Vajo, John J. | Engineering Papers

DOE OSTI2024

Chromium-Free Coating for Al Alloy Corrosion Protection Based on a Novel Ti/Mg Oxyfluoride

Chromium-free corrosion protection of aluminum alloys comparable to that of chromates (Cr(VI)) is demonstrated using a TiF 6 2– fluoro-anion-based coating recipe containing boric acid and a Mg salt. Boric acid drove TiF 6 2– hydrolysis enabling up to micrometer-scale thick coatings. The Mg salt led to deposition of a novel crystalline phase Ti/Mg oxyfluoride coating with an approximate composition of Ti 5 MgO 7 F 8 . Corrosion protection performance was characterized by polarization resistance measurements during immersion in 5% aqueous NaCl solution and neutral salt fog exposure following ASTM B.117. The performance is discussed in terms of the presence of fluoride in the coating enabling active behavior during its gradual depletion (in corrosion environments) toward a final composition approaching TiO 2 . This active corrosion protection mechanism may be more generally applicable for transition metal-based coatings that do not have high oxidation state oxo-anions, but do have stable fluoro-anions.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Electrolytes in Multiple-Phase Hydrogen Storage Reactions

Multiple-phase hydrogen storage materials such as metal alanates and borohydrides, and destabilized systems offer the possibility of high hydrogen storage capacity with favorable thermodynamics. However, the multiphase nature of these materials intrinsically limits the kinetics due to the required transport of species between phases, which are typically in dry powder form. To address this limitation, the influence of added electrolytes is explored. This approach is motivated by analogy with similar multiphase battery reactions that show reduced kinetic limitations while necessarily containing electrolytes. Previous experimental results showing improved kinetics for MgH2/Sn (using a LiBH4/KBH4 eutectic electrolyte) and NaAlH4 (using a diglyme electrolyte) are further analyzed in terms of this analogy. The results show that the analogy is useful and rate constants are increased. Importantly, the inclusion of an electrolyte also appears to alleviate the continuously decreasing rates with the extent of reaction, which is characteristic of many multiphase hydrides. Instead, reaction rates are approximately constant until near completion. Together, these effects can lead to >10× shorter overall reaction times. In addition, new results are presented for the hydrogenation of MgB2 using Li/K/CsI and Li/K/CsCl eutectic electrolytes, where >60% conversion to Mg(BH4)2 was demonstrated at 350 bar.

08 HYDROGEN↗