Made available in DSpace on 2014-10-09T12:51:14Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:10:05Z (GMT). No. of bitstreams: 1 11258.pdf: 15838745 bytes, checksum: 72b615533f5974e7ef5317e6caf1b388 (MD5) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

abstract: Precursors of carbon fibers include rayon, pitch, and polyacrylonitrile fibers that can be heat-treated for high-strength or high-modulus carbon fibers. Among them, polyacrylonitrile has been used most frequently due to its low viscosity for easy processing and excellent performance for high-end applications. To further explore polyacrylonitrile-based fibers for better precursors, in this study, carbon nanofillers were introduced in the polymer matrix to examine their reinforcement effects and influences on carbon fiber performance. Two-dimensional graphene nanoplatelets were mainly used for the polymer reinforcement and one-dimensional carbon nanotubes were also incorporated in polyacrylonitrile as a comparison. Dry-jet wet spinning was used to fabricate the composite fibers. Hot-stage drawing and heat-treatment were used to evolve the physical microstructures and molecular morphologies of precursor and carbon fibers. As compared to traditionally used random dispersions, selective placement of nanofillers was effective in improving composite fiber properties and enhancing mechanical and functional behaviors of carbon fibers. The particular position of reinforcement fillers with polymer layers was enabled by the in-house developed spinneret used for fiber spinning. The preferential alignment of graphitic planes contributed to the enhanced mechanical and functional behaviors than those of dispersed nanoparticles in polyacrylonitrile composites. The high in-plane modulus of graphene and the induction to polyacrylonitrile molecular carbonization/graphitization were the motivation for selectively placing graphene nanoplatelets between polyacrylonitrile layers. Mechanical tests, scanning electron microscopy, thermal, and electrical properties were characterized. Applications such as volatile organic compound sensing and pressure sensing were demonstrated. / Dissertation/Thesis / Masters Thesis Materials Science and Engineering 2020

Carbon concrete polyacrylonitrile (PAN)/lignin-based carbon fiber (CF) composites are a new promising material class for the building industry. The replacement of the traditional heavy and corroding steel reinforcement by carbon fiber (CF)-based reinforcements offers many significant advantages: a higher protection of environmental resources because of lower CO2 consumption during cement production, a longer lifecycle and thus, much less damage to structural components and a higher degree of design freedom because lightweight solutions can be realized. However, due to cost pressure in civil engineering, completely new process chains are required to manufacture CF-based reinforcement structures for concrete. This article describes the necessary process steps in order to develop CF reinforcement: (1) the production of cost-effective CF using novel carbon fiber lines, and (2) the fabrication of CF rebars with different geometry profiles. It was found that PAN/lignin-based CF is currently the promising material with the most promise to meet future market demands. However, significant research needs to be undertaken in order to improve the properties of lignin-based and PAN/lignin-based CF, respectively. The CF can be manufactured to CF-based rebars using different manufacturing technologies which are developed at a prototype level in this study.

M. Tech. (Mechanical Engineering, Faculty of Engineering and Technology), Vaal University of Technology. / The purpose of this study was to design a composite overwrapped pressure vessel by combining the best optimal structural options. This study investigated the effects of constituents such as fibre and shell thickness, on the bursting strength. Thereafter, these constituents were combined in order to achieve optimization of strength for an improved sustainable composite pressure vessel. The analytical method was carried out using the Tsai-wu failure theorem. The developed analytical equations were solved with Matlab 2016 software to determine composite fibre and shell thickness. With variation of the vessel’s liner, a total of 56 parts were created on two different profiles with purpose of generating of vessels resistant to bursting failure. Henceforth, the structural integrity of fibre imparted into the design was optimally analyzed at an angle of 55⁰, through the negative and positive directions. The shell thickness overwrapping the liner, being as well an influential factor to this optimization, was, therefore, analyzed on symmetrical and asymmetrical lamination patterns. The optimal fibre and shell thickness range were thereafter determined on a first ply failure and hoop stress threshold approach. Additionally, the identified optimal range of pressure vessel constituents were numerically validated, on Abaqus/CAE software, to have a degree of reassurance on the result generated, using Hashin failure criteria. Optimal design with improved strength and weight factor was therefore achieved by combining the generated optimal vessel constituents yielded from Minitab software version 2016. The generated results of the study revealed no change on the fibre thickness determined with respect to direction. For shell thickness on the other hand, asymmetrical pattern was identified as the desired sequence of lamination. In addition, with two profiles considered in the research, the composite constituents were found for a p value of 0.066, to be optimal on profile 1 at 0.0048 mm of liner, 0.0005 mm of fibre and 0.0027 mm of shell. The profile 2 on the other hand, revealed optimization of liner at 0.0095 mm, fibre at 0.0021 mm and shell at 0.0055 mm. Through combination of these ultimate constituents the response optimizer on Minitab software generated optimal bursting strength with factor of 4% improvement with a weight reduction of 33% compared to the stainless steel vessel. It was, therefore, concluded that profile 1 was the most optimal with hoop strength of 123.43 MPa, Von Mises of 178.56 MPa and Tresca of 179.48 MPa.

