Dissertations / Theses on the topic 'Polymer/nanocrystals composite material'

2010/2011
This thesis describes: (i) synthesis and characterization of colloidal nanocrystals of II-VI semiconductor compounds; (II) development of two novel materials using such nanocrystals as “building blocks”: (IIa) a nanocrystals/polymer composite, to be used as phosphor in LED-based lighting devices; (IIb) an inorganic, nano-structured multiphase material, showing a promising geometry as an electronic intermediate band material. Different typologies of nanocrystals (single-phase, alloyed or core-shells) were successfully synthesized using air-stable, safe reagents. Their optical properties (absorption spectrum, fluorescence wavelength and fluorescence quantum yield) were mapped as function of different parameters. Good results in engineering optical properties were achieved by: (a) changing size and/or composition in single-phase nanocrystals; (b) tuning shell composition and thickness and/or mutually diffusing one material into the other in multi-phase nanocrystals. The influence of different surface ligands on optical properties and on solubility in different media was also studied. Nanocrystal/polymer composite lenses were obtained from nanocrystals with desired fluorescence wavelength and quantum yield, mixed in an appropriate solvent with polymer pellets. The mixture was drop casted or tape casted on a solid substrate, obtaining solid, transparent lenses after solvent evaporation. A nano-structured, all-inorganic material (composed of semiconducor nanocrystals embedded into a wider bandgap semiconductor) was obtained through self-assembly and densification of colloidal core-shells nanocrystals. The realization of this composite supracrystal was achieved via a multi-step process: (i) colloidal synthesis of core-shell nanocrystals; (ii) surface ligands exchange; (iii) assembly; (iv) heat treatment. Evolution of the optical properties during heat treatment suggests that it is possible to sinter the shell material without altering the internal nano-heterostructure, if temperature and time of the treatment are controlled properly.
In questa tesi sono descritti: (I) la sintesi colloidale e la caratterizzazione di nanocristalli di semiconduttori II-VI; (II) lo sviluppo, utilizzando i suddetti nanocristalli quali “unità da costruzione”, di due materiali innovativi: (IIa) un composito nanocristalli/polimero, da usare come fosforo in dispositivi per illuminazione basati su LED; (IIb) un materiale inorganico nano-strutturato multifase, con una geometria promettente quale materiale a banda elettronica intermedia. Differenti semiconduttori II-VI sono stati sintetizzati in forma di nanocristalli (monofasici, in forma di lega o in struttura di tipo “core-shell”) usando reagenti sicuri e stabili in atmosfera. Le loro proprietà ottiche (spettro di assorbimento, lunghezza d’onda di fluorescenze e resa quantica di fluorescenza) sono state mappate in funzione di numerosi parametri. Sono stati raggiunti ottimi risultati nel controllo delle proprietà ottiche sia in nanocristalli a fase singola (modificandone le dimensioni o la composizione chimica) che in nanocristalli multifase (regolandone la composizione e lo spessore della “shell”, nonché mutualmente diffondendo un materiale nell’altro). È stata anche studiata l’influenza di differenti leganti superficiali sulle proprietà ottiche e sulla solubilità dei nanocristalli in differenti solventi. Lenti composite di nanocristalli/polimero sono state ottenute a partire da nanocristalli aventi la lunghezza d’onda e la resa quantica di fluorescenza desiderate, mescolandoli con pellet di polimero in solventi appropriati. La miscela è stata depositata su un supporto, tramite drop casting o tape casting, ottenendo lenti solide trasparenti dopo l’evaporazione del solvente. Un materiale inorganico nano strutturato (costituito da nanocristalli di semiconduttore racchiusi all’interno di un secondo materiale semiconduttore a bandgap maggiore) è stato ottenuto tramite l’autoassemblaggio e la densificazione di nanocristalli core-shell sintetizzati con procedure di chimica colloidale. La realizzazione di suddetto sovra-cristallo si è svolta in più fasi: (i) sintesi colloidale; (ii) sostituzione dei leganti superficiali; (iii) assemblaggio; (iv) trattamento termico. I risultati derivanti dallo studio dell’evoluzione delle proprietà ottiche durante il trattamento termico suggeriscono che sia possibile sinterizzare il materiale della shell senza alterare la nano-eterostruttura interna, se la temperatura e il tempo del trattamento sono scelti opportunamente.
XXIV Ciclo
1983

The goal of this research study was to create an artificial annulus fibrosus similar to that of the natural intervertebral disc, as well as find preliminary results for vertebral endplate connection and nucleus pulposus internal pressure, for the correction of disc degeneration in the spine. The three-part composite samples needed to demonstrate good shock absorption and load distribution while maintaining strength and flexibility, and removing the need for metal in the body, something of which no current total disc replacement or spinal fusion surgery can offer. For this study, the spinal disc was separated into its three different components, the annulus fibrosus, the nucleus pulposus, and the vertebral endplates, each playing a vital role in the function of the disc. Two low-cost materials were selected, a Covestro polyurethane and cellulose nanocrystals, for the purpose of creating a polymer composite spinal disc implant. A methodology was established for creating the cast composite material for use as an annulus fibrosus, while also investigating its mechanical properties. The same composite material was used to acquire preliminary results for vertebral endplate connection to the synthesized annulus, however no additional material was used to determine or mimic the mechanical properties of these endplates, due to time constraints. Also because of time constraints, the nucleus used in this study was only comprised of water with no other additives for preliminary testing since the natural nucleus is comprised of about 80-90% water. These properties were then compared to the mechanical properties of the natural disc, so that they could be finely tuned to emulate the natural disc. It is shown in this study that the composite material, when swelled in water, was able to mimic the annulus fibrosus in tensile strength and modulus, however showed higher compressive strength and modulus than ideal. The samples also did not undergo any permanent deformation within the realm of force actually introduced to the natural disc. The vertebral endplates showed decent adhesion to the synthesized annulus, however there were slight defects that became failure concentrators during compression testing. The nucleus showed promising results maintaining good internal pressure to the system causing better compressive load distribution, with barreling of the samples.
Master of Science
Spinal disc degeneration is a very prevalent problem in today’s society, effecting anywhere from 12% to 35% of a given population. It usually occurs in the lumbar section of the spine, and when severe enough, can cause bulging and herniation of the intervertebral disc itself. This can cause immense lower back pain in individual’s stricken with this disease, and in the US, medical costs associated with lower back pain to exceed $100 billion. Current solutions to this problem include multiple different treatment options of which, spinal fusion surgery and total disc replacement (TDR) are among the most common. Although these treatments cause pain relief for the majority of patients, there are multiple challenges that come with these options. For example, spinal fusion surgery severely limits the mobility of its patients by fusing two vertebrae together, disallowing any individual movement, and TDR can cause hypermobility in among the vertebrae and offer little to no shock absorption of loads. Therefore, a better treatment option is needed to relieve the pain of the patients, as well as maintain equal motion, shock absorption, and load cushioning to that of the normal intervertebral disc and remaining biocompatible. The goal of this research study was to create a three-component system, like that of the natural intervertebral disc, for the use of spinal disc replacement and to replace current options. The fabricated system was comprised of the three components found in the natural intervertebral disc; the annulus fibrosus, the nucleus pulposus, and the vertebral endplates. Because the system will need to go in-body, the materials used were all characterized as biocompatible materials; the polyurethane currently being used in medical devices and implants, and the cellulose nanocrystals (CNCs) coming from natural cellulose in sources such as wood and plants. The results determined that the mechanical properties of the system can be fine-tuned in order to mimic the natural strength and cushioning capabilities of the natural disc, based on CNC content added to the polyurethane, and when all three components of the system are added together, the compressive stress-strain is most similar to the natural disc in compression. However, the system did show failure in the connection between the annulus fibrosus and vertebral endplates, causing herniation of the nucleus similar to the initial problem attempting to be solved. For this, more ideal fabrication methods should be researched in the future including 3D printing techniques, injection molding, and roll milling. As well as alternate fabrication techniques, cell grow and viability should be determined to show that cells don’t die once the system in implanted.

The goal of this research study was to create an artificial annulus fibrosus similar to that of the natural intervertebral disc, as well as find preliminary results for vertebral endplate connection and nucleus pulposus internal pressure, for the correction of disc degeneration in the spine. The three-part composite samples needed to demonstrate good shock absorption and load distribution while maintaining strength and flexibility, and removing the need for metal in the body, something of which no current total disc replacement or spinal fusion surgery can offer. For this study, the spinal disc was separated into its three different components, the annulus fibrosus, the nucleus pulposus, and the vertebral endplates, each playing a vital role in the function of the disc. Two low-cost materials were selected, a Covestro polyurethane and cellulose nanocrystals, for the purpose of creating a polymer composite spinal disc implant. A methodology was established for creating the cast composite material for use as an annulus fibrosus, while also investigating its mechanical properties. The same composite material was used to acquire preliminary results for vertebral endplate connection to the synthesized annulus, however no additional material was used to determine or mimic the mechanical properties of these endplates, due to time constraints. Also because of time constraints, the nucleus used in this study was only comprised of water with no other additives for preliminary testing since the natural nucleus is comprised of about 80-90% water. These properties were then compared to the mechanical properties of the natural disc, so that they could be finely tuned to emulate the natural disc. It is shown in this study that the composite material, when swelled in water, was able to mimic the annulus fibrosus in tensile strength and modulus, however showed higher compressive strength and modulus than ideal. The samples also did not undergo any permanent deformation within the realm of force actually introduced to the natural disc. The vertebral endplates showed decent adhesion to the synthesized annulus, however there were slight defects that became failure concentrators during compression testing. The nucleus showed promising results maintaining good internal pressure to the system causing better compressive load distribution, with barreling of the samples.
Master of Science
Spinal disc degeneration is a very prevalent problem in today’s society, effecting anywhere from 12% to 35% of a given population. It usually occurs in the lumbar section of the spine, and when severe enough, can cause bulging and herniation of the intervertebral disc itself. This can cause immense lower back pain in individual’s stricken with this disease, and in the US, medical costs associated with lower back pain to exceed $100 billion. Current solutions to this problem include multiple different treatment options of which, spinal fusion surgery and total disc replacement (TDR) are among the most common. Although these treatments cause pain relief for the majority of patients, there are multiple challenges that come with these options. For example, spinal fusion surgery severely limits the mobility of its patients by fusing two vertebrae together, disallowing any individual movement, and TDR can cause hypermobility in among the vertebrae and offer little to no shock absorption of loads. Therefore, a better treatment option is needed to relieve the pain of the patients, as well as maintain equal motion, shock absorption, and load cushioning to that of the normal intervertebral disc and remaining biocompatible. The goal of this research study was to create a three-component system, like that of the natural intervertebral disc, for the use of spinal disc replacement and to replace current options. The fabricated system was comprised of the three components found in the natural intervertebral disc; the annulus fibrosus, the nucleus pulposus, and the vertebral endplates. Because the system will need to go in-body, the materials used were all characterized as biocompatible materials; the polyurethane currently being used in medical devices and implants, and the cellulose nanocrystals (CNCs) coming from natural cellulose in sources such as wood and plants. The results determined that the mechanical properties of the system can be fine-tuned in order to mimic the natural strength and cushioning capabilities of the natural disc, based on CNC content added to the polyurethane, and when all three components of the system are added together, the compressive stress-strain is most similar to the natural disc in compression. However, the system did show failure in the connection between the annulus fibrosus and vertebral endplates, causing herniation of the nucleus similar to the initial problem attempting to be solved. For this, more ideal fabrication methods should be researched in the future including 3D printing techniques, injection molding, and roll milling. As well as alternate fabrication techniques, cell grow and viability should be determined to show that cells don’t die once the system in implanted.

Thesis (Ph. D.) University of Missouri-Columbia, 2006.
The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file (viewed on August 2, 2007) Includes bibliographical references.

One interesting approach is the development of conductive polymer composite fibers for innovative textile applications such as in sensors, actuators and electrostatic discharge. In this study, conductive polymer composite fibers were prepared using several different blends containing conductive components: a conjugated polymer (polyaniline-complex) and/or carbon nanotubes. Different factors such as processing parameters, the morphology of the initial blends and the final fibers, fiber draw ratio and material selection were studied separately to characterize their effects on the fiber properties. In binary blends of PP/polyaniline-complex, the processing conditions, the matrix viscosity and the fiber draw ratio had substantial effects on the electrical conductivity of the fibers and linearity of resistance-voltage dependence. These factors were associated with each other to create conductive pathways through maintaining an appropriate balance of fibril formation and breakage along the fiber. The blend morphology was defined as the initial size of the dispersed conductive phase (polyaniline-phase), which depended on the melt blending conditions as well as the PP matrix viscosity. Depending on the initial droplet phase size, an optimum draw ratio was necessary to obtain maximum conductivity by promoting fibril formation (sufficient stress) and preventing fibril breakage (no excess stress) to create continuous pathways of conductive phase. Ternary blend fibers of PP/PA6/polyaniline-complex illustrated at least three-phase morphology with matrix/core-shell dispersed phase style. When ternary fibers were compared to binary fibers, the former could combine better mechanical and electrical properties only at a specific draw ratio; this showed that draw ratio was a more determinant factor for the ternary fibers, as both conductivity and tensile strength depended on the formation of fibrils from the core-shell droplets of the PA6/polyaniline-complex through the polypropylene matrix. The achieved maximum conductivity so far was in the range of 10 S/cm to 10 S/cm, which for different samples were observed at different fiber draw ratios depending on the mixing conditions, the matrix viscosity or whether the fiber was a binary or ternary blend. To improve the properties, PP/polyaniline-complex blends were filled with CNTs. The CNTs and the polyaniline-complex both had an increasing effect on the crystallization temperature and the thermal stability of PP. Furthermore, the maximum conductivity was observed in samples containing both CNTs and polyaniline-complex rather than the PP with either one of the fillers. Although increasing the content of CNTs improved the conductivity in PP/CNT fibers, the ease of melt spinning, diameter uniformity and mechanical properties of fibers were adversely affected. Diameter variation of PP/CNT as-spun fibers was shown to be an indication of hidden melt-drawings that had occurred during the fiber extrusion; this could lead to variations in morphology such as increases in the insulating microcracks and the distance between the conductive agglomerates in the drawn parts of the fiber. Variations in morphology result in variations in the electrical conductivity; consequently, the conductivity of such inhomogeneous fiber is no longer its physical property, as this varies with varying size.
Thesis to be defended in public on Friday, May 20, 2011 at 10.00 at KC-salen, Kemigården 4, Göteborg, for the degree of Doctor of Philosophy.

