New orthorhombic phases on the join NiAl2O4 (spinel analog)-Ni2SiO4 (olivine analog): Stability and implications to mantle mineralogy

Three new crystalline phases differing in Si/Al ratio have been synthesized from compositions along the join NiAl₂O₄-Ni₂SiO₄. Four reversible univariant equilibria involving these new phases plus Ni₂SiO₄ (olivine) have been located within the P-T region studied (1 atm–40 kb, 1000–1700° C); an invariant point occurs near 22 kb, 1150°C.All three new phases are orthorhombic. Precession photographs and electron microprobe analyses yield the following information:Phase I: 5NiO·3Al₂O₃·SiO₂ = 3NiAl₂O₄·Ni₂SiO₄, Pmma, a=5.67, b=11.51, c=8.10 (Å)Phase II: 7NiO·3Al₂O₃·2SiO₂ = 3NiAl₂O₄· 2Ni₂SiO₄, Imma, a=5.66, b=17.32, c=8.11Phase III: 3NiO· Al₂O₃· SiO₂ = NiAl₂O₄·Ni₂SiO₄, Imma, a=5.68, b=11.49, c=8.12Comparison with known structures suggests that these three phases plus NiAl₂O₄ spinel and high pressure Ni₂SiO₄ spinel belong to a homologous series based on a cubic close oxygen packing of the formula: M_2n O _n}-1 (T _n O_3n+1) where M and T are octahedrally and tetrahedrally coordinated cations, respectively. When n=1 the formula for spinel is obtained; n = 2 for phase I and phase III, both similar to the beta-phase of orthosilicates; and n = 3 for phase II which is related to the manganostibite structure.Similar phase equilibria and structural relations may occur on other joins of the aluminateorthosilicate type. Furthermore, the occurrence of such structural modifications between the spinel (aluminate) and olivine (orthosilicate) compositions suggests that there could be a corresponding polymorphic series between the olivine and spinel forms of orthosilicates.