La durabilité des matériaux employés en génie civil est remise en question par le vieillissement physico-chimique de ces matériaux pouvant engendrer des dégradations significatives qui peuvent mettre en péril la stabilité des structures du génie civil. Pour pallier à certains inconvénients des bétons hydrauliques, l'utilisation des matériaux composites à l'instar des bétons de résine, qui possèdent des qualités remarquables par rapport aux matériaux de construction conventionnels, s'avère très intéressant.À l'heure actuelle, les freins majeurs quant aux développements des bétons résines sont d'une part le coût de la résine dont le taux varie, selon l'application industrielle, de 5% à 25% et d'autre part leurs comportements aux températures élevées et au feu puisque les liants dans ces bétons sont des substances organiques qui résistent beaucoup moins à la chaleur que les matières inorganiques. L'objectif de l'étude est de favoriser le développement des bétons résines par la diminution du taux de la résine en optimisant les constituants du béton et l'amélioration de leurs ténues aux températures élevées par l'ajout des additions tout en assurant des performances mécaniques raisonnables. L'optimisation de la formulation du béton est menée sur deux étapes ; la première vise à optimiser le squelette granulaire (sable 0/4 et Gravier 4/10, silico-calcaires) expérimentalement en confrontant les résultats à ceux issus du modèle d'empilement compressible. La deuxième étape vise à optimiser la fraction massique du liant époxydique (6%, 9%, 13% et 16%) sur la base des essais de caractérisation mécaniques et physiques. Le deuxième objectif de l'étude a était menée par l'ajout des ignifugeants appartenant à deux familles différentes c'est-à-dire les hydroxydes de métal et les produits phosphorés inorganiques. Les propriétés physiques, thermiques et mécaniques des bétons additionnées et témoins, avant et après exposition à un cycle de chauffage-refroidissement de la température ambiante à une température de consigne de 100°C, 150°C, 200°C, 225°C et 250 °C avec une vitesse de montée fixée à 0.5°C/min, ont été évaluées par les techniques de caractérisation usuelles en plus des essais d'analyses chimiques et thermiques.Cette étude aboutit à la formulation d'un béton optimal en terme de composition et à évaluer l'effet de l'addition des ignifugeants surtout sur les propriétés thermiques et mécaniques.Mots clés : béton de résine, optimisation, température élevée, ignifugeants, propriétés mécaniques, propriétés physiques, propriétés thermiques. / The material used in civil engineering applications must be re-evaluated because of their physicochemical ageing which can generate significant damages and hence put the stability of civil engineering structures in danger.The replacement of the hydraulic concrete by composite materials as the polymer concrete which offer higher properties compared to conventional construction materials seems to be very interesting. At the present time, the major restrain for the development of polymer concrete are on one hand the cost of the polymer whose ratio varies according to the industrial applications between 5% and 25%, and on the other hand their behaviour when exposed to high temperatures or fire since the resin acting as binder in these polymer concretes are organic substances which are more sensitive to heat than the inorganic matters as cement.The aim of this study was to help the development of polymer concrete by optimizing the formulation and improving their behaviour when exposed the high temperatures by incorporating additions while keeping acceptable mechanical performances.The optimisation of the formulation is done in two steps; the first step consists of optimising the aggregates content (Natural River sands 0/4 mm and crushed gravels 4/10 mm). Experimental results are compared to those given by means Compressible Packing Model. The second step consists of optimizing the amount of polymer (6%, 9%, 13% et 16%) based on mechanical and physical tests.The second aim of this work was fulfilled by the incorporation of two flame retardants belonging to metal hydroxide and phosphorous components types. Physical, thermal and mechanical properties of concretes with or without flame retardant, before and after heating-cooling cycle from ambient temperature to exposure temperature of 100°C, 150°C, 200°C, 225°C et 250 °C with a rate of 0.5°C/min, are evaluated by common characterisation tests besides chemical and thermal ones. This study has leading to obtaining an optimum polymer concrete and evaluates the effect of flame retardant particularly on the thermal and mechanical properties.Keywords: polymer concrete, optimization, high temperatures, flame retardant, mechanical properties, physical properties, thermal properties.

