Pultrusão é um de vários processos de fabricação de compósitos poliméricos. Seu princípio de funcionamento envolve a utilização de um conjunto de fibras de reforço, impregnadas previamente por uma resina polimérica termorrígida, que percorre o interior de uma matriz aquecida a fim curar a resina e dar o formato a um perfil sólido. Muitas variáveis de processo, tais como a temperatura das zonas de aquecimento sobre a matriz, a velocidade de tracionamento, a impregnação das fibras, a viscosidade da resina, entre outras, afetam a eficiência do processo assim como a qualidade e o desempenho dos compósitos. Neste estudo, foi investigada a influência do teor de fibra de vidro, do teor de carbonato de cálcio e da temperatura do reservatório de resina nas propriedades mecânicas, como a resistência à tração, o módulo de elasticidade, o alongamento até a ruptura e a dureza de barras sólidas circulares que foram fabricadas utilizando uma resina poliéster insaturada e um único peróxido orgânico. Foi constatado que o processo de pultrusão pode ser realizado utilizando um único iniciador de reação. Além disto, os resultados mostraram que a temperatura do reservatório de resina, o teor de carbonato de cálcio e o teor de fibra de vidro influenciaram de forma significativa nas propriedades das barras pultrudadas. Por fim, este estudo mostrou que é possível melhorar as características destes compósitos e, desta forma, desenvolver materiais que apresentem melhor qualidade e desempenho. / Pultrusion is one of several manufacturing processes of polymer composites. Its operating principle involves the use of a set of reinforcing fibers pre-impregnated with a thermoset resin which run through the interior of a heated die in order to cure the resin and to form a solid profile. Many processing variables such as die temperature, pulling speed, fiber impregnation, resin viscosity, among others, affect the process efficiency as well as the quality and performance of the pultruded composites. In this research, the influence of the glass fiber content, calcium carbonate content and the temperature of the resin bath on the mechanical properties, such as tensile strength, elastic modulus, elongation at break and superficial hardness of solid rods made with an unsaturated polyester resin and a single organic peroxide were investigated. It was observed that pultrusion process can be carried out using a single reaction initiator. In addition, the results showed that the temperature of the resin bath, the calcium carbonate and the glass fiber content have influenced significantly in the properties of the solid rods. Finally, this study showed that it is possible to improve the characteristics of such composites and, therefore, to develop materials that have good quality and performance.

abstract: Soft polymer composites with improved thermal conductivity are needed for the thermal management of electronics. Interfacial thermal boundary resistance, however, prevents the efficient use of many high thermal conductivity fill materials. Magnetic alignment of ferrous fill material enforces percolation of the high thermal conductivity fill, thereby shifting the governing boundary resistance to the particle- particle interfaces and increasing the directional thermal conductivity of the polymer composite. Magnetic alignment maximizes the thermal conductivity while minimizing composite stiffening at a fill fraction of half the maximum packing factor. The directional thermal conductivity of the composite is improved by more than 2-fold. Particle-particle contact engineering is then introduced to decrease the particle- particle boundary resistance and further improve the thermal conductivity of the composite. The interface between rigid fill particles is a point contact with very little interfacial area connecting them. Silver and gallium-based liquid metal (LM) coatings provide soft interfaces that, under pressure, increase the interfacial area between particles and decrease the particle-particle boundary resistance. These engineered contacts are investigated both in and out of the polymer matrix and with and without magnetic alignment of the fill. Magnetically aligned in the polymer matrix, 350nm- thick silver coatings on nickel particles produce a 1.8-fold increase in composite thermal conductivity over the aligned bare-nickel composites. The LM coatings provide similar enhancements, but require higher volumes of LM to do so. This is due to the rapid formation of gallium oxide, which introduces additional thermal boundaries and decreases the benefit of the LM coatings. The oxide shell of LM droplets (LMDs) can be ruptured using pressure. The pressure needed to rupture LMDs matches closely to thin-walled pressure vessel theory. Furthermore, the addition of tungsten particles stabilizes the mixture for use at higher pressures. Finally, thiols and hydrochloric acid weaken the oxide shell and boost the thermal performance of the beds of LMDs by 50% at pressures much lower than 1 megapascal (MPa) to make them more suitable for use in TIMs. / Dissertation/Thesis / Doctoral Dissertation Mechanical Engineering 2019

