One-layer Polytype Research Articles

Effect of Hydration on Polytypism and Disorder in the Sulfate-Intercalated Layered Double Hydroxides of Li and Al

AbstractThe double hydroxide of Li+ and Al3+ is an anionic clay comprising positively charged metal hydroxide layers and intercalated anions. While the structure of the iono-covalently bonded metal hydroxide layer is well known, relatively less knowledge is available regarding the manner in which the anions and water molecules are packed in the interlayer region. The sulfate ion is of special interest as it can potentially intercalate in a multiplicity of orientations and grow an extended hydration sphere. The sulfate-intercalated double hydroxide was synthesized by the imbibition of Li2SO4 into both the gibbsite and bayerite forms of Al(OH)3 to obtain layered double hydroxides with the nominal formula Li2Al4(OH)12SO4·nH2O (n = 4–8). The as-prepared compounds were poorly ordered and did not yield any structural information. Temperature-induced partial dehydration yielded ordered phases of different structures in the two systems. Simulation of the powder patterns of different model structures, followed by structure refinement in both direct and reciprocal spaces, showed that the gibbsite-derived phase yielded a two-layer polytype of hexagonal symmetry (space group P63/m). The local symmetry of the sulfate ion was close to D2d with one of the C2 axes of the SO42− being nearly parallel to the c axis of the crystal. The bayerite-derived phase yielded a one-layer polytype of monoclinic symmetry (space group C2/m). The sulfate ion was oriented with its C3 axes tilted away from the stacking direction. Cooling and rehydration (relative humidity ~70%) resulted in a reversible expansion of the basal spacing due to the ingress of water molecules from the ambient humidity into the interlayer region. Hydration in both cases resulted in turbostratic disorder. The disorder in the bayerite-derived phase was a result of random intergrowth of motifs with rhombohedral and monoclinic symmetries.

Reappraisal of Polytypism in Layered Double Hydroxides: Consequences of Cation Ordering in the Metal Hydroxide Layer

Recent diffraction studies on layered double hydroxides have shown that the three-layer polytypes that were thought to crystallize in rhombohedral symmetry are actually one-layer polytypes of monoclinic symmetry. However, the prevailing Bookin and Drits (1993) scheme of polytypism, which is based on the widely accepted cation-disordered structure model, fails to predict the occurrence of low symmetry (monoclinic and orthorhombic) polytypes among the layered double hydroxides. In this work, a cation-ordered metal hydroxide layer (layer group p312/m or c12/m1) is chosen as the basic building block. Application of the structural synthon approach enables the description of the complete universe of polytypes comprising 1H, 1M1–7, 2H, 2O, 3R, 3H, 6H, and 6R among others (M: monoclinic; O: orthorhombic). These polytypes are characterized by their unique stacking vectors. The polytypes of large unit cell volume are obtained by a combination of two or more stacking vectors. This work has relevance to the understa...

Layered Double Hydroxides: Proposal of a One-Layer Cation-Ordered Structure Model of Monoclinic Symmetry.

Layered double hydroxides are obtained by partial isomorphous substitution of divalent metal ions by trivalent metal ions in the structure of mineral brucite, Mg(OH)2. The widely reported three-layer polytype of rhombohedral symmetry, designated as polytype 3R1, is actually a one-layer polytype of monoclinic symmetry (space group C2/m, a = 5.401 Å, b = 9.355 Å, c = 11.02 Å, β = 98.89°). This structure has a cation-ordered metal hydroxide layer defined by a supercell a = √3 × a0; b = 3 × a0 (a0 = cell parameter of the cation-disordered rhombohedral cell). Successive layers are translated by (1/3, 0, 1) relative to one another. When successive metal hydroxide layers are translated by (2/3, 0, 1) relative to one another, the resultant crystal, also of monoclinic symmetry, generates a powder pattern corresponding to the polytype hitherto designated as 3R2. This structure model not only removes all the anomalies intrinsic to the widely accepted cation-disordered structure but also abides by Pauling's rule that forbids trivalent cations from occupying neighboring sites and suggests that it is unnecessary to invoke rhombohedral symmetry when the metal hydroxide layer is cation ordered. These results have profound implications for the correct description of polytypism in this family of layered compounds.

