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This thesis deals with refractory concrete binding system based on aluminous cement and phosphoric acid. The prepared refractory concretes were fired at 1 000 °C. Various effects on compressive strength of refractory concrete were studied. The influence of aluminous cement content and phosphoric acid content, the influence of various admixtures, the influence of plasticizers and the influence of time and method of sample storage were studied. Simultaneous thermogravimetry and differential thermal analysis of the basic unfired sample were performed. Finally, selected refractory concretes were fired at 110, 200, 400, 600, 800, 900, 1 000 and 1 100 °C. The compressive strength of these samples was measured and powder X ray diffraction analysis was performed. The compressive strength of refractory concretes under intermediate temperatures (800–1 100 °C) was most increased in samples with metakaolin and gray microsilica.

The thesis deals with the possibility of specific weight lowering of kaolin suspensions using air-entraining agents. These agents are usually used as concrete admixtures. The goal of the thesis is to verify an alternative possibility of creating porous structure in kaolin suspensions in order to prepare heat insulating moulded refractory concretes without using lightweight fillers. The effect of several air-entraining agents was compared, after that the dosage of agent and mixing conditions were optimized. The stabilization of prepared foams and practical application of selected agents were also part of the thesis.

Ce travail de thèse s'inscrit dans le cadre du projet CNES-PERSEUS. L’objectif principal est l’étude et la caractérisation d’un béton réfractaire à base de carbure de silicium, avec une taille maximale d'agrégats de 800 microns, dans un environnement de type propulsion hybride. Le col de la tuyère doit résister à un environnement très oxydant, produit par la combustion de polyéthylène solide et de protoxyde d’azote liquide, avec des températures statiques de gaz qui peuvent atteindre 2800K. L’étude est divisée en trois parties : une caractérisation thermomécanique du matériau jusqu’à 1500K ; une étude du comportement à l’oxydation en atmosphère standard, sous un flux solaire maximal de 15 MW/m2 ; des tests au banc avec un moteur hybride à l'ONERA, sur des tuyères conçues et réalisées au laboratoire ICA. Le frittage et la céramisation du microbéton engendrent une densification du matériau et le passage de liaisons de type hydrauliques à des liaisons de type covalentes et ioniques, avec augmentation du module d'élasticité et de la contrainte à la rupture à haute température. Ce matériau présente un comportement visco-élastique-plastique aux hautes températures : il reste majoritairement élastique linéaire jusqu'à la température de stabilisation du matériau, puis une composante viscoplastique apparaît, provoquée par la formation de phases liquides à partir de la matrice cimentaire. Les tests d’oxydation à haute température ont été menés au laboratoire PROMES-CNRS, sur une installation solaire de 2 kW, permettant d'appliquer à un flux maximal de 15 MW/m2. Des observations MEB, en microscopie optique et des analyses EDS ont été menées pour étudier les évolutions microstructurales et la cinétique d’oxydation du matériau. Les tests d’oxydation à 15 MW/m2 ont montré des vitesses d'érosion maximales de l'ordre de 5 microns/s pour une température de 2800 K. L'érosion est générée par l'oxydation active et par la sublimation du carbure de silicium. L'oxydation active se développe à partir de 2100 K, avec formation de SiO et CO gazeux. La sublimation du carbure de silicium, à partir de 2600-2700 K, entraine la formation de Si, Si2C et SiC2 gazeux. Les essais menés sur les tuyères montrent une bonne résistance du matériau après 20 secondes de tir. Une vitesse d'ablation moyenne proche de 60 microns/s a été observée au col de la tuyère. Le comportement thermo-élastique-ablatable a été modélisé tout d'abord sur la base d'une géométrie cylindrique multicouche, puis étendue au cas de la tuyère expérimentale testée au banc d'essai. / This research is part of the PERSEUS project, a space program concerning hybrid propulsion and supported by CNES. The main goal of this study is to characterize a silicon carbide based micro-concrete with a maximum aggregates size of 800 microns, in a hybrid propulsion environment. The nozzle throat has to resist to a highly oxidizing polyethylene/N2O hybrid environment, under temperatures ranging from room temperature up to 2800K. The study is divided in three main parts: the first one deals with the thermo-mechanical characterization of the materials up to 1500K, the second one with an investigation on the oxidation behaviour in a standard atmosphere, under a solar flux up to 15 MW/m2, the last part deals with the conception, the realization and the test of three nozzles in a hybrid rocket motor at ONERA. Elastic modulus was determined by resonant frequency method: results show an increase with the stabilisation temperature. Four points bending tests have shown a rupture tensile strength increasing with stabilization temperature, up to 1500 K. Sintering and ceramization process are primary causes of this phenomenon. Visco-plastic behaviour appears at 1400 K on a material staiblized at the same temperature, due to the formation of liquid phases in cement ternary system. High-temperature oxidation in air was carried out at PROMES-CNRS laboratory, on a 2 kW solar furnace, with a maximum solar flux of 15 MW/m2. Optical microscopy, SEM, EDS analyses were used to study the microstructure evolution and the mass loss kinetics, with a maximal erosion speed of 5 microns second. During theses tests, silicon carbide undergoes active oxidation at 2100 K, with production of SiO and CO smokes and ablation. SiC sublimation is observed since 2600-2700 K, with Si, Si2C and SiC2 vapour generation. Test performed on nozzle in hybrid rocket motors at ONERA, showed an average ablation speed at nozzle throat of 60 microns second, after 20 seconds of test. Thermo-elastic-ablative behaviour has been modelled using first composite cylinder geometry, and then it has been extended to the experimental nozzle geometry, tested on the test bench.

There are applications of refractory concretes for places where these are exposed to corrosive environments. This diploma thesis deals with both description the corrosive effects and methodology of their testing. One of the most important properties of materials, affecting the chemical corrosion resistance, is their density. The practical part of the thesis is focused on testing the refractory concretes which are currently used for applications. The aggregates were tested for the resistance to sulfuric acid.

The use of thermal storage energy, using phase change materials appears to be an effective way to store thermal energy storage with the benefits of the high amount of energy while maintaining isothermal nature of the process. PCM methods are used in latent thermal storage systems for heat pumps, as well as in solar engineering or for temperature control in spacecraft. The past decade has extended these principles for cooling and heating in the building. There are a number of PCM systems, which operate over a wide temperature range, are used in various applications. This document includes a brief overview of the development and analysis of available thermal storage working mainly on the principle of PCM.