CHAPTER11High-TemperatureMetal–Gas-Share.ppt

CHAPTER 11High - Temperature Metal – Gas Reactions Scaling, Dry Corrosion At temp. increase ? Metal oxidation increase ? gas turbines, rocket engines, furnaces and high-temp. petrochemical process. Mechanisms and Kinetics Pilling-Bedworth Ratio “Oxidation resistance should be related to the volumn ratio of oxide and metal” R = Wd / Dw W = molecular wt. of the oxide w = atomic wt. of the metal D,d = the specific densities of the oxide and metal Volumn ratio 1? insufficient oxide to cover the metal and is unprotective. Volumn ratio 1? large compressive stresses ? poor oxidation resistance ? cracking and spalling. The ideal ratio = close to 1 This ratio does not accurately predict oxidation resistance . To be protective an oxide must posses a coefficient of expansion nearly equal to that of the metal substrate, good adherence, a high melting pt., a low vapor pressure, good high-temp. plasticity to resist fracture, low electrical conductivity or low diffusion coeff. For metal ions or oxygen, and a volume ratio close to 1 to avoid compressive stresses or lack of complete surface coverage. Thus, oxidation resistance of a metal or alloys depends on a numbers of complex factors. Electrochemical and Morphological Aspects of Oxidation Oxidation by gaseous oxygen is an electrochemical process. M M+2 + 2e (at the metal – scale interface) 1/2O2 + 2e O-2 (at the scale-gas interface) M + 1/2O2 MO (Overall) Metal ions are formed at the metal-scale interface and oxygen is reduce to oxygen ions at the scale-gas interface. Oxide layer serves simultaneously as 1. an ionic conductor (electrolyte) 2. an electronic conductor. 3. an electrode at which oxygen is reduced. 4. a diffusion barrier through which ions and electrons must migrate. * The electronic conductivities of oxides are usually one or more orders of magnitude greater than their ionic conductivities, so