Ekplexite (Nb,Mo)S2·(Mg1−xAlx)(OH)2+x, kaskasite (Mo,Nb)S2·(Mg1−xAlx)(OH)2+x and manganokaskasite (Mo,Nb)S2·(Mn1−xAlx)(OH)2+x, three new valleriite-group mineral species from the Khibiny alkaline complex, Kola peninsula, Russia

AbstractThree new valleriite-group minerals, ekplexite (Nb,Mo)S2·(Mg1−xAlx)(OH)2+x, kaskasite (Mo,Nb)S2·(Mg1−xAlx)(OH)2+x and manganokaskasite (Mo,Nb)S2·(Mn1−xAlx)(OH)2+x are found at Mt Kaskasnyunchorr, Khibiny alkaline complex, Kola Peninsula, Russia. They occur in fenite consisting of orthoclase−anorthoclase and nepheline with fluorophlogopite, corundum, pyrrhotite, pyrite, rutile, monazite-(Ce), graphite, edgarite, molybdenite, tungstenite, alabandite, etc. Ekplexite forms lenticular nests up to 0.2 mm × 1 mm × 1 mm consisting of near-parallel, radiating or chaotic aggregates of flakes. Kaskasite and manganokaskasite mainly occur as flakes and their near-parallel ‘stacks’ (kaskasite: up to 0.03 mm × 1 mm × 1.5 mm; manganokaskasite: up to 0.02 mm × 0.5 mm × 1 mm) epitaxially overgrow Ti-bearing pyrrhotite partially replaced by Ti-bearing pyrite. All three new minerals are opaque, ironblack, with metallic lustre. Cleavage is {001} perfect and mica-like. Flakes are very soft, flexible and inelastic. Mohs hardness is ∼1. D(calc.) = 3.63 (ekplexite), 3.83 (kaskasite) and 4.09 (manganokaskasite) g cm−3. In reflected light all these minerals are grey, without internal reflections. Anisotropism and bireflectance are very strong and pleochroism is strong. The presence of OH groups and an absence of H2O molecules are confirmed by the Raman spectroscopy data. Chemical data (wt.%, electron probe) for ekplexite, kaskasite and manganokaskasite, respectively, are: Mg 6.25, 5.94, 0.06; Al 4.31, 3.67, 3.00; Ca 0.00, 0.04, 0.00; V 0.86, 0.16, 0.15; Mn 0.00, 0.23, 11.44; Fe 0.44, 1.44, 2.06; Nb 18.17, 13.39, 14.15; Mo 15.89, 23.18, 20.08; W 8.13, 7.59, 9.12; S 27.68, 27.09, 24.84; O 16.33, 15.66, 13.36; H (calc.) 1.03, 0.99, 0.89; total 99.09, 99.08, 99.15. The empirical formulae calculated on the basis of 2 S a.p.f.u. are: ekplexite: (Nb0.45Mo0.38W0.10V0.04)S0.97S2· (Mg0.60Al0.37Fe0.02)S0.99(OH)2.36; kaskasite: (Mo0.57Nb0.34W0.10V0.01)S1.02S2· (Mg0.58Al0.32Fe0.06Mn0.01)S0.97(OH)2.32; manganokaskasite: (Mo0.54Nb0.39W0.13V0.01)S1.07S2· (Mn0.54Al0.29Fe0.10Mg0.01)S0.94(OH)2.28. All three minerals are trigonal, space groups Pm1, P3m1 or P321, one-layer polytypes (Z = 1). Their structures are non-commensurate and consist of the MeS2-type (Me = Nb, Mo, W) sulfide modules and the brucite-type hydroxide modules. Parameters of the sulfide (main) sub-lattices (a, c in Å, V in Å3) are: 3.262(2), 11.44(2), 105.4(4) (ekplexite); 3.220(2), 11.47(2), 102.8(4) (kaskasite); 3.243(3), 11.61(1), 105.8(3) (manganokaskasite). Parameters of the hydroxide sub-lattices (a, c in Å, V in Å3) are: 3.066(2), 11.52(2), 93.8(4) (ekplexite); 3.073(2), 11.50(2), 94.0(4) (kaskasite); 3.118(3), 11.62(1), 97.9(2) (manganokaskasite). Ekplexite was named from the Greek word έκπληξη meaning surprise, for its exotic combination of major chemical constituents, kaskasite after the discovery locality and manganokaskasite as a Mn analogue of kaskasite.

