Zinc Treatment Effects on Corrosion Behavior of 304 Stainless Steel in High Temperature, Hydrogenated Water

Trace levels of soluble zinc(II) ions (30 ppb) maintained in mildly alkaline, hydrogenated water at 260 C were found to lower the corrosion rate of austenitic stainless steel (UNS S30400) by about a factor of five, relative to a non-zinc baseline test after 10,000 hr. Characterizations of the corrosion oxide layer via grazing incidence X-ray diffraction and X-ray photoelectron spectroscopy in combination with argon ion milling and target factor analysis, confirmed the presence of two spinel oxide phases and minor amounts of recrystallized nickel. Based on the distribution of the three oxidized alloying constituents (Fe, Cr, Ni) with respect to depth and oxidation state, it was concluded that: (a) corrosion occurs in a non-selective manner, but approximately 30% of the oxidized iron is released to the water, and (b) the two spinel oxides exist as a ferrite-based outer layer (Ni{sub 0.1}Zn{sub 0.6}Fe{sub 0.3})(Fe{sub 0.95}Cr{sub 0.05}){sub 2}O{sub 4} on top of a chromite-based inner layer (Ni{sub 0.1}Zn{sub 0.2}Fe{sub 0.7})(Fe{sub 0.4}Cr{sub 0.6}){sub 2}O{sub 4}. These results suggest that immiscibility in the Fe{sub 3}O{sub 4}-ZnFe{sub 2}O{sub 4} binary may play a role in controlling the zinc content of the outer layer. On the other hand, the lower corrosion rate caused by zinc additions is believed to be a consequence of corrosion oxide film stabilization due to the substitution reaction equilibrium: z Zn{sup 2+}(aq) + FeCr{sub 2}O{sub 4}(s) {approx} z Fe{sup 2+}(aq) + (Zn{sub z}Fe{sub 1-z})Cr{sub 2}O{sub 4}(s). The liquid-solid distribution coefficient for the reaction, defined by the ratio of total zinc to iron ion concentrations in solution divided by the Zn(II)/Fe(II) ratio in the solid, z/(1-z), was found to be 0.184. This interpretation is consistent with the benefits of zinc treatment being concentration dependent

Corrosion Behavior of 304 Stainless Steel in High Temperature, Hydrogenated Water

The corrosion behavior of an austenitic stainless steel (UNS S30400) has been characterized in a 10,000 hour test conducted in hydrogenated, ammoniated water at 260 C. The corrosion kinetics were observed to follow a parabolic rate dependency, the parabolic rate constant being determined by chemical descaling to be 1.16 mg dm{sup -2} hr{sup -1/2}. X-ray photoelectron spectroscopy, in combination with argon ion milling and target factor analysis, was applied to provide an independent estimate of the rate constant that agreed with the gravimetric result. Based on the distribution of the three oxidized alloying constituents (Fe, Cr, Ni) with respect to depth and elemental state, it was found that: (a) corrosion occurs in a non-selective manner, and (b) the corrosion film consists of two spinel oxide layers--a ferrite-based outer layer (Ni{sub 0.2}Fe{sub 0.8})(Fe{sub 0.95}Cr{sub 0.05}){sub 2}O{sub 4} on top of a chromite-based inner layer (Ni{sub 0.2}Fe{sub 0.8})(Cr{sub 0.7}Fe{sub 0.3}){sub 2}O{sub 4}. These compositions agree closely with the solvi phases created by immiscibility in the Fe{sub 3}O{sub 4}-FeCr{sub 2}O{sub 4} binary, implying that immiscibility plays an important role in the phase separation process

Zinc Treatment Effects on Corrosion Behavior of Alloy 600 in High Temperature, Hydrogenated Water

Trace levels of soluble zinc(II) ions (30 ppb) maintained in mildly alkaline, hydrogenated water at 260 C were found to reduce the corrosion rate of Alloy 600 (UNS N06600) by about 40% relative to a non-zinc baseline test [2]. Characterizations of the corrosion oxide layer via SEM/TEM and grazing incidence X-ray diffraction confirmed the presence of a chromite-rich oxide phase and recrystallized nickel. The oxide crystals had an approximate surface density of 3500 {micro}m{sup -2} and an average size of 11 {+-} 5 nm. Application of X-ray photoelectron spectroscopy with argon ion milling, followed by target factor analyses, permitted speciated composition vs. depth profiles to be obtained. Numerical integration of the profiles revealed that: (1) alloy oxidation occurred non-selectively and (2) zinc(II) ions were incorporated into the chromite-rich spinel: (Zn{sub 0.55}Ni{sub 0.3}Fe{sub 0.15})(Fe{sub 0.25}Cr{sub 0.75}){sub 2}O{sub 4}. Spinel stoichiometry places the trivalent ion composition in the single phase oxide region, consistent with the absence of the usual outer, ferrite-rich solvus layer. By comparison with compositions of the chromite-rich spinel obtained in the non-zinc baseline test, it is hypothesized that zinc(II) ion incorporation was controlled by the equilibrium for 0.55 Zn{sup 2+}(aq) + (Ni{sub 0.7}Fe{sub 0.3})(Fe{sub 0.3}Cr{sub 0.7}){sub 2}O{sub 4}(s) {r_equilibrium} 0.40 Ni{sup 2+}(aq) + 0.15 Fe{sup 2+}(aq) + (Zn{sub 0.55}Ni{sub 0.3}Fe{sub 0.15})(Fe{sub 0.3}Cr{sub 0.7}){sub 2}O{sub 4}(s). It is estimated that only 8% of the Ni(II) ions generated during non-selective oxidation of the alloy were retained as Ni(II) in the corrosion layer; the remainder either recrystallized to Ni(0) (38%) or were released to the aqueous phase (54%)