Because of increasing environmental demands, especially on dealing with products end of life phase, product manufacturers and designers must consider the future disposal of their products. For conventional materials like steel and aluminium well-functioning recycling methods exists. This is not the case for structures of polymer composites, which are used more extensively, especially for structures like vehicles and vessels. Several techniques do exist but they are not yet commercially available. The current disposal methods of polymer composites are landfill and incineration. Polymer composites are materials, which consist of several materials like fibre, matrix, and additives. In the form of sandwich constructions also foam core material is added. This circumstance complicates the waste treatment of composite materials. In this thesis a model for assessing possible future waste treatment techniques for polymer composites including sandwich structures is presented. The model is meant to be used as an aid for preparing future disposal for end of life products for planning waste treatment and for facilitating communication in contacts with waste receivers. Recommendations for waste treatment have been formed for a number of polymer composites. These recommendations are based on the analysis of costs and environmental effects and they compare different scenarios for mechanical material recycling and energy recovery by waste incineration. The result of this study points out material recycling as the preferable method for the main part of the studied materials. But this recommendation is strongly dependent on type of virgin material replaced by the recycled material. Energy recovery can also be considered if the polymer composite waste replaces coal, which is non renewable. Though incineration will always result in a cost for the waste producer. In the recommendations mentioned above no information concerning implementation of the different waste disposal techniques is included. Therefore, in this study a model for assessing possible waste disposal techniques for polymer composites is presented. The model is based on internal factors, which are related to the waste and to the processes. To implement the model relevant waste properties must be identified in order to fulfil the conditions set by the required processes involved. A case study was carried out using the proposed model for assessing different waste disposal techniques for the hull of the Visby Class Corvette in the Royal Swedish Navy. Six different techniques were studied for the hull structure. Since almost all the important waste properties were known and the waste was assessed to be treatable all the included techniques except one are shown to be usable in the future. Many investigations have pointed out material recycling as the best alternative considering environmental effects. This is also valid for polymer composite materials. Since recycling polymer composites is a complicated process, especially recycling thermoset composite it is important to aquire comprehensive information about the constituents of these materials. / QC 20101021

This thesis research investigates the adhesion mechanisms of protein molecules to surfaces of biomaterials. New understanding in such adhesion mechanisms will lead to materials design and surface engineering in order to extend the lifespan of implants. The present research evaluates and analyzes the adhesive strength of proteins on pure High Density Polyethylene (HDPE), Single Wall Carbon Nanotube (SWCNT) enhanced HDPE composites, Ti-C:H coating and Ti6Al4V alloys (grade 2). The adhesive strength was studied through fluid shear stress and the interactions between the fluid and material surfaces. The adhesive strength of protein molecules was measured through the critical shear strength that resulted through the fluid shear stress. The effects of surface and material properties, such as roughness, topography, contact angle, surface conductivity, and concentration of carbon nanotubes on adhesion were analyzed. Research results showed that the surface roughness dominated the adhesion. Protein was sensitive to micro-scale surface roughness and especially favored the nano-porous surface feature. Results indicated that the unpurified SWCNTs influenced crystallization of HDPE and resulted in a nano-porous structure, which enhanced the adhesion of the protein onto a surface. Titanium hydrocarbon coating on silicon substrate also had a porous topography which enhanced its adhesion with protein, making it superior to Ti6Al4V.

