Mixture of changing uniaxial micellar forms in lyotropic biaxial nematics

Lyotropic nematics consisting of surfactant-cosurfactant water solutions may present a biaxial phase or direct U(+) <-> U(-) transitions, in different regions of the temperature-relative concentration phase diagram, for different systems and compositions. We propose that these may be related to changes of uniaxial micellar form, which may occur either smoothly or abruptly. Smooth change of cylinder-like into disc-like shapes requires a distribution of Maier-Saupe interaction constants and we consider two limiting cases for the distribution of forms: a single Gaussian and a double Gaussian. Alternatively, an abrupt change of form is described by a discontinuous distribution of interaction constants. Our results show that the dispersive distributions yield a biaxial phase, while an abrupt change of shape leads to coexistence of uniaxial phases. Fitting the theory to the experiment for the ternary system KL/decanol/D2O leads to transition lines in very good agreement with experimental results. In order to rationalise the results of the comparison, we analyse temperature and concentration form dependence, which connects micellar and experimental macroscopic parameters. Physically consistent variations of micellar asymmetry, amphiphile partitioning and volume are obtained. To the best of the authors` knowledge, this is the first truly statistical microscopic approach that is able to model experimentally observed lyotropic biaxial nematic phases.

Micelles forming biaxial lyotropic nematic phases

The paper by Yu and Saupe on the first biaxial nematic phase created excitement for a number of reasons. Some theories of biaxial phases already existed, but experimental observation was still lacking. The phase was discovered in a lyotropic system with three components, which in theory is difficult. Lyotropic liquid crystals are composed of supramolecular assemblies of amphiphilic molecules, which may change shape and size as a function of concentration and temperature. The experimental phase diagram of the lyotropic biaxial phase was rather complex, with the biaxial region inserted between nematic cylindrical and nematic discotic phases via second-order transitions. In addition, re-entrant behaviour was evident. Saupe investigated further systems experimentally, observing that the biaxial phase might be absent in cases where a direct transition between the cylindrical and discotic phases occurred. He provided a range of theoretical and experimental contributions on the properties of these lyotropics, but was very cautious regarding the detailed amphiphilic assemblies involved. The present paper reviews this area, focusing on proposals for the structure of the micellar assemblies. Emphasis is placed on recent papers which indicate a transformation of the two uniaxial shapes, in mixing conditions, both from the theoretical and the experimental point of view, and to questions still requiring further study.

Bendadaite, a new iron arsenate mineral of the arthurite group

Bendadaite, ideally Fe(2+)Fe(2)(3+)(AsO(4))(2)(OH)(2 center dot).4H(2)O, is a new member of the arthurite group It was found as a weathering product of arsenopyrite on a single hand specimen from the phosphate pegmatite Bendada. central Portugal (type locality) Co-type locality is the granite pegmatite of La via do Almerindo (Almerindo mine), Linopolis, Divmo das Laranjeiras county, Minas Gerais, Brazil Further localities are the Vein Negra mine, Copiapo province, Chile, mid-East, Bou Azzer district, Morocco, and Para Inferida yard, Fenugu Sibirt mine, Gonnosfanadiga, Medio Campidano Province, Sardinia. Italy Type bendadaite occurs as blackish green to dark brownish tufts (<0 1 mm long) and flattened radiating aggregates. in intimate association with an intermediate member of the scorodite-mansfieldite series It is monoclinic. space group P2(l/c). with a = 10 239(3) angstrom. b = 9 713(2) angstrom, c = 5 552(2) angstrom. beta = 94 11(2)degrees. = 550 7(2) angstrom(3). Z = 2 Electron-microprobe analysis yielded (wt %). CaO 0 04, MnO 0 03. CuO 006, ZnO 004. Fe(2)O(3) (total) 43 92, Al(2)O(3) 115. SnO(2) 0 10, As(2)O(5) 43 27. P(2)O(5) 1 86, SO(3) 0.03 The empirical formula is (Fe(0 52)(2+)Fe(0 32)(3+)rectangle(0 16))(Sigma 1 00)(Fe(1 89)(3+)Al(0 11))(Sigma 2 00)(As(1 87)P(0 13))(Sigma 2 00)O(8)(OH)(2 00) 4H(2)O based. CM 2(As,P) and assuming ideal 80, 2(OH), 4H2O and complete occupancy of the ferric on site by Fe(3+) and Al Optically, bendadaite is biaxial, positive, 2V(est) = 85+/-4 degrees, 2V(eale) = 88 degrees, with alpha 1 734(3). 13 1 759(3), 7 1 787(4) Pleochrosim is medium strong X pale reddish brown. Y yellowish brown, Z dark yellowish brown. absorption Z > V > X, optical dispersion weak, r > v. Optical axis plane Is parallel to (010), with X approximately parallel to a and Z nearly parallel to c Bendadaite has vitreous to sub-adamantine luster, is translucent and non-fluorescent It is brittle, shows irregular fracture and a good cleavage parallel to 1010} 3 15 0 10 g/cm(3), 3 193 g/cm3 (for the empirical formula) The five strongest powder diffraction lines [d in angstrom (I)(hkl] are 10 22 (10)(100), 7 036 (8)(110), 4 250 (5)(11 I), 2 865 (4)(311), 4 833 (3)(020,011) The d spacings are very similar to those of its Zn analogue, ojelaite The crystal structure of bendadaite was solved and refined using a crystal from the co-type locality with the composition (Fe(0 95)(2+)rectangle(0 05))(Sigma 1 00)(Fe(1 80)(3+)Al(0 20))Sigma(2 00)(As(1 48)P(0 52))(Sigma 2 00)O(8)) (OH)(2) 4H(2)O (R = 16%) and confirms an arthurite-type atomic arrangement