Tato dizertační práce se zabývá studiem morfogeneze dimethakrylátových sítí. V práci byly využity zjednodušené systémy založené na monomerech, které bývají typicky využívány jako složky matric pryskyřičných kompozitních materiálů využívaných v oblasti záchovné stomatologie. Kinetika a mechanismy formování polymerních sítí byly studovány především s ohledem na strukturu jednotlivých monomerů, jejich vzájemný molární poměr a koncentraci iniciačního systému využitého pro radikálovou polymeraci. Vypočtené profily konverze funkčních skupin a reakčních rychlostí byly využity jako základ pro pochopení a interpretaci mechanismů morfogeneze sítí a porovnání se známými modely. Dále byla studována kinetika termické degradace, která je s morfologií vytvrzených sítí přímo spjata. V rámci takto charakterizovaných systémů byla stanovena teplotní závislost dynamického modulu a byl popsán vztah mezi supra-molekulární strukturou dimethakrylátových sítí a jejich viskoelastickou odezvou v daném teplotním rozmezí. Kinetika polymerace byla studována pomocí diferenční kompenzační foto-kalorimetrie (DPC) a infračervené spektroskopie (FTIR). Proces termické degradace byl analyzován pomocí termo-gravimetrické analýzy (TGA). Viskoelastické parametry byly charakterizovány pomocí dynamicko-mechanické analýzy (DMA). Reaktivita jednotlivých systémů je přímo odvozena od molekulární struktury monomerů, která ovlivňuje mobilitu reagujících složek v průběhu polymerace. Kinetika polymerace je řízena především difúzí, přičemž její rychlost je dána tuhostí monomerní páteře, koncentrací funkčních skupin a vlivem fyzikálních interakcí. Omezená mobilita rostoucích řetězců, postranních funkčních skupin i samotných monomerů vede k monomolekulární terminaci makro-radikálů a omezení stupně konverze funkčních skupin. Vzhledem k tomu, že k zásadnímu omezení mobility dochází již v počáteční fázi polymerace, tj. v bodu gelace, je případná termodynamická nestabilita vedoucí k fázové separaci polymerujícího systému potlačena a proces kopolymerace je ve své podstatě náhodný. To bylo prokázáno i prostřednictvím identifikace jedné teploty skelného přechodu u charakterizovaných kopolymerů. Heterogenní charakter morfogeneze je spjat s rozdílnou reaktivitou postranních funkčních skupin. V počátečních fázích polymerace dochází k propagaci reakcí postranní funkční skupiny s radikálem na stejném rostoucím řetězci, což vede ke vzniku tzv. primárního cyklu. Pravděpodobnost cyklizace souvisí především s flexibilitou monomerní páteře. Heterogenita polymerace je charakterizována vznikem vnitřně zesítěných struktur, tzv. mikrogelů, a jejich následným spojováním. Tuhost monomeru naopak přispívá k vyšší efektivitě zesítění a více homogenní morfologii vytvrzené sítě. Heterogenita dimethakrylátových sítí se odráží v mechanismu termické degradace, přičemž přítomnost strukturně odlišných domén vede k rozkladu ve dvou krocích. Průběh soufázového modulu a teplota skelného přechodu korelují s tuhostí polymerních sítí, efektivitou zesítění a přítomností fyzikálních interakcí, které vyztužují strukturu sítě nad rámec kovalentního zesítění. Heterogenní morfologie sítí se projevuje rozšiřováním spektra relaxačních časů. Experimentální data jsou v kvalitativní shodě s existujícími numerickými modely popisujícími kinetiku radikálové polymerace multifunkčních monomerů.

This diploma thesis investigated thermal stability and the degradation of hyaluronan (HA) in HA with a molecular mass of 90–130 kDa and in HA with a molecular mass of 1 500–1 750 kDa. The following methods were used for the research: rheology, SEC-MALLS, TGA and DSC. Low-molecular HA was subject to time dependency of degradation investigation, where it was dried at a temperature of 90 °C for a period of 30 minutes and 60 minutes prior to the preparation of the solutions itself. High-molecular HA was investigated not only from the point of view of time but from the point of view of temperature dependency of degradation as well. In the case of investigating the time dependency of degradation, high-molecular HA was dried at a temperature of 75 °C at a time range from 15 minutes to 120 minutes prior to the preparation of the solutions. During the preparation of the solutions for discovering the temperature dependency of degradation, the high-molecular HA was then dried for a period of 30 minutes at a temperature range from 60 °C to 90 °C. For low-molecular HA, thermal stability was proven. Therefore, there is no decrease in the molecular mass and the solutions did not demonstrate a significant decrease of viscosity. For high-molecular HA, thermal stability was not proven. Degradation due to the temperature of drying as well as the time of drying occurred, which was demonstrated by a significant decrease in molecular mass and viscosity of the solutions. While in the case of using a drying temperature of 60 °C, a decrease in the molecular mass occurred by approximately 5 %, the molecular mass decreased by approximately 20 % at a drying temperature of 90 °C compared to undried HA. Due to this reason, high-molecular HA was also further investigated by means of the TGA method, where the decrease of humidity of HA samples in relation to the drying temperature was observed. The DSC method was also used. The objective of the DSC method was to find out temperatures, at which evaporation of humidity contained in an HA sample in relation to its form (undried HA, dried HA and lyophilized HA) occurs. This method further finds out the heat necessary to evaporate humidity from an HA sample. To conclude this research, the results obtained for high-molecular HA were compared with the results of other drying processes – lyophilized proved to be a very gentle drying method because a decrease in the molecular mass for lyophilized HA compared with undried HA almost did not occur.