This thesis employs a finite element (FE) method for numerically simulating the mechanical response of constituents in a fiber-reinforced polymer (FRP) composite to indentation. Indentation refers to a procedure that subsumes a rigid indenter of specific geometry to impress the surface of a relatively softer material, with a view of estimating its mechanical properties. FE analyses are performed on a two-dimensional simplified microstructure of the FRP composite comprising perfectly bonded fiber, interphase and matrix sections. Indentation response of the constituents is first examined within the context of linearized elasticity. Time-dependent response of the polymer matrix is invoked by modeling the respective constituent section as a linear isotropic viscoelastic material. Furthermore, indentation responses to non-mechanical stimulus, like moisture absorption, is also simulated through a sequentially coupled analysis. A linear relationship describing the degradation of elastic moduli of the individual constituents with increasing moisture content has been assumed. The simulations subsume a point load idealization for the indentation load eventually substituted by indenter tips with conical and spherical profiles. Results from FE analyses in the form of load-displacement curves, displacement contours and stress contours are presented and discussed. With the application of concentrated load on linearly elastic constituents for a given/known degree of heterogenity in the FRP, simulations indicated the potential of indentation technique for determining interphase properties in addition to estimating the matrix-fiber interphase bond strength. Even with stiffer surrounding constituents, matrix characterization was rendered difficult. However, fiber properties were found to be determinable using the FE load-displacement data, when the load-displacement data from experimentation is made available. In the presence of a polymer (viscoelastic) matrix, the surrounding elastic constituents could be characterized for faster loading rates when viscoelastic effects are insignificant. Displacements were found to be greater in the presence of a polymer matrix and moisture content in comparison with a linearly elastic matrix and dry state. As one would expect, the use of different indenter tips resulted in varying responses. Conical tips resulted in greater displacements while concentrated load produced greater stresses. Further it was found that, despite the insignificant effects due to surrounding constituents, analytical (Flamant) solution for concentrated, normal force on a homogeneous, elastic half-plane becomes inapplicable in back calculating the elastic moduli of individual FRP constituents. This can be attributed to the finite domain and the associated boundary conditions in the problem of interest.

The aim of this study was to improve electrical properties of conductive polymer composites. For this purpose, various studies were performed using different materials in this dissertation. In order to investigate the effect of alternative composite preparation methods on electrical conductivity, nylon 6/carbon black systems were prepared by both in-situ polymerization and melt-compounding techniques. When compared with melt compounding, in-situ polymerization method provided enhancement in electrical conductivity of nylon 6 composites. Furthermore, it was aimed to improve electrical conductivity of polymer composites by modifying surface chemistry of carbon black. 1 wt. % solutions of 3-Aminopropyltriethoxysilane and formamide were tried as chemical modifier, and treated carbon black was melt mixed with low-density polyethylene (LDPE) and nylon 6. According to electron spectroscopy for chemical analysis (ESCA), chemicals used for surface treatment may have acted as doping agent and improved electrical conductivity of polymer composites more than untreated carbon black did. Formamide was more effective as dopant compared to the silane coupling agent. In order to investigate electromagnetic interference (EMI) shielding effectiveness and dielectric properties of conductive polymer composites, 1, 2 and 3 wt. % solutions of formamide were tried as chemical modifier and treated carbon black was melt mixed with poly(ethylene terephthalate) (PET). Composites containing formamide treated carbon black exhibited enhancement in electrical conductivity, EMI shielding effectiveness and dielectric constant values compared to composites with untreated carbon black. In order to enhance electrical conductivity of polymer composites, the selective localization of conductive particles in multiphase polymeric materials was aimed. For this purpose, carbon nanotubes (CNT) were melt mixed with polypropylene (PP)/PET. Grinding, a type of solid state processing technique, was applied to PP/PET/CNT systems to reduce the average domain size of blend phases and to improve interfacial adhesion between these phases. Grinding technique exhibited improvement in electrical conductivity and mechanical properties of PP/PET/CNT systems at low PET compositions. To investigate application potential of conductive polymer composites, polyaniline (Pani)/carbon nanotubes (CNT) composites were synthesized and electrochemical capacitance performances of these systems, as electrode material in electrochemical capacitors, were studied. Polyaniline/carbon nanotubes composites resulted in a higher specific capacitance than that of the composite constituents. Pseudocapacitance behavior of Pani might contribute to the double layer capacitance behavior of nanotubes. Additionally, as an alternative to Pani/CNT systems, polyaniline films were deposited on treated current collectors and electrochemical capacitance performances of these electrode systems were investigated. The highest specific capacitance of polyaniline/carbon nanotubes composites was 20 F/g and this value increased to 35.5 F/g with polyaniline film deposited on treated current collector.

