Les techniques d’analyse thermique et de calorimétrie sont des méthodes d’essai largement utilisées dans les laboratoires d’analyse physico-chimique, pour des finalités de recherche ou de contrôle qualité. Comme tout appareil de mesure, un analyseur thermique ou un calorimètre doit être étalonné en température et en énergie avec des matériaux de référence certifiés. Les matériaux de référence recommandés correspondent généralement aux points fixes de l'échelle internationale de température (EIT-90), à savoir gallium, indium, étain, zinc et aluminium. Il existe peu de matériaux de référence certifiés au-dessus de 420 °C, alors que certains analyseurs thermiques peuvent être utilisés jusqu'à 1000 °C, voire au-delà.L’élaboration et la certification de matériaux de référence doivent employer des méthodes de mesure très précises avec un raccordement métrologique des mesures au système international d’unités (SI). Le Laboratoire Commun de Métrologie (LCM) s'est engagé dans le développement d'un moyen de référence métrologique en calorimétrie permettant des mesures précises en enthalpie de fusion et en capacité thermique massique sur la plage de température [23 °C, 1000 °C]. La solution métrologique retenue a été de modifier un calorimètre de type Calvet, et de mettre au point des procédures d’étalonnage et de mesure afin d’atteindre des incertitudes de mesures suffisamment faibles pour la certification des matériaux de référence.Dans ce travail, un système d'étalonnage fonctionnant à haute température a été spécifiquement conçu et intégré dans le calorimètre pour permettre l'étalonnage par substitution électrique. Ce système permet de réaliser successivement des étalonnages par effet Joule et des mesures d’enthalpie de fusion, sans modification des conditions expérimentales.Ce travail comprend également le développement des systèmes d’acquisition et traitement des résultats des mesures. La détermination de l'enthalpie de fusion de plusieurs métaux (indium, étain et argent notamment) avec une recherche des facteurs d’influence sur cette grandeur, et une estimation des incertitudes de mesure. La mesure de l’enthalpie de fusion d’un alliage eutectique argent-cuivre, candidat comme matériau de référence en énergie à 779 °C, est également présentée. / Differential scanning calorimeters are widely used in many academic and industrial laboratories to study the thermal behavior of materials for research or quality control. Like any measuring device, a thermal analyzer or calorimeter must be calibrated in temperature and energy with certified reference materials. Recommended reference materials generally correspond to fixed points of the International Temperature Scale (ITS- 90), namely: gallium, indium, tin, zinc and aluminum. However, there are few certified reference materials above 420 °C, while the operating range of some thermal analyzers and calorimeters exceeds 1000 °C.The certification of reference materials insures the metrological traceability of measurements to the International System of Units (SI). The LCM-LNE has been working in the development of a metrological standard facility for accurate measurements of the enthalpy of fusion and heat capacity in the temperature range [23 °C, 1000 °C]. The metrological approach is based on the modification of a commercial Calvet calorimeter and of the procedures implemented for calibration and measurement, so as to get measurement uncertainties sufficiently low to fulfill the objectives of the certification of reference materials.A new in-situ high temperature calibration system (constituted by a resistance wire wound around the crucible containing the material sample) was integrated into the calorimeter to perform the calibration by electrical substitution. The system allows both calibration and measurement without modification of the apparatus, so that the experimental conditions during both steps remain unchanged.This work also includes the development of data acquisition system and processing of measurement results. The determination of the enthalpy of fusion of several metals (indium, tin and silver in particular) with an estimation of the measurement uncertainty has been made. The measurement of the enthalpy of fusion of a silver-copper eutectic alloy, as candidate reference material at 779 °C, is also presented.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The enthalpy of fusion of a perfect crystal of cellulose acetate was calculated in this thesis. In order to do so, cellulose samples from different sources were acetylated through the heterogenous acetilation methodology. The cellulose acetate samples were characterized by differencial scanning calorimetry (DSC) and by wide angle X-ray diffraction (WAXD). The X-ray diffractograms were deconvoluted into halos and peaks using the Pseudo-Voigt peak function of program Origin® 7.0. Two hypotheses were proposed in order to fit the deconvolution patterns into the two-phase model. In the first, the amorphous regions of the material was considered to be represented by the area of the halo located at 21º and the crystalline area by the maxima at 8º, 11º, 13º and 16º. In the second hypothesis, the amorphous region was considered to be represented by the areas of the maxima at 11º and 21º, and the crystalline region by the maxima at 8º, 13º and 16º. The WAXD crystallinities of the samples were then calculated from these values. The first hypothesis was ignored for presenting a very high crystallinity value for a sample that did not present an enthalpy of fusion. The second hypothesis was used, but the linear regression that defined the relationship between the enthalpy of fusion and the crystallinity of the materials was forced through zero. Through this relationship, the enthalpy of fusion of a perfect crystal of cellulose acetate was calculated to be 58.8 J/g. / A entalpia de fusão de um cristal perfeito de acetato de celulose foi calculada nessa dissertação. Para isso, amostras de celulose de diferentes origens foram acetiladas através do método de acetilação heterogêneo. As amostras de acetato de celulose foram caracterizadas por calorimetria diferencial de varredura (DSC) e difração de raios-X a alto ângulo (WAXD). Os difratogramas de raios-X foram deconvoluídos em halos e picos utilizando a função pico Pseudo-Voigt do programa Origin® 7.0. Duas hipóteses foram propostas para que as deconvoluções estivessem de acordo com o modelo de duas fases. Na primeira, foi considerado que a parte amorfa do material era representada pela área do halo localizado em 21º e a área cristalina pela soma das áreas dos máximos em 8º, 11º, 13º e 16º. Na segunda hipótese, a região amorfa foi considerada como sendo representada pelas áreas dos máximos em 11º e 21º, e a região cristalina pelos máximos em 8º, 13º e 16º. A partir desses valores se calculou a cristalinidade das amostras de acetato de celulose via WAXD. A primeira hipótese foi desconsiderada por apresentar um valor muito alto de cristalinidade para uma amostra que não apresentou entalpia de fusão. A segunda hipótese foi utilizada, porém a regressão linear que definiu a relação entre a entalpia de fusão e cristalinidade dos materiais foi forçada a passar pela origem. Através dessa relação, calculou-se a entalpia de fusão de um cristal perfeito de acetato de celulose como sendo 58,8 J/g. / Mestre em Química