Carbon fibre reinforced polymer (CFRP) composites have found a wide range of applications in the aerospace, marine, sports and automotive industries owing to their lightweight and acceptable mechanical properties compared to the commonly used metallic materials. The currently dominating method of machining CFRP is by mechanical means that has found many problems including extensive tool wear, fibre pull-out and delamination. Lasers as non-contact tools have been widely applied for cutting and drilling materials. However, machining of CFRP composites using lasers can be challenging due to inhomogeneity in the material properties and structures, which can lead to thermal damage such as charring, heat affected zones (HAZs), resin recession and delamination. In previous studies, Nd:YAG, diode pumped solid state (DPSS), CO2 (continuous wave), disk and fibre lasers were used in machining CFRP composites and the control of damage such as the size of heat affected zones (HAZ) and achieving comparable material removal rate with the mechanical processes remain a challenge. Most reported work showed a typical heat affected zone of 0.2-1.2 mm. The availability of short pulsed transversely excited atmospheric (TEA) CO2 lasers and ultra-short laser pulse sources such as picosecond lasers make it possible to improve the laser machining quality of CFRP materials. In this research, the machining of CFRP composites using a microsecond pulsed TEA CO2 laser, a state of the art high power picosecond laser and a 1 kW single mode fibre laser system was investigated. The yielded heat affected zone was less than < 25 µm for the TEA CO2 and the picosecond laser machining, although the material removal rate was low. Additionally, it has been shown that the pulsed fibre laser improved the machining quality compared to that with the continuous mode. A potential application of the fibre laser for composite repair and remanufacturing was investigated. The interactions between picosecond laser beam and CFRP composite were studied in more detail including understanding the self-limiting effect in single and multiple parallel tracks drilling/machining through both experimental and theoretical studies. Furthermore, a sequential laser and mechanical drilling of CFRP was investigated to improve the machining rate. The work performed in this PhD was driven by aerospace industry needs, with the collaboration of Rolls-Royce plc and BAE Systems as industrial partners.

An increasing need for smaller, higher-power-density devices is driving the development of more advanced topologies for use in power architectures. The challenge, however, is to reduce the size of the passive components in circuit boards (e.g., the inductors), which are typically the most bulky. There are two ways to approach this problem. The first is to redesign the flux in the inductor in order to minimize its size; the second is to optimize the magnetic properties of the constituent magnetic materials, which include permeability, density, resistivity, core loss density, saturation magnetization value, fluidity, sintering temperature, and others. Compared to altering the nature of solid magnetic materials to reduce space constraints, modifying the magnetic composite is preferred. The most popular candidates for use in magnetic composites are magnetic powders and polymer composites. In particular, when metal alloys are chosen as magnetic powders they have high initial permeability, high saturation magnetization values, but low electrical resistivity. Since polymers can serve as insulation materials, mixing metal alloys with polymers will increase electrical resistivity. The most common metal alloy used is nickel-iron (permalloy) and Metglas. Since existing modeling methods are limited in (a) that multiphasic composites cannot be utilized and (b) the volume fraction of magnetic particles must be low, this investigation was designed to utilize FE (finite element) simulation to analyze how magnetic properties change with the distribution of permalloy powder or Metglas flakes in composites. The primary magnetic properties of interest in this study are permeability and core loss density. Furthermore two kinds of magnetic composites were utilized in this investigation: a benzocyclobutene (BCB) matrix-permalloy and a benzocyclobutene (BCB) matrix-permalloy-based amorphous alloy (Metglas 2705M) material. In our FE simulations, a BCB matrix-permalloy composite was utilized in a body-centered cubic model with half-diameter smaller particles serving as padding. The composite was placed in a uniform magnetic field surrounded by a material whose relative permeability was equal to zero in simulation. In comparison to experimental results, our model was able to predict permeability of composites with volume fraction higher than 52%. It must be noted, however, that although our model was able to predict permeability with only 10% off, it was less effective with respect to core loss density findings. The FE model also showed that permeability will increase with an increasing volume fraction of magnetic particles in the composite. To modify the properties of the composite material, the model of the BCB matrix-permalloy-Metglas composite followed model simulations up to the point at which flakes were inserted in BCB matrix-permalloy composite. The thickness of flakes was found to be an important factor in influencing resulting magnetic properties. Specifically, when the thickness of flakes decreased to quarter size at the same volume fraction, the permeability increased by 15%, while core loss density decreased to a quarter of the original value. The analysis described herein of the important relationship between magnetic properties and the composites is expected to aid in the development and design of new magnetic composite materials.
Master of Science

Thesis (MSc)--University of Stellenbosch, 2007.
ENGLISH ABSTRACT: Silicone rubber, particularly poly(dimethylsiloxane) (PDMS), has been increasingly used in the manufacture of outdoor high voltage insulators in the recent years. PDMS offers several advantages that make it suitable for outdoor use, such as low weight, a hydrophobic surface, stability, and excellent performance in heavily polluted environments. PDMS surfaces can, however, become progressively hydrophilic due to surface oxidation caused by corona discharge, UV radiation and acid rain. In this study, PDMS samples of controlled formulations as well as six commercial insulator materials four PDMS based and two ethylene propylene diene monomer (EPDM) based were exposed to various accelerated weathering conditions for various periods of time in order to track changes in the material over time. The ageing regimes developed and used to simulate the potential surface degradation that may occur during in-service usage included needle corona and French corona ageing, thermal ageing, UV-B irradiation (up to 8000 hours) and acid rain (up to 200 days). Both the chemical and physical changes in the materials were monitored using a wide range of analytical techniques, including: static contact angle measurements (SCA), optical microscopy (OM), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), gas chromatography (GC), gas chromatography/mass spectroscopy (GC/MS), size-exclusion chromatography (SEC), Fourier-transform infrared photoacoustic spectroscopy (FTIR-PAS) and slow positron beam techniques (PAS). A low molecular weight (LMW) uncrosslinked PDMS model compound was used to further study the chemical effects of corona exposure on PDMS materials. PDMS showed far better performance than EPDM, in terms of resistance to the various ageing regimes and “hydrophobicity recovery”.
AFRIKAANSE OPSOMMING: Silikoonrubber, spesifiek polidimetielsiloksaan (PDMS), is gedurende die afgelope paar jaar toenemend gebruik in die vervaardiging van buitelughoogspanningisolators. PDMS het baie voordele vir gebruik in elektriese isolators soos ‘n laer massa, ʼn hidrofobiese oppervlak, stabiliteit en uitstekende werking in hoogsbesoedelde omgewings. Die hidrofobiese oppervlakte kan egter gelydelik hidrofilies word weens oppervlakoksidasie as gevolg van korona-ontlading, UV-bestraling en suurreën. In hierdie studie is PDMS monsters van verskillende samestellings sowel as ses kommersiële isolators (vier PDMS en twee etileenpropileenrubber (EPDM)) blootgestel aan verskillende versnelde weersomstandighede vir verskillende periodes om die veranderinge in die materiale te monitor. Die verskillende materiale is gerangskik volgens hulle werking oor ‘n periode van tyd. Dit het ook ‘n geleentheid gebied om die eienskappe van die verskillende samestellings te bestudeer. Die tegnieke wat ontwikkel is om die moontlike oppervlakdegradasie te simuleer, het naald-korona, “French” korona, UVB-bestraling (tot 8000 uur) en suurreën (tot 200 dae) ingesluit. Beide die chemiese en die fisiese veranderinge in die materiale is gemonitor met behulp van verskeie tegnieke soos statiese kontakhoekbepaling, optiese mikroskopie, skandeerelektronmikroskopie, energieverspreidingsspektroskopie, gaschromatografie, grootte-uitsluitingschromatografie, foto-akoestiese Fouriertransforminfrarooi (PASFTIR) en stadige-positronspektroskopie (PAS). ʼn Lae molekulêre massa PDMS modelverbinding is gebruik om die chemiese effek van korona te bestudeer. Die PDMS materiale het baie beter vertoon teenoor die EPDM materiale in terme van hulle herstel van hidrofobisiteit.

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.

Innovative new flooring systems utilising lightweight fibre reinforced polymer composite materials may have the significant potential to offer both economic and performance benefits for infrastructure asset owners compared to conventional concrete and steel systems. Over recent years, a range of prototype floor systems using fibre reinforced polymer composites have been developed by researchers at the University of Southern Queensland. However before such structural systems can be widely adopted by industries, fundamental understanding of their behaviour must be improved. Such work will allow for the development of new design and analysis procedures which will enable engineers to efficiently and accurately design and analyse such structures. This dissertation presents an investigation into a new two-way fibre reinforced composite floor slab system. The proposed new two-way slab system is, in essence, a sandwich structure with an innovative hollow core made from a castable particulate filled resin system. The key focus of this dissertation is the development of a new analysis tool to analyse the two-way fibre reinforced composite slab and facilitate subsequent parametric studies into slab configurations for concept refinement. The detailed 3D finite element analyses and experimental investigations are performed to verify the new analysis tool, and provide more detailed insight into the structural behaviour of this new two-way fibre reinforced composite slab. Comparisons with detailed 3D FEA and experiments illustrate that the simplified analysis tool is capable of providing sufficient accuracy for the preliminary analysis of a slab structure. Moreover, the 3D finite element analyses agree well with the experiments, and it is concluded that the behavioural responses of the proposed new slab structure can be reliably predicted. The experimental results show that this new slab concept exhibits quite a robust static behaviour and is likely to have a robust fatigue performance.

In this work a new material, the conducting polymer-DNA composite, has been reported for the first time due to its promise in micro extraction, transfer, and release of cations under controlled potential conditions by using electrochemically assisted solid phase micro extraction (SPME). The Polypyrrole/DNA composite can be formed easily by oxidation of pyrrole monomers in the presence of chromosomal DNA by electropolymerization. Environmental significant pollutants such as Cd, Pb, Hg, Co, Zn, Cu, and Bi metal ions can be extracted from the aqueous solution and are able to be transferred to another medium defined as the release solution where the metals were detected by anodic stripping voltammetry. Using Cd2+ as a model, this method has been examined to optimize its operational condition. Extraction efficiency and potential interference for this method were studied.

This thesis presents an investigation into the factors affecting the morphology of hybrid inorganic/organic photoactive layers used in photovoltaic cells. Although optimisation of the organic (polymer) phase has received substantial attention, research into the morphology of the inorganic phase (semiconducting nanocrystals) remains limited. It is believed that there is a strong link between the morphology of the final photoactive film and the quality of the initial nanocrystal dispersion. To this end, two nanocrystal systems were investigated; zinc oxide (ZnO) and lead sulphide (PbS). ZnO nanocrystals were synthesised and found to possess reproducible characteristics. It was determined that colloid stability was initially dependent upon the presence of acetate groups bound to the surface, which in turn required a small quantity of methanol to be present in the organic dispersant. It was also discovered that while methanol evaporated readily from the surface of the nanocrystals, another molecule, 1-propylamine (1-PA), did not. Further investigations showed that while methanol only weakly physisorbed to the surface of ZnO nanocrystals, 1-PA formed strong, dative covalent bonds with Zn2+, preventing evaporation despite a low boiling point. Subsequent investigations into the effects of different ligands upon colloid stability found that amine-based groups typically possessed superior stabilising capabilities compared to alcohol-based analogues. The characteristics of nanocrystal / polymer blends were also investigated. It was determined that the nanocrystal dispersion became unstable at higher concentrations of polymer due to depletion aggregation. Films of nanocrystal / polymer blends were cast from dispersions containing either alcohol or amine-based ligands, and it was observed that dispersions stabilised with 1-PA possessed smooth morphologies on the micrometer scale. Investigations at the nanometer scale, however, revealed aggregates large enough to favour recombination.The latter half of this thesis regards the characterisation of PbS nanocrystals and investigations into triggered aggregation. It was determined that while PbS nanocrystals possessed reproducible characteristics, the stabilising molecule, oleic acid (OA) was insulating. The effects of exchanging the OA groups for a shorter ligand, butylamine (BA) were investigated.Finally, PbS nanocrystals were treated with a bidentate ligand, 1,2-ethanedithiol (EDT) to induce triggered aggregation. It was observed that the system was highly sensitive to the concentration of EDT in dispersion, forming small, relatively dispersed aggregates at low [EDT], and micrometer-sized crystalline structures at high [EDT]. The characterisation and entrapment of these nanocrystal structures within semi-conducting polymer films is also discussed.

As the use of fiber reinforced plastics increases in such industries as aerospace, wind energy, and sporting goods, factors effecting long-term durability, such as environmental exposure, are of increasing interest. The primary objectives of this study were to examine the effects of extensive environmental exposure (specifically UV radiation and moisture) on carbon/epoxy composite laminate structures and to determine the relative effectiveness of polymer-based coatings at mitigating degradation incurred due to such exposure. Carbon/epoxy composite specimens, both coated and uncoated, were subjected to accelerated weathering in which prolonged outdoor exposure was simulated by controlling the radiation wavelength (in the UV region), temperature, and humidity. Mechanical test data obtained for the uncoated specimens indicated a reduction in strength of approximately 6% after an environmental exposure duration of 750 hours. Test data revealed that no further degradation occurred with increased exposure duration. This reduction resulted from the erosion of the epoxy matrix in additional to the formation of matrix microcracks. The protective coatings evaluated were all epoxy based and included two different surfacing films applied during initial cure of the carbon/epoxy composite laminate and a chromate containing epoxy based paint primer applied after the cure was complete. Although the chromate primer performed well initially, degradation of the underlying substrate was detected with extended exposure durations. In contrast, the surfacing films provided superior protection against environmentally induced degradation. Although similar degradation attributes were identified in the surfacing film as observed in the uncoated composite, it is likely that this degradation was either confined within the surfacing film layer or only penetrated the very near surface of the carbon/epoxy substrate, as it did not result in a substantial reduction in mechanical strength.
M.S.
Department of Mechanical, Materials and Aerospace Engineering;
Engineering and Computer Science
Materials Science & Engr MSMSE

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Dyneema HB-25 is an orthotropic polyethylene fiber-epoxy matrix material that is being investigated for use in a next generation layered armor concept. Dyneema was chosen due to its high variation in sound speeds in the through direction and along the fiber direction, thereby making it a good candidate for a wave spreading layer in our proposed armored layer concept. The shock properties in the through fiber direction have been investigated using traditional window experiments and experiments using buffer materials at projectile velocities varying from 0.250 km/s to 1.800 km/s. The shock Hugoniot relationship was found to be non-linear in the low pressure regime that was investigated here and was found to be: 2 Us 1.673u p 4.847u p 0.902 . The shock properties of polycrystalline Molybdenum were also investigated; specifically the sound speed at shock state stress level. The relationship between sound speed and stress can be useful in predicting phase changes within materials. The low pressure regime of these properties was investigated in order to provide anchor data for previous work completed on Molybdenum.