Inorganic-polymer hybrid materials have a high potential to enable major advances in material performance in a wide range of applications. This research focuses on characterizing and tailoring the physics and chemistry of inorganic-polymer interfaces in fabricating high-performance zeolite-polymer mixed-matrix membranes for energy-efficient gas separations. In addition, the topic of novel metal nanoparticle-coated polymer microspheres for optical applications is treated in the Appendix. In zeolite/polymer mixed-matrix membranes, interfacial adhesion and interactions between dope components (zeolite, polymer and solution) play a crucial role in determining interfacial morphology and particle dispersion. The overarching goal is to develop accurate and robust tools for evaluating adhesion and interactions at zeolite-polymer and zeolite-zeolite interfaces in mixed-matrix membrane systems. This knowledge will be used ultimately for selecting proper materials and predicting their performance. This project has two specific goals: (1) development of an AFM methodology for characterizing interfacial interactions and (2) characterization of the mechanical, thermal, and structural properties of zeolite-polymer composites and their correlation to the zeolite-polymer interface and membrane performance. The research successfully developed an AFM methodology to determine interfacial interactions, and these were shown to correlate well with polymer composite properties. The medium effect on interactions between components was studied. We found that the interactions between two hydrophilic silica surfaces in pure liquid (water or NMP) were described qualitatively by the DLVO theory. However, the interactions in NMP-water mixtures were shown to involve non-DLVO forces arising from bridging of NMP macroclusters on the hydrophilic silica surfaces. The mechanism by which nanostructured zeolite surfaces enhanced in zeolite-polymer interfacial adhesion was demonstrated to be reduced entropy penalties for polymer adsorption and increased contact area. ¡¡¡¡¡¡Metal nanoparticle (NP)-coated polymer microspheres have attracted intense interest due to diverse applications in medical imaging and biomolecular sensing. The goal of this project is to develop a facile preparation method of metal-coated polymer beads by controlling metal-polymer interactions. We developed and optimized a novel solvent-controlled, combined swelling-heteroaggregation (CSH) technique. The mechanism governing metal-polymer interaction in the fabrication was determined to be solvent-controlled heteroaggregation and entanglement of NPs with polymer, and the optical properties of the metal/polymer composite beads were shown to make them useful for scattering contrast agent for biomedical imaging and SERS (Surface-Enhanced Raman Scattering) substrates.

The UV-Visible spectra of a-C composites and nano composites have provided a very useful information about the electronic states and band structure. The UV-Visible spectra of a-C as well as nanoparticle are qualitatively similar. They do not show any absorption cutoff in wavelength (_max). In fact they are good absorbers of UV-Visible light in whole range. Composites show some absorptions which could be the combined effect of filler as we as host matrix. Since there is no _max, hence it is very unlikely to define any optical band gap. The nanoparticle is a good absorber in midinfrared compared to a-C. That may be due to presence of complicated kind of vibrational modes of carbon cased nanoparticle.Besides Fe3C also produces some additional modes. With kind of spectrum we have it is difficult to identify the different modes unambiguously for nanoparticle. The combined effects of filler as well as host polymer are reflected in both sets of composites. A new absorption is observed in a-C as well as in nanoparticle composites at 2370 cm−1 and 3462 cm−1 respectively. This peak may arise in composites due to interaction between filler and host matrix. The thermo gravimetric analysis is a useful characterization techniques for polymer and composites. It gives the information about the stability, phase change, degradation, chemical reaction and many more. The a-C composites as well as nano composites are stable up to 200_ C. These composites can be safely used for any practical purpose below this temperature. During the synthesis of composites the filler does not take part in any reaction. This fact is reflected in the DTG curve. The composites degrade in the way host polymer degrades.

