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Ce travail de thèse s‟articule autour de l‟apport des techniques de l‟analyse thermique à l‟étude et au suivi des phénomènes de vieillissement thermique et photochimique des matériaux polymères. Après une étude bibliographique sur l‟état de l‟art dans ce domaine, la thèse a présenté les résultats obtenus lors de l‟application de l‟Analyse Thermique Différentielle (DSC) à l‟étude du vieillissement de ces matériaux. Le travail de cette partie a porté sur la cristallinité du Poly (Acide Lactique) (PLA) et du Poly (Ethylène Téréphtalate) (PET). Une corrélation a été établie entre les résultats issus de la DSC et ceux obtenus par Spectroscopie Infrarouge à Transformée de Fourier (FTIR) en ce qui concerne l‟évolution de la cristallinité au cours du vieillissement du polymère. Une seconde partie du travail a porté sur le suivi des propriétés thermo-optiques par photo-DSC. Ce travail a été illustré par l‟étude du Poly (Chlorure de Vinyle) (PVC). Une dernière section de ce travail s‟est attachée au suivi, par DSC et par Analyse Thermogravimétrique (ATG), de la diffusion de l‟eau dans la matrice polymère en cours de vieillissement. Ici, c‟est la technique dite thermoporosimétrie qui a été choisie. Les résultats ont été comparés à ceux obtenus par le couplage ATG-DSC-Humidité. Le travail, dans cette partie, a porté sur le PolyIsoprène (PI) et sur le PolyDiMéthylSiloxane) (PDMS). / This work focuses on the contribution of thermal analysis techniques to the multi-scale study and monitoring of the phenomena of thermal and photochemical aging of polymer materials.After a bibliographic study on the state of the art in this field, the thesis presented the results obtained during the application of the Differential Scanning Calorimetry (DSC) to the study of the aging of these materials. First of all, this part focused on the crystallinity of Poly (Lactic Acid) (PLA) and Poly (Ethylene Terephthalate) (PET). A correlation was established between the results obtained from the DSC and those obtained by Fourier Transform Infrared Spectroscopy (FTIR) with respect to the evolution of the crystallinity during aging of the polymer.Furthermore, our work focused on the follow-up of the thermo-optical properties by photo-DSC. This work was illustrated by the study of Poly (Vinyl Chloride) (PVC).A final section of this work focuses on the DSC and ThermoGravimetric Analysis (TGA) monitoring of the diffusion of water in the polymer matrix during aging. Here, the technique known as Thermoporosimetry was chosen. The results were compared with those obtained by coupling ATG-DSC-Moisture. The type of products which are chosen in this part of study, were Polyisoprene (PI) and on PolyDiMethylSiloxane (PDMS).

The current research is part of a wider experimental program on creep modeling of glass mat reinforced polypropylene composites which are increasingly being used in molding automotive parts. This specific study is focused on the dimensional and thermal stability of chopped fibre mat and long fibre mat composites. The objective of the study is two-fold. First, to characterize in-situ the micro-failure mechanisms associated with damage accumulation during creep at room temperature and at service temperature (80°C) for stresses up to 67% of the ultimate tensile strength. Second, to characterize the effects of prolonged exposure at elevated temperature on the crystallinity and chemical degradation of the polypropylene matrix. In the first part of the investigation, micro-failure mechanisms including fibre-matrix interface, matrix yielding and cracking during the creep process have been captured in-situ using reflection microscopy. Specimens with 12 mm gauge length were mounted onto a Minimat tensile tester. The applied stress levels of interest were 33% and 67% of the ultimate tensile strength (UTS) at room temperature (RT) and high temperature (HT), respectively. It was found that the deformation mechanisms do not change with temperature but creep in the chopped fibre material is substantially higher than that in the long-fibre. Creep deformation is typically associated with multiple transverse crack initiation at the fibre-matrix interface, crack crazing and rapid coalescence of the small cracks leading to abrupt fracture. Debonding of the fibres is usually detected at the loading stage of the test but fibre breakage is minimal even at high temperature. The change in creep strain at room temperature is similar for both composites but creep strains are highly sensitive to the fibre-mat type at higher temperature. Long-fibre mat structures offer greater creep resistance. Micro-indentations on the matrix-rich regions showed elongation along the loading direction but shear yielding (distortion of indentations) was not noticeable. Using scanning electron microscopy (SEM), the fibre pullout was observed to be pronounced thus suggesting poor adhesion at the fibre-matrix interface. In the second part of this study, the effects of elevated temperature aging on the microstructural changes of isotactic polypropylene matrix in a composite have been studied using wide-angle X-ray scattering (WAXS) and Fourier-transform infrared spectroscopy (FTIR). The objective was to quantify small and slow changes in crystallinity due to thermal aging. To minimize sample variability, polypropylene resin was extracted from the molded composite plaque. Changes in crystallinity level and crystalline form were detected using WAXS after prolonged aging at 90 and 140 °C. FTIR was utilized to monitor in-situ crystallinity changes and to detect oxidation products due to thermal decomposition. The level of crystallinity was monitored by changes in the absorbance ratio of A997/A973 and A841/A973; the former ratio was found to be more sensitive for detecting crystallinity changes. Aging at 140°C resulted in oxidation. The kinetics of secondary crystallization for the aging conditions studied was characterized using Avrami plots.