In this thesis, the focus has been on micro-mechanical mechanisms in polymer-based materials and structures. The first part of the thesis treats length-scale effects on polymer materials. Experiments have showed that the smaller the specimen, the stronger is the material. The length-scale effect was examined experimentally in two different polymers materials, polystyrene and epoxy. First micro-indentations to various depths were made on polystyrene. The experiments showed that length-scale effects in inelastic deformations exist in polystyrene. It was also possible to show a connection between the experimental findings and the molecular length. The second experimental study was performed on glass-sphere filled epoxy, where the damage development for tensile loading was investigated. It could be showed that the debond stresses increased with decreasing sphere diameter. The debonding grew along the interface and eventually these cracks kinked out into the matrix. It was found that the length to diameter ratio of the matrix cracks increased with increasing diameter. The experimental findings may be explained by a length-scale effect in the yield process which depends on the strain gradients. The second part of the thesis treats mechano-sorptive creep in paper, i.e. the acceleration of creep by moisture content changes. Paper can be seen as a polymer based composite that consists of a network of wood fibres, which in its turn are natural polymer composites. A simplified network model for mechano-sorptive creep has been developed. It is assumed that the anisotropic hygroexpansion of the fibres leads to large stresses at the fibre-fibre bonds when the moisture content changes. The resulting stress state will accelerate creep if the fibre material obeys a constitutive law that is non-linear in stress. Fibre kinks are included in order to capture experimental observations of larger mechano-sorptive creep effects in compression than in tension. Furthermore, moisture dependent material parameters and anisotropy are taken into account. Theoretical predictions based on the developed model are compared to experimental results for anisotropic paper both under tensile and compressive loading at varying moisture content. The important features in the experiments are captured by the model. Different kinds of drying conditions have also been examined.
QC 20100910

Bioplastic research has become more diverse and different types of research on bioplastic production have been conducted from fruits and vegetable waste, for example, orange waste. The wastes that come from oranges contain more than just vitamins, it has soluble sugars, starch, hemicellulose, cellulose, and pectin. The intention of this project was to study the possibility to produce bio-composite films from orange waste, after removing the soluble sugars. It was also to analyze the properties of the material by tensile strength, visual observation, and to find a methodology that suits this study. An ultrafine grinder was used to mechanically separate the cellulose fibres, with the intention to compare the fibrillation cycles on the properties of the bio-composite films. A total of 30fibrillation cycle was performed. In addition, different film casting strategies were performed and evaluated. The primary plan was to produce a biofilm without the use of chemicals. After the observing the results three new routes for the methodology was developed where the usage of chemicals was be included. The citric acid was used as a solvent for pectin and glycerol was used as a plasticizer. In the first method, different concentration of citric acid and glycerol were added and observed. The combination which gave uniformed films that contained 0.3 g of citric and 0.375 g of glycerol for a 75 ml hydrogel. The second method was to infuse citric acid before grinding the orange waste suspension. Lastly, the third method was to bleach the orange waste before grinding. The films that were produced gave interesting results and from the tensile testing implied that an impact was made on the strength by every fibrillation. The amount of glycerol was consistent throughout the project, but by adding different amount of citric acid gave the films differentIIproperties. The same happened when changing the mould of the film. The best values of the films were from the 30th fibrillation, gave the mean value of 31.6 MPa in tensile strength, and had a strain in elongation at 6.1 %. The tensile strength and elongation had increased drastically compared the fifth fibrillation which had 9.8 MPa and 7.6%.

This thesis describes the use of an ultrasonic goal-seeking algorithm while using ionic polymer metal composite (IPMC), an electroactive polymer, as the actuator to drive a vessel towards a goal. The signal transmitting and receiving circuits as well as the goal seeking algorithm are described in detail. Two test vessels were created; one was a larger vessel that contained all necessary components for autonomy. The second was a smaller vessel that contained only the sensors and IPMC strips, and all power and signals were transmitted via an umbilical cord. To increase the propulsive efforts of the second, smaller vessel, fins were added to the IPMC strips, increasing the surface area over 700%, determined to yield a 22-fold force increase. After extensive testing, it was found that the three IPMC strips, used as oscillating fins, could not generate enough propulsion to move either vessel, with or without fins. With the addition of fins, the oscillating frequency was reduced from 0.86-Hz to 0.25-Hz. However, the goal-seeking algorithm was successful in guiding the vessel towards the target, an ultrasonic transmitter. When moved manually according to the instructions given by the algorithm, the vessel successfully reached the goal. Using assumptions based on prior experiments regarding the speed of an IPMC propelled vessel, the trial in which the goal was to the left of the axis required 18.2% more time to arrive at the goal than the trial in which the goal was to the right. This significant difference is due to the goal-seeking algorithm’s means to acquire the strongest signal. After the research had concluded and the propulsors failed to yield desired results, many factors were considered to rationalize the observations. The operating frequency was reduced, and it was found that, by the impulse-momentum theorem, that the propulsive force was reduced proportionally. The literature surveyed addressed undulatory motion, which produces constant propulsive force, not oscillatory, which yields intermittent propulsive force. These reasons among others were produced to rationalize the results and prove the cause of negative results was inherent to the actuators themselves. All rational options have been considered to yield positive results.

Nanocrystalline cerium oxide thin films on metal and semiconductor substrates have been fabricated with a novel electrodeposition approach - anodic oxidation. X-ray diffraction analysis indicated that as-produced cerium oxide films are characteristic face-centered cubic fluorite structure with 5 ~ 20 nm crystal sizes. X-ray photoelectron spectroscopy study probes the non-stoichiometry property of as-produced films. Raman spectroscopy and Scanning Electron Microscopy have been applied to analyze the films as well. Deposition mode, current density, reaction temperature and pH have also been investigated and the deposition condition has been optimized for preferred oriented film formation: galvanostatic deposition with current density of -0.06 mA/cm2, T > 50oC and 7 < pH < 10. Generally, potentiostatic deposition results in random structured cerium oxide films. Sintering of potentiostatic deposited cerium oxide films leads to crystal growth and reach nearly full density at 1100oC. It is demonstrated that in-air heating favors the 1:2 stoichiometry of CeO2. Nanocrystalline cerium oxide powders (4 ~ 10 nm) have been produced with anodic electrochemical synthesis. X-ray diffraction and Raman spectroscopy were employed to investigate lattice expansion phenomenon related to the nanoscale cerium oxide particles. The pH of reaction solution plays an important role in electrochemical synthesis of cerium oxide films and powder. Cyclic voltammetry and rotation disk electrode voltammetry have been used to study the reaction mechanisms. The results indicate that the film deposition and powder formation follow different reaction schemes. Ce(III)-L complexation is a reversible process, Ce3+ at medium basic pH region (7~10) is electrochemically oxidized to and then CeO2 film is deposited on the substrate. CE mechanism is suggested to be involved in the formation of films, free Ce3+ species is coordinated with OH- at high basic pH region (>10) to Ce2O3 immediately prior to electrochemically oxidation Ce2O3 to CeO2. CeO2 / montmorillonite nanocomposites were electrochemically produced. X-ray diffraction and Raman spectroscopy illustrate the retaining of FCC structure for cerium oxide. Fourier Transform Infrared Spectroscopy and Differential Scanning Calorimetry of composites indicate the insertion of montmorillonite platelets into the structural matrix of cerium oxide. Sintering study of the nanocomposites demonstrates that low concentration of montmorillonite platelet coordination into cerium oxide matrix increases crystal growth rate whereas high concentration of montmoillonite in nanocomposites retards the increase of crystallite size during the densification process.

With excellent electrical, thermal and mechanical properties as well as large specific surface area, graphene has been applied in next-generation nano-electronics, gas sensors, transparent electrical conductors, thermally conductive materials, and superior energy capacitors etc. Convenient and productive preparation of graphene is thereby especially important and strongly desired for its manifold applications. Chemically developed functionalized graphene from graphene oxide (GO) has significantly high productivity and low cost, however, toxic chemical reduction agents (e.g. hydrazine hydrate) and raised temperature (400-1100°C) are usually necessary in GO reduction yet not preferred in current technologies. Here, microwaves (MW) are applied to reduce the amount of graphene oxide (GO) at a relatively low temperature (~165°C). Experimental results indicate that resurgence of interconnected graphene-like domains contributes to a low sheet resistance with a high optical transparency after MW reduction, indicating the very high efficiency of MW in GO's reduction. Moreover, graphene is usually recumbent on solid substrates, while vertically aligned graphene architecture on solid substrate is rarely available and less studied. For TIMs, electrodes of ultracapacitors, etc, efficient heat dissipation and electrical conductance in normal direction of solid surfaces is strongly desired. In addition, large-volume heat dissipation requires a joint contribution of a large number of graphene sheets. Graphene sheets must be aligned in a large scale array in order to meet the requirements for TIM application. Here, thermally conductive fuctionalized multilayer graphene sheets (fMGs) are efficiently aligned in a large scale by vacuum filtration method at room temperature, as evidenced by SEM images and polarized Raman spectroscopy. A remarkably strong anisotropy in properties of aligned fMGs is observed. Moreover, VA-fMG TIMs are prepared by constructing a three-dimensional vertically aligned functionalized multilayer graphene architecture between contact Silicon/Silicon surfaces with pure Indium as a metallic medium. Compared with their counterpart from recumbent A-fMGs, VA-fMG TIMs have significantly higher equivalent thermal conductivity and lower contact thermal resistance. Electrical and thermal conductivities of polymer composite are also greatly interested here. Previous researches indicated that filler loading, morphology of fillers, and chemical bonding across filler/polymer interfaces have significant influence on electrical/thermal conductivity of polymer composite. Therefore, the research also pays substantial attention to these issues. First, electrical resistivity of CPCs is highly sensitive on volume or weight ratio (filler loading) of conductive fillers in polymer matrix, especially when filler loading is close to percolation threshold (pc). Thermal oxidation aging usually can cause a significant weight loss of polymer matrix in a CPC system, resulting in a filler loading change which can be exhibited by a prompt alteration in electrical resistivity of CPCs. Here, the phenomena are applied as approach for in-situ monitoring thermal oxidation status of polymeric materials is developed based on an electrical sensors based on conductive polymeric composites (CPCs). The study developed a model for electrical resistivity of sensors from the CPCs as a function of aging time at constant aging temperature, which is in a good agreement with a Boltzmann-Sigmoidal equation. Based on the finding, the sensors show their capability of in-situ in-situ monitor and estimate aging status of polymeric components by a fast and convenient electrical resistance measurement. Second, interfacial issues related to these thermal conductive fillers are systemically studied. On the one hand, the study focuses on relationship between morphology of h-BN particles and thermal conductivity of their epoxy composites. It is found that spherical-agglomeration of h-BN particles can significantly enhance thermal conductivity of epoxy resin, compared with dispersed h-BN plates, by substantially reducing specific interfacial area between h-BN and epoxy resin. On the other hand, surface of high thermal conductive fillers such as SiC particles and MWNTs are successfully functionalized, which makes their surface reactive with bisphenol A diglycidyl ether and able to form chemical bonding between fillers and epoxy resin. By this means, thermal conductivity of polymer composites is found to be significantly enhanced compared with control samples, indicating the interfacial chemical bonding across interface between thermal conductive fillers and polymer matrix can promote heat dissipation in polymeric composites. The finding can benefit a development of high thermal conductive polymer composites by interfacial chemical bonding enhancement to meet the demanding requirements in current fine pitch and Cu/low k technology.

La contamination par les métaux lourds est un problème actuel qui affecte les écosystèmes et leurs organismes constitutifs. Ce problème a été reconnu dans le monde entier comme l'un des plus grands défis de notre époque. Depuis le milieu du siècle dernier, les innovations dans le domaine de la science des matériaux ont permis de mettre au point de nouvelles méthodes pour faire face à ce risque, avec des techniques telles que la précipitation chimique ou la flottation. Toutefois, il reste encore beaucoup à faire dans ce domaine. En outre, des recherches récentes ont exploré comment combiner des biomolécules telles que les protéines avec des matériaux tels que les polymères pour créer des solutions plus actives. Ce travail de thèse vise à créer un prototype de matériau adsorbant hybride capable de capturer spécifiquement les ions métalliques divalents Ni(II), Cd(II) et Pb(II) grâce à la présence d'une métalloprotéine synthétique dans sa structure. Pour atteindre cet objectif, le travail de thèse se concentre sur le développement d'une métalloprotéine synthétique capable de capturer spécifiquement les trois ions métalliques cibles, de la conception in silico à sa synthèse in vivo. D'autre part, le support de matériau est traité avec la technique d'électrofilage qui consiste en un matériau membranaire fibreux, étant optimisé pour accueillir la métalloprotéine synthétique dans sa structure. En outre, une méthode permettant d'intégrer la métalloprotéine dans le support polymère est recherchée. Ceci est réalisé au moyen d'une voie de greffage à travers des nanoparticules de silice modifiées en surface. À la fin, l'intégration des deux composants crée le prototype attendu de matériau biosorbant synthétique. Ce matériau a été caractérisé afin d'évaluer sa capacité à adsorber les trois ions métalliques d'intérêt, ce qui permet de dégager certaines tendances des perspectives futures de développement pour créer des matériaux plus efficaces pour l'industrie
Heavy metal contamination is a current problem which affects the ecosystems and their constituent organisms. This problem has been worldwide recognized as one of the biggest challenges of our time. Since the middle of the last century, innovations in the material science field have developed new methods to confront this risk, with techniques such as chemical precipitation or flotation. However, there is still significant room for improvement in this line. Furthermore, recent research has explored how to combine biomolecules such as proteins with materials like polymers to create more active solutions. This thesis work seeks to create a prototype hybrid biosorbent material capable to capture specifically the divalent metal ions Ni(II), Cd(II) and Pb(II) thanks to the presence of a synthetic metalloprotein in its structure. To address this objective, the thesis work focuses on the development of a synthetic metalloprotein capable to specifically capture the three target metal ions, from the in silico conception to its in vivo synthesis. On the other hand, the biosorbent material support is processed with the electrospinning technique that consists of a fibrous membrane material, being optimized to host the synthetic metalloprotein in its structure. Additionally, a method to integrate the metalloprotein into the polymeric support is researched. This is achieved by means of a grafting route through surface modified silica nanoparticles. At the end, the integration of both components creates the expected prototype synthetic biosorbent material. This material has been characterized to evaluate its capacity to adsorb the three metal ions of interest, providing some trends of the future perspectives for further development to create more efficient materials for the industry