L’utilisation croissante des matériaux composites à matrice thermoplastique dans l’industrie aéronautique passe par une meilleure compréhension de leur comportement mécanique lors d’une exposition à un flux rayonnant (conséquence d’un incendie). Cette étude, portant sur le comportement thermo-mécanique de stratifiés tissés quasi-isotropes composés d’une matrice PPS renforcée par des fibres de carbone, se divise en 3 parties. Tout d’abord, la décomposition thermique du matériau et l’évolution de ses propriétés mécaniques avec la température sont étudiées. Ces données permettent ensuite d’appréhender le comportement de ces matériaux soumis à des chargements combinés (flux rayonnant et chargement mécanique en traction ou en compression, de type monotone à rupture et en fluage). La dernière partie vise à identifier les paramètres matériau nécessaires pour la simulation thermo-mécanique aux échelles macroscopique et mésoscopique. / The increasing use of thermoplastic-based composite materials in the aeronautical industry requires a better understanding of their mechanical behavior when exposed to radiant heat flux (consequence of a fire exposure). This study, which examines the thermo-mechanical behavior of quasi-isotropic woven laminates composed of PPS reinforced with carbon fibers, is divided into 3 parts. First, the thermal decomposition of the material and the evolution of its mechanical properties with temperature is studied. These data help to understand the behavior of these materials subjected to combined loads (radiant heat flux and tensile or compressive loadings). The last part aims to identify the material parameters necessary for thermo-mechanical simulation at macroscopic and mesoscopic scales.

In unserem alltäglichen Leben nehmen Kunststoffe eine immer größere Rolle ein. Die organische Struktur dieser Materialien bedingt die Brennbarkeit derselbigen und birgt somit eine Gefahr, die allgegenwärtig ist. Flammschutz von Polymeren ist daher eine wichtige Eigenschaft. Der Markt an Flammschutzadditiven ist bereits sehr breit gefächert. Allerdings gibt es nur wenig Studien, die systematisch Struktur und Flammschutzwirkung betrachten. So war es das Ziel dieser Arbeit, durch die Untersuchung zweier systematisch variierter Polymergruppen Struktur-Eigenschafts-Beziehungen zu entwicklen, die das Verständnis von Flammschutzadditiven erweitern. Die erste Gruppe bestand aus Polyestern mit einem gleichbleibenden Polymerrückrat an dem phosphorhaltige Seitenketten systematisch variiert wurden. In der zweiten Gruppe wurde das Polymergrundgerüst bei gleichbleibendem Substituenten variiert. Die Strukturen wurden umfassend hinsichtlich ihres Abbaus untersucht, so das durch Korrelation von Abbauverhalten und erarbeiteten Abbaumechanismen Zusammenhänge zwischen der nativen Polymerstruktur und dem Flammschutzverhalten gefunden werden konnten. Es lässt sich nachweisen, dass das Hauptabbaumaximum fast vollständig durch die Polymergrundkette dirigiert wird. Der Substituent hat wenig Einflauss darauf, womit sich die Möglichkeit ergibt Flammschutzadditive gezielt and das Abbaumaximum des zu schützenden Matrixpolymers anzupassen. Die strukturelle Veränderung des phosphorhaltigen Substituenten hingegen ermöglich es das Flammschutzadditv in seiner Wirkungsweise, also Aktivität in der Gasphase oder kondensierten Phase, anzupassen. Sehr wesentlich, besonders mit Blick auf die Rückstandbildung, ist das Zusammenspiel zwischen Substituent und Polymerrückgrat. Bei geeigneter Wahl aliphatischer und aromatischer Anteile lassen sich so Flammschutzadditive herstellen, die einerseits gut zu verarbeiten sind, andererseits aber auch einen möglichst hohen Rückstand erzeugen. Mit Kenntnis dieser Struktur-Eigenschafts-Beziehungen ist es zukünftig möglich, polymere Flammschutzadditive zielgerichteter zu entwickeln. So lässt sich das Additiv in seiner Wirkung nicht nur an das Matrixpolymer anpassen, sondern auch an die primären Brandgefahren in dessen Endanwendung. Eine Under-the-hood-Anwendung im Automobilbau fordert andere Flammschutzeigenschaften als die Verwendung im häuslichen Küchenbedarf.