D. Tech. (Department of Mechanical Engineering, Faculty of Engineering and Technology), Vaal University of Technology. / On account of their lightweight, low-cost, corrosion resistance, and good formability, conductive polymer composites (CPCs) are promising for the production bipolar plate (BP) for polymer electrolyte membrane fuel cell (PEMFC). However, a high conductive filler loading is needed to impart the required level of electrical conductivity to the insulating polymer matrix and as a consequence, the toughness of the plate deteriorates considerably. By using immiscible blend of polymers that have complementary hardness and ductility as matrix, with conducting multi-fillers of different morphologies, it is possible to optimize the matrix strength characteristics and favour the formation of conducting network to produce CPC meeting BP performance standards. Of course, a lot will depend on the formulation of the most favourable composition and production variables. In this regard, polypropylene-epoxy and polyethylene-epoxy blends, filled with zero- and two-dimensional carbon forms – graphite, carbon black (CB), and graphene (Gr) – were investigated over an extensive range of compositions and compression moulding pressures, in this study. Several compounding runs (using melt mixing), at different stages, followed by compression molding, were done. The goal is to obtain combination of composite formulation and processing conditions that will produce the most promising combination of properties for BP application. In the first stage of the investigations, by using thermogravimetric analysis, two-stage decomposition behavior of PP-epoxy and PE-epoxy blends was revealed, which confirms the immiscibility of PP and PE with epoxy resin. Scanning electron microscope (SEM) micrographs of the PP-epoxy and PE-epoxy blends revealed a co-continuous structure, which can be attributed to the close-to-symmetric composition of the blend and compatibilizers added. Preferential localization of synthetic graphite (SG), CB, and Gr in the polymer blends was also revealed by the SEM micrographs. This confirms the fact that CPCs based on PP-epoxy and PE-epoxy blends can be explored further. PP-epoxy and PE-epoxy blends filled with only SG, 30 – 80 wt %, were produced and characterized for their electrical conductivity and flexural properties. In-plane electrical conductivity ranged from 12.09 to 68.03 Scm-1 for PP-epoxy/SG and 11.68 to 72.96 Scm-1 for PE-epoxy/SG composites produced. These are higher than values reported for several single matrix polymer composites at similar filler loadings. With reference to the United States Department of Energy performance targets for BPs, PE-epoxy/SG composites performed better in terms of electrical conductivity, while PP-epoxy/SG composites exhibited better flexural properties. Thereafter, using SG and CB double filler, PE-epoxy/SG/CB composites performed better than PP-epoxy/SG/CB composites in terms of electrical conductivity, while PP-epoxy/SG/CB composites exhibited superior flexural properties than the PE-epoxy/SG/CB composites at similar filler loadings. However, with respect to the DOE targets, composites based on PP-epoxy blend exhibited a more promising combination of electrical conductivity and flexural properties than PE-epoxy blend matrix. PP-epoxy filled with SG/CB was studied further, by using graphene (Gr) as second minor filler. In-plane and through plane electrical conductivities as well as thermal conductivity and thermal diffusivity of the PP-epoxy/SG/CB/Gr composites increased as total filler content was increased from 65 to 85 wt%. It implies that more conductive networks between filler particles were formed. Also, flexural strength, flexural modulus, and impact strength decreased as the total filler content increased from 65 to 85 wt%. The reduced flexural properties could be due to increased agglomeration of CB and Gr, and poor filler wetting at higher filler loadings and low matrix material, which leads to the formation of microvoids and a reduction of the load bearing capacity of composites. With respect to the DOE targets, PP-EP/SG/CB/Gr composite with 80 wt% (i.e., PP/EP/73G/6.2CB/0.8Gr) filler has the best combination of properties. Further improvement in properties of the PP-EP/SG/CB/Gr composite with 80 wt% filler was achieved by molding at higher pressures. As molding pressure was increased from 4.35 to 13.05 MPa, in-plane electrical conductivity increased from 116.31 to 144.99 Scm-1, while flexural strength increased from 29.62 to 42.57 MPa, satisfying the performance requirement targets for bipolar plates.