In the effort to improve oil production riser performance, new materials are being studied. In the present case, a Polymer Matrix Composite (PMC) is being considered as a replacement for carbon steel in flexible risers manufactured by Wellstream Inc., Panama City, Florida. The Materials Response Group (MRG) at Virginia Tech had the primary responsibility to develop the models for long-term behavior, especially remaining strength and life. The MRG is also responsible for the characterization of the material system with a focus on the effects of time, temperature, and environmental exposure. The present work is part of this effort. The motivation to use a composite material in a non-bonded flexible riser for use in the offshore oil industry is put forth. The requirements for such a material are detailed. Strength analysis and modeling methods are presented with experimental data. The effect of matrix crystallinity on composite mechanical properties is shown. A new method for investigating matrix behavior at elevated temperatures developed. A remaining strength life prediction methodology is recalled and applied to the case of combined fatigue and rupture loading.
Master of Science

Master of Science
Department of Mechanical & Nuclear Engineering
Gurpreet Singh
Carbon nanotubes (CNT) and polymer-derived ceramics (PDC) have gained considerable research attention due to their unique structure and physical properties. Carbon nanotubes are known for their exceptional mechanical (Young’s modulus= 1 TPa) and thermal properties (thermal conductivity = 4000 W/m.K). However, CNTs tend to lose their unique -sp2 carbon structure and cylindrical geometry at temperatures close 400°C in air. PDC, which are obtained by the controlled degradation of certain organosilicon polymers however exhibit high temperature stability (upto approx. 1400 °C). To this end, a hybrid composite material consisting of PDC functionalized CNT is of interest as it can combine the unique physical properties of the two materials for applications requiring operation under harsh conditions. Here, we report synthesis and chemical characterization of an Al-modified polysilazane polymer, which was later utilized to functionalize the outer surfaces of four commercially available CNTs. This polymer-CNT composite upon heating in nitrogen environment resulted in Si(Al)CN-CNT ceramic composite. The composite was characterized using a variety of spectroscopic methods such Raman, FTIR and electron microscopy. The thermal stability of the ceramic composite was studied by use of Thermogravimetric analysis (TGA) that showed an improvement in the thermal stability compared to bare nanotubes. Further, we also demonstrate that a stable dispersion of the composite in organic solvents such as toluene can be spray coated on a variety of substrates such as copper disks and foils. Such coatings have application in high energy laser power meters. This research opens new avenues for future applications of this novel material as coatings on surfaces that require both good thermal properties and protection against degradation in high temperature environments. We also suggest the future use of this material as an electrode material in high electrochemical capacity rechargeable batteries.

Thermal energy storage (TES) consists in storing heat for a later use, thereby reducing the gap between energy availability and demand. The most diffused materials for TES are the organic solid-liquid phase change materials (PCMs), such as paraffin waxes, which accumulate and release a high amount of latent heat through a solid-liquid phase change, at a nearly constant temperature. To avoid leakage and loss of material, PCMs are either encapsulated in inert shells or shape-stabilized with porous materials or a nanofiller network. Generally, TES systems are only a supplementary component added to the main structure of a device, but this could unacceptably rise weight and volume of the device itself. In the applications where weight saving and thermal management are both important (e.g. automotive, portable electronics), it would be beneficial to embed the heat storage/management in the structural components. The aim of this thesis is to develop polymer composites that combine a polymer matrix, a PCM and a reinforcing agent, to reach a good balance of mechanical and TES properties. Since this research topic lacks a systematic investigation in the scientific literature, a wide range of polymer/PCM/reinforcement combinations were studied in this thesis, to highlight the effect of PCM introduction in a broad range of matrix/reinforcement combinations and to identify the best candidates and the key properties and parameters, in order to set guidelines for the design of these materials. The thesis in divided in eight Chapters. Chapter I and II provide the introduction and the theoretical background, while Chapter III details the experimental techniques applied on the prepared composites. The results and discussion are then described in Chapters IV-VII. Chapter IV presents the results of PCM-containing composites having a thermoplastic matrix. First, polyamide 12 (PA12) was melt-compounded with either a microencapsulated paraffin (MC) or a paraffin powder shape-stabilized with carbon nanotubes (ParCNT), and these mixtures were used as matrices to produce thermoplastic laminates with a glass fiber fabric via hot-pressing. MC was proven more suitable to be combined with PA12 than ParCNT, due to the higher thermal resistance. However, also the MC were considerably damaged by melt compounding and the two hot-pressing steps, which caused paraffin leakage and degradation, as demonstrated by the relative enthalpy lower than 100 %. Additionally, the PCM introduction decreased the mechanical properties of PA12 and the tensile strength of the laminates, but for the laminates containing MC the elastic modulus and the strain at break were not negatively affected by the PCM. Higher TES properties were achieved with the production of a semi-structural composite that combined PA12, MC and discontinuous carbon fibers. For example, the composite with 50 wt% of MC and 20 wt% of milled carbon fibers exhibited a total melting enthalpy of 60.4 J/g and an increase in elastic modulus of 42 % compared to the neat PA. However, the high melt viscosity and shear stresses developed during processing were still responsible for a not negligible PCM degradation, as also evidenced by dynamic rheological tests. Further increases in the mechanical and TES properties were achieved by using a reactive thermoplastic matrix, which could be processed as a thermosetting polymer and required considerably milder processing conditions that did not cause PCM degradation. MC was combined with an acrylic thermoplastic resin and the mixtures were used as matrices to produce laminates with a bidirectional carbon fabric, and for these laminates the melting enthalpy increased with the PCM weight fraction and reached 66.8 J/g. On the other hand, the increased PCM fraction caused a rise in the matrix viscosity and so a decrease in the fiber volume fraction in the final composite, thereby reducing the elastic modulus and flexural strength. Dynamic-mechanical investigation evidenced the PCM melting as a decreasing step in ’; its amplitude showed a linear trend with the melting enthalpy, and it was almost completely recovered during cooling, as evidenced by cyclic DMA tests. Chapter V presents the results of PCM-containing thermosetting composites. A further comparison between MC and ParCNT was performed in a thermosetting epoxy matrix. First, ParCNT was mixed with epoxy and the mixtures were used as matrices to produce laminates with a bidirectional carbon fiber fabric. ParCNT kept its thermal properties also in the laminates, and the melting enthalpy was 80-90 % of the expected enthalpy. Therefore, ParCNT performed better in thermosetting than in thermoplastic matrices due to the milder processing conditions, but the surrounding matrix still partially hindered the melting-crystallization process. Therefore, epoxy was combined with MC, but the not optimal adhesion between the matrix and the MC shell caused a considerable decrease in mechanical strength, as also demonstrated by the fitting with the Nicolais-Narkis and Pukanszky models, both of which evidenced scarce adhesion and considerable interphase weakness. However, the Halpin-Tsai and Lewis-Nielsen models of the elastic modulus evidenced that at low deformations the interfacial interaction is good, and this also agrees with the data of thermal conductivity, which resulted in excellent agreement with the Pal model calculated considering no gaps at the interface. These epoxy/MC mixtures were then reinforced with either continuous or discontinuous carbon fibers, and their characterization confirmed that the processing conditions of an epoxy composite are mild enough to preserve the integrity of the microcapsules and their TES capability. For continuous fiber composites, the increase in the MC fraction impaired the mechanical properties mostly because of the decrease in the final fiber volume fraction and because the MC phase tends to concentrate in the interlaminar region, thereby lowering the interlaminar shear strength. On the other hand, a small amount of MC enhanced the mode I interlaminar fracture toughness (Gic increases of up to 48 % compared to the neat epoxy/carbon laminate), as the MC introduced other energy dissipation mechanisms such as the debonding, crack deflection, crack pinning and micro-cracking, which added up to the fiber bridging. Chapter VI introduces a fully biodegradable TES composite with a thermoplastic starch matrix, reinforced with thin wood laminae and containing poly(ethylene glycol) as the PCM. The wood laminae successfully acted as a multifunctional reinforcement as they also stabilized PEG in their inner pores (up to 11 wt% of the whole laminate) and prevent its leakage. Moreover PEG was proven to increase the stiffness and strength of the laminate, thereby making the mechanical and TES properties synergistic and not parasitic. Finally, Chapter VII focused on PCM microcapsules. The synthesis of micro- and nano-capsules with an organosilica shell via a sol-gel approach clarified that the confinement in small domains and the interaction with the shell wall modified the crystallization behavior of the encapsulated PCM, as also evidenced by NMR and XRD studies and confirmed by DSC results. In the second part of Chapter VII, a coating of polydpamine (PDA) deposited onto the commercial microcapsules MC. The resulting PDA coating was proven effective to enhance the interfacial adhesion with an epoxy matrix, as evidenced by SEM micrographs. XPS demonstrated that the PDA layer was able to react with oxirane groups, thereby evidencing the possibility of forming covalent bond with the epoxy matrix during the curing step.

Les métaux micro ou nanoporeux sont très attrayants notamment pour leur grande surface spécifique. Le désalliage dans un bain de métal liquide permet une dissolution sélective d'une espèce chimique (l'élément soluble) à partir d'un alliage d'origine (le précurseur) composé de l'élément soluble et d'un élément cible (qui deviendra nano/micro poreux) non soluble dans le bain de métal liquide. Quand le précurseur est plongé dans le bain de métal liquide, à son contact, l'élément soluble va se dissoudre dans le bain tandis que l'élément cible va en parallèle se réorganiser spontanément afin de former une structure poreuse. Quand l'échantillon est retiré du bain, il est sous la forme d'une structure bi-continue composée de deux phases : l'une étant la structure poreuse composée de l'élément cible et l'autre est une phase dans laquelle est présente l'élément du bain avec l'élément sacrificiel en solution solide. Cette phase peut être dissoute par une attaque chimique afin d’obtenir le métal nano/micro poreux. Les objectifs principaux de cette thèse sont l'élaboration et la caractérisation microstructurale et mécanique de 3 différents types de matériaux par désalliage dans un bain de métal liquide : des composites métal-métal (FeCr-Mg), des métaux poreux (FeCr) et des composites métal-polymère (FeCr-matrice époxy). Le dernier objectif est l'évaluation des possibilités d'utiliser la technique de désalliage dans un bain de métal liquide dans un contexte industriel. L'étude de la microstructure est basée sur des observations 3D faites par tomographie aux rayons X et des analyses 2D réalisées en microscopie électronique (SEM, EDX, EBSD). Pour mieux comprendre le désalliage, le procédé a été suivi in situ en tomographie aux rayons X et diffraction. Enfin, les propriétés mécaniques ont été évaluées par nanoindentation et compression
Nanoporous metals have attracted considerable attention for their excellent functional properties. The first developed technique used to prepare such nanoporous noble metals is dealloying in aqueous solution. Porous structures with less noble metals such as Ti or Fe are highly desired for various applications including energy-harvesting devices. The less noble metals, unstable in aqueous solution, are oxidized immediately when they contact water at a given potential so aqueous dealloying is only possible for noble metals. To overcome this limitation, a new dealloying method using a metallic melt instead of aqueous solution was developed. Liquid metal dealloying is a selective dissolution phenomenon of a mono-phase alloy solid precursor: one component (referred as soluble component) being soluble in the metallic melt while the other (referred as targeted component) is not. When the solid precursor contacts the metallic melt, only atoms of the soluble component dissolve into the melt inducing a spontaneously organized bi-continuous structure (targeted+sacrificial phases), at a microstructure level. This sacrificial phase can finally be removed by chemical etching to obtain the final nanoporous materials. Because this is a water-free process, it has enabled the preparation of nanoporous structures in less noble metals such as Ti, Si, Fe, Nb, Co and Cr. The objectives of this study are the fabrication and the microstructure and mechanical characterization of 3 different types of materials by dealloying process : (i) metal/metal composites (FeCr-Mg), (ii) porous metal (FeCr) (iii) metal/polymer composites (FeCr-epoxy resin). The last objective is the evaluation of the possibilities to apply liquid metal dealloying in an industrial context. The microstructure study was based on 3D observation by X-ray tomography and 2D analysis with electron microscopy (SEM, SEM-EDX, SEM-EBSD). To have a better understanding of the dealloying, the process was followed in situ by X-ray tomography and X-ray diffraction. Finally the mechanical properties were evaluated by nanoindentation and compression

