Incommensurately modulated crystal structure of flamite – natural analogue of \alpha _{\rm H}^{\prime}-Ca2SiO4

Abstract

Crystal structures of unquenchable high-temperature polymorphs of Ca2SiO4, important in cement chemistry, have eluded single-crystal X-ray analysis. However, the problem may be addressed by studying chemically stabilized Ca2SiO4 polymorphs at ambient temperature. Here an incommensurately modulated crystal structure of flamite [Pnma(0β0)00s, q = 0.2728 (2)b*, a = 6.8588 (2) Å, b = 5.4301 (2) Å, c = 9.4052 (3) Å] is described. It is a mineral analogue of orthorhombic \alpha _{\rm H}^{\prime}-Ca2SiO4 (stable between 1160 and 1425°C), naturally stabilized by substitution with phosphorus. The incommensurate modulation results from wave-like displacement of cation sites accompanied by tilting of (Si,P)O4 tetrahedra and variation of the Na/(Ca + Na + K) ratio along the modulation period. The studied sample from Hatrurim Basin (Negev Desert, Israel) with composition (Ca1.75K0.12Na0.12)1.99(Si0.74P0.26)1.00O4 also demonstrates pseudomerohedral cyclic twinning around the a axis, which results from pseudohexagonal topology of the crystal structure and complicates the indexing of X-ray diffraction data.