High-temperature stability of Mg(Al,Cr)2O4 spinel co-existing with calcium aluminates in air

Cr 2 O 3 is a well-known corrosion resistant oxide used in refractory applications. However, it can oxidize into toxic and water-soluble Cr(VI) compounds upon reaction with calcium aluminate cement phases in the presence of oxygen, which subsequently causes disposal problems after use. This study describes the extent to which chromium in the spinel Mg(Al,Cr) 2 O 4 phase can be oxidized to Cr(VI) when it reacts with the calcium aluminate cement phases C 12 A 7 , CA, CA 2 and free CaO at 1300 °C in air, using XRD, XPS and leaching tests (TRGS 613 standard) as analytical tools. On reaction with CaO, the Mg(Al,Cr III ) 2 O 4 spinel mainly transformed into hauyne (Ca 4 Al 6 Cr VI O 16 ) and Ca 5 Cr 3 O 12 which contains both Cr(IV) and Cr(VI). The reaction of C 12 A 7 and CA with the spinel phase also resulted in the formation of Ca 4 Al 6 CrO 16 . Conversely, the reaction of Mg(Al,Cr III ) 2 O 4 spinel with CA 2 resulted in the formation of only a trace amount of Cr(VI). Water-soluble Cr(VI) leached in large quantities (>100 mg/L) from samples where the Mg(Al,Cr III ) 2 O 4 reacted with either C 12 A 7 or CA. Almost no Cr(VI) leached from the sample when Mg(Al,Cr III ) 2 O 4 reacted with CaO, using the standard TRGS 613 leach test, but a significant amount of Cr(VI) was released into solution when leached with a HCl solution for 12 h. Both Cr(IV) and Cr(VI) present in the Ca 5 Cr 3 O 12 dissolved into acidic solution. Only a small amount of Cr(VI) leached from the sample that resulted when spinel was reacted with CA 2 , even after a prolonged HCl leach. Cr(III) in spinel Mg(Al,Cr) 2 O 4 is very stable and does not leach in either distilled water or acidic solution.