Les structures composites intégrant des transducteurs piézoélectriques au cœur de la matière sont utilisées pour leur capacité à modifier leurs propriétés mécaniques en fonction de l’environnement, à contrôler leur intégrité structurale et à interagir avec l’homme ou avec d’autres structures.Ce travail se concentre sur les phases de conception préliminaire des structures composites intelligentes. Ces phases ne représentent que 5% du coût total d’un projet, mais conditionnent 80% du coût final du produit. Les principaux problèmes rencontrés lors de ces phases de conception préliminaire portent sur la détermination des propriétés matériau des transducteurs piézoélectriques et des matériaux composites utilisés, de l'influence de l'emplacement des transducteurs dans la structure ainsi que de l’influence du processus de fabrication, de la température et des endommagements sur le comportement final des structures composites intelligentes.Dans le processus de fabrication développé à l’Université de Technologies Belfort-Montbéliard (UTBM), l’élément-clé est un produit semi-fini appelé “soft layer”. Cette couche permet d’intégrer le réseau de transducteurs piézoélectriques au cœur de la structure composite. Le processus de fabrication de la “soft layer” ainsi que celui des structures intelligentes sont abordés dans cette thèse.Afin de trouver des solutions aux problèmes décrits ci-dessus, deux méthodes de caractérisation de composites intelligents ou adaptatifs sont présentées et utilisées : la méthode dite Resonalyser et la méthode du temps de vol. Après des études expérimentales et une comparaison des résultats obtenus, la méthode du temps de vol a été choisie comme méthode principale en raison de son faible coût de mise en œuvre et du fait qu’il s’agit d’une méthode de caractérisation in-situ. De plus, une nouvelle méthode appelée méthode CMB, basée sur la méthode du temps de vol a été développée afin de pouvoir facilement et rapidement extraire les constantes élastiques, en particulier le coefficient de Poisson.Des analyses expérimentales de sensibilité appliquées aux composites adaptatifs ont été effectuées.Premièrement, l’étude de l’influence de l’emplacement des transducteurs démontre qu’il est nécessaire de tenir compte de la position de la “soft layer” dans la modélisation du comportement de produit final. La position de cette couche dans l’épaisseur du produit a une influence notable sur les fréquences propres ainsi que les amplitudes modales de la structure. Cependant, l’ajout de la “soft layer” n’accroît pas le taux d’amortissement de la structure finale; et sa position dans l’épaisseur n’a aucune influence sur ce taux d’amortissement. La propagation des ondes de Lamb à l’intérieur du composite n’est pas impactée par le “soft layer”.Deuxièmement, l’étude de l’impact du processus de la fabrication nous renseigne sur l’influence notable des divers paramètres de réglage du processus de fabrication sur le comportement final de la structure composite intelligente.Troisièmement, l’étude de l’influence de la température sur des structures constituées de différents matériaux composites montre que le module de Young du produit final décroît quand la température augmente. Mais la diminution du module de Young en fonction de la température est différente selon les et les types de matériaux et les directions des fibres, en particulier pour les structures composites unidirectionnelles. De plus, cette étude montre également la sensibilité de la méthode du temps de vol vis-à-vis de la température. Ce dernier point est par ailleurs consolidé par la comparaison avec des résultats obtenus par une méthode de caractérisation ex-situ standard : l'analyse dynamique de la mécanique (DMA).Enfin, l'étude de l'impact des dommages mécaniques fournit une assez bonne référence pour les recherches futures. De cette façon, il est clair qu’une méthode de temps de vol peut être utilisée dans la surveillance de la santé structurale
The composite structures embedding piezoelectric implants are developed due to their abilities of modifying mechanical properties according to the environment, of keeping their integrity, of interacting with human beings or with other structures.This study is focused on the preliminary design stages of smart composite structures, which represent only 5% of the total costs of a project, whereas 80% of the life cycle cost are set during the preliminary study phases. The top few problems during the preliminary design of smart composite structures are addressed in this work such as the determination of the material properties of the piezoelectric transducers and composite material used, the influence of transducers location, manufacturing process, temperature and damage on the behavior of the smart composite structures.Due to the manufacturing process developed at the Université de Technologie de Belfort-Montbéliard (UTBM), the most important element is a semi-finished product called “soft layer”. This special layer is used to embed the transducers system into the composite structures. The manufacturing process of “soft layer” as well as the smart composite structures are compiled in this report.In order to solve the problems described above, two characterization methods of composite material (Resonalyser method and Time-of-Flight method (T-o-F method)), are introduced and discussed. After experimental studies and comparing the results of these two methods, the T-o-F method is chosen as the main method for the following studies due to the fact that it is a low-cost and in-situ characterization method. Furthermore, a new method based on the T-o-F method is developed to easily and quickly extract the elastic constants, in particular the Poisson’s ratio.Experimental sensitivity analyses applied to the smart composite structures are performed with respect to the problems describes above. First of all, the study of the influence of transducers location demonstrates that the "soft layer” cannot be neglected to model the behavior of the final product. In particular, the through-the-thickness position has an influence on the eigenfrequencies and the modal amplitudes. However, the "soft layer” does not increase the overall damping ratio of the final structures and the through-the-thickness position of the "soft layer” has no influence on the damping ratios. The Lamb wave propagation inside the composite material is not impacted by the "soft layer”. Secondly, the study of the impact of manufacturing process demonstrates that the impact of variability of parameters due to the manufacturing process is very important on the final response of the structure. Thirdly, the study of the influence of temperature on different kinds of smart composite structures proves that when temperature increases, the Young’s modulus of the smart composites decreases. But the attenuation of Young’s modulus according to temperature is different along different fiber directions, especially for the unidirectional composite structures. Furthermore, in this study, the sensitivity of Time-of-Flight method with respect to temperature is well proved by comparing the results with a traditional method like Dynamic-Mechanical Analysis (DMA). Last but not least, the study of the impact of the mechanical damage gives a quite good reference for the future investigations. Along this way, it is possible to use a Time-of-Flight method in Structural Health Monitoring. In addition, some smart composite structures manufactured by the research team are given and their potential applications are discussed

Kohlenstofffaserverstärkter Kohlenstoff weist ausgezeichnete thermische, mechanische und chemische Eigenschaften auf. Aufgrund seiner Faserarchitektur und Porosität zeigt dieser eine mit metallischen und polymeren Werkstoffen vergleichbar hohe Schadenstoleranz. Die Herstellung komplexer Leichtbaustrukturen aus C/C-Verbunden ist jedoch zeit- und kostenintensiv. Ein neuer Ansatz stellt die Integration geometrisch simpler C/C-Verbunde in komplexe, problemlos zu realisierende polymere Strukturen dar. Ein derartiges Werkstoffkonzept vereint die Vorteile seiner Komponenten in einem ganzheitlichen Werkstoffsystem. Einen Nachteil stellt jedoch die geringe wechselseitige Adhäsion seiner Komponenten dar. Die Innovation dieses Beitrags stellt sich einerseits der Herausforderung die mechanischen Eigenschaften der C/C-Verbunde in Abhängigkeit der intrinsischen Porosität zu beeinflussen. Dies geschieht durch Veränderung der chemischen und physikalischen Vernetzungsbedingungen des Matrixprecursors. Andererseits soll die dadurch herrührende inhärente Porosität zur Vergrößerung der wirksamen äußeren Oberfläche und zur gezielten Verbesserung der Adhäsion zum Polymer führen. Es wird ein Kohlenstoffprecursor mit variabler offener Porosität entwickelt und daraus neuartige verschiedenporöse C/C-Verbunde hergestellt und untersucht. Im Anschluss werden die verschiedenporösen C/C-Verbunde mit ausgewählten Polymeren unter definierten Konsolidierungsparametern thermisch gefügt und deren wechselseitiges Adhäsionsverhalten bewertet
Fibre-reinforced ceramic matrix composite materials are characterized by excellent thermal, mechanical and chemical properties. Their high tolerance regarding damaging is a result of the intrinsic fibre structure and porosity. Due to this fact, they offer outstanding dampening characteristics, as is the case for polymeric materials. The production of complex structures is very time consuming and expensive. The integration of simple geometric ceramic composite materials in complex polymeric structures is regarded as a new approach for the production of these materials. These easy-to-produce hybrid ceramic/polymer compound materials combine the advantages of ceramics and polymers in one material system. However, one main disadvantage of these materials is the mutual adhesion of the two components. This article deals with the challenge of the manipulation of the mechanical properties of the C/C composites depending on the intrinsic porosity. This is realized by altering the physical and chemical wetting/coating conditions of the matrix precursor. In addition, the inherent porosity is supposed to increase the effective outer surface and specifically improve the adhesion. For this purpose, a novel carbon precursor with an adjustable open porosity is developed and investigated further. During this different versions of the CFRP and various C/C materials of different production steps are produced and examined. The variation of the precursors is supposed to take place in the polymeric state. The different C/C composites are subsequently thermally bonded with selected polymers and defined consolidation parameters. The mutual joining and connection behaviour is investigated further

Les matériaux composites carbone/carbone réfractaires sont constitués de charges granulaires carbonées mises en forme à l’aide d’un liant carbonisable. Jusqu’à présent, le liant utilisé est généralement le brai de goudron houille, cancérigène et visé par REACH. Afin de le substituer par un produit plus respectueux de l’environnement et de la santé des manutentionnaires, nous proposons une solution innovante dans ces travaux de thèse. Les glucides, et plus particulièrement les sucres, sont des composés carbonisables possédant un rendement en carbone faible. En présence de polyacide carboxylique, ceux-ci peuvent former un mélange à transition de phase basse température se caractérisant par un eutectique ou une température d’écoulement plus faible que celle de ses constituants pris séparément. Ce type de mélange est capable de réagir à des températures de l'ordre de 100 °C, donc inférieures à celles communément requises pour des réactions d'estérification. Ce comportement s'apparente à celui déjà décrit pour les BADES (Brønsted Acidic Deep Eutectic Solvent). Dans ces conditions sont obtenus des copolymères (ester-co-oside) linéaires et branchés qui conduisent à un réseau poly(ester-co-oside) en poursuivant la réaction sous vide. Par le choix des constituants et le contrôle du temps de réaction, il est possible de piloter la viscosité des polymères pour les utiliser comme liant dans des composites carbone/carbone à charges granulaires. Dans ce cas, nous avons montré que l’utilisation de polyacides carboxyliques présente trois avantages : i) en mélange avec des sucres, des LTTMs (Low Transition Temperature Mixtures) liquide à température ambiante sont formés, ce qui facilite leur utilisation dans le procédé, ii) ils servent de réactif et de catalyseur pour la polymérisation des sucres et iii) ils permettent d’augmenter le rendement en carbone des liants. Ces résultats sont très prometteurs pour la fabrication de composites carbone/carbone réfractaire comme électrode pour l’électrolyse de l’alumine
Refractory carbon/carbon composite materials consist of carbonaceous granular fillers shaped with a carbonisable binder. Until now, the binder used has generally been coal tar pitch, which is carcinogenic and covered by REACH. In order to replace it with a product that is more respectful of the environment and of the health of handlers, we are proposing an innovative solution in this thesis work. Carbohydrates, and more particularly sugars, are carbonisable compounds with a low carbon yield. In the presence of polycarboxylic acid, they can form a low transition temperature mixtures characterised by a eutectic or a lower flow temperature than that of its constituents taken separately. This type of mixture is capable of reacting at temperatures of the order of 100°C, thus lower than those commonly required for esterification reactions. This behaviour is similar to that already described for BADES (Brønsted Acidic Deep Eutectic Solvent). Under these conditions, linear and branched (ester-co-oside) copolymers are obtained which lead to a poly(ester-co-oside) network by continuing the reaction under vacuum. By choosing the constituents and controlling the reaction time, it is possible to control the viscosity of the polymers for use as a binder in carbon/carbon composites with granular fillers. In this case, we have shown that the use of polycarboxylic acids has three advantages: i) when mixed with sugars, LTTMs (Low Transition Temperature Mixtures) that are liquid at room temperature are formed, which facilitates their use in the process, ii) they act as a reagent and catalyst for the polymerisation of sugars and iii) they make it possible to increase the carbon yield of the binders. These results are very promising for the manufacture of refractory carbon/carbon composites as an electrode for alumina electrolysis

Ce travail de thèse porte sur la caractérisation d'un matériau composite polyacide lactique-bioverre pour application comme dispositif de réparation osseuse. Le bioverre étant trop fragile pour être utilisé seul comme dispositif de réparation osseuse, celui-ci est associé à une matrice polymère résorbable permettant d'apporter le caractère bioactif à des matériaux pouvant être mis en forme par des procédés de plasturgie. Le matériau composite polyacide lactique-bioverre est ainsi mis en forme par injection à partir de granules élaborés par voie solvant. La caractérisation des propriétés de ce matériau composite a révélé une augmentation du module élastique avec l'ajout de charges, mais une diminution des contraintes maximales admissibles et de la déformation à la rupture. Les modifications des propriétés mécaniques ont été associées à une modification des propriétés de la matrice et notamment de sa masse moléculaire. Un autre mode d'élaboration par pressage à chaud a permis de limiter la dégradation du polymère. Une meilleure maitrise de la masse moléculaire du composite serait ainsi un moyen de contrôler sa cinétique de dégradation in vivo et ainsi d'adapter ses propriétés en fonction du cahier des charges des applications visées. Dans une seconde partie, l'effet du taux de bioverre sur le caractère bioactif du composite a été évalué par immersion dans un fluide biologique de composites chargés à 20, 30 et 50% (en masse de bioverre). Un scénario de cristallisation à la surface des différents composites a ainsi été proposé. Tous les composites se sont révélés bioactifs et d'autant plus que le taux de bioverre est élevé. Le composite chargé à 50% apparait ainsi comme le matériau le plus bioactif, mais sa vitesse de dégradation est très rapide. Ce matériau étant destiné à être implanté, une étude de biocompatibilité in vitro a été menée par culture de cellules ostéoblastiques à la surface des matériaux. Enfin la biocompatibilité du composite in vivo, son caractère biorésorbable et ostéoconducteur ont été évalués par implantation du matériau composite dans les tissus musculaires et osseux de lapins. Le caractère biocompatible, bioactif et ostéoconducteur du composite chargé à 30% en masse de bioverre en fait un candidat de choix pour les applications proposées.

The sectional beam is the essential detail of an overhead conveyor. The construction element is stressed by time-varying mechanical and tribological loads. Here, we discuss the influence of the manufacturing process on the mechanical properties and the serviceability of the extruded profile in a selected application. The development of existing formulas and processing parameters are shown with the objective to expand the material application from WPC-decking to use in mechanical engineering
Das Tragprofil ist das zentrale Element in einem Hängefördersystem. Das Bauteil wird durch zeitlich veränderliche mechanische und tribologische Lasten beansprucht. Nachfolgend wird der Einfluss des Herstellungsprozesses auf die mechanischen Eigenschaften und die Gebrauchsfähigkeit eines extrudierten Trag- und Gleitprofils aus WPC im gewählten Anwendungsfall vorgestellt. Die notwendige Weiterentwicklung bestehender Rezepturen und Verarbeitungsverfahren wird aufgezeigt, um den Anwendungsbereich des Werkstoffes WPC vom Bereich Terassendielen auf den Maschinenbau zu erweitern

Powertrain mounts' purpose is to mount the engine and the gearbox in the car. Besides that, it isolate the body from the powertrain movements and road excitation. The most common material in powertrain mounts bracket is aluminum but lately, fibre reinforced polymer (FRP) has been acting as a substitute for the aluminum. The major drive forces for the change is the possibility to decrease the weight and improve the attribute noise, vibrations and harshness (NVH). The main objective of this study was to compare aluminum and FRP in order to find advantages and disadvantages for use in a powertrain mount bracket. FRP's have in earlier investigations at Volvo Cars been assumed to be isotropic, although it is orthotropic due to fiber orientation. Hence, a comparison between isotropic and orthotropic material properties for the powertrain mount bracket was conducted. There was no established method for modelling orthotropic materials available at the powertrain mount department, so a suggestion of a work process was presented in this thesis. Information regarding FRP, as well as a comparison to aluminum was presented in a literature study. The different materials and material models were compared in series of stress-strain and eigenmode FEM analyses. The results from the stress-strain analyses evinced that the design for the aluminum bracket can withstand the loads without exceeding the design limit. In the FRP bracket with orthotropic material properties, the design limit was exceeded for the load cases with the highest load. The results from the stress-strain and eigenmode analyses of the isotropic and orthotropic material models showed significant differences. According to the isotropic material model, the bracket could withstand the loads, and the eigenfrequencies was 25-30% higher compared to the orthotropic material model. The conclusions drawn from this study was that FRP's may be an advantageous material for the powertrain mount bracket, compared to aluminum. The FRP's bracket will decrease the cost, weight, and carbon footprint as well as improve the NVH. However, difficulties of using FRP's have been observed and need to be further investigated. The main difficulties identified are creep, fatigue, moisture absorption, and aging. This study has also proved that orthotropic material properties must be included in order to understand the material behavior and find critical areas.

