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[ES] Los avances tecnológicos se encuentran, en algunas ocasiones, limitados debido a la imposibilidad de combinar las excelentes prestaciones de los materiales conocidos con algunas funcionalidades críticas necesarias para desarrollar nuevas aplicaciones tecnológicas. Estos nuevos materiales con un diseño a la carta resultan extremadamente interesantes ya que permiten combinar propiedades y funcionalidades actualmente inalcanzables. La circona, u oxido de zirconio (ZrO2), es un sólido cristalino blanco con enlaces iónicos altamente estables que es principalmente obtenido en forma de polvo para aplicaciones tecnológicas. Debido a sus propiedades física y químicas, la circona es un material cerámico que posee una serie de características excepcionales, que incluyen una dureza, tenacidad y fractura relativamente altas en comparación con otros materiales cerámicos, bajo coeficiente de fricción y alto punto de fusión. Además, es un material relativamente no reactivo cuando se expone a ambientes húmedos y corrosivos en comparación con otros materiales como metales y polímeros, con buena resistencia a altas temperaturas y abrasión. Todas estas propiedades posicionan a la circona como un material muy versátil con un amplio espectro de aplicaciones que abarca intercambiadores de calor, celdas de combustible, componentes de turbinas para sistemas aeronáuticos y generación de electricidad, así como para medicina, odontología y otras aplicaciones. El propósito de esta tesis doctoral es la obtención de materiales base circona que puedan ser empleados en la fabricación de nuevos composites con funcionalidades a la carta en sectores tecnológicos como el transporte, energía, medicina, etc. Para ello se utilizarán técnicas de sinterización no-convencionales: Microondas (MW) y Spark Plasma Sintering (SPS). Para este trabajo se plantea el estudio de distintos composites base circona: circona reforzada con óxido de niobio (Nb2O5), Titania (TiO2) y composites de circona reforzados con, [CA] Els avenços tecnològics són, en algunes ocasions, limitats per la impossibilitat de combinar l'excel·lent comportament dels materials coneguts amb algunes funcionalitats crítiques necessàries per desenvolupar noves aplicacions tecnològiques. Aquests nous materials amb disseny a la carta resulten summament interessants ja que permeten combinar propietats i funcionalitats actualment inabastables. La circonia, o òxid de zirconi (ZrO2), és un sòlid cristal·lí blanc amb enllaços iònics altament estables que s'obté principalment en forma de pols per a aplicacions tecnològiques. A causa de les seves propietats físiques i químiques, la zircònia és un material ceràmic que posseeix una sèrie de característiques excepcionals, que inclouen duresa, tenacitat i fractura relativament altes en comparació amb altres materials ceràmics, baix coeficient de fricció i alt punt de fusió. A més, és un material relativament no reactiu quan s'exposa a ambients humits i corrosius en comparació amb altres materials com metalls i polímers, amb bona resistència a altes temperatures i abrasió. Totes aquestes propietats posicionen a la zircònia com un material molt versàtil amb un ampli espectre d'aplicacions que inclou intercanviadors de calor, piles de combustible, components de turbines per a sistemes aeronàutics i generació d'electricitat, així com per a medicina, odontologia i altres aplicacions. L'objectiu d'aquesta tesi doctoral és l'obtenció de materials base de zircònia que puguin ser utilitzats en la fabricació de nous compòsits amb funcionalitats sota demanda en sectors tecnològics com transport, energia, medicina, etc. Per a això, s'utilitzaran tècniques de sinterització no convencionals utilitzat: microones (MW) i sinterització per plasma d'espurna (SPS) Per a aquest treball es proposa l'estudi de diferents composites a força de zircònia: zircònia reforçada amb òxid de niobi (Nb2O5), titanat (TiO2) i composites de zircònia reforçats amb manganita de lantani dopat amb estronci (L, [EN] Technological advances are, on some occasions, limited due to the impossibility of combining the excellent performance of known materials with some critical functionalities necessary to develop new technological applications. These new materials of great design are extremely interesting since they allow combining properties and functionalities currently unattainable. Zirconia, or zirconium oxide (ZrO2), is a white crystalline solid with highly stable ionic bonds that is mainly obtained in powder form for technological applications. Due to its physical and chemical properties, zirconia is a ceramic material that possesses several exceptional characteristics, including relatively high hardness, toughness and fracture compared to other ceramic materials, low coefficient of friction, and high melting point. Furthermore, it is a relatively non-reactive material when exposed to humid and corrosive environments compared to other materials such as metals and polymers, with good resistance to high temperatures and abrasion. All these properties position zirconia as a very versatile material with a wide spectrum of applications that includes heat exchangers, fuel cells, turbine components for aeronautical systems and electricity generation, as well as for medicine, dentistry, and other applications. The purpose of this doctoral thesis is to obtain zirconia base materials that can be used in the manufacture of new composites with on-demand functionalities in technological sectors such as transport, energy, medicine, etc. For this, non-conventional sintering techniques will be used: Microwaves (MW) and Spark Plasma Sintering (SPS) For this work, the study of different zirconia-based composites is proposed: zirconia reinforced with niobium oxide (Nb2O5), titania (TiO2) and zirconia composites reinforced with strontium-doped lanthanum manganite (LSM). The result of this research will make it possible to determine whether rapid non-conventional sintering techniques allow the

