On the incorporation of strontium into the crystal structure of bredigite: structural effects and phase transition

Sr-substitution in the crystal structure of bredigite has been studied in detail. Samples of a hypothetical solid-solution series with nominal composition Ca7-xSrxMg[SiO4]4 (x = 0, 2, …,7) have been prepared from sinter reactions in the temperature range between 1275 and 1325 °C and characterized using powder and single-crystal X-ray diffraction. Synthesis runs between x = 1 and x = 4 resulted in compounds with increasing Sr contents, for which single-crystal diffraction studies revealed the following Sr/(Sr + Ca) atomic ratios: 0.133,0.268, 0.409 and 0.559. They are isostructural to the pure calcium end-member (x = 0) and adopt the orthorhombic space group Pnnm. Evolution of the unit-cell parameters and cell volumes of the solid-solution series are defined by linear or nearly linear trends when plotted against the Sr/(Sr + Ca) atomic ratio. Replacement of calcium with strontium atoms on the different sites shows clear preferences for specific positions. For the experiment with x = 5, formation of bredigite-related single-crystals with Sr/(Sr + Ca) = 0.675 was observed. These samples, however, exhibited a halved c lattice parameter when compared with the corresponding value in the Pnnm structure, pointing to a compositionally induced phase transition somewhere in region between Sr/(Sr + Ca) = 0.559 and 0.675. The crystal structure of this new phase with composition Ca2.32Sr4.82Mg0.86[SiO4]4 was successfully determined in space group Pbam. Basic crystallographic data are as follows: a = 18.869(2) Å, b = 6.9445(8) Å, c = 5.5426(6) Å, V = 726.28(14) Å3, Z = 2. Structure determination was accomplished using charge flipping. Subsequent least-squares refinements resulted in a residual of R(|F|) = 2.70% for 822 independent reflections and 87 parameters. The Pbam- and the Pnnm-structures are in a group-subgroup relationship and topologically related. Both are based on so-called pinwheel-like MSi6O24 clusters consisting of a central magnesium-dominated [MO6]-octahedron as well as six attached [SiO4]-tetrahedra. The clusters are linked into chain-like elements running along [001]. Linkage between the chains is provided by mixed Sr/Ca positions with 6 to 10 oxygen ligands. Differences between the two phases result from changes in Sr-Ca site occupancies in combination with displacements of the atoms and tilts of the tetrahedra. The distortion pattern has been studied using group-theoretical methods including mode analysis. Notably, for the samples with x = 6 and x = 7—the latter corresponding to the hypothetical pure strontium end-member composition—no bredigite-type phases could be identified, indicating that there is an upper limit for the Sr-uptake.

Coupled Substitutions in Natural MnO(OH) Polymorphs: Infrared Spectroscopic Investigation

Solid solutions involving natural Mn3+O(OH) polymorphs, groutite, manganite, and feitknechtite are characterized and discussed based on original and literature data on the chemical composition, powder and single-crystal X-ray diffraction, and middle-range IR absorption spectra of these minerals. It is shown that manganite forms two kinds of solid-solution series, in which intermediate members have the general formulae (i) (Mn4+, Mn3+)O(OH,O), with pyrolusite as the Mn4+O2 end-member, and (ii) (Mn3+, M2+)O(OH, H2O), where M = Mn or Zn. In Zn-substituted manganite from Kapova Cave, South Urals, Russia, the Zn2+:Mn3+ ratio reaches 1:1 (the substitution of Mn3+ with Zn2+ is accompanied by the coupled substitution of OH− with H2O). Groutite forms solid-solution series with ramsdellite Mn4+O2. In addition, the incorporation of OH− anions in the 1 × 2 tunnels of ramsdellite is possible. Feitknechtite is considered to be isostructural with (or structurally related to) the compounds (M2+, Mn3+)(OH, O)2 (M = Mn, Zn) with a pyrochroite-related layered structure.

Synthesis and characterization of a solid solution series of the type Bi2MxMn4-xO10 (M = Cr3+, Co3+ and 0.0 ≤ x ≤ 2.0.)