Diploma work deals with the proposal of single purpose maschine for the maschining of test dumb bells of polymer composite material filled with glass fibre. The purpose of this maschine is to process the test parts with dimensions of 3x5 mm up to 4x8 mm. The maschined part can have a profile with a maximum cross section 20 mm, or 20x20 mm. Based on the given parametres I prepared the proposal of the engineering process the overall set up including the drive force, its own feeding of the object, cooling and waste removal.

Dans les matériaux composites autolubrifiants, la génération de particules d’usure est nécessaire pour assurer la lubrification. Dans les roulements à billes, ce type de lubrification est possible grâce au matériau de la cage, composé d’un matériau composite autolubrifiant, tandis que le reste du roulement est fait en métal (AISI 440C). Pour les applications spatiales, le RT/Duroid 5813 est un composite autolubrifiant reconnu pour les cages de ce type de roulements. Ce matériau a été largement utilisé car il a répondu aux besoins de la lubrification sèche dans l’espace. Cependant, la production de ce matériau a été arrêtée dans les années 90. Cette situation a conduit à la recherche d’un « matériau équivalent » , répondant à la fois aux besoins du marché spatial et aux « besoins tribologiques ». Aujourd’hui, le principal inconvénient lié à ces matériaux est le manque de prévisibilité de leur comportement tribologique. Dans ce travail, une approche couplée expérimentale et numérique a été proposée afin de modéliser le comportement tribologique des matériaux composites autolubrifiants. Le modèle numérique proposé a été nourri par des caractérisations expérimentaux (comme la tomographie à rayons X pour la création de la morphologie du matériau numérique, ou la microscopie à force atomique pour informer la valeur de l’adhésion entre les composants). Le but d’une telle démarche numérique est de palier les limites d’une approche entièrement expérimentale qui ne permet pas d’observer in-situ le contact de par son caractère confiné. L’objectif du présent travail est de donner une réponse au problème de compréhension du comportement tribologique de matériaux composites autolubrifiants dans le mécanisme de double transfert. Ceci en vue de contribuer au développement d’un nouveau matériau tribologique répondant aux besoins des applications spatiales. Parmi tous les matériaux autolubrifiants, le PGM-HT a été sélectionné dans cette étude car sa morphologie grossière a permis de construire une version numérique du matériau (avec la résolution du tomographe à rayons X utilisé dans ce travail). Néanmoins, l’approche proposée ici pour construire le modèle numérique peut être étendue à d’autres matériaux composites autolubrifiants. Le modèle numérique proposé dans ces travaux ouvre de nouvelles perspectives en termes de conception de matériaux, car il permet d’étudier directement les scénarios de dégradation et d’usure des matériaux composites. D’un point de vue général, il est à noter que la tribologie numérique est un outil offrant de multiples possibilités pour la compréhension des matériaux autolubrifiants, et permet d’aider dans le processus de prédiction du comportement tribologique des matériaux autolubrifiants
In self-lubricating composite materials, the generation of a stable third body layer is necessary to ensure contact lubrication. This is specially true for the contact in which these materials are directly involved, and also in other contacts implicating its counterface. Such type of lubrication is possible in self-lubricating bearings thanks to its cage material, which is made of the self-lubricating composite, while the rest of the bearing is usually made of AISI 440C. For space applications, RT/Duroid 5813 is a recognized self-lubricating composite cage material for this kind of bearings. This material has been widely used not only because of the space heritage, but also because it has satisfied the needs of space dry lubrication. However, the production of this material has been stopped in the 90’s, and it has placed the latter out of the market. This situation has led to the search for an equivalent material, that meets both the needs of the space market and the "tribological needs." Today, the main inconvenient related to these materials is the lack of predictability of their tribological behaviour. In this work, the "making of" a coupled numerical-experimental approach has been proposed in order to carry out the understanding of these materials. The goal of this numerical approach is to let to "complement" the limitations of a fully experimental or a fully numerical approach (the confined nature of the contact does not allow in situ observation). Such numerical approach has been informed with experimental test (as X-ray tomography for the creation of the numerical morphology, or atomic force microscopy to inform the value of adhesion between the components). Among all the self-lubricating materials, PGM-HT has been selected in this study because its coarse morphology let to build a numerical version of the material (with the resolution of the X-ray tomograph used in this work). Nevertheless, the approach that has been proposed here to build the numerical model, can be extended to other self-lubricating composite materials. The numerical model developed in this work opens new perspectives in terms of material design, as it makes it possible to directly study the scenarios of damage and wear of self-lubricating composite materials. From a general point of view, from this work it can be highlighted that numerical tribology is a tool that offers multiple possibilities in the understanding of self-lubricating materials, and that helps in the predictionof the tribological behaviour of self-lubricating materials. This work has then let to advance in the understanding of these materials

In this work, long-term behaviour of FRP RC beams has been investigated both analytically and experimentally to further extend the knowledge in this particular research domain. In this respect, a new methodology to determine the long-term deflections due to creep and shrinkage is presented. Based on multiplicative coefficients, the methodology is straightforward and simple, and therefore suitable to be used in design. In addition, an experimental campaign on two series of GFRP RC beams subject to long-term loading has been performed. Different reinforcement ratios, concrete strengths and sustained load levels have been considered. For comparison purposes steel reinforcement has also been used. The experimental long-term results have been reported and discussed. Furthermore they have been compared to predictions using the most representative procedures, as well as, the proposed methodology presented in this work.
En aquest treball, es presenta una nova metodologia per a la determinació de fletxes diferides degudes als efectes de la fluència i la retracció del formigó. La metodologia presentada es basa en coeficients multiplicadors, essent així un mètode directe i simple, apte per ser utilitzar en el disseny. Addicionalment, l’estudi presenta els resultats d’una campanya experimental realitzada en dues etapes, on bigues armades amb barres de material compost han estat sotmeses a càrregues a llarg termini. S’han considerat diferents quanties de reforç, resistències de formigó i nivells de càrrega. Per tal de comparar-ne els resultats, també s’han assajat bigues armades amb barres d’acer. Els resultats experimentals han estat analitzats i comparats amb els models de predicció més significatius, així com amb la metodologia desenvolupada i presentada en aquest estudi.

A problem is not a problem anymore if no solution exists; therefore, in the present dissertation, a novel manufacturing technique, the In Situ Forming of a Liquid Infused Preform (ISFLIP), is proposed as a solution to some typical problems that manufacturing of Fibre Reinforced Polymer (FRP) parts through Vacuum Infusion (VI) involves, such as not taking advantage of the full potential of FRPs, long processing times and lack of reproducibility. ISFLIP is a hybrid process between VI and diaphragm forming in which a flat preform of a stack of reinforcement fabrics is firstly impregnated with a low viscosity matrix and, then, formed over a mould while the matrix is still in the low viscosity state. Being focused on high performance FRPs and shell components, from simple to complex double curvature shapes, a number of trade-offs between VI and diaphragm forming were overcome to lay the foundations from which ISFLIP ability to manufacture FRP components has been proven. In order to adopt a VI manufacturing methodology that fitted ISFLIP targets, important contributions to more general VI have also been made in terms of part quality optimization, addressing the major concern that void content is in VI, with competitive manufacturing times. An effective vacuum degassing procedure in which bubble formation is enhanced through high speed stirring, and a non-conventional filling and post-filling strategy are proposed for this purpose. Eventually, void content was virtually eliminated and post-filling time minimized without affecting fibre content. In ISFLIP, textile preforms are formed together with a series of auxiliary materials (plastic films and sheets, textile fabrics and knitted meshes), most of them showing different in-plane deformation mechanisms. Forming performance of preforms, as well as final part quality, are severely affected by interactions between all these materials different in nature. Uncertainties on this respect and an initial evaluation of attainable shapes were also addressed to define a more focused research plan to the final goal, still distant, of implementing ISFLIP in a real production environment. Results obtained throughout the research project give cause for reasonable optimism in ISFLIP potential and future prospects.
Un problema deja de ser un problema si no existe solución; por lo tanto, en esta disertación, una novedosa técnica de fabricación, el Conformado In Situ de una Preforma Infusionada con resina Líquida (ISFLIP, por sus siglas en inglés), se propone como solución a algunos problemas típicos relacionados con la fabricación de piezas de Polímero Reforzado con Fibra (FRP) a través de la Infusión por Vacío (VI), problemas tales como el desaprovechamiento de todo el potencial de los FRPs, largos tiempos de procesado y falta de reproducibilidad. ISFLIP es un proceso híbrido entre la VI y el conformado por membrana elástica en el que una preforma plana formada a partir de un apilado de tejidos de refuerzo es en primera instancia impregnada con una resina de baja viscosidad y, entonces, conformada sobre un molde mientras que la matriz permanece todavía en el estado de baja viscosidad. Estando centrado en los FRPs de altas prestaciones y en componentes con formas tipo concha, desde curvaturas simples hasta formas con doble curvatura complejas, un número importante de compensaciones entre la VI y el conformado por membrana se han ido superando para asentar las bases a partir de las cuales se ha probado la capacidad de ISFLIP para fabricas componentes de FRP. Con la vista puesta en implementar una metodología de fabricación por VI que cumpliese los objetivos definidos para ISFLIP, también se han realizado importantes contribuciones de carácter más general relacionadas con la VI en términos de optimización de parámetros de calidad de las piezas, abordando la gran preocupación que la porosidad final supone en la VI, y consiguiendo unos tiempos de fabricación competitivos. Con este propósito se han propuesto un proceso de desgasificación por vacío muy efectivo en el que se favorece la nucleación de burbujas mediante la agitación a alta velocidad, y una prometedora y no convencional estrategia de llenado y post-llenado de la preforma. Finalmente, se consiguió virtualmente eliminar la porosidad atrapada en las piezas, minimizando el tiempo de post-llenado sin afectar la fracción de fibra contenida. En ISFLIP las preformas textiles se conforman junto con una serie de materiales auxiliares (films y hojas plásticas, mallas y tejidos textiles), que muestran diferentes mecanismos de deformación en plano. El conformado de las preformas y el acabado final de las piezas se ve severamente afectado por todas las interacciones entre todos estos materiales diferentes en naturaleza. También se han abordado las incertidumbres que surgen al respecto y una evaluación inicial de las geometrías abarcables para definir un plan de investigación más concreto con el que poder afrontar la meta final, todavía distante, de implementar ISFLIP en un entorno productivo real. Los resultados obtenidos a lo largo de este proyecto de investigación permiten ser razonablemente optimistas en cuanto al potencial de ISFLIP y sus expectativas.

Vielschichtige Eigenschaftsprofile benötigen zunehmend moderne Verbundwerkstoffe und Werkstoffverbunde einschließlich der raschen Entfaltung neuer Fertigungstechnologien, da der monolithische Werkstoff bzw. ein einziger Werkstoff den heutigen komplexen Anforderungen nicht mehr genügen kann. Zukünftige Werkstoffsysteme haben wirtschaftlich eine Schlüsselposition und sind auf den Wachstumsmärkten von grundlegender Bedeutung. Gefragt sind maßgeschneiderte Leichtbauwerkstoffe (tailor-made composites) mit einem adaptierten Design. Dazu müssen Konzepte entwickelt werden, um die Kombination der Komponenten optimal zu gestalten. Das erfordert werkstoffspezifisches Wissen und Korrelationsvermögen sowie die Gestaltung komplexer Technologien, auch unter dem Aspekt der kontinuierlichen Massen- und Großserienfertigung (in-line, in-situ) und damit der Kostenreduzierung bislang teurer Verbundwerkstoffe und Werkstoffverbunde. In der vorliegenden Arbeit wird in vergleichbarer und vergleichender Art und Weise sowie abstrahierter Form ein Bogen über das Gesamtgebiet der Verbundwerkstoffe und Werkstoffverbunde gespannt. Eine zusammenfassende Publikation über dieses noch sehr junge, aber bereits breit aufgestellte Wissenschaftsgebiet fehlt bislang. Das ist der Separierung der einzelnen, fest aufgeteilten Gruppierungen der Verbundwerkstoffe geschuldet. Querverbindungen werden selten hergestellt. Dieses Defizit in einem gewissen Maße auszugleichen, ist Ziel der Arbeit. Besondere Berücksichtigung finden Begriffsbestimmungen und Klassifikationen, Herstellungsverfahren und Eigenschaften der Werkstoffe. Es werden klare Strukturierungen und Übersichten herausgearbeitet. Zuordnungen von etablierten und neuen Technologien sollen zur Begriffsstabilität der Terminologien „Mischbauweise“ und „Hybrider Verbund“ beitragen. Zudem wird die Problematik „Recycling und Recyclingtechnologien“ diskutiert. Zusammenfassend werden Handlungsfelder zukünftiger Forschungs- und Entwicklungsprojekte spezifiziert. Aus dem Blickwinkel der verschiedenen Herstellungsrouten insbesondere für Halbzeuge und Bauteile und der dabei gewonnenen Erkenntnisse werden verallgemeinerte Konzepte für tailor-made Verbundwerkstoffe und Werkstoffverbunde vorgeschlagen („Stellschraubenschema“). Diese allgemeinen Werkstoffkonzepte werden auf eigene aktuelle Forschungsprojekte der Schwerpunktthemen Metallmatrix- und Polymermatrix-Verbundwerkstoffe sowie der hybriden Werkstoffverbunde appliziert. Forschungsfelder für zukünftige Projekte werden abgeleitet. Besonderes Augenmerk gilt den hybriden Verbunden als tragende Säule zukünftiger Entwicklungen im Leichtbau. Hier spielen in-line- und in-situ-Prozesse eine entscheidende Rolle für eine großseriennahe, kosteneffiziente und ressourcenschonende Produktion
Complex property profiles require increasingly advanced composite materials and material compounds, including the rapid deployment of new production technologies, because the monolithic material or a single material can no longer satisfy today's complex requirements. Future material systems are fundamentally important to growth markets, in which they have an economically key position. Tailor-made lightweight materials (tailor-made composites) with an adapted design are needed. These concepts have to be developed to design the optimum combination of components. This requires material-specific knowledge and the ability to make correlations, as well as the design of complex technologies. Continuous large-scale and mass production (in-line, in-situ), thus reducing the costs of previously expensive composite materials and material compounds, is also necessary. The present work spans the entire field of composite materials and material compounds in a comparable and comparative manner and abstract form. A summarizing publication on this still very new, but already broad-based scientific field is not yet available. The separation of the individual, firmly divided groups of the composite materials is the reason for this. Cross-connections are rarely made. The objective of this work is to compensate to some extent for this deficiency. Special consideration is given to definitions and classifications, manufacturing processes and the properties of the materials. Clear structures and overviews are presented. Mapping established and new technologies will contribute to the stability of the terms "mixed material compounds" and "hybrid material compounds". In addition, the problem of recycling and recycling technologies is discussed. In summary, areas for future research and development projects will be specified. Generalized concepts for tailor-made composite materials and material compounds are proposed ("adjusting screw scheme") with an eye toward various production routes, especially for semi-finished products and components, and the associated findings. These general material concepts are applied to own current research projects pertaining to metal-matrix and polymer-matrix composites and hybrid material compounds. Research fields for future projects are extrapolated. Particular attention is paid to hybrid material compounds as the mainstay of future developments in lightweight construction. In-line and in-situ processes play a key role for large-scale, cost- and resource-efficient production