Conventional microelectronic and power electronic packages based on Si devices usually work below 150°C. The emergence of wide-bandgap devices, which potentially operate above a junction temperature of 250°C, results in growing research interest in high-density and high-temperature packaging. There are high-temperature materials such as encapsulants on the market that are claimed for capability of continuous operation at or above 250°C. With an objective of identifying encapsulants suitable for packaging wide-bandgap devices, some of commercial high-temperature encapsulants were obtained and evaluated at the beginning of this study. The evaluation revealed that silicone elastomers are processable for various types of package structure and exhibit excellent dielectric performance in a wide temperature range (25 - 250°C) but are insufficiently stable against long-term aging (used by some manufacturers, e.g., P²SI, to evaluate polymer stability) at 250°C. These materials cracked during aging, causing their dielectric strength to decrease quickly (as soon as 3 days) and significantly (60 - 70%) to approximately 5 kV/mm, which is below the value required by semiconductor packaging. The results of this evaluation clearly suggested that silicone needs higher thermal stability to reliably encapsulate wide-bandgap devices. Literature survey then investigated possible methods to improve silicone stability. Adding fillers is reported to be effective possibly due to the interaction between filler surface and polymer chains. However, the interaction mechanism is not clearly documented. In this study, the effect of Al₂O₃ filler on thermal stability was first investigated by comparing the performance of unfilled and Al₂O₃-filled silicones in weight-loss measurements and dielectric characterization. All test results on composites filed with Al₂O₃ micro-rods indicated that thermal stability increased with increasing filler loading. Thermogravimetric analysis (TGA) test demonstrated that the temperature of degradation onset increased from 330 to 379°C with a 30 wt% loading of Al₂O₃ rods. In isothermal soak test, unfilled and 30-wt%-filled silicones lost 10% of polymer weight in 700 and 1800 hours, respectively. The dielectric characterization found that both Weibull parameters, characteristic dielectric strength (E₀, representing the electric field at which 62.3% of samples are electrically broken down) and shape parameter (β, representing the spread of data. The larger the β, the narrower the distribution) can reflect the thermal stability of polymers. Both of them were influenced by microstructure evolution, to which β was found to be more sensitive than E₀. The characteristic dielectric strength of unfilled silicone decreased significantly after 240 hours of aging at 250°C, whereas that of Al₂O₃/silicone composites exhibited no significant change within 560 hours. The shape parameter of Al₂O₃-filled silicone decreased slower than that of unfilled silicone, also indicating the positive effect of Al₂O₃ micro-rods on thermal stability. Improved thermal stability can be explained by restrained chain mobility caused by interfacial hydrogen bonds, which are formed between hydroxyl groups on Al₂O₃ surface and silicone backbone. In this study, the effect of hydrogen bonds was investigated by dehydrating Al₂O₃ micro-rods at high temperature in N₂ to partially destroy the bonds. Removal of hydrogen bonds impaired thermal stability by increasing the initial weight-loss rate from 0.025 to 0.036 wt%/hour. The results explained the importance of interfacial hydrogen bond, which effectively reduced the average chain mobility, hindered the formation of degradation products, and led to higher thermal stability. The main discoveries of this study are listed below: 1. Al₂O₃ micro-rods were found to efficiently improve the thermal stability of silicone elastomer used for high-temperature encapsulation. 2. Characteristic dielectric strength and shape parameter obtained from Weibull distribution reflected the change of material microstructure caused by thermal aging. The shape parameter was found to be more sensitive to microscale defects, which were responsible for dielectric breakdown at low electric field. 3. Hydrogen bonds existing at filler/matrix interface were proven to be responsible for the improvement of thermal stability because they effectively restrained the average chain mobility of the silicone matrix. / Ph. D.