Bi2Mn4O10 was synthesized from corresponding metal salts in glycerin by using an organic precursor-based glycerin nitrate method. The precursor was heated at various temperatures (300 – 800 °C) for about 18 hours to determine the lowest synthesis temperature for the formation of Bi2Mn4O10. The XRD patterns of the calcined samples revealed that the desired mullite type phase started to form at 600 °C, which became more crystalline with further increase of calcination temperature. Attempts were also taken to prepare chromium and cobalt incorporated solid solution series with nominal composition Bi2MxMn4-xO10 (M = Cr3+ and Co3+) by the same procedure. The XRD data of these series exhibited mullite type single phase up to x = 0.7 and 0.1 compositions for chromium and cobalt, respectively. For further insertion of M, an extra phase appeared along with the mullite type phase. J. Bangladesh Acad. Sci. 45(1); 13-26: June 2021

Structural systematics of SFCA-I type solid-solutions in the system CaO–Fe2O3–FeO–Al2O3

Effects of Fe ↔ Al substitution on triclinic SFCA-I-type compounds with general formula A40O56 (A: Ca, Al, Fe3+, Fe2+) have been studied using single-crystal X-ray diffraction. Crystals of sufficient quality and size were synthesized in the temperature range between 1200 and 1300 °C. Six samples with Al/FeTot ratios of 0.127, 0.173, 0.216, 0.310, 0.349 and 0.459 have been structurally characterized. SFCA-I can be described with a modular approach involving the stacking sequence < PSS > of “P” and “S” modules that can be imagined as being cut from the well-known pyroxene (P) and spinel (S) structure types. Furthermore, SFCA-I is related to the sapphirine supergroup of minerals. Within the present solid-solution series, the contents in calcium show only minor variations (≈ 6.7 a.p.f.u.). The twenty crystallographically independent tetrahedrally (T) and octahedrally (M) coordinated cation sites exhibit considerable differences concerning the Al uptake. Indeed, Al is preferentially incorporated into the tetrahedra belonging to the single-chains located in the pyroxene modules. Ferrous iron, on the other hand, is restricted to one of the T-positions within the spinel blocks. Most structural aspects from unit-cell parameters and cell volumes to site occupancies, tetrahedral chain kinking as well as polyhedral distortions are defined by linear or nearly linear trends when plotted against the Al/FeTot ratio. Analysis of the < T–O > and < M–O > distances showed a complex interplay between the different coordination polyhedra resulting in a contrasting behavior of these values with positive or negative change rates as a function of composition. Evaluation of the average chemical strain tensor derived from the sets of lattice parameters for the two samples of the abovementioned series showing the highest and lowest Al/FeTot ratios indicated, that the major contraction with increasing Al content is perpendicular to the pyroxene- and spinel modules. Furthermore, the pyroxene module seems to be more affected when compared with the spinel block. There is evidence that the SFCA-I-type solid-solution series is limited on both the Al- and Fe-rich sides. The present investigation provides—for the first time—a detailed crystallographic analysis on the impact of chemical variations on a compound that is of relevance to the field of applied mineralogy related to the technologically important process of iron-ore sintering.

Solving nonlinear and non-autonomous ODEs systems by the ADM using a new several-variables Adomian polynomials

In this work, we adapted another time the Adomian decomposition method for solving nonlinear and non-autonomous ODEs systems. Therefore, our expressions of the Adomian polynomials are determined for a several-variable differential operators. The solution series is shown that it stay coincide with the Taylor series. Thus new conditions of convergence have been established, some systemes has been solved by ADM using Maple 2020. keywords Adomian decomposition method, Adomian polynomials, ODEs systems, initial value problems, several-variables differential operators. Classification 26B12, 34L30, 47E05, 65B10, 65L05, 65L80

Crystal chemistry of lamprophyllite-group minerals from the Murun alkaline complex (Russia) and pegmatites of Rocky Boy and Gordon Butte (USA): single crystal X-ray diffraction and Raman spectroscopy study