[ES] Los avances tecnológicos se encuentran, en algunas ocasiones, limitados debido a la imposibilidad de combinar las excelentes prestaciones de los materiales conocidos con algunas funcionalidades críticas necesarias para desarrollar nuevas aplicaciones tecnológicas. Estos nuevos materiales con un diseño a la carta resultan extremadamente interesantes ya que permiten combinar propiedades y funcionalidades actualmente inalcanzables. La circona, u oxido de zirconio (ZrO2), es un sólido cristalino blanco con enlaces iónicos altamente estables que es principalmente obtenido en forma de polvo para aplicaciones tecnológicas. Debido a sus propiedades física y químicas, la circona es un material cerámico que posee una serie de características excepcionales, que incluyen una dureza, tenacidad y fractura relativamente altas en comparación con otros materiales cerámicos, bajo coeficiente de fricción y alto punto de fusión. Además, es un material relativamente no reactivo cuando se expone a ambientes húmedos y corrosivos en comparación con otros materiales como metales y polímeros, con buena resistencia a altas temperaturas y abrasión. Todas estas propiedades posicionan a la circona como un material muy versátil con un amplio espectro de aplicaciones que abarca intercambiadores de calor, celdas de combustible, componentes de turbinas para sistemas aeronáuticos y generación de electricidad, así como para medicina, odontología y otras aplicaciones. El propósito de esta tesis doctoral es la obtención de materiales base circona que puedan ser empleados en la fabricación de nuevos composites con funcionalidades a la carta en sectores tecnológicos como el transporte, energía, medicina, etc. Para ello se utilizarán técnicas de sinterización no-convencionales: Microondas (MW) y Spark Plasma Sintering (SPS). Para este trabajo se plantea el estudio de distintos composites base circona: circona reforzada con óxido de niobio (Nb2O5), Titania (TiO2) y composites de circona reforzados con, [CA] Els avenços tecnològics són, en algunes ocasions, limitats per la impossibilitat de combinar l'excel·lent comportament dels materials coneguts amb algunes funcionalitats crítiques necessàries per desenvolupar noves aplicacions tecnològiques. Aquests nous materials amb disseny a la carta resulten summament interessants ja que permeten combinar propietats i funcionalitats actualment inabastables. La circonia, o òxid de zirconi (ZrO2), és un sòlid cristal·lí blanc amb enllaços iònics altament estables que s'obté principalment en forma de pols per a aplicacions tecnològiques. A causa de les seves propietats físiques i químiques, la zircònia és un material ceràmic que posseeix una sèrie de característiques excepcionals, que inclouen duresa, tenacitat i fractura relativament altes en comparació amb altres materials ceràmics, baix coeficient de fricció i alt punt de fusió. A més, és un material relativament no reactiu quan s'exposa a ambients humits i corrosius en comparació amb altres materials com metalls i polímers, amb bona resistència a altes temperatures i abrasió. Totes aquestes propietats posicionen a la zircònia com un material molt versàtil amb un ampli espectre d'aplicacions que inclou intercanviadors de calor, piles de combustible, components de turbines per a sistemes aeronàutics i generació d'electricitat, així com per a medicina, odontologia i altres aplicacions. L'objectiu d'aquesta tesi doctoral és l'obtenció de materials base de zircònia que puguin ser utilitzats en la fabricació de nous compòsits amb funcionalitats sota demanda en sectors tecnològics com transport, energia, medicina, etc. Per a això, s'utilitzaran tècniques de sinterització no convencionals utilitzat: microones (MW) i sinterització per plasma d'espurna (SPS) Per a aquest treball es proposa l'estudi de diferents composites a força de zircònia: zircònia reforçada amb òxid de niobi (Nb2O5), titanat (TiO2) i composites de zircònia reforçats amb manganita de lantani dopat amb estronci (L, [EN] Technological advances are, on some occasions, limited due to the impossibility of combining the excellent performance of known materials with some critical functionalities necessary to develop new technological applications. These new materials of great design are extremely interesting since they allow combining properties and functionalities currently unattainable. Zirconia, or zirconium oxide (ZrO2), is a white crystalline solid with highly stable ionic bonds that is mainly obtained in powder form for technological applications. Due to its physical and chemical properties, zirconia is a ceramic material that possesses several exceptional characteristics, including relatively high hardness, toughness and fracture compared to other ceramic materials, low coefficient of friction, and high melting point. Furthermore, it is a relatively non-reactive material when exposed to humid and corrosive environments compared to other materials such as metals and polymers, with good resistance to high temperatures and abrasion. All these properties position zirconia as a very versatile material with a wide spectrum of applications that includes heat exchangers, fuel cells, turbine components for aeronautical systems and electricity generation, as well as for medicine, dentistry, and other applications. The purpose of this doctoral thesis is to obtain zirconia base materials that can be used in the manufacture of new composites with on-demand functionalities in technological sectors such as transport, energy, medicine, etc. For this, non-conventional sintering techniques will be used: Microwaves (MW) and Spark Plasma Sintering (SPS) For this work, the study of different zirconia-based composites is proposed: zirconia reinforced with niobium oxide (Nb2O5), titania (TiO2) and zirconia composites reinforced with strontium-doped lanthanum manganite (LSM). The result of this research will make it possible to determine whether rapid non-conventional sintering techniques allow the