The current research is part of a wider experimental program on creep modeling of glass mat reinforced polypropylene composites which are increasingly being used in molding automotive parts. This specific study is focused on the dimensional and thermal stability of chopped fibre mat and long fibre mat composites. The objective of the study is two-fold. First, to characterize in-situ the micro-failure mechanisms associated with damage accumulation during creep at room temperature and at service temperature (80°C) for stresses up to 67% of the ultimate tensile strength. Second, to characterize the effects of prolonged exposure at elevated temperature on the crystallinity and chemical degradation of the polypropylene matrix. In the first part of the investigation, micro-failure mechanisms including fibre-matrix interface, matrix yielding and cracking during the creep process have been captured in-situ using reflection microscopy. Specimens with 12 mm gauge length were mounted onto a Minimat tensile tester. The applied stress levels of interest were 33% and 67% of the ultimate tensile strength (UTS) at room temperature (RT) and high temperature (HT), respectively. It was found that the deformation mechanisms do not change with temperature but creep in the chopped fibre material is substantially higher than that in the long-fibre. Creep deformation is typically associated with multiple transverse crack initiation at the fibre-matrix interface, crack crazing and rapid coalescence of the small cracks leading to abrupt fracture. Debonding of the fibres is usually detected at the loading stage of the test but fibre breakage is minimal even at high temperature. The change in creep strain at room temperature is similar for both composites but creep strains are highly sensitive to the fibre-mat type at higher temperature. Long-fibre mat structures offer greater creep resistance. Micro-indentations on the matrix-rich regions showed elongation along the loading direction but shear yielding (distortion of indentations) was not noticeable. Using scanning electron microscopy (SEM), the fibre pullout was observed to be pronounced thus suggesting poor adhesion at the fibre-matrix interface. In the second part of this study, the effects of elevated temperature aging on the microstructural changes of isotactic polypropylene matrix in a composite have been studied using wide-angle X-ray scattering (WAXS) and Fourier-transform infrared spectroscopy (FTIR). The objective was to quantify small and slow changes in crystallinity due to thermal aging. To minimize sample variability, polypropylene resin was extracted from the molded composite plaque. Changes in crystallinity level and crystalline form were detected using WAXS after prolonged aging at 90 and 140 °C. FTIR was utilized to monitor in-situ crystallinity changes and to detect oxidation products due to thermal decomposition. The level of crystallinity was monitored by changes in the absorbance ratio of A997/A973 and A841/A973; the former ratio was found to be more sensitive for detecting crystallinity changes. Aging at 140°C resulted in oxidation. The kinetics of secondary crystallization for the aging conditions studied was characterized using Avrami plots.