<p>Because of increasing environmental demands, especially on dealing with products end of life phase, product manufacturers and designers must consider the future disposal of their products. For conventional materials like steel and aluminium well-functioning recycling methods exists. This is not the case for structures of polymer composites, which are used more extensively, especially for structures like vehicles and vessels. Several techniques do exist but they are not yet commercially available. The current disposal methods of polymer composites are landfill and incineration.</p><p>Polymer composites are materials, which consist of several materials like fibre, matrix, and additives. In the form of sandwich constructions also foam core material is added. This circumstance complicates the waste treatment of composite materials. In this thesis a model for assessing possible future waste treatment techniques for polymer composites including sandwich structures is presented. The model is meant to be used as an aid for preparing future disposal for end of life products for planning waste treatment and for facilitating communication in contacts with waste receivers.</p><p>Recommendations for waste treatment have been formed for a number of polymer composites. These recommendations are based on the analysis of costs and environmental effects and they compare different scenarios for mechanical material recycling and energy recovery by waste incineration. The result of this study points out material recycling as the preferable method for the main part of the studied materials. But this recommendation is strongly dependent on type of virgin material replaced by the recycled material. Energy recovery can also be considered if the polymer composite waste replaces coal, which is non renewable. Though incineration will always result in a cost for the waste producer.</p><p>In the recommendations mentioned above no information concerning implementation of the different waste disposal techniques is included. Therefore, in this study a model for assessing possible waste disposal techniques for polymer composites is presented. The model is based on internal factors, which are related to the waste and to the processes. To implement the model relevant waste properties must be identified in order to fulfil the conditions set by the required processes involved.</p><p>A case study was carried out using the proposed model for assessing different waste disposal techniques for the hull of the Visby Class Corvette in the Royal Swedish Navy. Six different techniques were studied for the hull structure. Since almost all the important waste properties were known and the waste was assessed to be treatable all the included techniques except one are shown to be usable in the future.</p><p>Many investigations have pointed out material recycling as the best alternative considering environmental effects. This is also valid for polymer composite materials. Since recycling polymer composites is a complicated process, especially recycling thermoset composite it is important to aquire comprehensive information about the constituents of these materials.</p>

