Abstract: Voids are frequently generated and dispersed in oxide scales formed in high temperature oxidation of metals. The divergence of ionic flux may play an important role in the void formation in a growing scale. Kinetic equations were derived for describing chemical potential distribution, ionic fluxes and their divergence in the scale. The divergence was found to be the measure of void formation. Defect chemistry in scales is directly related to the sign of divergence and gives an indication of the void formation behavior. The quantitative estimation on the void formation was successfully applied to a growing magnetite scale in high temperature oxidation of iron at 823 K.
Abstract: Starting from some fundamentals of solid-state diffusion, we remind the reader to the major techniques for lattice diffusion measurements. Self-diffusion is the most basic diffusion phenomenon in any solid. The paper covers main features of self-diffusion in pure fcc and bcc metals and some important facts about diffusion of substitutional solutes in metals. Binary intermetallics are compounds of two metals or of a metal and a semimetal. Their structures are different from those of the constituents. Some intermetallics are interesting functional materials others have attracted attention as high-temperature structural materials. The paper reviews some results mainly from our laboratory on diffusion in binary intermetallics from the systems Cu-Zn, Ni-Al, Fe-Al, Ni-Ge, Ni-Ga, Fe-Si, Ti-Al, Ni-Mn, Mo-Si and Co-Nb, which have been published in detail elsewhere. Some results for the ternary system Ni-Fe-Al are also mentioned.
Abstract: This paper presents selected experimental observations of phase constituents, growth kinetics, and microstructural development of aluminide phases that develop in solid-to-solid diffusion couples assembled with U-7wt.%Mo, U-10wt.%Mo and U-12wt.%Mo vs. Al and 6061 alloy after a diffusion anneal at 600°C for 24 hours. Scanning electron microscopy coupled with energy dispersive spectroscopy, electron microprobe analysis, and transmission electron microscopy via focused ion beam in-situ lift-out were employed to characterize the interaction layer that develops by interdiffusion. While concentration profiles exhibited no significant gradients, microstructural analysis revealed the presence of extremely complex and nano-scale phase constituents with presence of orthorhombic--U, cubic-UAl3, orthorhombic-UAl4, hexagonal-U6Mo4Al43 and diamond cubic-UMo2Al20 phases. Presence of multi-phase layers with microstructure, which suggest a significant role of grain boundary diffusion, was observed.
Abstract: Dusting of iron results from partial disintegration of a cementite scale which grows on the metal surface during reaction with carbon-supersaturated gas. Scaling kinetics are shown to be consistent with diffusion of carbon through the cementite. Further diffusion of carbon into the iron supersaturates it to a very high degree. Dusting of nickel and austenitic alloys leads to no carbide formation. Instead graphite grows into the metal, supported by diffusion of dissolved carbon to growth sites. Variations in rate with alloy iron content reflect the known effects of iron on carbon solubility and diffusivity. Alloying with copper also changes coking and dusting rates, although copper does not affect carbon permeability. The effect is shown to be due to interaction of copper with graphite nucleation sites.
Abstract: The atomic-scale graded structure of In-Pb alloy was formed by an ultracentrifuge under a gravitational field of 0.81 x 106 g for 100 hours at 150 °C in solid state. The isotope ratio measurements were performed on the centrifuged sample with secondary ion mass spectrometer (SIMS, CAMECA IMS-6f). 206Pb/208Pb and 207Pb/208Pb isotope ratio changed with negative gradient in the direction of centrifugal force approximately 1.5% and 0.8%, respectively. There was a tendency that the heavy 208Pb isotope abundance increased and the light 206Pb isotope abundance decreased in the direction of centrifugal force. Three-isotope diagram of 206Pb/208Pb versus 207Pb/208Pb proved that the isotope fractionation depends on the isotopic mass difference. These results showed that a strong gravitational field not only affected the inter-diffusion but also the self-diffusion in this alloy by causing isotope fractionation effect, which was dependent on the mass-difference.
Abstract: TiAl, TA6V and titanium coupons were treated by a phosphoric acid solution by dipping. They were then submitted to a heat treatment and, in the case of TiAl and TA6V, to high temperature discontinuous oxidation under laboratory air. The H3PO4 treatment allowed to decrease the mass gains for TiAl and TA6V, in particular during the first 100 hours. XRD analyses demonstrated for the three substrates the formation of a pyrophosphate layer during the heating period. This pyrophosphate evolved towards TiO2 with oxidation time increase, quicker for smaller aluminium content (or higher titanium content) in the metallic substrate. The decrease of mass gains was attributed to a diffusion barrier effect of the pyrophosphate layer as long as it was present.