This research investigates second harmonic generation in Rayleigh surface waves propagating in 9%Cr ferritic martensitic steel. Previous experimental results show that the nonlinearity parameter is sensitive to certain changes in a material's properties such as thermal embrittlement and hardness changes. Therefore, the nonlinearity parameter can be used as an indicator of thermal damage due to changes in dislocation density and precipitations. The specimens are isothermally aged for different holding times to create progressive changes in the microstructure and obtain different levels of thermal aging damage. As aging progresses the dislocation density decreases and precipitations are formed; these microstructural evolutions lead to changes in the nonlinearity parameter β. Nonlinear ultrasonic experiments are conducted for each specimen using a wedge transducer for generation and an air-coupled transducer for detection of Rayleigh surface waves. The amplitudes of the first and second order harmonics are measured at different propagation distances, and these amplitudes are used to obtain the relative nonlinearity parameter for each specimen at different aging stages. Conclusions about microstructural changes are drawn based on the nonlinear Rayleigh surface wave measurement and complementary measurements including scanning electron microscopy (SEM) and Rockwell HRC hardness. The results indicate that the nonlinearity parameter is very sensitive to the dislocation density and precipitate formation, and thus can be used to track the microstructural change in this material during the process of thermal aging.

abstract: Increasing demand for high strength powder metallurgy (PM) steels has resulted in the development of dual phase PM steels. In this work, the effects of thermal aging on the microstructure and mechanical behavior of dual phase precipitation hardened powder metallurgy (PM) stainless steels of varying ferrite-martensite content were examined. Quantitative analyses of the inherent porosity and phase fractions were conducted on the steels and no significant differences were noted with respect to aging temperature. Tensile strength, yield strength, and elongation to fracture all increased with increasing aging temperature reaching maxima at 538oC in most cases. Increased strength and decreased ductility were observed in steels of higher martensite content. Nanoindentation of the individual microconstituents was employed to obtain a fundamental understanding of the strengthening contributions. Both the ferrite and martensite hardness values increased with aging temperature and exhibited similar maxima to the bulk tensile properties. Due to the complex non-uniform stresses and strains associated with conventional nanoindentation, micropillar compression has become an attractive method to probe local mechanical behavior while limiting strain gradients and contributions from surrounding features. In this study, micropillars of ferrite and martensite were fabricated by focused ion beam (FIB) milling of dual phase precipitation hardened powder metallurgy (PM) stainless steels. Compression testing was conducted using a nanoindenter equipped with a flat punch indenter. The stress-strain curves of the individual microconstituents were calculated from the load-displacement curves less the extraneous displacements of the system. Using a rule of mixtures approach in conjunction with porosity corrections, the mechanical properties of ferrite and martensite were combined for comparison to tensile tests of the bulk material, and reasonable agreement was found for the ultimate tensile strength. Micropillar compression experiments of both as sintered and thermally aged material allowed for investigation of the effect of thermal aging. / Dissertation/Thesis / M.S. Materials Science and Engineering 2011