Abstract My Ph.D. project focused on the tailoring of the surface properties of oxide substrates for the preparation of advanced composite materials and devices. The initial focus of my research activity was the surface modification of halloysite nanotubes (HNT), a natural material with unique structural features. I then extended my investigation to other oxides (titanium dioxide, TiO2, and Superparamagnetic Iron Oxide Nanoparticles, SPION), applying the surface modification approaches developed for HNT substrates. The resulting oxide-based hybrid systems showed promising properties as stimuli-responsive devices for health and environmental applications, and as fillers for polymeric nanocomposites with enhanced durability. The main results obtained for each oxide material will be presented in the following sections. 1. Halloysite nanotubes (HNT) Halloysite is a polymorph of kaolinite which naturally wraps itself to form tubular structures (Figure 1A). It is one of the few nanotubular systems presenting an inner lumen and an outer surface characterized by different surface charge and structural composition: the internal surface exposes aluminium hydroxyl groups, while the outermost layer is silica[1]. Among its many potential applications, its tubular dual structure has sparked interest in the field of nanomedicine and polymer nanocomposites[2]. However, only few reports investigated the possibility of a selective functionalization of the inner and outer HNT surfaces. During my first year of PhD, I investigated the selective functionalization of HNT with phosphonates, hetero-organic compounds bearing a C PO(OH)2 group, as potential site-specific linkers for the grafting of active molecules. I took advantage of the phosphonic acid selectivity towards certain oxides (especially aluminium oxides) to achieve surface-specific functionalization of HNT. An in-depth comprehension of such hybrid systems is no trivial matter, as the inner and outer HNT surfaces possess different accessibility and reactivity but are not separable. For this reason, beside HNT, I used purposely prepared model oxides, mimicking the inner and outer nanotube surfaces, to better study the actual selectivity towards SiO2 and AlOOH exhibited by the phosphonate moiety. Octylphosphonic acid (OPA) was chosen as functionalizing agent, as its alkyl chain allowed me to monitor the surface modification through changes in the water contact angle (θ). I found that the oxide isoelectric point (pHIEP) plays a major role in determining a stable OPA adsorption: while AlOOH showed good reactivity towards OPA, SiO2, which is negatively charged at the impregnation pH (pH 4), did not react with the phosphonate heads. The functionalization reversibility was also assessed: Samples showed OPA release at pH values more alkaline than the oxide isoelectric point, when the surface charge is negative. Overall, these results support an OPA-oxide bond governed both by electrostatic and covalent forces. The selective functionalization of HNT inner lumen was also demonstrated via a combination of characterization techniques, including FTIR spectroscopy, ζ-potential measurement and water dispersibility assay. Another scantly investigated topic regarding HNT nanosystems is their covalent modification. Covalent grafting allows for a superior control over the release kinetics of active principles, as the initial release burst observed in the case of electrostatically bound compounds is greatly reduced. In this respect, I studied the covalent attachment of a biologically active molecule to HNT via an imine bond. This type of covalent bond was chosen to open up the possibility for a controlled release of the bioactive molecule activated by pH changes. To this purpose, HNT was functionalized with (3 aminopropyl)triethoxysilane (APTES), a bifunctional linker which can cover the oxide surface with amino groups. Despite being non-selective for either of the two phases, it was chosen based on the relative ease with which it can be grafted to the substrate. Then, tetrathia[7]helicene aldehyde (7-THA) was bound to HNT via APTES, exploiting imine chemistry. 7-THA belongs to a group of polyaromatic molecules capable, thanks to their peculiar helicoidal shape, of intercalating DNA strands, which is at the basis of anti-sense therapy[3]. Nonetheless, HNT abysmal water solubility highly reduces their bioavailability and makes the use of hydrophilic nanocarriers necessary. I tested the relative release efficiency of 7-THA under slightly different pH conditions, representative of lysosomal, tumoral and healthy extracellular pH values. The resulting HNT-7TH system was studied in detail via XPS and angle-resolved near edge X-ray absorption fine structure spectroscopy (NEXAFS) at the Material Science Beamline of the Elettra synchrotron facility. The latter characterization technique required the synthesis and functionalization of oxide films replicating HNT surfaces, in order to probe the orientation of a population of adsorbed molecules with respect to the surface plane. NEXAFS results suggested a preferential orientation of the aromatic rings of helicene normal to the oxide surface, possibly as a result of π-π stacking interactions (Figure 1B). XPS analyses were performed at each stage of the preparation process of HNT-7TH and after the release test at pH 5 (Figure 1C): the observed change in the elemental composition indicated a release of 70% of the loaded 7-THA as a result of pH change. Given the interest for tumour therapy applications, in vitro tests were carried out to assess the selectivity of this system on cancer cells. The effect of HNT-7TH on the viability of bladder cancer cells was tested by Dr Riccardo Vago at the IRCCS San Raffaele Scientific Institute. Two different cell lines, named 5637 and HT-1376, with an extracellular pH of 7.2 and 6.8 respectively, were subjected to increasing concentrations of HNT 7TH and bare HNT as control. HNT 7TH was found to cause a more marked reduction in cell viability on the HT-1376 cell line, suggesting a faster release of the cytotoxic 7-THA at slightly acidic pH values. Release kinetics also supported this hypothesis: a new model system utilizing benzodithiophene (BDT), a more water-soluble mimic of 7-THA, was prepared analogously to the HNT-7TH powders. The release of BDT was monitored via UV-vis spectroscopy at pH 5.0, 6.8 and 7.4. The amount of released BDT at pH 7.4 was negligible even after 48 h; decreasing the pH value to 6.8 visibly increased release rates, while the release efficiency was highest for the treatment at pH 5.0. The natural origin of HNT causes a marked variability in its physicochemical features, such as its morphology and surface charge, depending on the extraction site[4]. I investigated this aspect, often overlooked in the literature, with respect to the integration of HNT as nanofillers in polymer composites. Halloysite has been investigated as filler owing to its low cost, thermal and mechanical resistance, and high aspect ratio, which is crucial to guarantee strong polymer-filler interactions[5]. In this regard, I investigated also the effect of surface functionalization in promoting HNT compatibility with the chosen polymer matrix, Polyamide 6 (PA6). PA6 has a broad range of applications, from the automotive sector to the textile industry, owing to its good mechanical performances and high thermal resistance. However, when exposed to humid conditions, it suffers from degradation in a matter of few weeks[6], as water can interpenetrate within the hydrogen bonds between –NH and C=O groups and disrupt them, leading to the loss of tensile strength and elasticity[6–9]. The addition of nanotubular fillers represents a viable strategy for overcoming this issue, although the additive/polymer interface at high filler content can become a privileged site for moisture accumulation[10]. For this reason, HNT were added to PA6 in very low amounts (< 5%w). The roles played in the reinforcement of the polymer by the physicochemical properties of HNT from two different sources and their functionalization with APTES were investigated in composites prepared by two different dispersion techniques (in situ polymerization vs. melt blending). The aspect ratio (5 vs. 15) and surface charge (−31 vs. −59 mV) of the two HNT samples proved crucial in determining their distribution within the polymer matrix: both in situ and melt blending dispersion techniques showed that lower surface area, higher aspect ratio and greater surface charge enhance filler incorporation and improve the final composite performance. Finally, filler surface modification with APTES played a major role in the durability of the PA6-HNT nanocomposites: after 1680 h of hydrothermal ageing, functionalized HNT reduced the diffusion of water into the polymer, lowering water uptake after 600 h up to 90%, increasing the materials durability. Positive effects could also be measured regarding the molecular weight distribution and rheological behaviour. These improvements could be related to the presence of amino groups on the HNT surface, which lowered the filler surface energy and prevented the diffusion of water molecules into the nanocomposites[11]. 2. Titanium dioxide TiO2 is arguably the most extensively investigated semiconductor for photocatalytic applications, from solar cells to pollutant abatement. However, applications of TiO2 for the preparation of smart surfaces are comparatively less common. My research interest in TiO2 started with the preparation of surfaces with controlled wetting features. First, the surface of commercial TiO2 powders was functionalized with perfluorinated alkylsilanes. Then, I employed the photocatalytic features of TiO2 films to produce patterned surfaces with superhydrophilic/superhydrophobic contrast by means of photocatalytic lithography. During the course of my second year of PhD, I focused on the deposition of TiO2 films with controlled porosity followed by their surface modification to impart them functional properties. These systems were applied as photo renewable coatings for electrochemical sensors and stimuli-responsive surfaces for the controlled release of active compounds. Control over film porosity was achieved by a hard-template approach using polystyrene (PS) nanospheres of different sizes, both commercial and synthesized in-house following a classical procedure[12]. Different film deposition strategies were investigated. First, I deposited a TiO2 layer on top of a porous SiO2 coating on a FTO electrode. Extensive characterization via cyclic voltammetry showed that the addition of a TiO2 layer increased peak currents due to the promoted diffusion of the analyte in the porous structure, driven by capillary effects[13] (Figure 2A). Furthermore, the TiO2 layer promoted the light-activated regeneration of the electrode surface after having been fouled. Starting from there, I investigated the possibility of pure TiO2 mesoporous films, a task made difficult by the intrinsic incompatibility between an alcohol-based TiO2 sol, extremely prone to hydrolysis, and a water-based PS suspension. This issue was solved by either adopting an aqueous TiO2 sol, slowly evaporated in presence of the particle templates (Figure 2B), or by performing a solvent exchange procedure on the PS suspension. The latter procedure resulted in pure TiO2 films with easily tuneable thickness and homogeneous porosity, opening the door to a fine tuning of the cyclovoltammetric response. The self-cleaning features of the pure TiO2 films were also tested by purposely fouling their surface with long-alkyl chain substituents: a fast and complete regeneration of the surface was achieved upon irradiation with UV light. The prepared pure TiO2 porous films were also used as substrates for the loading of bioactive substances. Cinnamaldehyde, a natural substance known for its antimicrobial properties but unstable in environmental conditions, was anchored to the film surface via APTES linkers through an imine bond, using a protocol similar to the one developed for 7-THA-loaded HNT. The immobilized cinnamaldehyde proved stable to environmental conditions for months and tests of pH triggered release performed at pH 5.5 and 7.4, showed a faster release at lower pH values. Finally, the photoactive nature of the oxide substrate could be used to promote the self-cleaning of the fouled surface after usage: after UV-light regeneration, the TiO2 film could be functionalized anew and reused. 3. Superparamagnetic Iron Oxide Nanoparticles (SPION) During my third year of PhD, I spent six months at the Technische Universiteit Delft, Netherlands, in the Advanced Soft Matter group, under the supervision of Dr Laura Rossi. There my research focused on the synthesis and surface modification of Ultrasmall SPION. SPION have gained increasing attention thanks to their peculiar behaviour: being smaller than a single magnetic crystal domain, they are free to rotate unless a specific orientation is induced by an external field. Due to their magnetic properties, they can be adopted in hyperthermia, drug delivery and as contrast agents (CA) for magnetic resonance imaging (MRI)[14]. Contrast agents are commonly used to speed up either T1 or T2 relaxation, enhancing the local contrast in pathological tissue to produce more detailed images. T1 CA are commonly represented by gadolinium complexes, while SPION are generally adopted as T2 CA. The first are preferred by radiologists, while the latter are less favoured because the darker tones they provide can be mistaken with low resolution and background interference[15,16]. Nonetheless, Gd-based CA present a serious health risk for those patients unable to efficiently remove these heavy metal complexes due to pre-existent kidney or liver pathologies[17]. While most SPION act as T2 CA, several papers report their potential use as T1 CA if their size is sufficiently small, indicatively less than 4 nm[18,19]. These materials are known as Ultrasmall SPION, or USPION. My aim was to develop a synthetic protocol to prepare USPION suitable as T1 contrast agents via co-precipitation, to minimize synthetic requirements. To this purpose, the influence of several parameters such as reaction temperature, base type, purification procedure, stabilizing agent and precursor concentration was investigated. Particles were synthesised at room temperature (RT) and 50°C, using NH4OH, N(CH3)4OH or NaOH as base. Particle purification was performed via magnetic decantation, centrifugation and dialysis against different solutions (water, citric acid and sodium citrate solutions). Sodium oleate, (3-aminopropyl)triethoxysilane (APTES) and citric acid were tested as stabilizing agents and precursor concentration was varied between 1 M and 0.5 M. It was found that the best results were obtained at room temperature and that the peptizing effect of the tetramethylammonium ion is crucial to guarantee an optimal colloidal stability, making N(CH3)4OH the base of choice. The concentration of starting precursor solutions proved to be the determining factor acting on particle size, as halving it led to a narrow particle size distribution centred around 3 nm, a significant shift from the starting 7 nm (Figure 3). Centrifugation was ineffective when adopted to wash the nanoparticles, but it proved a promising size-selection tool that could be combined with dialysis in an efficient work up protocol. Dialysis proved to be the most efficient technique to remove potentially toxic impurities, but it negatively impacted the colloidal stability, which could be mitigated by the use of a proper stabilizing agent. To preserve a high colloidal stability even after the removal of N(CH3)4OH, surface modification with several stabilizing agents was tested. Among the tested molecules, citric acid was the only one to show positive effects on particle size and aggregation, more so when added before the start of particle nucleation. These results represent a promising advance in the development of efficient T1 contrast agents based on USPION in terms of lowering the synthetic requirements: monodisperse magnetic nanoparticles were prepared through a simple co-precipitation procedure, performed at room temperature, without the aid of any polymeric additive. References [1] Y. Lvov, W. Wang, L. Zhang, R. Fakhrullin, Halloysite Clay Nanotubes for Loading and Sustained Release of Functional Compounds, Adv. Mater. 28 (2016) 1227–1250. doi:10.1002/adma.201502341. [2] E. Abdullayev, V. Abbasov, A. Tursunbayeva, V. Portnov, H. Ibrahimov, G. Mukhtarova, Y. Lvov, Self-healing coatings based on halloysite clay polymer composites for protection of copper alloys, ACS Appl. Mater. Interfaces. 5 (2013) 4464–4471. doi:10.1021/am400936m. [3] E. Licandro, S. Cauteruccio, D. Dova, Thiahelicenes, in: 2016: pp. 1–46. doi:10.1016/bs.aihch.2015.12.001. [4] E. Joussein, S. Petit, J. Churchman, B. Theng, D. Righi, B. Delvaux, Halloysite clay minerals – a review, Clay Miner. 40 (2005) 383–426. doi:10.1180/0009855054040180. [5] M.R. Ayatollahi, S. Shadlou, M.M. Shokrieh, M. Chitsazzadeh, Effect of multi-walled carbon nanotube aspect ratio on mechanical and electrical properties of epoxy-based nanocomposites, Polym. Test. 30 (2011) 548–556. doi:10.1016/j.polymertesting.2011.04.008. [6] I. Ksouri, O. De Almeida, N. Haddar, Long term ageing of polyamide 6 and polyamide 6 reinforced with 30% of glass fibers: physicochemical, mechanical and morphological characterization, J. Polym. Res. 24 (2017) 133. doi:10.1007/s10965-017-1292-6. [7] H. Shinzawa, J. Mizukado, Water absorption by polyamide (PA) 6 studied with two-trace two-dimensional (2T2D) near-infrared (NIR) correlation spectroscopy, J. Mol. Struct. 1217 (2020) 128389. doi:10.1016/j.molstruc.2020.128389. [8] K.R. Rajeesh, R. Gnanamoorthy, R. Velmurugan, Effect of humidity on the indentation hardness and flexural fatigue behavior of polyamide 6 nanocomposite, Mater. Sci. Eng. A. 527 (2010) 2826–2830. doi:10.1016/j.msea.2010.01.070. [9] D.P.N. Vlasveld, J. Groenewold, H.E.N. Bersee, S.J. Picken, Moisture absorption in polyamide-6 silicate nanocomposites and its influence on the mechanical properties, Polymer (Guildf). 46 (2005) 12567–12576. doi:10.1016/j.polymer.2005.10.096. [10] K.P. Pramoda, T. Liu, Effect of moisture on the dynamic mechanical relaxation of polyamide-6/clay nanocomposites, J. Polym. Sci. Part B Polym. Phys. 42 (2004) 1823–1830. doi:10.1002/polb.20061. [11] K. Prashantha, M.F. Lacrampe, P. Krawczak, Processing and characterization of halloysite nanotubes filled polypropylene nanocomposites based on a masterbatch route: effect of halloysites treatment on structural and mechanical properties, Express Polym. Lett. 5 (2011) 295–307. doi:10.3144/expresspolymlett.2011.30. [12] J.W. Goodwin, J. Hearn, C.C. Ho, R.H. Ottewill, Studies on the preparation and characterization of monodisperse polystyrene latices, Colloid Polym. Sci. 252 (1974) 464–471. [13] L. Rimoldi, V. Pifferi, D. Meroni, G. Soliveri, S. Ardizzone, L. Falciola, Three-dimensional mesoporous silica networks with improved diffusion and interference-abating properties for electrochemical sensing, Electrochim. Acta. 291 (2018) 73–83. doi:10.1016/j.electacta.2018.08.131. [14] J. Dulińska-Litewka, A. Łazarczyk, P. Hałubiec, O. Szafrański, K. Karnas, A. Karewicz, Superparamagnetic Iron Oxide Nanoparticles—Current and Prospective Medical Applications, Materials (Basel). 12 (2019) 617. doi:10.3390/ma12040617. [15] Y. Okuhata, Delivery of diagnostic agents for magnetic resonance imaging, Adv. Drug Deliv. Rev. 37 (1999) 121–137. doi:10.1016/S0169-409X(98)00103-3. [16] J.-C. Brisset, M. Sigovan, F. Chauveau, A. Riou, E. Devillard, V. Desestret, M. Touret, S. Nataf, J. Honnorat, E. Canet-Soulas, N. Nighoghossian, Y. Berthezene, M. Wiart, Quantification of Iron-Labeled Cells with Positive Contrast in Mouse Brains, Mol. Imaging Biol. 13 (2011) 672–678. doi:10.1007/s11307-010-0402-1. [17] M. Rogosnitzky, S. Branch, Gadolinium-based contrast agent toxicity: a review of known and proposed mechanisms, BioMetals. 29 (2016) 365–376. doi:10.1007/s10534-016-9931-7. [18] H. Wei, O.T. Bruns, M.G. Kaul, E.C. Hansen, M. Barch, A. Wiśniowska, O. Chen, Y. Chen, N. Li, S. Okada, J.M. Cordero, M. Heine, C.T. Farrar, D.M. Montana, G. Adam, H. Ittrich, A. Jasanoff, P. Nielsen, M.G. Bawendi, Exceedingly small iron oxide nanoparticles as positive MRI contrast agents, Proc. Natl. Acad. Sci. 114 (2017) 2325–2330. doi:10.1073/pnas.1620145114. [19] Y. Bao, J.A. Sherwood, Z. Sun, Magnetic iron oxide nanoparticles as T 1 contrast agents for magnetic resonance imaging, J. Mater. Chem. C. 6 (2018) 1280–1290. doi:10.1039/C7TC05854C.