The project is aimed at investigating the effect of laser surface modification of dental-grade zirconia (3Y-TZP) to guide cellular behaviour. A nanosecond laser was employed to fabricate groove patterns on the surface of 3Y-TZP, yielding three different topographies according to the groove periodicity (30, 50 and 100µm). The resulting topography, microstructure, hardness and hydrothermal degradation resistance of the modified zirconia was assessed by means of advanced characterization techniques. A cellular study was conducted to evaluate the behaviour of human mesenchymal stem cells on the patterned samples in terms of adhesion and cell morphology. The results showed grooves of approximately 1.7µm heigh with pronounced pile-up due to the melting and re-solidification of the material. The phase analysis revealed that no phase transformation is induced during the laser modification; however, a non-homogeneous monoclinic phase distribution was observed on the patterned surfaces after hydrothermal degradation. Finally, all the patterned surfaces allowed cell attachment, increased cell area and favoured cell elongation and alignment in the direction of the laser patterns., Postprint (published version)

The changes in mechanical properties, hydrothermal degradation and cell adhesion were studied in 3Y-TZP under two different superficial modification patterns (uni- and multidirectional) with a surface roughness ranging from 16 to 603 nm. In this sense, mechanical properties (i.e. hardness, indentation fracture toughness and scratch) and accelerated tests in water steam were measured to evaluate the influence of the surface treatments on the superficially modified layer. Moreover, a detailed characterization through micro-Raman spectroscopy and X-Ray diffraction was performed. Finally, SaOS-2 osteoblasts were used for the evaluation of the cell adhesion behaviour on the surfaces. Overall, ground/polished specimens increased the mechanical properties and ageing resistance of mirror-like polished specimens, although resistance to degradation was maximum at intermediate conditions (Sa ˜ 40-180 nm). The studied surfaces allowed cell attachment, but promoted contact guidance (i.e. cell alignment) only on unidirectionally ground surfaces above Sa = 150 nm., Peer Reviewed, Postprint (author's final draft)

