dynamic and static mechanical properties of new copolymers with two and three blocks having linear and star architecture , AB, ABC, AnBn and An(B-b-C)n, as well as the effect of various factors in the properties above. Block copolymers were prepared via “living” anionic polymerization, where the arms of star block copolymers were connected in one core. The phase A was PS, the B phase was PHMA or PEMA proportionally the case and the C phase was PMMA. Finishing of present work, we conclude that the careful control of macromolecular chemistry and her combination with macro-mechanical test allow the determination of all important parameters that influence the mechanical behavior. The comprehension of effect of molecular parameters such as the choice of suitable polymers – phases, the percent of each component and the architecture, linear and star configuration, in the mechanical properties are possible. Star architecture shows better mechanic behavior than linear. Also, the presence of two glassy phases in AnDn gives high strength/ modulus and reasonable ductility. The addition of PHMA as phase B gave an increase in ductility and reasonable strength modulus. Finally, the addition of PMMA, as phase C in star copolymers did not have an important changes while the number of arm had positive effect in the mechanical properties.

In this work the relationships between penetrant structure, its transport properties, and its effects on the mechanical properties of a polymer matrix were investigated. Although there is a vast amount of data on the diffusion of low molecular weight molecules into polymeric materials and on the mechanical properties of various polymer-penetrant systems, no attempts have been made to inter-relate the two properties with respect to the chemical structure of the diffusant. Therefore, two series of penetrants - n-alkanes and esters - were examined in this context, with the goal of correlating molecular size, shape, and chemical nature of the penetrant to its final transport and matrix mechanical properties. These correlations have been demonstrated to allow quantitative prediction of one property, given a reasonable set of data on the other parameters. A series of n-alkanes (C6-C17) and esters (C5-C17) have been used to separate the effects of penetrant size and shape, from those due to polymer-penetrant interactions, in the diffusion through a polyamide polymeric adhesive. These effects have been taken into account in order to yield a qualitative relationship that allows for prediction of diffusivity based upon penetrant structural information. Transport properties have been analyzed using mass uptake experiments as well as an in-situ FTIR-ATR technique to provide detailed kinetic as well as thermodynamic information on this process. The phenomenon of diffusion and its effects on the resulting dynamic mechanical response of a matrix polymeric adhesive have been studied in great detail using the method of reduced variables. The concept of a diffusion-time shift factor (log aDt) has been introduced to create doubly-reduced master curves, taking into account the effects of temperature and the variations in the polymer mechanical response due to the existence of a low molecular weight penetrant. / Ph. D.

<p>Polymers are subjected to physical and chemical changes during their processing, service life, and further recovery, and they may also interact with impurities that can alter their composition. These changes substantially modify the stabilisation mechanisms and mechanical properties of recycled polymers. Detailed knowledge about how the different stages of their life cycle affect the degree of degradation of polymeric materials is important when discussing their further waste recovery possibilities and the performance of recycled plastics. A dual-pronged experimental approach employing multiple processing and thermo-oxidation has been proposed to model the life cycle of recycled high-impact polystyrene (HIPS). Both reprocessing and thermo-oxidative degradation are responsible for coexistent physical and chemical effects (chain scission, crosslinking, apparition of oxidative moieties, polymeric chain rearrangements, and physical ageing) on the microstructure and morphology of polybutadiene (PB) and polystyrene (PS) phases; these effects ultimately influence the long-term stability, and the rheological and mechanical behaviour of HIPS. The PB phase has proved to be the initiation point of HIPS degradation throughout the life cycle. Thermo-oxidation seems to have more severe effects on HIPS properties; therefore, it can be concluded that previous service life may be the part of the life cycle with the greatest influence on the recycling possibilities and performance of HIPS recyclates in second-market applications. The results from the life cycle degradation simulation were compared with those obtained from real samples from a large-scale mechanical recycling plant. A combination of different analytical strategies (thermal analysis, vibrational spectroscopy, and chromatographic analysis) is necessary to obtain a detailed understanding of the quality of recycled HIPS as defined by three key properties: degree of mixing, degree of degradation, and presence of low molecular weight compounds.</p>

This thesis deals with computational modelling of rubber damper using Finite element method (FEM). This thesis includes experimental measurement of material properties of rubber subjected to static and dynamic loading and their implementation into viscoelastic and hyperelastic material models with respect to given task. Dependance of dynamic stiffness on loading frequency obtained from the simulation is validated with experimental measurement. In the end the difference between results is investigated and possible causes of that are introduced.

Polymers are subjected to physical and chemical changes during their processing, service life, and further recovery, and they may also interact with impurities that can alter their composition. These changes substantially modify the stabilisation mechanisms and mechanical properties of recycled polymers. Detailed knowledge about how the different stages of their life cycle affect the degree of degradation of polymeric materials is important when discussing their further waste recovery possibilities and the performance of recycled plastics. A dual-pronged experimental approach employing multiple processing and thermo-oxidation has been proposed to model the life cycle of recycled high-impact polystyrene (HIPS). Both reprocessing and thermo-oxidative degradation are responsible for coexistent physical and chemical effects (chain scission, crosslinking, apparition of oxidative moieties, polymeric chain rearrangements, and physical ageing) on the microstructure and morphology of polybutadiene (PB) and polystyrene (PS) phases; these effects ultimately influence the long-term stability, and the rheological and mechanical behaviour of HIPS. The PB phase has proved to be the initiation point of HIPS degradation throughout the life cycle. Thermo-oxidation seems to have more severe effects on HIPS properties; therefore, it can be concluded that previous service life may be the part of the life cycle with the greatest influence on the recycling possibilities and performance of HIPS recyclates in second-market applications. The results from the life cycle degradation simulation were compared with those obtained from real samples from a large-scale mechanical recycling plant. A combination of different analytical strategies (thermal analysis, vibrational spectroscopy, and chromatographic analysis) is necessary to obtain a detailed understanding of the quality of recycled HIPS as defined by three key properties: degree of mixing, degree of degradation, and presence of low molecular weight compounds. / QC 20101119