L'acétate de cellulose (CA) est un bio-polymère issu de la cellulose du bois. Sa température de dégradation (dont le degré de substitution 2,5 est développé et commercialisé par le Groupe Solvay) étant très proche de sa température de fusion, son procédé de mise en oeuvre par voie fondue ne peut être envisagé qu'avec l'ajout d'une quantité importante de plastifiant externe (entre 15 et 30% en poids). Le polymère plastifié obtenu est classé parmi les thermoplastiques amorphes et ses propriétés sont régies par un «réseau» de très fortes interactions polaires. La plastification de l'acétate de cellulose à fait l'objet de nombreux travaux nous permettant de nous concentrer in fine sur deux plastifiants: la triacétine (TA), un plastifiant biosourcé fréquemment utilisé dans l'acétate de cellulose et le Diethyl Phthalate (DEP) qui est le plastifiant historique de l'acétate de cellulose et constitue une référence. Les propriétés mécaniques de l'acétate de cellulose plastifié obtenu par voie fondue étant peu étudiées dans la littérature, nous avons dans un premier temps évalué le comportement en traction et l'influence de différents paramètres tels que le taux et le choix du plastifiant mais également l'influence du procédé d'injection sur ces propriétés. Nous avons ainsi pu mettre en évidence l'apparition d'un régime de durcissement plastique (strain hardening en anglais) dès 8% de déformation sous certaines conditions. Il apparaît que le choix du plastifiant, la température d'analyse et la pré-orientation macroscopique des chaînes influencent significativement ce régime. Le durcissement plastique a déjà été observé dans d'autre polymères amorphes tels que le polycarbonate (PC) ou le poly(méthyle methacrylate) (PMMA) qui sont classés parmi les polymères amorphes dit « ductiles ». L'origine de ce régime est encore peu connue et suscite de nombreux débats, cependant il semblerait qu'il stabilise la déformation en évitant la localisation de l'endommagement et serait donc un paramètre clé pour l'amélioration de la ductilité de ces polymères. Afin de mieux comprendre cette ductilité nous avons réalisé des observations par microscopie électronique à balayage en transmission (STEM) ainsi que par diffusion des rayons X aux très petits angles (USAXS). Grâce à ces caractérisations nous avons pu décrire les micro-mécanismes d'endommagement sous traction de nos polymères depuis l'échelle macroscopique jusqu'à l'échelle nanométrique et ainsi décrire précisément les micro-mécanismes liés à l'initiation et la propagation de l'endommagement. Par ces analyses nous mettons en évidence la nucléation simultanée de craquelures nanométriques autour des défauts préexistants (liés au processus de mise en oeuvre). Ces craquelures vont ensuite croitre de façon très limitée jusqu'à atteindre la centaine de micron. Cependant lorsque la contrainte appliquée devient suffisamment élevée, une petite portion de ces craquelures vont se mettre à croitre plus rapidement jusqu'à entrainer la rupture de l'échantillon. Avec le DEP la cinétique de croissance est très rapide, entrainant une rupture brutale de l'échantillon dès qu'une craquelure atteint une dimension critique. Avec la TA néanmoins cette vitesse est plus lente, ce qui permet d'observer l'évolution d'une deuxième famille de craquelures. Ces travaux proposent un nouveau mécanisme d'endommagement dans l'acétate de cellulose plastifié basé sur des résultats expérimentaux et un modèle physique permettant une meilleure compréhension de la ductilité dans ces polymères / Cellulose acetate (CA) is a bio based polymer. Melt processing of cellulose based thermoplastic polymers is a real challenge. One problem is the existence of a narrow window between the melting point and the degradation temperatures for cellulose acetate with a substitution degree (DS) around 2.45 (which is developed and commercialized by Rhodia Acetow). As a consequence, its processing can only be considered with a sufficient amount of externalplasticizer (between 15 and 30% by weight). The corresponding polymer/plasticizer blends areamorphous and their mechanical properties are mainly governed by the presence of a high volume fraction of strong hydrogen bonds. The plasticization of cellulose acetate has been thesubject of many studies allowing us to focus on two plasticizers: triacetin (TA), an eco-friendlyplasticizer frequently used for cellulose acetate and diethyl phthalate (DEP) which is the historicplasticizer of cellulose acetate which constitutes a reference for this work as it is usually the case in the literature. Few studies have been published regarding the mechanical properties of bulk cellulose acetate (prepared via injection molding). It is described that they are comparable to those of PS or poly(methyl methacrylate) (PMMA) and have proven to be particularly interesting. Cellulose acetate based materials usually display a high Young modulus. But its small deformation at break limits its potential for new applications. The objectives of this thesis are to deeply understand the mechanical properties and damage mechanisms of bulk plasticized cellulose acetate polymers. For this purpose we first analyzed the tensile behavior and the influence of various parameters such as nature and content of the plasticizer, but also the influence of the injection process. We have thus been able to highlight the appearance of a strain hardening regime from 8% of deformation under certain conditions. It appears that the choice of the plasticizer, the temperature of the experiment and the macroscopic pre-orientation of the chains significantly influence this regime. Strain hardening has already been observed in other amorphous polymers such as polycarbonate (PC) or poly (methyl methacrylate) (PMMA) which are classified as amorphous polymers called "ductile". The origin of this regime is still undeveloped and much debated, however it appears that it stabilizes the deformation by avoiding the localization of damage and is therefore a key parameter for improving the ductility of these polymers. In order to better understand this ductility, we have made some analysis by Scanning Transmission Electron Microscopy (STEM) as well as Ultra Small Angles X-ray Scattering (USAXS). Thanks to these characterizations we have been able to describe the micromechanisms of damage from macro to nano-scales and thus precisely describe the micromechanisms related to initiation and propagation of damage. By these analyzes we highlight the simultaneous nucleation of nano crazes around pre-existing defects (related to the injection process). These crazes grow slowly until reaching the hundred microns. However, when the applied stress becomes sufficiently high, a small portion of these crazes starts to grow faster until the failure of the sample. With DEP the kinetics of growth is very fast, causing a brittle failure of the sample. With TA this growth is slower, which makes it possible to observe the evolution of the larger crazes. This work proposes a new mechanism of damage in plasticized cellulose acetate based on experimental results and physical interpretations