Footemineite, the Mn-analog of atencioite, from the Foote mine, Kings Mountain, Cleveland County, North Carolina, USA, and its relationship with other roscherite-group minerals

Footemineite, ideally Ca2Mn2+square Mn22+Be4(PO4)(6)(OH)(4)-6H(2)O, triclinic, is a new member of the roscherite group. It occurs on thin fractures crossing quartz-microcline-spodumene pegmatite at the Foote mine, Kings Mountain, Cleveland County, North Carolina, U.S.A. Associated minerals are albite, analcime, eosphorite, siderite/rhodochrosite, fairfieldite, fluorapatite, quartz, milarite, and pyrite. Footemineite forms prismatic to bladed generally rough to barrel-shaped crystals up to about 1.5 mm long and I mm in diameter. Its color is yellow, the streak is white, and the luster is vitreous to slightly pearly. Footemineite is transparent and non-fluorescent. Twinning is simple, by reflection, with twin boundaries across the length of the crystals. Cleavage is good on {0 (1) over bar1}) and {100}. Density (calc.) is 2.873 g/cm(3). Footemineite is biaxial (-), n(alpha) = 1.620(2), n(beta) = 1.627(2), n(gamma) = 1.634(2) (white light). 2V(obs) = 80 degrees, 2V(calc) = 89.6 degrees. Orientation: X boolean AND b similar to 12 degrees, Y boolean AND c similar to 15 degrees, Z boolean AND a similar to 15 degrees. Elongation direction is c, dispersion: r > v or r < v, weak. Pleochroism: beta (brownish yellow) > alpha = gamma (yellow). Mossbauer and IR spectra are given. The chemical composition is (EDS mode electron microprobe, Li and Be by ICP-OES, Fe3+:Fe2+ y Mossbauer, H2O by TG data, wt%): Li2O 0.23, BeO 9.54, CaO 9.43, SrO 0.23, BaO 0.24, MgO 0.18, MnO 26.16, FeO 2.77, Fe2O3 0.62, Al2O3 0.14, P2O5 36.58, SiO2 0.42, H2O 13.1, total 99.64. The empirical formula is (Ca1.89Sr0.03Ba0.02)Sigma(1.94)(Mn-0.90(2+)square(0.10))Sigma(1.00)(square 0.78Li0.17Mg0.05) Sigma(1.00)(Mn3.252+Fe0.432+ Fe0.093+Al0.03)Sigma(3.80) Be-4.30(P5.81Si0.08O24)[(OH)3.64(H2O)0.36]Sigma(4.00)center dot 6.00H(2)O . The strongest reflection peaks of the powder diffraction pattern [d, angstrom (1, %) (hkl)] are 9.575 (53) (010), 5.998 (100) (0 (1) over bar1), 4.848 (26) (021), 3.192 (44) (210), 3.003 (14) (0 (2) over bar2), 2.803 (38) ((1) over bar 03), 2.650 (29) ((2) over bar 02), 2.424 (14) (231). Single-crystal unit-cell parameters are a = 6.788(2), b = 9.972(3), c = 10.014(2) A, (x = 73.84(2), beta = 85.34(2), gamma = 87.44(2)degrees,V = 648.74 angstrom(3), Z = 1. The space group is P (1) over bar. Crystal structure was refined to R = 0.0347 with 1273 independent reflections (F > 2(5). Footemineite is dimorphous with roscherite, and isostructural with atencioite. It is identical with the mineral from Foote mine described as ""triclinic roscherite."" The name is for the Foote mine, type locality for this and several other minerals.