[EN] Self-reinforced polymer composites (SRCs) are proposed as a suitable alternative for composite development, based in the combination of a polymeric matrix and a polymeric fibre made of the same polymer. SRCs based in polylactide (PLA) could be fully biodegradable and their valorisation routes could presumably be assimilated to those for neat PEA. In this sense, the aim of this study was to develop new self-reinforced PLA-based composites and ascertain their biodegradability. For this purpose, PLA-based SRCs were obtained through a thermo-compression procedure and their biodegradability corroborated under standard conditions (ISO 20200). Moreover, a deep study of the effect of the different factors involved in the biodegradation of the composites such as the temperature, the water and the compost medium was considered relevant to delimitate the long-term properties and valorisation routes for these materials. The macroscopic and microscopic appearance as well as the thermo-oxidative stability, the thermal properties and the molar mass were evaluated. Although degradation was perceived due to the effect of temperature, the synergistic combination of water and temperature and compost was found to play a key role in the biodegradation of these materials. Overall, these SRCs can be considered as promising candidates, since their end-of-life management options can be guaranteed under standardised composting conditions. (C) 2018 Elsevier Ltd. All rights reserved.

© 2018 Elsevier Ltd Self-reinforced polymer composites (SRCs) are proposed as a suitable alternative for composite development, based in the combination of a polymeric matrix and a polymeric fibre made of the same polymer. SRCs based in polylactide (PLA) could be fully biodegradable and their valorisation routes could presumably be assimilated to those for neat PLA. In this sense, the aim of this study was to develop new self-reinforced PLA-based composites and ascertain their biodegradability. For this purpose, PLA-based SRCs were obtained through a thermo-compression procedure and their biodegradability corroborated under standard conditions (ISO 20200). Moreover, a deep study of the effect of the different factors involved in the biodegradation of the composites such as the temperature, the water and the compost medium was considered relevant to delimitate the long-term properties and valorisation routes for these materials. The macroscopic and microscopic appearance as well as the thermo-oxidative stability, the thermal properties and the molar mass were evaluated. Although degradation was perceived due to the effect of temperature, the synergistic combination of water and temperature ‒and compost‒ was found to play a key role in the biodegradation of these materials. Overall, these SRCs can be considered as promising candidates, since their end-of-life management options can be guaranteed under standardised composting conditions.

Effective high-yield recycling of waste paper to well-defined future platform chemicals and carbon nanospheres was demonstrated. The developed process utilized the exceptional combined effect of microwave irradiation and dilute acid catalyst to hydrothermally degrade cellulose in waste paper. The process was evaluated for three different waste papers, brown and white paper tissues and white printing paper. Different pretreatment processes were investigated to further increase the cellulose liquefaction efficiency. By utilizing soda pretreatment, liquefaction efficiencies as high as 8896 were achieved. The obtained liquefaction products were fingerprinted by NMR and LDI-MS, while the solid residues were analyzed by XRD, SEM, TGA, and FTIR As industrial-scale microwave reactors are currently under development, the developed method displays significant potential for recycling waste paper to green platform chemicals at the industrial scale., QC 20150209

A green closed-loop water-based process for chemical recycling of starch was demonstrated. The process starts from microwave-assisted controllable starch degradation to functional chemicals and continues to utilization of the formed degradation products, glucose and levulinic acid (LA), as starch plasticizers. The degradation process and the effect of process parameters on the formed degradation products and residues were carefully fingerprinted by multiple techniques, e.g., NMR, ESI-MS, FTIR imaging, UV-vis, and SEM. The degradation process took place in three steps, proceeding from rupture of starch granules and oligosaccharide formation to further hydrolysis to glucose. Finally, at well-defined time point rapid degradation of glucose to LA and formic acid (FA) was initiated through a 5-hydroxymethyl furfural (5-HMF) intermediate. 5-HMF also participated in carbonization reactions leading to formation of solid carbon spheres. Through selection of processing parameters, LA could be produced in high yield with 9596 selectivity. The results demonstrated that microwave-assisted degradation of starch leads to well-defined controllable degradation products. These products are directly reusable as plasticizers for new starch products, which suggest great opportunities for biomass and starch recycling, opening the door toward potential industrial applications., QC 20140929