El estudio muestra la existencia de tres estados en el comportamiento en fatiga de la poliamida reforzada con fibra de vidrio corta su rotura.En el estado I se genera deformación por fluencia transitoria, lo que conlleva disipación de energía en el material que aumenta su temperatura. Si el incremento térmico se estabiliza el materialsoporta un número ilimitado de ciclos. Si aumenta la temperatura, la deformación del material alcanza un valor para el que se produce la transición al estado II.En el estado II el material se deforma a velocidad constante. Se inician fenómenos de crazing o pseudo-fisuración en el material, con cierta capacidad portante de carga. El proceso conduce a una inestabilidad final cuando la deformación del material alcanza el valor para el que sucede la transición al estado III.En el estado III se produce la inestabilidad local en el material que antecede a su rotura. Se debe a que el desarrollo de los crazes produce un crecimiento acelerado de la deformación del material y se obtiene su rotura tras un número de ciclos bajo. / The work shows the existence of three states in the fatigue behaviour of short fibre-glass reinforced polyamide up to the moment of failure. In the state I creep transient deformation processes are produced. If temperature, associated to the dynamic process, stabilises, the material is able to withstand an unlimited number of cycles. On the other hand, if temperature grows continuously the material takes a critical strain for which a transition to the state II is reached. This new state shows a constant material´s deformation rate and a homogeneous nucleation of crazing phenomena. The hysteresis energy per cycle grows in a constant way and the material´s temperature increases. These conditions lead to the final instability that starts when the material´s deformation reaches a new critical value for which a second transition to the state III takes place. Under these circumstances local instabilities precede material´s final fracture. This is due to the quantity of crazes and their sizes, which are important enough to origin high concentration of mechanical effects to produce a material´s accelerated growth deformation to obtain its fracture.

Some researchers have suggested that the weakest link of dental composites is thefiller-matrix bond. However, due to incompleteness of information dealing with this bond and its stability in a humid environment, it was considered desirable to investigate the effect of water on this region, as well as the influence of filler bonding and filler fraction on compressive strength and therm al expansion. Experimental composites containing different filler fractions of either silane-treatedor untreated fillers were made. Compressive strength and coefficient of thermalexpansion were determined using routine methods, while the hydrolytic degradation was investigated by measuring changes in concentrations of elements in the storagewater using atomic absorption spectrophotom etry. Scanning electron microscopicinvestigations were made on fractured samples. The diffusion coefficient of a representative resin system was determined gravimetrically. Seven commercial composites were investigated regarding hydrolyticdegradation. The filler compositions of these composite materials were determined by emission spectroscopy or energy-dispersive x-ray analysis before storage in distilledwater. This water was replaced and analyzed m onthly using plasma spectrophotom etryor atomic absorption spectrophotom etry. After completed water storage the samples were fractured and investigated by useof scanning electron microscopy.From the results of these studies the following conclusions were drawn: 1. The compressive strength of composites changes linearly with increased fillerfraction. Contrary to bonded fillers, composites containing unbonded fillers loststrength with increased filler fraction. 2. Water diffuses through the polymer m atrix and attacks the filler particles. This degradation is most pronounced for untreated fillers containing glass modifying elements such as sodium, barium and strontium. 3. The resin, used as a matrix, influences the speed with which the hydrolyticdegradation of the filler proceeds. 4. The hydrolytic degradation of the filler seemed to be associated w ith micro-crackform ation occurring in the matrix. Of the investigated composites, the micro-filledresin showed the lowest frequency of such crack formations. 5. The coefficient of ther al expansion decreases linearly with increased fillerfraction. Silane treatment did not influence this coefficient. 6. Using a simplified model to predict stresses in a particle filled composite indicatesthat rather high stress levels are induced in the polymer m atrix due to polym erizationshrinkage. This shrinkage induces radial compressive and tangential tensilestresses with respect to the filler surface. Increased filler fraction increases thetangential tensile stresses but reduces the compressive radial stresses. / <p>S. 1-66: sammanfattning, s. 67-168: 6 uppsatser</p> / digitalisering@umu