Submitted by Bruna Rodrigues (bruna92rodrigues@yahoo.com.br) on 2016-10-17T12:55:37Z No. of bitstreams: 1 DissRS.pdf: 4073988 bytes, checksum: da1928533791f458afedb1273b891cab (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-10-21T14:00:07Z (GMT) No. of bitstreams: 1 DissRS.pdf: 4073988 bytes, checksum: da1928533791f458afedb1273b891cab (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-10-21T14:00:13Z (GMT) No. of bitstreams: 1 DissRS.pdf: 4073988 bytes, checksum: da1928533791f458afedb1273b891cab (MD5) / Made available in DSpace on 2016-10-21T14:00:19Z (GMT). No. of bitstreams: 1 DissRS.pdf: 4073988 bytes, checksum: da1928533791f458afedb1273b891cab (MD5) Previous issue date: 2016-03-23 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / In this work, the mechanical and corrosion properties of two lean duplex steels (LDSS) 2101 and 2404 aged at 475 °C for up to 2000 h were assessed, and the obtained results were compared with the standard duplex stainless steel (DSS) 2205. The microstructural changes were analyzed by means of optical microscopy (OM), X ray diffraction (XRD), measured by ferritescope and transmission electron microscopy (TEM). The mechanical properties were assessed based on Vickers microhardness measurements and Charpy impact tests. The corrosion resistance was assessed by double loop electrochemical potentiokinetic reactivation (DL-EPR), anodic polarization in 3.5% NaCl solution and immersion tests in ferric chloride solution. The analysis by optical microscope and X ray diffraction of the samples solution treated and aged for 2000 h of the studied materials do not reveal microstructural change as a function of thermal aging. However, the measurements by ferritescope show a decrease in magnetic permeability of the ferrite with the extension of aging time for 2000 h. TEM analysis of the samples aged for 2000 h show that the formation of α’ phase occurs in all materials. However, precipitation of G phase is much greater in the AID 2205. Hardness measurements show that the hardening effect caused by the formation of α’ phase is higher in DSS 2205. On the other hand, impact tests show that the LDSS 2404 has the smaller impact toughness property of the studied alloys as a function of thermal aging. DL-EPR results show that the LDSS 2101 has the greater degree of Cr depletion with aging for 2000 h. Anodic polarization measurements of the materials studied show that the thermal aging for 2000 h promotes a decrease in Epit, causing an increase in the density and size of pits. Immersion tests in ferric chloride solution showed a higher corrosion rate for the DSS 2205 as a function of aging time for 2000 h / Neste trabalho, as propriedades mecânicas e de corrosão de dois aços lean duplex (AILD) 2101 e 2404 envelhecidos a 475 °C por até 2000 h foram avaliadas, e os resultados obtidos foram comparados com o aço inoxidável duplex (AID) padrão 2205. As mudanças microestruturais foram analisadas por meio de microscopia ótica (MO), difração de raios X (DRX), medidas por ferritoscópio e microscopia eletrônica de transmissão (MET). As propriedades mecânicas foram avaliadas com base em medidas de microdureza Vickers e ensaios de impacto Charpy. A resistência à corrosão foi avaliada por testes de reativação eletroquímica potenciocinética de ciclo duplo (DL-EPR), polarização anódica em solução de NaCl 3,5% e ensaios de imersão em solução de cloreto férrico. As análises em microscópio ótico e difração de raios X das amostras solubilizadas e envelhecidas por 2000 h dos materiais estudados não revelaram nenhuma alteração microestrutural em função do envelhecimento térmico. No entanto, as medidas por ferritoscópio mostraram uma diminuição na permeabilidade magnética da ferrita com o prolongamento do tempo de envelhecimento por 2000 h. As análises de MET das amostras envelhecidas por 2000 h mostraram que a formação da fase α’ ocorre em todos os materiais. No entanto, a precipitação da fase G é muito maior no AID 2205. As medidas de dureza indicaram que o efeito endurecedor provocado pela formação da fase α’ é maior no AID 2205. Os ensaios de impacto revelaram que o AILD 2404 possui a menor propriedade de tenacidade ao impacto das ligas estudadas em função do envelhecimento térmico. Os resultados de DL-EPR mostraram que o AILD 2101 apresenta o maior grau de empobrecimento em Cr com o envelhecimento por 2000 h. As medidas de polarização anódica dos materiais estudados revelaram que o envelhecimento térmico por 2000 h promove uma diminuição nos Epite, causando um aumento na densidade e no tamanho dos pites. Os ensaios de imersão em solução de cloreto férrico mostraram uma maior taxa de corrosão para o AID 2205 em função do tempo de envelhecimento por 2000 h.