Exceptionally high cellulose liquefaction yields, up to 87% as calculated from the amount of solid residue, were obtained under mild conditions by utilizing the synergistic effect of microwave radiation and acid catalysis. The effect of processing conditions on degradation products was fingerprinted by rapid laser desorption ionization-mass spectrometry (LDI-MS) method. The reaction was chemo-tunable, enabling production of glucose (Glc) or levulinic acid (LeA) at significantly high selectivity and yields, the relative molar yields being up to 50 and 69%, respectively. A turning point from pure depolymerization to glucose to further degradation to levulinic acid and formic acid was observed at approximately 50% liquefaction or above 140 degrees C. This was accompanied by the formation of small amounts of solid spherical carbonized residues. The reaction was monitored by multiple analytical techniques. The high yields were connected to the ability of the process to break the strong secondary interactions in cellulose. The developed method has great potential for future production of green platform chemicals., QC 20141002

The performance of biocomposites of poly(hydroxybutyrate-co-valerate) (PHBV) and sisal fibre subjected to hydrothermal tests at different temperatures above the glass transition of PHBV (T-H = 26, 36 and 46 degrees C) was evaluated in this study. The influences of both the fibre content and presence of coupling agent were focused. The water absorption capability and water diffusion rate were considered for a statistical factorial analysis. Afterwards, the physico-chemical properties of water-saturated biocomposites were assessed by Fourier-Transform Infrared Analysis, Size Exclusion Chromatography, Differential Scanning Calorimetry and Scanning Electron Microscopy. It was found that the water diffusion rate increased with both temperature and percentage of fibre, whereas the amount of absorbed water was only influenced by fibre content. The use of coupling agent was only relevant at the initial stages of the hydrothermal test, giving an increase in the diffusion rate. Although the chemical structure and thermal properties of water-saturated biocomposites remained practically intact, the physical performance was considerably affected, due to the swelling of fibres, which internally blew-up the PHBV matrix, provoking cracks and fibre detachment., QC 20141121. Updated from manuscript to article in journal.

An accelerated hydrothermal degrading test was designed in order to analyse the synergic effect of water and temperature on PLA/sisal biocomposites with and without coupling agent. As well, the physicochemical properties of biocomposites were monitored along the hydrothermal test by means of Scanning Electron Microscopy, Size Exclusion Chromatography and Differential Scanning Calorimetry. The addition of fibre induced higher water absorption capability and promoted physical degradation, as observed in the surface topography. During the processing of biocomposites and throughout the hydrothermal ageing, a reduction of molecular weight due to chain scission was found. As a consequence, a faster formation of crystalline domains in the PIA matrix occurred the higher the amount of fibre was, which acted as a nucleating agent. Higher crystallinity was considered as a barrier against the advance of penetrant and a reduction in the diffusion coefficient was shown. The addition of coupling agent presented a different influence depending on the composition, showing an inflection point around 20% of sisal fibre., QC 20141217

Accelerated ageing was performed in distilled water at different temperatures (25, 30, 40 and 50°C) on poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), which is a biodegradable biopolymer, in order to estimate its lifetime in aqueous environment. In a first part, degradation mechanisms were followed by gravimetry, tensile tests and steric exclusion chromatography. Both immersion and relative humidity have been examined. In a second part, the strain at break was used as an indicator for lifetime prediction with an Arrhenius extrapolation. The study revealed the presence of only one irreversible degradation mechanism, i.e. hydrolytic degradation, which is temperature dependant. So, within the approach assumptions, the lifetime in distilled water of PHBV following Arrhenius behaviour can be predicted.

The aim of this study is to establish a baseline for poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) lifetime prediction in a marine environment, by means of mechanical and physico-chemical characterization of specimens immersed in continuously renewed and filtered natural seawater in the laboratory at different temperatures (4, 25 and 40°C). Samples were also aged at sea in Lorient harbour in order to compare laboratory and natural degradation mechanisms and kinetics. Due to its morphology, hydrolysis of PHBV in natural seawater is quite slow, and samples were observed to undergo preferentially an enzymatic surface degradation. Increasing the aging temperature in the laboratory promotes the water uptake and causes hydrolysis. As two degradation mechanisms occur in parallel, the choice of test conditions is critical, and the lifetime of PHBV in a marine environment is difficult to predict accurately.