Die Kunststoffschweißverfahren Infrarot- und Vibrationsschweißen sind in der Serienfertigung etablierte Fügetechnologien. Sie sind durch eine wirtschaftliche und effiziente Prozessführung gekennzeichnet und sind verfahrenstechnisch prinzipiell zum Einsatz im Apparate-, Behälter- und Rohrleitungsbau geeignet. Aufgrund fehlender Erkenntnisse und Nachweise zum Zeitstandverhalten ist die Anwendung dieser Verfahren im Halbzeugbereich jedoch nur eingeschränkt möglich. Im Rahmen der Untersuchungen wurden das Vibrations- und Infrarotschweißen hinsichtlich ihres Potentials für Langzeitanwendungen mit dem konventionellen Halbzeugschweißverfahren Heizelementschweißen verglichen und erreichbare Zeitstandzug-Schweißfaktoren ermittelt. Die Ergebnisse zeigen, dass sowohl für das Vibrations- als auch Infrarotschweißen, in Abhängigkeit der Prozessparameter, Zeitstandzug-Schweißfaktoren von ca. 0,7 bis 0,9 erreicht werden. Darüber hinaus führen die Resultate dieser Arbeit zu einer Erweiterung der Wissensbasis über die Mechanismen des Zeitstandbruchverhaltens geschweißter Polyolefinhalbzeuge. Die für die Kurzzeitfestigkeit von Vibrations- und Infrarotschweiß-verbindungen vielfach nachgewiesene Prozess-Struktur-Eigenschaftskorrelation wurde für die Zeitstandfestigkeit erforscht und angewendet. / The infrared and vibration welding processes are joining technologies established in series fabrication. They are characterised by their economically viable and efficient process management and they are suitable for utilisation in apparatus, tank and pipeline construction. However, their application in the field of semi-finished procucts is restricted due to the lack of knowledge and proof in relation to the Environmental Stress Cracking (ESC). Within the framework of the research, the vibration and infrared welding processes were compared with the conventional welding process heated tool butt welding. Furthermore achievable tensile creep welding factors were determined. The results show achievable tensile creep welding factors from ca. 0.7 to 0.9 for the vibration welding process as well as for the infrared welding process dependent on their process parameters. Moreover, the knowledge base of the mechanisms of the failure behaviour of welded joints between semi-finished products undergoing ESC was extended. The process-structure-property correlation, which has been proven for the short-term strength of vibration and infrared welded joints many times, was investigated and applied for the long-term strength.

No description available.

Die Kunststoffschweißverfahren Infrarot- und Vibrationsschweißen sind in der Serienfertigung etablierte Fügetechnologien. Sie sind durch eine wirtschaftliche und effiziente Prozessführung gekennzeichnet und sind verfahrenstechnisch prinzipiell zum Einsatz im Apparate-, Behälter- und Rohrleitungsbau geeignet. Aufgrund fehlender Erkenntnisse und Nachweise zum Zeitstandverhalten ist die Anwendung dieser Verfahren im Halbzeugbereich jedoch nur eingeschränkt möglich. Im Rahmen der Untersuchungen wurden das Vibrations- und Infrarotschweißen hinsichtlich ihres Potentials für Langzeitanwendungen mit dem konventionellen Halbzeugschweißverfahren Heizelementschweißen verglichen und erreichbare Zeitstandzug-Schweißfaktoren ermittelt. Die Ergebnisse zeigen, dass sowohl für das Vibrations- als auch Infrarotschweißen, in Abhängigkeit der Prozessparameter, Zeitstandzug-Schweißfaktoren von ca. 0,7 bis 0,9 erreicht werden. Darüber hinaus führen die Resultate dieser Arbeit zu einer Erweiterung der Wissensbasis über die Mechanismen des Zeitstandbruchverhaltens geschweißter Polyolefinhalbzeuge. Die für die Kurzzeitfestigkeit von Vibrations- und Infrarotschweiß-verbindungen vielfach nachgewiesene Prozess-Struktur-Eigenschaftskorrelation wurde für die Zeitstandfestigkeit erforscht und angewendet. / The infrared and vibration welding processes are joining technologies established in series fabrication. They are characterised by their economically viable and efficient process management and they are suitable for utilisation in apparatus, tank and pipeline construction. However, their application in the field of semi-finished procucts is restricted due to the lack of knowledge and proof in relation to the Environmental Stress Cracking (ESC). Within the framework of the research, the vibration and infrared welding processes were compared with the conventional welding process heated tool butt welding. Furthermore achievable tensile creep welding factors were determined. The results show achievable tensile creep welding factors from ca. 0.7 to 0.9 for the vibration welding process as well as for the infrared welding process dependent on their process parameters. Moreover, the knowledge base of the mechanisms of the failure behaviour of welded joints between semi-finished products undergoing ESC was extended. The process-structure-property correlation, which has been proven for the short-term strength of vibration and infrared welded joints many times, was investigated and applied for the long-term strength.