Synthesis of AlON and MgAlON Ceramics and Their Chemical Corrosion Resistance

Abstract: In view of the excellent mechanical, chemical and opticalproperties, AlON (Aluminum oxynitride) as well as MgAlON(Magnesium Aluminum oxynitride) have drawn the attention ofmaterials scientists in past decades. In this thesis,thermodynamic properties, synthesis and corrosion resistance tooxygen and slag of AlON and MgAlON ceramics have beeninvestigated.Gibbs energy of AlON and MgAlON with different compositionsand temperatures were estimatedby using thermodynamicquasi-parabola rule. Phase stability diagrams of Al-O-N andMg-Al-O-N systems at different conditions have been calculated.On the basis of thermodynamic analysis, AlON and MgAlONceramics were synthesized by hot-press sintering andcharacterized by XRD, TEM and HREM analyses. An X-raydiffraction standard file of MgAlON is suggested and sent toJCPDS.The density of AlON synthesized was 3.63g/cm3, about 97.8% of its theoretical density. Thedensity of MgAlON is 3.55 g/cm3. Fracture toughness of AlON and MgAlON is 3.96 and4.06 MPa.m1/2. Three-point bending strength of AlON and MgAlONare 248 and 268 MPa, respectively, at room temperature andkeeps very high until 1723K. However the strength drops 189 and202 MPa for AlON and MgAlON, respectively, at 1723K. Thefracture section of AlON and MgAlON were examined and found tobe a mixed fracture of intercrystalline and cleavage fracturefor AlON and a mixed intercrystalline and transcrystallinefracture for MgAlON.Oxidation experiments of AlON and MgAlON and a comparison ofthe oxidation behavior of AlON, MgAlON, O'SiAlON-ZrO2and NB-ZCM have been carried out. Undernon-isothermal oxidation conditions, oxidation of AlON exhibitstwo steps with a "S"-shaped curve due to the phasetransformation of oxidation product. As temperature increases,the oxidation product, ? -Al2O3formed at lower temperatures will transform into?-Al2O3. Due to the differences in the molar volumesbetween ?-Al2O3and ? -Al2O3, cracks are likely to be formed in the productlayer promoting further oxidation. MgAlON, O'SiAlON-ZrO2and NB-ZCM show only one step with paraboliccurves.Isothermal oxidation experiments of AlON, MgAlON,O'SiAlON-ZrO2and NB-ZCM have been carried out in thetemperature range of 1373-1773K. At lower temperatures, MgAlONshows the best resistance to oxidation. But at highertemperatures, such as 1773K, AlON shows the best resistance tooxidation. O'SiAlON-ZrO2shows very good oxidation resistance in the lowtemperature range up to 1673K. But, as the temperature goes upabove 1673K, there is liquid phase produced during theoxidation process. Gas bubbles are also formed in the productlayer causing the flaking-off of some parts of the productlayer. Therefore its oxidation rate increases greatly astemperature rises to 1673K. In the case of BN-ZCM ceramics, dueto the evaporation of B2O3, the oxidation resistance seems to be poorest. Thechemical reaction activation energies for the initial stage ofoxidation of AlON, MgAlON, O'SiAlON-ZrO2and BN-ZCM are 218, 330, 260 and 254 kJ/molerespectively. And the activation energies at the laterdiffusion controlling stages are 227, 573, 367 and 289 kJ/molefor AlON, MgAlON, O'SiAlON-ZrO2and BN-ZCM respectively.The roughness of the oxidation sample surfaces has beenmeasured by Atomic Force Microscope. As the temperatureincreases, the degrees of roughness of AlON and MgAlON surfacesincrease slightly due to the growth of crystal grain. Theroughness degree of BN-ZCM increases greatly because of theevaporation of B2O3. However the roughness of O'SiAlON-ZrO2decreases as the temperature increases from 1473Kto 1673K. The main reason is that the liquid phase (glass)produced during the oxidation process at high temperatures suchas 1673K and 1773K. The roughness degree of MgAlON, AlON,O'SiAlON-ZrO2and BN-ZCM are 234, 174, 75 and 63 nm respectivelyat 1473K, and 297, 284, 52 and 406 nm respectively at1673K.Experiments of corrosion of AlON by CaO-MgO-"FeO"-Al2O3-SiO2slags were conducted in the temperature range of1693-1753K under static conditions as well as under forcedconvection. XRD, SEM-EDS and TEM analyses on the corrodedsamples were carried out.The results showed that the diffusion was therate-controlling step in the initial stage of the corrosion.Thereafter, the slag formation (the product layer dissolvinginto the liquid slag) became more and more important. Thisaspect was further confirmed by fractal dimension analysis ofthe interface. The overall activation energy for the corrosionprocess with slag No.1 was evaluated to be 1002 kJ. Adding"FeO" to the slag greatly enhanced the corrosion rate probablydue to the reaction of the sample with "FeO".Key words:AlON, MgAlON, Thermodynamics, Synthesis,Oxidation, Slag corrosion