Cette étude est consacrée à la modélisation, par les lois de mélange, de la permittivité diélectrique de matériaux composites absorbants aux ondes hyperfréquences. Ces matériaux sont constitués d'inclusions conductrices (noir de carbone ou polymères conducteurs) dispersées dans une matrice polymère isolante. Leurs propriétés électromagnétiques dépendent fortement de la fraction volumique et de la répartition géométrique des charges au sein des matériaux, et notamment du phénomène de percolation. Les modèles basés sur la représentation géométrique asymétrique, présentés au premier chapitre, ne peuvent pas rendre compte d'un seuil de percolation différent de 0 ou de 1. Les modèles de milieu effectif, décrits au deuxième chapitre, constituent un important progrès dans la modélisation des données expérimentales, grâce à la représentation géométrique symétrique. Ils sont cependant mal adaptés au voisinage du seuil de percolation, car la percolation présente une forte analogie avec une transition de phase du second ordre. Le troisième chapitre développe cette analogie, et montre que les propriétés des composites au voisinage du seuil de percolation doivent être décrites par les lois de changement d'échelle. Les techniques pour abaisser le seuil de percolation sont présentées dans le quatrième chapitre. Enfin, le cinquième chapitre est consacré aux modèles récents de milieu effectif généralisé (GEM). Ces modèles combinent les lois de milieu effectif et les lois de changement d'échelle, et fournissent la meilleure modélisation des données expérimentales envisagées dans ce mémoire

Vielschichtige Eigenschaftsprofile benötigen zunehmend moderne Verbundwerkstoffe und Werkstoffverbunde einschließlich der raschen Entfaltung neuer Fertigungstechnologien, da der monolithische Werkstoff bzw. ein einziger Werkstoff den heutigen komplexen Anforderungen nicht mehr genügen kann. Zukünftige Werkstoffsysteme haben wirtschaftlich eine Schlüsselposition und sind auf den Wachstumsmärkten von grundlegender Bedeutung. Gefragt sind maßgeschneiderte Leichtbauwerkstoffe (tailor-made composites) mit einem adaptierten Design. Dazu müssen Konzepte entwickelt werden, um die Kombination der Komponenten optimal zu gestalten. Das erfordert werkstoffspezifisches Wissen und Korrelationsvermögen sowie die Gestaltung komplexer Technologien, auch unter dem Aspekt der kontinuierlichen Massen- und Großserienfertigung (in-line, in-situ) und damit der Kostenreduzierung bislang teurer Verbundwerkstoffe und Werkstoffverbunde. In der vorliegenden Arbeit wird in vergleichbarer und vergleichender Art und Weise sowie abstrahierter Form ein Bogen über das Gesamtgebiet der Verbundwerkstoffe und Werkstoffverbunde gespannt. Eine zusammenfassende Publikation über dieses noch sehr junge, aber bereits breit aufgestellte Wissenschaftsgebiet fehlt bislang. Das ist der Separierung der einzelnen, fest aufgeteilten Gruppierungen der Verbundwerkstoffe geschuldet. Querverbindungen werden selten hergestellt. Dieses Defizit in einem gewissen Maße auszugleichen, ist Ziel der Arbeit. Besondere Berücksichtigung finden Begriffsbestimmungen und Klassifikationen, Herstellungsverfahren und Eigenschaften der Werkstoffe. Es werden klare Strukturierungen und Übersichten herausgearbeitet. Zuordnungen von etablierten und neuen Technologien sollen zur Begriffsstabilität der Terminologien „Mischbauweise“ und „Hybrider Verbund“ beitragen. Zudem wird die Problematik „Recycling und Recyclingtechnologien“ diskutiert. Zusammenfassend werden Handlungsfelder zukünftiger Forschungs- und Entwicklungsprojekte spezifiziert. Aus dem Blickwinkel der verschiedenen Herstellungsrouten insbesondere für Halbzeuge und Bauteile und der dabei gewonnenen Erkenntnisse werden verallgemeinerte Konzepte für tailor-made Verbundwerkstoffe und Werkstoffverbunde vorgeschlagen („Stellschraubenschema“). Diese allgemeinen Werkstoffkonzepte werden auf eigene aktuelle Forschungsprojekte der Schwerpunktthemen Metallmatrix- und Polymermatrix-Verbundwerkstoffe sowie der hybriden Werkstoffverbunde appliziert. Forschungsfelder für zukünftige Projekte werden abgeleitet. Besonderes Augenmerk gilt den hybriden Verbunden als tragende Säule zukünftiger Entwicklungen im Leichtbau. Hier spielen in-line- und in-situ-Prozesse eine entscheidende Rolle für eine großseriennahe, kosteneffiziente und ressourcenschonende Produktion.
Complex property profiles require increasingly advanced composite materials and material compounds, including the rapid deployment of new production technologies, because the monolithic material or a single material can no longer satisfy today's complex requirements. Future material systems are fundamentally important to growth markets, in which they have an economically key position. Tailor-made lightweight materials (tailor-made composites) with an adapted design are needed. These concepts have to be developed to design the optimum combination of components. This requires material-specific knowledge and the ability to make correlations, as well as the design of complex technologies. Continuous large-scale and mass production (in-line, in-situ), thus reducing the costs of previously expensive composite materials and material compounds, is also necessary. The present work spans the entire field of composite materials and material compounds in a comparable and comparative manner and abstract form. A summarizing publication on this still very new, but already broad-based scientific field is not yet available. The separation of the individual, firmly divided groups of the composite materials is the reason for this. Cross-connections are rarely made. The objective of this work is to compensate to some extent for this deficiency. Special consideration is given to definitions and classifications, manufacturing processes and the properties of the materials. Clear structures and overviews are presented. Mapping established and new technologies will contribute to the stability of the terms "mixed material compounds" and "hybrid material compounds". In addition, the problem of recycling and recycling technologies is discussed. In summary, areas for future research and development projects will be specified. Generalized concepts for tailor-made composite materials and material compounds are proposed ("adjusting screw scheme") with an eye toward various production routes, especially for semi-finished products and components, and the associated findings. These general material concepts are applied to own current research projects pertaining to metal-matrix and polymer-matrix composites and hybrid material compounds. Research fields for future projects are extrapolated. Particular attention is paid to hybrid material compounds as the mainstay of future developments in lightweight construction. In-line and in-situ processes play a key role for large-scale, cost- and resource-efficient production.

Ce travail traite de l'étude des suspensions de particules axisymétriques et rigides dans une matrice fluide. Plus précisément, nous nous sommes intéressés au comportement rhéologique de ces matériaux. Le contexte industriel associe est la mise en forme des thermoplastiques renforces par des fibres courtes. Dans une partie théorique, nous proposons un modèle de comportement, issu d'une approche micromécanique, pour les suspensions de sphéroïdes rigides dans une matrice newtonienne : une loi reliant les contraintes et les taux de déformations macroscopiques, une équation pour décrire le mouvement des particules. Ce modèle de comportement est applicable au cas des solutions en régime semi-dilue. Dans une partie expérimentale, nous proposons d'identifier des paramètres rhéologiques du modèle de comportement. A cet effet, des mesures de viscosité en cisaillement sont présentées, ainsi qu'un nouvel écoulement. Ce dernier écoulement, dit écoulement en croix, doit permettre d'identifier le paramètre rhéologique caractérisant l'anisotropie des suspensions.