Wood is a viscoelastic composite material that has been historically prominent in the construction of buildings and continues to see widespread use. When used for exterior applications, wood is exposed to dynamic environmental conditions and can degrade if left untreated. Previous research by Lemaire-Paul et al. (2022) has proven that vacuum impregnation of the wood cell structure with a silica (SiO₂) nanoparticle colloid under a vacuum pressure of -90 kPa can enhance the viscoelastic properties, increase the density, and reduce the water uptake of white spruce wood. However, the behaviour of SiO₂-treated wood under different environmental conditions over time has yet to be fully explored. This research aims to examine the durability and performance of SiO₂-treated spruce wood samples subjected to accelerated aging conditions under high temperature and humidity as well as freeze-thaw cycling. Spruce wood samples were treated with 40% SiO₂ nanoparticle colloid under a vacuum pressure of -90 kPa. One set was placed in a hydrolytic aging chamber at 90°C and 80% RH. Another set was placed in a freeze-thaw cycling chamber that cycled from 25°C to -18°C and back at a rate of 6 cycles per day. The samples were removed at regular intervals and thermogravimetric analysis, dynamic mechanical analysis, tensiometry, X-Ray diffraction, and scanning electron microscopy were performed. When compared to the results obtained from a set of non-treated samples, it was found that the SiO₂-treated samples exhibited lower water uptake values that stabilized over time, as well as a lower rate of decrease in peak cellulose degradation temperatures under hydrolytic aging and a slight increase in peak cellulose degradation temperature over time under freeze-thaw aging. The effects of both aging conditions on the viscoelastic properties of the samples were also found to be insignificant. Both types of samples under both types of aging also exhibited an increase in crystallinity over time. These results indicate that the durability and properties of wood can be improved through nano-SiO₂ impregnation as the material remains relatively stable when subjected to high temperature and humidity conditions as well as freeze-thaw cycling over time.

No description available.

Les matériaux polymères sont aujourd'hui très présents dans notre environnement et deviennent irremplaçables pour de nombreuses applications : emballage, textile, mobilier,... La connaissance du cycle de vie de ces matériaux, de la production à leur destruction, devient importante pour nos sociétés. Par exemple ces matériaux peuvent émettre des Composés Organiques Volatils qui sont souvent toxiques et leur impact sur le milieu doit être évalué. L’objectif de ce travail de thèse a été de développer une méthode au laboratoire pour identifier et quantifier ces émissions. La difficulté provient de la grande diversité des composés qui peuvent être émis. Par ailleurs la méthode nécessite une fréquence de mesure élevée (temps réel) souvent incompatible avec les techniques actuelles. Une solution analytique couplant un four et un spectromètre de masse haute résolution associé à une méthode d’ionisation chimique contrôlée a été développée. Celle-ci est basée sur un spectromètre FT-ICR compact à bas champ magnétique : BTrap. Les points forts de cette technique sont la très haute résolution en masse qui permet de mesurer la masse exacte des composés et la détection multi composés, simultanée sur toute la gamme de masse. L’ionisation chimique contrôlée permet l'ionisation douce et quantitative des molécules d’intérêt. Le transfert de proton à partir de l’ion H₃O⁺ (PTRMS) a montré son potentiel pour la détection des COV dans de nombreux domaines. Après une présentation du contexte et du besoin, le dispositif expérimental développé est détaillé. La validation de celui-ci pour l'analyse de gaz traces a été effectuée au LPGP, sur un système de dépollution par plasma froid. Les résultats de dégradation de l'acétaldéhyde en fonction des conditions de fonctionnement du réacteur sont présentés.L’ionisation par PTR conduit habituellement à la molécule protonée ce qui simplifie l’identification. Cependant des fragmentations peuvent être observées. L’utilisation d’un précurseur d’ionisation chimique plus lourd et moins réactif que H₃O⁺ pourrait minimiser ces phénomènes. L’utilisation du diflurobenzène protoné a été testée et comparée à celle de l’ion H₃O⁺. Pour cela, des études cinétiques ont été menées sur une série d’alcools connus pour fragmenter avec H₃O⁺, et confirment l'intérêt du nouveau précurseur.Le poly(méthacrylate de méthyle) (PMMA) est un matériau très répandu : plexiglass. Sa dégradation est a priori relativement simple puisqu’il s’agit très majoritairement d’une dépolymérisation, accompagnée de la formation de produits minoritaires. En conséquence, son étude nous a paru intéressante pour la mise au point et la validation de la méthode. La dégradation du PMMA a été étudiée sous atmosphère inerte, puis oxydante. Les résultats obtenus sont présentés : produits émis, bilan en masse, et apport du suivi en temps réel de la dégradation, montrant en particulier que les produits minoritaires sont émis après le monomère.Enfin une dernière partie de conclusion présente les perspectives pour cette