An electrophoretic deposition (EPD) process of micro-quartz (MQ) powder is applied to carbon fibers (CFs) with the aim to enhance their interfacial bond to cementitious matrices and to investigate its influence on the microstructural and mechanical properties of the CFs itself. The electrophoretic mobility of the MQ particles with negative charge in aqueous media was confirmed by potential sweep experiments and zeta-potential measurements. High amounts of MQ were successfully deposited onto the fiber surface, as proven by scanning electron microscopy. Single-fiber tension tests and thermogravimetric analysis showed that EPD treatment had little impact on the tensile properties and thermal stability of the modified fibers. However, storing the CFs in cement pore solution impaired temperature stability of untreated and modified fibers. X-ray diffraction and Raman spectroscopy reveal specific changes of CF's microstructure upon EPD treatment and immersion in pore solution. Single-fiber pullout tests showed that the pullout resistance of MQ-modified CFs was enhanced, relative to untreated CFs. This augmentation can be explained by an enhanced interlocking mechanisms between CF and matrix due to the deposited quartz particles on the CF surface.

The use of Fibre Reinforced Polymer (FRP) composite materials in structural applications has increased in the past decades in high­performance sectors, such as in the automotive and aeronautic industries, for weight reduction purposes. However, FRP composite materials can offer more significant innovation potential. The application of CNTs in conjunction with composite material can allow the creation of multifunctional materials, relying on FRP for the structural side and CNT for the sensing ability. In this master thesis, the embedment of a Vertical Aligned Carbon Nanotube (VACNT) layer into the interlaminar region of Carbon Fibre (CF) laminates to provide polyvalent sensing ability to the material was investigated. In order to obtain accurate results, the sensor had to be isolated from the rest of the laminate. For this reason, the main problem to be solved in this project was the electrical isolation on the CNT layer and its contacts from the layers of CF laminate. This study aims to find a suitable isolation technique in order to apply the CNT sensor technology, developed in previous studies, into CF laminate. Although thought for aerospace applications, these sensors could be applied to different structural components in various fields. / Användningen av fiberförstärkta polymerer (FRP)-­kompositmaterial i strukturella applikationer har ökat under de senaste decennierna i högpresterande sektorer, såsom i fordons­ och flygindustrin, för viktminskningsändamål. FRP-­kompositmaterial kan dock erbjuda mer betydande innovationspotential. Användningen av CNTs i kombination med kompositmaterial kan möjliggöra skapandet av multifunktionella material, beroende på FRP för den strukturella sidan och CNT för avkänningsförmågan. I denna masteruppsats undersöktes inbäddningen av ett Vertical Aligned Carbon Nanotube (VACNT) lager i den interlaminära regionen av Carbon Fiber (CF) laminat för att ge polyvalent avkänningsförmåga till materialet. För att få exakta resultat måste sensorn isoleras från resten av laminatet. Av denna anledning var huvudproblemet som skulle lösas i detta projekt den elektriska isoleringen på CNT-­lagret och dess kontakter från lagren av CF­-laminat. Denna studie syftar till att hitta en lämplig isoleringsteknik för att tillämpa CNT­sensorteknologin, utvecklad i tidigare studier, i CF-­laminat. Även om de är tänkta för flygtillämpningar, kan dessa sensorer appliceras på olika strukturella komponenter inom olika områden.

Fiber-metal laminates (FML) are the advanced materials that are developed to improve the high performance of lightweight structures that are rapidly becoming a superior substitute for metal structures. The reasons behind their emerging usage are the mechanical properties without a compromise in weight other than the traditional metals. The bond remains a concern. This thesis reviews the effect of pre-treatments, say heat, P2 etch and laser treatments on the substrate which modifies the surface composition/roughness to impact the bond strength. The constituents that make up the FMLs in our present study are the Aluminum 2024 alloy as the substrate and the carbon fiber prepregs are the fibers. These composite samples are manufactured in a compression molding process after each pre-treatment and are then subjected to different tests to investigate its properties in tension, compression, flexural and lap shear strength. The results indicate that heat treatment adversely affects properties of the metal and the joint while laser treatments provide the best bond and joint strength.

