The 3 CaO · AI 2 0 3 (=C 3 A)-Na z O solid solutions (Ca 9 _ x/2 Na I -[A1 2 0 18 ]), have been crystal-chemically characterized based on four new structures:(i) 2.4wt% Na 2 0 (x = 0.625), a = 15.248(2)Ä, Ρ2^, Ζ = 8. (ii) 3.3% Na z O, a = 10.879(1), b = 10.845(2), c = 15.106(2), Pbca, Ζ = 4. (iii) 5.7 wt% Na 2 0 {x = 1.5), a = 10.877 (6), b = 10.854(13), c = 15.135(13), y = 90.1(1)°, P2Ja, Ζ = 4. (iv) 6.6 wt% Na 2 0, a = 10.844(2), 6 = 10.855(2), c= 15.122(4), y = 90.38(1)°, P2 1 /a, Ζ = 4. Among these, (ii) contains 0.45 Fe and 0.375 Si, and (iv) 0.465 Si per 18 oxygen atoms. The structures have been refined to R = 3.5 ~ 4.9%.The structure (i) represents the structure type of a hitherto unreported cubic phase, which is here denoted by CII (the C 3 A is then denoted by CI); the compositional range of the new phase possibly extends from around 1.0 to 2.4 in wt % of Na 2 0. The Na atoms in the structure substitute for Ca at Ca3B and Ca4B which respectively correspond to the Ca(3) and Ca(4) sites in C 3 A, and excess Na atoms, resulting from the replacement in the Ca/Na ratio of 1/2, go to the centers of the six-membered rings. The substitution gives rise to an expansion of the polyhedra particularly about Ca4B; such an effect would presumably limit the CII structure type at the Na z O content of around 2.4%. With increasing Na 2 0 content, the cubic arrangement of the sixmembered rings undergoes a drastic change to yield an orthorhombic arrangement. In the orthorhombic structure type, Na substitutes for Ca only at the Ca5 site, and the Na occupancy in the rings is increased compared to the cubic cases; the rings are more contracted compared to those in CII. When Si is present in the orthorhombic solid solution, it gives an effect of reducing the Na occupancy in the rings and thus extends the solid-solution Brought to you by | New York University Bobst Library Technical Service Authenticated Download Date | 8/2/15 4:08 AM Y. Takeuchi et al.: 3 CaO • A1 2 0 3 -Na 2 0 solid-solution series range towards the compositions of Na-poor range. As the content of Na increases further, the Ca5 site splits into two nonequivalent sites, Ca5A and Ca5B, which accommodate Na in different amounts, thus distorting the orthorhombic structure to monoclinic; the arrangement of rings is essentially the same as that for the orthorhombic structure type. When Si is present in the monoclinic solid solution, it permits the Na occupancy of 100 % at Ca5B and reduces the Na occupancy in the rings; as the total effect, the Na content in the structure increases and the solid-solution range is extended to a region which is richer in Na.The X-ray, single-crystal study at high temperatures have confirmed that the monoclinic structure type is transformed to orthorhombic in a transition which is reversible. The transition is caused by an order-disorder of Na and Ca in the Ca5A and Ca5B sites. The inversion twins that occur in monoclinic crystals, and the growth twins that commonly occur in non-cubic crystals, can be structurally interpreted.* In cement...