nouvelle méthode. / Polymeric materials are now ubiquitous in our environment and become irreplaceable for many applications such as packaging, textile or furniture. Knowledge of the life cycle of these materials from production to destruction becomes important for our societies. For instance, plastics may release Volatile Organic Compounds: VOCs are often toxic and their impact on the environment must be evaluated. The aim of this thesis work is the development of a laboratory method for identification and quantification of these emissions. The difficulty arises from the wide variety of compounds being potentially emitted. Moreover the desired method requires a high measurement rate ("real time") often incompatible with existing techniques. An analytical device coupling a furnace and a high-resolution mass spectrometer associated with a controlled chemical ionization method has been developed. This device is based on a low magnetic field FT-ICR compact mass spectrometer. The strengths of this technique are (i) high mass resolution allowing exact mass measurements, (ii) recording of the whole mass range simultaneously, allowing detection of a large variety of compounds. Controlled chemical ionization allows soft and quantitative ionization of molecules of interest. Proton transfer from H₃O⁺ ion (PTRMS) has shown its potentialities for VOC detection in many areas. After presenting the background and need, the developed experimental device is described in detail.The validation of this instrument for trace gas analysis has been performed at LPGP, using a nonthermal plasma depollution device. The results of acetaldehyde degradation according to operating conditions in the discharge reactor are presented.PTR ionization usually leads to the protonated molecule, so that identification is simplified. However fragmentations are sometimes observed. Use of a chemical ionization precursor ion heavier and less reactive than H₃O⁺ may minimize these drawbacks. Protonated difluorobenzene was selected as a precursor and its reactivity was tested and compared with H3O+ reactivity. In this purpose, kinetic studies were performed on a series of alcohols known for their fragmentation behavior with H₃O⁺. The results confirm the interest of the new precursor.Polymethyl methacrylate (PMMA) is a widespread material: plexiglass. Its degradation process is relatively simple since it consists in predominant depolymerization, along with formation of minor products. Consequently, PMMA study appeared interesting for method development and validation. Thermal degradation of PMMA has been studied under inert, then oxidative atmosphere conditions. The presented results include identification of minor products and mass balance under different temperature conditions. Real-time monitoring of VOC emission showed time differences in emission peaks of MMA monomer and minor products, each of them being emitted slightly later than MMA. Finally, a conclusive part presents the perspectives opened for this new method.

Applications of Hot Melt Extrusion (HME) in pharmaceuticals have become increasingly popular over the years but nonetheless a few obstacles still remain before wide scale implementation. In many instances these improvements are related to both processing and product performance. It is observed that HME process optimisation is majorly focused on the active pharmaceutical ingredient's (API) properties. Characterising polymeric properties for their suitability in HME should be equally studied since the impact of excipients on both product and process performance is just as vital. In this work, two well-established cellulose ester derivatives: Hydroxy Propyl Methyl Cellulose Acetate Succinate (HPMCAS) and Hydroxy Propyl Methyl Cellulose Phthalate (HPMCP) are studied for their HME suitability. Their thermal, thermodynamic, rheological, thermo-chemical and degradation kinetic properties were evaluated with model plasticisers and APIs. It was found the thermal properties of HPMCP are severely compromised whereas HPMCAS is more stable in the processing zone of 150 to 200 °C. Thermodynamic properties revealed that both polymers share an important solubility parameter range (20-30 MPa P1/2P) where the majority of plasticisers and BCS class II APIs lie. Thus, greater miscibility/solubility can be expected. Further, the processability of these two polymers investigated by rheometric measurements showed HPMCAS possesses better flow properties than HPMCP because HPMCP forms a weak network of chain interactions at a molecular level. However, adding plasticisers such as PEG and TEC the flow properties of HPMCP can be tailored. The study also showed that plasticisers have a major influence on thermo-chemical and kinetic properties of polymers. For instance, PEG reduced polymer degradation with reversal in kinetic parameters whereas blends of CA produced detrimental effects and increased polymer degradation with reduction in onset degradation temperatures. Further, both polymers are observed to be chemically reactive with the APIs containing free -OH, -SOR2RN- and -NH2 groups. Finally, these properties prove that suitability of HPMCP is highly debated for HME and demands great care in use while that of HPMCAS is relatively better than HPMCP in many instances.