[EN] The performance of biocomposites of poly(hydroxybutyrate-co-valerate) (PHBV) and sisal fibre subjected to hydrothermal tests at different temperatures above the glass transition of PHBV (TH ¿ 26, 36 and 46 C) was evaluated in this study. The influences of both the fibre content and presence of coupling agent were focused. The water absorption capability and water diffusion rate were considered for a statistical factorial analysis. Afterwards, the physico-chemical properties of water-saturated biocomposites were assessed by Fourier-Transform Infrared Analysis, Size Exclusion Chromatography, Differential Scanning Calorimetry and Scanning Electron Microscopy. It was found that the water diffusion rate increased with both temperature and percentage of fibre, whereas the amount of absorbed water was only influenced by fibre content. The use of coupling agent was only relevant at the initial stages of the hydrothermal test, giving an increase in the diffusion rate. Although the chemical structure and thermal properties of water-saturated biocomposites remained practically intact, the physical performance was considerably affected, due to the swelling of fibres, which internally blew-up the PHBV matrix, provoking cracks and fibre detachment.

An accelerated hydrothermal degrading test was designed in order to analyse the synergic effect of water and temperature on PLA/sisal biocomposites with and without coupling agent. As well, the physicochemical properties of biocomposites were monitored along the hydrothermal test by means of Scanning Electron Microscopy, Size Exclusion Chromatography and Differential Scanning Calorimetry. The addition of fibre induced higher water absorption capability and promoted physical degradation, as observed in the surface topography. During the processing of biocomposites and throughout the hydrothermal ageing, a reduction of molecular weight due to chain scission was found. As a consequence, a faster formation of crystalline domains in the PIA matrix occurred the higher the amount of fibre was, which acted as a nucleating agent. Higher crystallinity was considered as a barrier against the advance of penetrant and a reduction in the diffusion coefficient was shown. The addition of coupling agent presented a different influence depending on the composition, showing an inflection point around 20% of sisal fibre. (C) 2014 Elsevier Ltd. All rights reserved.

[EN] The performance of biocomposites of poly(hydroxybutyrate-co-valerate) (PHBV) and sisal fibre subjected to hydrothermal tests at different temperatures above the glass transition of PHBV (TH ¿ 26, 36 and 46 C) was evaluated in this study. The influences of both the fibre content and presence of coupling agent were focused. The water absorption capability and water diffusion rate were considered for a statistical factorial analysis. Afterwards, the physico-chemical properties of water-saturated biocomposites were assessed by Fourier-Transform Infrared Analysis, Size Exclusion Chromatography, Differential Scanning Calorimetry and Scanning Electron Microscopy. It was found that the water diffusion rate increased with both temperature and percentage of fibre, whereas the amount of absorbed water was only influenced by fibre content. The use of coupling agent was only relevant at the initial stages of the hydrothermal test, giving an increase in the diffusion rate. Although the chemical structure and thermal properties of water-saturated biocomposites remained practically intact, the physical performance was considerably affected, due to the swelling of fibres, which internally blew-up the PHBV matrix, provoking cracks and fibre detachment.

An accelerated hydrothermal degrading test was designed in order to analyse the synergic effect of water and temperature on PLA/sisal biocomposites with and without coupling agent. As well, the physicochemical properties of biocomposites were monitored along the hydrothermal test by means of Scanning Electron Microscopy, Size Exclusion Chromatography and Differential Scanning Calorimetry. The addition of fibre induced higher water absorption capability and promoted physical degradation, as observed in the surface topography. During the processing of biocomposites and throughout the hydrothermal ageing, a reduction of molecular weight due to chain scission was found. As a consequence, a faster formation of crystalline domains in the PIA matrix occurred the higher the amount of fibre was, which acted as a nucleating agent. Higher crystallinity was considered as a barrier against the advance of penetrant and a reduction in the diffusion coefficient was shown. The addition of coupling agent presented a different influence depending on the composition, showing an inflection point around 20% of sisal fibre. (C) 2014 Elsevier Ltd. All rights reserved.

