Crystal chemistry of type paulkerrite and establishment of the paulkerrite group nomenclature

A single-crystal structure determination and refinement has been conducted for the type specimen of paulkerrite. The structure analysis showed that the mineral has monoclinic symmetry, space group P21/c, not orthorhombic, Pbca, as originally reported. The unit-cell parameters are a=10.569(2), b=20.590(4), c=12.413(2) Å, and β=90.33(3)∘. The results from the structure refinement were combined with electron microprobe analyses to establish the empirical structural formula A1[(H2O)0.98K0.02]Σ1.00 A2K1.00 M1(Mg1.02Mn0.982+)Σ2.00 M2(Fe1.203+Ti0.544+Al0.24Mg0.02)Σ2.00 M3(Ti0.744+ Fe0.263+)Σ1.00 (PO4)4.02 X[O1.21F0.47(OH)0.32]Σ2.00(H2O)10 ⋅ 3.95H2O, which leads to the end-member formula (H2O)KMg2Fe2Ti(PO4)4(OF)(H2O)10 ⋅ 4H2O. A proposal for a paulkerrite group, comprising orthorhombic members benyacarite, mantiennéite, pleysteinite, and hochleitnerite and monoclinic members paulkerrite and rewitzerite, has been approved by the International Mineralogical Association's Commission for New Minerals, Nomenclature and Classification. The general formulae are A2M12M22M3(PO4)4X2(H2O)10 ⋅ 4H2O and A1A2M12M22M3(PO4)4X2(H2O)10 ⋅ 4H2O for orthorhombic and monoclinic species, respectively, where A= K, H2O, □ (= vacancy); M1 = Mn2+, Mg, Fe2+, Zn (rarely Fe3+); M2 and M3 = Fe3+, Al, Ti4+ (and very rarely Mg); X= O, OH, F. In monoclinic species, K and H2O show an ordering at the A1 and A2 sites, whereas O, (OH), and F show a disordering over the two non-equivalent X1 and X2 sites, which were hence merged as X2 in the general formula. In both monoclinic and orthorhombic species, a high degree of mixing of Fe3+, Al, and Ti occurs at the M2 and M3 sites of paulkerrite group members, making it difficult to get unambiguous end-member formulae from the structural determination of the constituents at individual sites. To deal with this problem an approach has been used that involves merging the compositions at the M2 and M3 sites and applying the site-total-charge method. The merged-site approach allows end-member formulae to be obtained directly from the chemical analysis without the need to conduct crystal-structure refinements to obtain the individual site species.</p

Enthalpy of formation of ye’elimite and ternesite

Calcium sulfoaluminate clinkers containing ye’elimite (Ca4Al6O12(SO4)) and ternesite (Ca5(SiO4)2SO4) are being widely investigated as components of calcium sulfoaluminate cement clinkers. These may become low energy replacements for Portland cement. Conditional thermodynamic data for ye’elimite and ternesite (enthalpy of formation) have been determined experimentally using a combination of techniques: isothermal conduction calorimetry, X-ray powder diffraction and thermogravimetric analysis. The enthalpies of formation of ye’elimite and ternesite at 25 °C were determined to be − 8523 and − 5993 kJ mol−1, respectively

Accelerated discovery of two crystal structure types in a complex inorganic phase field

The discovery of new materials is hampered by the lack of efficient approaches to the exploration of both the large number of possible elemental compositions for such materials, and of the candidate structures at each composition1. For example, the discovery of inorganic extended solid structures has relied on knowledge of crystal chemistry coupled with time-consuming materials synthesis with systematically varied elemental ratios2,3. Computational methods have been developed to guide synthesis by predicting structures at specific compositions4,5,6 and predicting compositions for known crystal structures7,8, with notable successes9,10. However, the challenge of finding qualitatively new, experimentally realizable compounds, with crystal structures where the unit cell and the atom positions within it differ from known structures, remains for compositionally complex systems. Many valuable properties arise from substitution into known crystal structures, but materials discovery using this approach alone risks both missing best-in-class performance and attempting design with incomplete knowledge8,11. Here we report the experimental discovery of two structure types by computational identification of the region of a complex inorganic phase field that contains them. This is achieved by computing probe structures that capture the chemical and structural diversity of the system and whose energies can be ranked against combinations of currently known materials. Subsequent experimental exploration of the lowest-energy regions of the computed phase diagram affords two materials with previously unreported crystal structures featuring unusual structural motifs. This approach will accelerate the systematic discovery of new materials in complex compositional spaces by efficiently guiding synthesis and enhancing the predictive power of the computational tools through expansion of the knowledge base underpinning them

A study, mainly of hematite quartzites from the Middleback Ranges, with some remarks on their magnetic properties.

This item is only available electronically.Some sort of study of the rocks of the Middleback Ranges has been attempted. This has been rather limited to the hematite quartzites, the most prominent rocks in the ranges proper. These were examined in polished section - the specimens used came mainly from DDH20. They were both surface and subsurface specimens. In tying this mineragraphic approach in with the later study of the magnetitic properties (again mainly of the hematite quartzites) note was taken of the magnetite content of the rocks. This it was estimated was limited to only about 1-2% of the total minerals present - the predominant ones being hematite and quartz. This small mount of magnetite, it was found, did not vary much with depth (over about 800'), and it was also nearly the same as the amount present in those specimens taken at the surface at DDH20. This would suggest that the amount of magnetite present in the hematite quartzites need not be dependent on the present erosion level, thus indicating that the conversion of the original magnetite of the hematite quartzites to hematite, is perhaps not dependent on supergene processes as much as others (for instance hypogene). The hematite quartzites from DDH20 possess consistently high magnetic properties: this even in view of the fact that they contain relatively little magnetite compared with others found in the range area. This suggests the fact, which is obvious anyway, that large magnetic anomalies will be more so associated with these rocks than any others. The 1 mile aeromagnetic sheets are good for large scale reconnaissance investigations, and when used in conjunction with lower level maps, and ground gravimetric plots, become distinctly useful. The anomaly north of the race course area, in the vicinity of the Corunna Hills, and those southern elongated types on the Wilton sheet would bear further investigation on the surface. The large anomalies to the side of the ranges warrant thought too. They could be put down to basement highs (this outcrops in many places), or concentrations of magnetic material in the same. Sometimes the basement where it outcrops seems to be associated with magnetic highs, other times, for instance on the Roopena sheet, the outcropping basement does not bear any such relation to marked magnetic highs.Thesis (B.Sc.(Hons)) -- University of Adelaide, School of Earth and Environmental Sciences, 195