Photoconductivity and luminescence anisotropy in ZnIn2S4 and ZnIn2S4:Cu2+ single crystals

ZnIn2S4 and ZnIn2S4:Cu2+ single crystals are shown to exhibit considerable photoconductivity and luminescence anisotropy. The mechanism of carrier recombination in the crystals is polarization-dependent. Their spectra can be understood in terms of optical transitions involving donor and acceptor levels. The degree and spectral distribution of the anisotropy can be tuned via doping and alternating growth of the three- and one-layer polytypes.

Polytypism and superstructure in CoInGaS4

It is established that a one-layer polytype 1T with the unit-cell parameters a = 3.758, c = 12.135 A, sp. gr. P3m1 and the structure module hThOhThE is mixed with the three-layer polytype 3R with the unit-cell parameters a = 3.758, c = 36.405 A, sp. gr. R3m and the structure module hTcOcThE, where T and O are two-dimensional nets of tetrahedra and octahedra, respectively, E is the empty intermediate layer, and h and c indicate the hexagonal and cubic packings of atomic planes S. The microdiffraction pattern in the hexagonal basis shows a monoclinic superlattice with the parameters \(A = \sqrt {19} a, B = \sqrt {13} a, \gamma = 110.485^\circ\) related to the main hexagonal lattice as A = [520] and \(B = [\bar 130]\).

Microstructures, Mixed Layering, and Polymorphism of Chlorite and Retrograde Berthierine in the Kidd Creek Massive Sulfide Deposit, Ontario

AbstractTransmission electron microscopy (TEM) was utilized to determine the origins of berthierine and chlorite in the core of the footwall alteration zone of the Kidd Creek massive sulfide deposit, Ontario. TEM images show lamellar intergrowths of packets of berthierine, mixed-layer chlorite/berthierine, Fe-Mg chlorite, and relatively Fe-rich chlorite that contain dislocations, stacking faults, kink bands, and gliding along (001). Interstratification of packets of berthierine and chlorite with one to several tens of layers commonly is associated with terminations of a layer of chlorite by two layers of berthierine. Layers in adjacent domains of berthierine and chlorite are continuous across interfaces that transect their common {001} planes. High-strain zones that cut across cleavage planes, consisting of distorted layers and lens-shaped pores, are associated with stacking faults and gliding along cleavage planes in chlorite crystals. Similar features separate interstratified chlorite/berthierine of different structures and textures, implying development of such composite grains after deformation of chlorite. Electron diffraction patterns show that the chlorite is an ordered one- or two-layer polytype or a one-layer polytype with semi-random stacking, and that the berthierine is a one-layer polytype with semi-random stacking epitaxially intergrown with chlorite.Coexisting chlorite and berthierine have nearly identical ranges of compositions, containing Si ≅ 5, Al ≅ 6, and Fe ≅ 6.5–8.5 pfu, and minor, variable Mg and Mn contents, in formulae normalized on the basis of 20 total cations. This implies polymorphism among Fe,Al-rich members of the serpentine and chlorite groups. In one of the samples, berthierine and mixed-layer chlorite/berthierine coexist with chlorite having two compositional ranges, including Fe-rich chlorite with a relatively wide range of Fe-Mg contents, and a dominant Fe-Mg chlorite. In another sample, compositionally homogeneous Fe-rich chlorite is associated with berthierine and mixed-layer chlorite/berthierine; Fe-Mg chlorite was not detected.The microstructural relations and the presence of coexisting polymorphs, complex mixed layering, heterogeneous polytypism, and wide ranges of mineral compositions are consistent with replacement of chlorite by berthierine under non-equilibrium retrograde conditions, in contrast to the generally assumed prograde origin for other berthierine occurrences.