Accelerated ageing was performed in distilled water at different temperatures (25, 30, 40 and 50°C) on poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), which is a biodegradable biopolymer, in order to estimate its lifetime in aqueous environment. In a first part, degradation mechanisms were followed by gravimetry, tensile tests and steric exclusion chromatography. Both immersion and relative humidity have been examined. In a second part, the strain at break was used as an indicator for lifetime prediction with an Arrhenius extrapolation. The study revealed the presence of only one irreversible degradation mechanism, i.e. hydrolytic degradation, which is temperature dependant. So, within the approach assumptions, the lifetime in distilled water of PHBV following Arrhenius behaviour can be predicted.

The aim of this study is to establish a baseline for poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) lifetime prediction in a marine environment, by means of mechanical and physico-chemical characterization of specimens immersed in continuously renewed and filtered natural seawater in the laboratory at different temperatures (4, 25 and 40°C). Samples were also aged at sea in Lorient harbour in order to compare laboratory and natural degradation mechanisms and kinetics. Due to its morphology, hydrolysis of PHBV in natural seawater is quite slow, and samples were observed to undergo preferentially an enzymatic surface degradation. Increasing the aging temperature in the laboratory promotes the water uptake and causes hydrolysis. As two degradation mechanisms occur in parallel, the choice of test conditions is critical, and the lifetime of PHBV in a marine environment is difficult to predict accurately.

The surface stability of yttria-doped tetragonal polycrystalline zirconia is critical for load-bearing biomedical applications. In this work, the small-scale mechanical behavior of this material is probed by employing the in situ micro-cantilever bending technique to near-surface regions. Micro-cantilevers are milled by the focused ion beam technique in the as-sintered condition as well as after hydrothermal degradation by water vapor and tested in order to investigate the effect of degradation on the local flexural response. Results demonstrate that the technique is reliable for assessing the mechanical properties of thin superficial layers and their dependence on orientation. In the non-degraded material, the flexural strength is surprisingly higher than in standard-size specimens and transformation-induced plasticity takes place during testing, inducing defects that become critical at the failure stress. The strength and stiffness of cantilevers obtained from the degraded surface are indeed much lower, and the magnitude of the effect clearly depends on their orientation with respect to the surface. These results are discussed in terms of the presence and spatial distribution of microcracks nucleated during hydrothermal degradation., Peer Reviewed, Postprint (published version)

Accelerated ageing was performed in distilled water at different temperatures (25, 30, 40 and 50°C) on poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), which is a biodegradable biopolymer, in order to estimate its lifetime in aqueous environment. In a first part, degradation mechanisms were followed by gravimetry, tensile tests and steric exclusion chromatography. Both immersion and relative humidity have been examined. In a second part, the strain at break was used as an indicator for lifetime prediction with an Arrhenius extrapolation. The study revealed the presence of only one irreversible degradation mechanism, i.e. hydrolytic degradation, which is temperature dependant. So, within the approach assumptions, the lifetime in distilled water of PHBV following Arrhenius behaviour can be predicted.

The aim of this study is to establish a baseline for poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) lifetime prediction in a marine environment, by means of mechanical and physico-chemical characterization of specimens immersed in continuously renewed and filtered natural seawater in the laboratory at different temperatures (4, 25 and 40°C). Samples were also aged at sea in Lorient harbour in order to compare laboratory and natural degradation mechanisms and kinetics. Due to its morphology, hydrolysis of PHBV in natural seawater is quite slow, and samples were observed to undergo preferentially an enzymatic surface degradation. Increasing the aging temperature in the laboratory promotes the water uptake and causes hydrolysis. As two degradation mechanisms occur in parallel, the choice of test conditions is critical, and the lifetime of PHBV in a marine environment is difficult to predict accurately.

The performance of biocomposites of poly(hydroxybutyrate-co-valerate) (PHBV) and sisal fibre subjected to hydrothermal tests at different temperatures above the glass transition of PHBV (T-H = 26, 36 and 46 degrees C) was evaluated in this study. The influences of both the fibre content and presence of coupling agent were focused. The water absorption capability and water diffusion rate were considered for a statistical factorial analysis. Afterwards, the physico-chemical properties of water-saturated biocomposites were assessed by Fourier-Transform Infrared Analysis, Size Exclusion Chromatography, Differential Scanning Calorimetry and Scanning Electron Microscopy. It was found that the water diffusion rate increased with both temperature and percentage of fibre, whereas the amount of absorbed water was only influenced by fibre content. The use of coupling agent was only relevant at the initial stages of the hydrothermal test, giving an increase in the diffusion rate. Although the chemical structure and thermal properties of water-saturated biocomposites remained practically intact, the physical performance was considerably affected, due to the swelling of fibres, which internally blew-up the PHBV matrix, provoking cracks and fibre detachment. (C) 2014 Elsevier Ltd. All rights reserved.