Carbon Fiber / Epoxy Laminates are increasingly being used in the primary structure of aircraft. To make effective use these materials, it is necessary to consider the ability of a laminate to resist damage, as well as material strength and stiffness. A possible means for improving damage tolerance is the use of non-traditional composite laminates, in which the longitudinal 0 plies are replaced with 5 or 10 plies. The main objectives of this collaborative Georgia Tech / Boeing research was the characterization of these non-traditional laminates, and the determination of appropriate lamina-level analytical techniques that are capable of predicting the changes caused by the use of slightly off-axis longitudinal plies. A quasi-isotropic [45/90/-45/theta/45/90/-45/-theta]s and hard [45/theta/-45/theta/90/45]s lay-up, where theta =0,5 or 10, were tested in open hole tension, filled hole tension, open hole compression, single shear bearing, and unnotched tension. These coupon level tests illustrated the effects of lay-up, notch constraint, and load type on traditional and non-traditional laminates. Die penetrant enhanced in-situ radiography was performed to determine the extent of damage suppression. The use of non-traditional laminates was found to reduce longitudinal ply cracking and delamination, with significant effect on the stress distribution around the notch. The use of non-traditional laminates also resulted in a 15%-20% improvement in bearing strength of the traditional laminates. Several predictive techniques were implemented to evaluate their ability to predict the effect of slight changes in ply orientations. A progressive damage model was written to compare Tsai-Wu, Hashin, and Maximum Stress unnotched strength criterion. Additionally, several semi-empirical failure theories for notched strength prediction were compared with linear and bi-linear cohesive zone models to determine applicability to non-traditional laminates.

Le travail présenté dans ce mémoire de thèse s’est inscrit dans le cadre du développement de la technologie flamme oxyacétylénique pour la synthèse de nanotubes de carbone (NTC) au Laboratoire de Physique et Mécanique Textile. La simplicité et l’originalité de ce procédé en font un candidat très sérieux pour envisager la mise en œuvre d’un pilote industriel pour la production de fibres de renforcement multidimensionnelles, notamment composées de fibres de carbone sur lesquelles ont cru de nanotubes de carbone. Ce travail a consisté à :- Réaliser une étude bibliographique sur les procédés de croissance de NTC,- Etablir la preuve de concept de la croissance des nanotubes sur des fibres,- Concevoir et réaliser un dispositif assurant une bonne maîtrise de la croissance,- Mettre au point le procédé de croissance sur des fibres,- Identifier les principaux paramètres influençant la qualité et la quantité des nanotubes,- Caractériser les nanotubes obtenus,- Faire croître ces nanotubes sur des fibres de carbone,- Intégrer des nouveaux matériaux multidimensionnels dans des matrices afin de réaliser des matériaux composites structurels,- Caractériser ces matériaux,- Décrire les mécanismes de croissance dans la flamme.Notre effort a porté sur le traitement des fibres avant exposition à la flamme et à évaluer les conditions de croissance des NTC en faisant varier notamment, la température d’exposition des fibres et la qualité des catalyseurs de croissance. Après synthèse des NTC sur les fibres de carbone et leur caractérisation nous avons réalisé des matériaux composites. Nous avons mesuré que les NTC améliorent significativement le module d’Young des composites mais altèrent sensiblement la contrainte à la rupture. Les propriétés électriques longitudinales et transversales sont améliorées d’un facteur 8 et 5 respectivement. Nous avons proposé des mécanismes de croissance des NTC. Ces mécanismes sont directement en relation avec propriétés physiques et chimiques des particules de catalyseur. / The research presented in this work aims to develop the oxyacetylene flame method for the Carbon Nanotubes (CNT) synthesis at the Laboratory of Physics and Mechanics of Textiles. The simplicity and the degree of innovation of this process make of it a serious candidate for manufacturing a pilot in order to produce new kind of tridimensional material made of CNT having grew on carbon fibres. This work consisted of:- Make a bibliographic study,- Establish a proof of concept of the growth of CNT,- Design and manufacture a device allowing process control,- Setup the process of growth on the fibres,- Identify the main parameters influencing CNT quality and quantity,- Characterize CNT,- Assume the CNT growth on carbon fibers,- Integrate these multidimensional materials into an organic matrix to realize structural composite materials,- Characterize these materials,- Describe and explain the growth mechanism in the flame.First, we focused our work on the fibres chemical treatment before flame exposition to evaluate the NTC growth conditions by varying notably, the fibres exposition temperature and the quality of the catalysts. After, the NTC syntheses on carbon fibres (CF) was done. The multidimensional product was characterized par various examinations and analyses. Composite materials were molded with epoxy resin to evaluate mechanical properties of NTC-FC. Young’s modulus was increased and tensile strength at break decreased. Transverse and longitudinal electrical properties were increased by 500 to 800 % respectively. Finally, we proposed NTC growth mechanisms. They are directly linked to the chemical and physical catalyst particles properties.