Kinematic studies of transport across an island wake, with application to the Canary islands

Transport from nutrient-rich coastal upwellings is a key factor influencing biological activity in surrounding waters and even in the open ocean. The rich upwelling in the North-Western African coast is known to interact strongly with the wake of the Canary islands, giving rise to filaments and other mesoscale structures of increased productivity. Motivated by this scenario, we introduce a simplified two-dimensional kinematic flow describing the wake of an island in a stream, and study the conditions under which there is a net transport of substances across the wake. For small vorticity values in the wake, it acts as a barrier, but there is a transition when increasing vorticity so that for values appropriate to the Canary area, it entrains fluid and enhances cross-wake transport.Comment: 28 pages, 13 figure

Magnetite solubility and phase stability in alkaline media at elevated temperatures

Magnetite, Fe{sub 3}O{sub 4}, is the dominant oxide constituent of the indigenous corrosion layers that form on iron base alloys in high purity, high temperature water. The apparent simultaneous stability of two distinct oxidation states of iron in this metal oxide is responsible for its unique solubility behavior. The present work was undertaken to extend the experimental and theoretical bases for estimating solubilities of an iron corrosion product (Fe{sub 3}O{sub 4}/Fe(OH){sub 2}) over a broader temperature range and in the presence of complexing, pH-controlling reagents. These results indicate that a surface layer of ferrous hydroxide controls magnetite solubility behavior at low temperatures in much the same manner as a surface layer of nickel(II) hydroxide was previously reported to control the low temperature solubility behavior of NiO. The importance of Fe(III) ion complexes implies not only that most previously-derived thermodynamic properties of the Fe(OH){sub 3}{sup {minus}} ion are incorrect, but that magnetite phase stability probably shifts to favor a sodium ferric hydroxyphosphate compound in alkaline sodium phosphate solutions at elevated temperatures. The test methodology involved pumping alkaline solutions of known composition through a bed of Fe{sub 3}O{sub 4} granules and analyzing the emerging solution for Fe. Two pH-controlling reagents were tested: sodium phosphate and ammonia. Equilibria for the following reactions were described in thermodynamic terms: (a) Fe(OH){sub 2}/Fe{sub 3}O{sub 4} dissolution and transformation, (b) Fe(II) and Fe(III) ion hydroxocomplex formation (hydrolysis), (c) Fe(II) ion amminocomplex formation, and (d) Fe(II) and Fe(III) ion phosphatocomplex formation. 36 refs

Zinc(II) oxide solubility and phase behavior in aqueous sodium phosphate solutions at elevated temperatures

A platinum-lined, flowing autoclave facility is used to investigate the solubility/phase behavior of zinc(II) oxide in aqueous sodium phosphate solutions at temperatures between 290 and 560 K. ZnO solubilities are observed to increase continuously with temperature and phosphate concentration. At higher phosphate concentrations, a solid phase transformation to NaZnPO{sub 4} is observed. NaZnPO{sub 4} solubilities are retrograde with temperature. The measured solubility behavior is examined via a Zn(II) ion hydrolysis/complexing model and thermodynamic functions for the hydrolysis/complexing reaction equilibria are obtained from a least-squares analysis of the data. The existence of two new zinc(II) ion complexes is reported for the first time: Zn(OH){sub 2}(HPO{sub 4}){sup 2{minus}} and Zn(OH){sub 3}(H{sub 2}PO{sub 4}){sup 2{minus}}. A summary of thermochemical properties for species in the systems ZnO-H{sub 2}O and ZnO-Na{sub 2}O-P{sub 2}O{sub 5}-H{sub 2}O is also provided. 21 refs., 10 figs., 7 tabs

Excitable media in open and closed chaotic flows

We investigate the response of an excitable medium to a localized perturbation in the presence of a two-dimensional smooth chaotic flow. Two distinct types of flows are numerically considered: open and closed. For both of them three distinct regimes are found, depending on the relative strengths of the stirring and the rate of the excitable reaction. In order to clarify and understand the role of the many competing mechanisms present, simplified models of the process are introduced. They are one-dimensional baker-map models for the flow and a one-dimensional approximation for the transverse profile of the filaments.Comment: 14 pages, 16 figure

Oxidative Dissolution of Nickel Metal in Hydrogenated Hydrothermal Solutions

A platinum-lined, flowing autoclave facility is used to investigate the solubility behavior of metallic nickel in hydrogenated ammonia and sodium hydroxide solutions between 175 and 315 C. The solubility measurements were interpreted by means of an oxidative dissolution reaction followed by a sequence of Ni(II) ion hydrolysis reactions: Ni(s) + 2H+(aq) = Ni2+(aq) + H2(g) and Ni{sup 2+}(aq) + nH{sub 2}O = Ni(OH){sub n}{sup 2-n}(aq) + nH{sup +}(aq) where n = 1 and 2. Gibbs energies associated with these reaction equilibria were determined from a least-squares analysis of the data. The extracted thermochemical properties ({Delta}fG{sup 0}, {Delta}fH{sup 0} and S{sup 0}) for Ni2{sup +}(aq), Ni(OH){sup +}(aq) and Ni(OH){sub 2}(aq) were found to be consistent with those determined in a previous solubility study of NiO/Ni(OH){sub 2} conducted in our laboratory. The thermodynamic basis of the Ni/NiO phase boundary in aqueous solutions is examined to show that Ni(s) is stable relative to NiO(s) in solutions saturated at 25 C with 1 atm H{sub 2} for temperatures below 309 C