Experiments on hydrothermal degradation of Pyrococcus abyssi biomass were conducted at elevated pressure (40 MPa) over a 200–450 °C temperature range in sapphire reaction cells. Few organic compounds could be detected in the 200 °C experiment. This lack was attributed to an incomplete degradation of P. abyssi cells. On the contrary, a wide range of soluble organic molecules were generated at temperatures ≥350 °C including toluene, styrene, C8–C16 alkyl-benzenes, naphthalene, C11–C16 alkyl-naphthalenes, even carbon number C12–C18 polycyclic aromatic hydrocarbons, C15–C18 alkyl-phenanthrenes and C8:0–C16:0 n-carboxylic acids. The effect of time on the final organic composition of the degraded P. abyssi solutions at 350 °C was also investigated. For that purpose the biomass was exposed for 10, 20, 60, 90, 270 and 720 min at 350 °C. We observed a similar effect of temperature and time on the chemical diversity obtained. In addition, temperature and time increased the degree of alkylation of alkyl-benzenes. This study offers additional evidence that a portion of the aliphatic hydrocarbons present in the fluids from the Rainbow ultramafic-hosted hydrothermal field may be abiogenic whereas a portion of the aromatic hydrocarbons and n-carboxylic acids may have a biogenic origin. We suggest that aromatic hydrocarbons and linear fatty acids at the Rainbow site may be derived directly from thermogenic alteration of material from the sub-seafloor biosphere. Yet we infer that the formation and dissolution of carboxylic acids in hydrothermal fluids may be controlled by other processes than in our experiments., MOMARNET

Zirconia has found wide application in dentistry because of its high mechanical strength and superior esthetic properties. However, zirconia degradation caused by phase transformation occurring in a hydrothermal environment is of concern. In the present study, phase transformation and microstructure of tetragonal zirconia polycrystal partially stabilized with yttrium oxide (Y-TZP) and alumina-toughened zirconia (ATZ) sintered at different temperatures were estimated. On grazing angle X-ray diffraction analysis, ATZ showed less phase transformation to the monoclinic phase during hydrothermal treatment and this transformation appeared to occur within a few micrometers below the surface. At a higher sintering temperature the monoclinic phase content of ATZ was found to be lesser than that of Y-TZP, indicating that the alumina in ATZ was effective in suppressing hydrothermal degradation. Examination by transmission electron microscopy and studying of electron backscatter diffraction patterns indicated that grain growth in ATZ was slightly suppressed compared with that in Y-TZP at higher sintering temperatures. The present study demonstrated the effect of adding alumina to zirconia for suppressing hydrothermal degradation and studied the effect of this addition on grain growth in zirconia.

Zirconia has found wide application in dentistry because of its high mechanical strength and superior esthetic properties. However, zirconia degradation caused by phase transformation occurring in a hydrothermal environment is of concern. In the present study, phase transformation and microstructure of tetragonal zirconia polycrystal partially stabilized with yttrium oxide (Y-TZP) and alumina-toughened zirconia (ATZ) sintered at different temperatures were estimated. On grazing angle X-ray diffraction analysis, ATZ showed less phase transformation to the monoclinic phase during hydrothermal treatment and this transformation appeared to occur within a few micrometers below the surface. At a higher sintering temperature the monoclinic phase content of ATZ was found to be lesser than that of Y-TZP, indicating that the alumina in ATZ was effective in suppressing hydrothermal degradation. Examination by transmission electron microscopy and studying of electron backscatter diffraction patterns indicated that grain growth in ATZ was slightly suppressed compared with that in Y-TZP at higher sintering temperatures. The present study demonstrated the effect of adding alumina to zirconia for suppressing hydrothermal degradation and studied the effect of this addition on grain growth in zirconia.