Τα σύνθετα υλικά πολυμερικής μήτρας - ανόργανων/κεραμικών εγκλεισμάτων ελκύουν όλο και περισσότερο το ενδιαφέρον χάρη στο ευρύ φάσμα των εφαρμογών. Ως σύνθετο υλικό ορίζεται το υλικό το οποίο αποτελείται από τουλάχιστον 2 διαφορετικές διακριτές μεταξύ τους φάσεις. Συνδυάζοντας τις ιδιότητες της μήτρας και του εγκλείσματος έχουμε ένα υλικό με νέες ιδιότητες. Οι ηλεκτρικές ιδιότητες των σύνθετων υλικών πολυμερικής μήτρας τους δίνουν σημαντικό ρόλο στην βιομηχανία της μικροηλεκτρονικής καθώς μπορούν να χρησιμοποιηθούν σαν διηλεκτρικά υλικά σε συσκευές αποθήκευσης ενέργειας, σαν στοιχεία κυκλωμάτων αλλά και σαν μονωτές παρεμβολών ηλεκτρομαγνητικής ακτινοβολίας Στην παρούσα εργασία χρησιμοποιήθηκε ως μήτρα εποξειδική ρητίνη και σαν έγκλεισμα καρβίδιο του Βορίου ( Β4C). To Β4C είναι το τρίτο σκληρότερο υλικό, μετά το διαμάντι και το κυβικό νιτρίδιο του Βορίου, έχει χαμηλή πυκνότητα και πολύ καλές μηχανικές ιδιότητες. Μέχρι πρότινος χρησιμοποιούταν κυρίως σε πλάκες θωράκισης και σαν απορροφητικό νετρονίων στην πυρηνική βιομηχανία αλλά τελευταίες μελέτες υποδεικνύουν και πολύ καλές ηλεκτρικές ιδιότητες και χρήση στην μόνωση παρεμβολών ηλεκτρομαγνητικής ακτινοβολίας. Στην παρούσα εργασία παρασκευάστηκαν 6 δοκίμια εποξειδικής ρητίνης και B4C, με μεταβαλλόμενη συγκέντρωση της εγκλεισμένης φάσης, έτσι ώστε να εξεταστεί εμπεριστατωμένα η σχέση -συγκέντρωσης εγκλεισμένης φάσης και ηλεκτρικών ιδιοτήτων-. Για τον διηλεκτρικό χαρακτηρισμό των δοκιμίων χρησιμοποιήθηκε διάταξη Διηλεκτρικής Φασματοσκοπίας (Broadband Dielectric Spectroscopy) με μεταβαλλόμενη θερμοκρασία στον χώρο μετρήσεων. Το εύρος συχνοτήτων στο οποίο έλαβε χώρα το πείραμα ήταν 10-1 - 107 Hz και το θερμοκρασιακό εύρος 30oC-160oC. Τα αποτελέσματα του ηλεκτρικού χαρακτηρισμού υποδηλώνουν την ύπαρξη τριών διεργασιών, στο εξεταζόμενο φάσμα συχνοτήτων. Στις υψηλές συχνότητες είχαμε την εμφάνιση της διεργασίας της β-χαλάρωσης, η οποία σχετίζεται με τον επαναπροσανατολισμό των πλευρικών πολικών ομάδων της πολυμερικής αλυσίδας, στις μεσαίες συχνότητες είχαμε την εμφάνιση της α-χαλάρωσης, η οποία σχετίζεται με την μετάπτωση από την υαλώδη στην ελαστομερική φάση της πολυμερικής μήτρας και τέλος στις χαμηλές συχνότητες παρατηρήθηκε το φαινόμενο Maxwell-Wagner-Sillars το οποίο σχετίζεται με την διεπιφανειακή πόλωση. / Nowadays, polymer matrix composites filled with inorganic/ceramic inclusions gather the scientific interest because of their vast uses in numerous applications. A composite refers to a materials system that consists of at least two different separated phases. Combining the properties of the matrix and the filler we achieve a material with superior properties than that of its constituents. The electrical properties of polymer matrix composites give them a significant position in the microelectronics industry because of their potential applications such as energy storage devices, welding elements in circuit and electromagnetic interference shielding. In the present study as a matrix was used a commercially available epoxy resin and as a filler Boron carbide (B4C) in the form of powder. Boron carbide is the third hardest material on earth after diamond and cubic Boron nitride, with low density and excellent mechanical properties. Until recently Boron carbide was used primarily in armor plates and as a neutron absorber in the nuclear industry but latest studies suggest interesting electrical properties and possible applications in the electromagnetic interference shielding. In this study 6 epoxy resin – Boron carbide specimens were manufactured, varying the concentration of the encapsulated phase, in order to investigate thoroughly the dependence of the filler content in the presented results. For the dielectric characterization of the specimens we used a Broadband Dielectric Spectroscopy device varying the frequency (10-1 - 107 Hz) and temperature range (30oC-160oC). The results of the dielectric characterization suggest the existence of three distinct relaxation processes which can be attributed to the interfacial polarization, known as Maxwell-Wagner-Sillars effect, glass to rubber transition and reorientation of polar side groups of the polymeric matrix.