Specific features of the crystal chemistry of lamprophyllite-group minerals (LGMs) are discussed using the available literature data and the results of the single-crystal X-ray diffraction and a Raman spectroscopic studies of several samples taken from the Murun alkaline complex (Russia), and Rocky Boy and Gordon Butte pegmatites (USA) presented here. The studied samples are unique in their chemical features and the distribution of cations over structural sites. In particular, the sample from the Gordon Butte pegmatite is a member of the barytolamprophyllite–emmerichite solid solution series, whereas the samples from the Murun alkaline complex and from the Rocky Boy pegmatite are intermediate members of the solid solution series formed by lamprophyllite and a hypothetical Sr analogue of emmerichite. The predominance of O2− over OH− and F− at the X site is a specific feature of sample Cha-192 from the Murun alkaline complex. New data on the Raman spectra of LGMs obtained in this work show that the wavenumbers of the O—H stretching vibrations depend on the occupancies of the M2 and M3 sites coordinating with (OH)− groups. Cations other than Na+ and Ti4+ (mainly, Mg and Fe3+) can play a significant role in the coordination of the X site occupied by (OH)−. Data on polarized Raman spectra of an oriented sample indicate that the OH groups having different local coordinations have similar orientations with respect to the crystal. The calculated measures of similarity (Δ) for lamprophyllite and ericssonite are identical (0.157 and 0.077 for the 2M- and 2O-polytypes, respectively), which indicates that these minerals are crystal-chemically isotypic and probably should be considered within the same mineral group by analogy to the other mineralogical groups which combine isotypic minerals.

Structural and spectroscopic study of the kieserite-dwornikite solid-solution series, (Mg,Ni)SO4·H2O, at ambient and low temperatures, with cosmochemical implications for icy moons and Mars

The investigation of the presence and role of sulfates in our solar system receives growing attention because these compounds play a crucial role in the water budget of planets such as Mars and significantly influence melting equilibria on the icy moons of Saturn and Jupiter, leading to the formation of subsurface oceans and even cryovolcanism. Despite the dominant presence of higher sulfate hydrates such as epsomite, MgSO4·7H2O, and mirabilite, Na2SO4·10H2O, on these moons' surfaces, it is not excluded that lower-hydrated sulfates, such as kieserite, MgSO4·H2O, are also present, forming from higher hydrates under pressures relevant to the mantle of the icy moons. Given the composition of the soluble fraction in C1 and C2 chondritic meteorites, which are high in Ni content and also considered to represent the composition of the rocky cores of the Jovian icy moons, the actual compositions of potentially present monohydrate sulfates likely lie at intermediate values along the solid-solution series between kieserite and transition-metal kieserite-group end-members, incorporating Ni in particular. Moderate Ni contents are also probable in kieserite on Mars due to the planet's long-term accumulation of meteoritic nickel, although likely to a much lesser extent than Fe. Structural and spectroscopic differences between the pure Mg- and Ni-end-members have been previously documented in the literature, but no detailed crystal chemical and spectroscopic investigation along the Mg-Ni solid solution has been done yet. The present work proves the existence of a continuous (Mg,Ni)SO4·H2O solid-solution series for the first time. It provides a detailed insight into the changes in lattice parameters, structural details, and positions of prominent bands in infrared (transmission, attenuated total reflectance, diffuse reflectance) and Raman spectra in synthetic samples as the Ni/Mg ratio progresses, at both ambient as well as low temperatures relevant for the icy moons and Mars. UV-Vis-NIR crystal field spectra of the Ni end-member also help to elucidate the influence of Ni2+-related bands on the overtone- and combination modes. The (Mg,Ni)SO4·H2O solid-solution series shows Vegard-type behavior, i.e., lattice parameters as well as spectral band positions, change along linear trends with increasing Ni content. Infrared spectra reveal significant changes in the wavenumber positions of prominent bands, depending on the Ni/Mg ratio. We show that the temperature during measurement also has an influence on band position, mainly in the case of H2O-related bands. The changes observed for several absorption features in the IR spectra enable rough estimation of the Ni/Mg ratio in the monohydrate sulfate, which is applicable to present and future remote sensing data, as well as in situ measurements on Mars or the icy moons. The spectral features most diagnostic of composition are the vibrational stretching modes of the H2O molecule and a band unique to kieserite-group compounds at around 900 cm–1 in the IR spectra, as well as the pronounced ν3 and ν1 sulfate stretching modes visible in Raman spectra.