Transmission Electron Microscopic Study of the Kaolinitization of Muscovite

AbstractHydrothermally kaolinitized muscovite from the Otago schist of Brighton, New Zealand, has been studied by transmission and analytical electron microscopy (TEM and AEM) to determine the mechanism of alteration and to compare reactant-product relations for di- and trioctahedral micas. The muscovite is a primary metamorphic phase having a phengitic composition. It occurs as well-ordered, two- and three-layer polytypes, in grains as thick as 30 μm. Kaolinite occurs as packets of layers, each about 100–600 Å thick, which alternate with packets of muscovite or smectite-like layers. Most of the kaolinite is highly disordered in stacking sequence, although a one-layer polytype is also present, occurring as relatively thick sequences of layers. Phase boundaries between kaolinite and muscovite are invariably parallel to the 001 lattice fringes with no strain contrast; i.e., no transitions exist along layers. Parallelism of 00l and 11l reflection rows of both kaolinite and muscovite implies a topotaxial intergrowth. A smectitelike phase is also present, occurring as packets of wavy layers, which locally have periodic contrast that may reflect R1 ordering of illite/smectite. This material appears to be a direct, “along-layer” alteration product of muscovite. Electron diffraction data and lattice-fringe images imply that kaolinite alternates with micaceous phase(s) with some regularity; i.e., micaceous layers are separated by approximately equal numbers of kaolinite layers. Similar long-range periodicity occurs in contrast variations within packets of kaolinite layers.The data collectively suggest that the alteration interface was self-perpetuating and that alteration proceeded rapidly along layers once it initiated in 2:1 layers at crystal edges or strained areas, with no observable component normal to the layers. They also suggest that smectite may have formed as an intermediate phase during the hydrothermal kaolinitization of muscovite. In the previous study of alteration of biotite in the same sample, “along-layer” transition boundaries were commonly observed, and a second, intermediate product phase was not detected, implying a relation between the alteration mechanisms and the chemical differences between reactants and products.

Polysynthetically-twinned structures of enstatite and wollastonite

Crystal structures of clinoenstatite, orthoenstatite, wollastonite-1T and wollastonite-2M (parawollastonite) were refined to an R factor 3–4 percent level. Molar volumes at room temperature are 31.270(15), 31.315(8), 39.842(5) and 39.901(10) cm3/MSiO3, in the above-mentioned order, indicating that one-layer polytypes (clinoenstatite and wollastonite-1T) are stable at higher pressures than two-layer polytypes (orthoenstatite and wollastonite-2M). The polytypic relation of the enstatite polytypes can be described by four twinning operations — b glide ∥ to (110), a glide ∥ to (001), twofold screw axis ∥ to a (of orthoenstatite) and a twofold screw axis ∥ to c. For the wollastonite polytypes, twinning operations are twofold screw axis ∥ to b and a glide ∥ to (010). Structural adjustments after twinning are not necessarily the largest at the twin boundary (true in enstatite but not so in wollastonite). In both cases octahedral sites that involve bridging oxygens tend to show relatively large changes. Lattice strain ellipsoids associated with twinning are also different for enstatite and wollastonite, which implies that wollastonite may react differently from enstatite to non-hydrostatic pressure.