Currently, there are two major driving forces for considering alternative materials to lead- based products, specifically interconnections, in electronics applications, including the impending legislation or regulations which may tax, restrict, or eliminate the use of lead and the trend toward advanced interconnection technology, which may challenge the limits of present soldering technology. The reliability of solder joints is a concern because fracture failures in solder joints accounts for 70% of failures in electronic components. Lead-free solders are being investigated as replacements for lead solders currently used in electronics. Thermo-mechanical properties describe the stresses accumulated due to thermal fatigue as a result of CTE mismatch within the system. By understanding the failure mechanisms related to lead-free solders, the application of lead- free solders could be more strategically designed for specific applications. The objective of this thesis is to observe microstructural change in large-area solder joints caused by thermal cycling and relate these changes to reliability issues in large-area lead and lead-free solder constructed semiconductor power devices. This study focused on the microstructural changes within the solder alloy of a large-area solder joint under thermal cycling conditions. Two major primary observations were made from this research, they are: 1) due to a combination of testing conditions and material properties, the lead-free solders, Sn/3.5Ag and Sn/Ag/0.7Cu, sustained the most severe damage as compared to Sn/37Pb, and 2) due to elevated stresses at the solder/substrate interface in a simulated power semiconductor device sample damage was found to be most severe. / Master of Science

There is a growing awareness of the risks of pollution in biological systems and one potential problem is the synthetic antioxidants, used for e.g. the stabilisation of polymeric materials. Natural antioxidants are an interesting alternative, if the high efficiency and thermal stability of the synthetic compounds can be reached. In the work described in this thesis, vitamin E (alfa-tocopherol) was studied as a natural antioxidant for the stabilisation of one of the major plastics, polyethylene (PE). The dependence of the surrounding environment for the efficiency of alfa-tocopherol in polyethylene (PE), throughout thermal aging, was characterised by sensitive techniques. Two techniques which have shown a high sensitivity in oxidation detection of polymers; chemiluminescence (CL) and gas chromatographic analysis, were compared with the commonly used methods, infrared spectroscopy (FT-IR) and thermal analysis. Three different additive systems were selected as active domains for -tocopherol in PE. Two of these contained carboxylic acid groups, poly (ethylene-co-acrylic acid) (EAA) and polyTRIM/PAA core-shell particles (Core), and the third, oat starch, had no such groups. The additives containing carboxylic groups improved the long-term efficiency of alfa-tocopherol in PE, according to carbonyl index measurements made by FT-IR, while the additive without carboxylic acid groups gave no improvement. The amount of carboxylic acids emitted from the materials after thermal aging, assessed by head-space solid-phase microextraction (HS-SPME) and gas chromatography-mass spectroscopy (GC-MS), also showed that EAA increased the antioxidant efficiency of alfa-tocopherol, whereas the Core system showed lower antioxidant efficiency. Reference systems containing the synthetic antioxidant Irganox 1076 and EAA or oat starch had the same performance as the materials stabilised with only the antioxidants. CL measurements in an inert atmosphere (TLI) have earlier been shown to give earlier oxidation detection than carbonyl index measurements in unstabilised PE. In this work, the TLI analysis and the carbonyl index measurements had the same sensitivity in the detection of oxidation in the stabilised materials. Assessment of low-molecular weight carboxylic acids in PE during the aging was made by gas chromatographic analysis together with solid-phase extraction. Propanoic acid showed the best correlation with the carbonyl index measurements, even if the carbonyl index showed earlier detection of oxidation. It was also found that TLI and CL in an oxidative atmosphere (CL-OIT) had the same sensitivity and were in accordance for all of the materials, with exception of the materials containing EAA and alfa-tocopherol or Irganox 1076. CL-OIT was also compared to the oxygen induction time determined by thermal analysis. / QC 20100921

In high performance electronic systems, with increasing chip speed and larger number of processors, the system performance is being limited by off-chip metal interconnects. In such systems, polymer optical waveguides are being considered to replace electrical interconnects because of their high capacity for bandwidth and less constraints on interconnect length. The optical loss in the polymer optical waveguides is the key criterion used to evaluate their performance, and is significantly affected by thermal curing and aging. The evolution of degree-of-cure is determined from differential scanning calorimetry and compared to optical absorption from spectroscopy. Optical loss due to scattering mechanisms is related to local density fluctuations, which is studied using dielectric analysis. Based on the optical loss trends in uncladded and cladded waveguides, the underlying mechanisms for the optical loss variations are proposed and a cure process schedule to realize the lowest optical loss is recommended. Process-induced thermal stresses can also affect the polymer waveguide by introducing stress birefringence. The stress-optical coefficients of the siloxane polymer are extracted and employed in a numerical modeling method to determine the stress-induced birefringence in an optical waveguide system. The thermal-aging dependent optical loss is determined for waveguide samples at several different accelerated temperature conditions. To get the field-use conditions, the temperature distribution in the vicinity of the embedded laser and the polymer waveguide is determined. Using such thermal experimental data, the analytical reliability models were employed to relate the optical loss with time, and provide a practical way of determining whether the optical waveguides would perform within the optical loss budget during field-use conditions.