Synthesis of bio-based poly limonene oxide with green catalyst

In the present work, the polymerization of limonene oxide (LO) catalyzed by Maghnite H+ (Mag- H+) is investigated. Mag-H+ is Algerian montmorillonite sheet silicate clay exchanged with protons. The poly limonene oxide (PLO) is obtained by cationic ring opening polymerization in bulk and with solvent. The effect of the reaction time, the temperature and the amount of catalyst are studied and discussed in order to find the optimal reactions conditions. The polymerization in solution at 0 °C with 5% by weight of catalyst leads to the best yield 61.34% for a reaction time of 1h. The structure of the obtained products is characterized by XRD, 1H-NMR, 13C-RMN, ATR-FTIR, DSC and TGA.

Mineralogical and Geotechnical Properties of Clay Minerals in Northern Borno, Nigeria

Clay generally refers to either fine grained earth material with particle size of less than two micron (< 2 m) or group of hydrous aluminum silicate minerals that are characterized by sheet silicate structure of composite layers stacked along the C-axis. They are common deposits found in most geological setting like in fine grained sedimentary rocks such as shale, mudstone, and siltstone, in fine grained metamorphic slate and phyllite. The interest in clay deposits arises from its numerous uses of the mineral group and the behaviour of soils constituents when used as engineering soil and its resultant effects on engineering structures like roads, dams, bridges and houses. Evaluation of the soil properties of the Chad Formation indicated that the plasticity characteristics of the samples are of low to medium plasticity as indicated by matching the result with the DIN. chart. The results of free swell showed that the samples are susceptible to swelling when they absorbed water. The particle size distribution tests indicate that the percentage of fine (i.e. samples passing the 75µm sieve) is about 1.7 % implying that the grain sizes are within the texture of medium grain fraction

A structure hierarchy for silicate minerals: chain, ribbon, and tube silicates

A structure hierarchy is developed for chain-, ribbon- and tube-silicate based on the connectedness of one-dimensional polymerisations of (TO4)n− tetrahedra, where T = Si4+ plus P5+, V5+, As5+, Al3+, Fe3+, B3+, Be2+, Zn2+ and Mg2+. Such polymerisations are described by a geometrical repeat unit (with ng tetrahedra) and a topological repeat unit (or graph) (with nt vertices). The connectivity of the tetrahedra (vertices) in the geometrical (topological) repeat units is denoted by the expression cTr (cVr) where c is the connectivity (degree) of the tetrahedron (vertex) and r is the number of tetrahedra (vertices) of connectivity (degree) c in the repeat unit. Thus cTr = 1Tr12Tr23Tr34Tr4 (cVr = 1Vr12Vr23Vr34Vr4) represents all possible connectivities (degrees) of tetrahedra (vertices) in the geometrical (topological) repeat units of such one-dimensional polymerisations. We may generate all possible cTr (cVr) expressions for chains (graphs) with tetrahedron (vertex) connectivities (degrees) c = 1 to 4 where r = 1 to n by sequentially increasing the values of c and r, and by ranking them accordingly. The silicate (sensu lato) units of chain-, ribbon- and tube-silicate minerals are identified and associated with the relevant cTr (cVr) symbols. Following description and association with the relevant cTr (cVr) symbols of the silicate units in all chain-, ribbon- and tube-silicate minerals, the minerals are arranged into decreasing O:T ratio from 3.0 to 2.5, an arrangement that reflects their increasing structural connectivity. Considering only the silicate component, the compositional range of the chain-, ribbon- and tube-silicate minerals strongly overlaps that of the sheet-silicate minerals. Of the chain-, ribbon- and tube-silicates and sheet silicates with the same O:T ratio, some have the same cVr symbols (vertex connectivities) but the tetrahedra link to each other in different ways and are topologically different. The abundance of chain-, ribbon- and tube-silicate minerals decreases as O:T decreases from 3.0 to 2.5 whereas the abundance of sheet-silicate minerals increases from O:T = 3.0 to 2.5 and decreases again to O:T = 2.0. Some of the chain-, ribbon- and tube-silicate minerals have more than one distinct silicate unit: (1) vinogradovite, revdite, lintisite (punkaruaivite) and charoite have mixed chains, ribbons and/or tubes; (2) veblenite, yuksporite, miserite and okenite have clusters or sheets in addition to chains, ribbons and tubes. It is apparent that some chain-ribbon-tube topologies are favoured over others as of the ~450 inosilicate minerals, ~375 correspond to only four topologically unique graphs, the other ~75 minerals correspond to ~46 topologically unique graphs.

Serpentine–Hisingerite Solid Solution in Altered Ferroan Peridotite and Olivine Gabbro

We present microanalyses of secondary phyllosilicates in altered ferroan metaperidotite, containing approximately equal amounts of end-members serpentine ((Mg,Fe2+)3Si2O5(OH)4) and hisingerite (□Fe3+2Si2O5(OH)4·nH2O). These analyses suggest that all intermediate compositions can exist stably, a proposal that was heretofore impossible because phyllosilicate with the compositions reported here have not been previously observed. In samples from the Duluth Complex (Minnesota, USA) containing igneous olivine Fa36–44, a continuous range in phyllosilicate compositions is associated with hydrothermal Mg extraction from the system and consequent relative enrichments in Fe2+, Fe3+ (hisingerite), Si, and Mn. Altered ferroan–olivine-bearing samples from the Laramie Complex (Wyoming, USA) show a compositional variability of secondary FeMg–phyllosilicate (e.g., Mg–hisingerite) that is discontinuous and likely the result of differing igneous olivine compositions and local equilibration during alteration. Together, these examples demonstrate that the products of serpentinization of ferroan peridotite include phyllosilicate with iron contents proportionally larger than the reactant olivine, in contrast to the common observation of Mg-enriched serpentine in “traditional” alpine and seafloor serpentinites. To augment and contextualize our analyses, we additionally compiled greenalite and hisingerite analyses from the literature. These data show that greenalite in metamorphosed banded iron formation contains progressively more octahedral-site vacancies (larger apfu of Si) in higher XFe samples, a consequence of both increased hisingerite substitution and structure modulation (sheet inversions). Some high-Si greenalite remains ferroan and seems to be a structural analogue of the highly modulated sheet silicate caryopilite. Using a thermodynamic model of hydrothermal alteration in the Fe–silicate system, we show that the formation of secondary hydrothermal olivine and serpentine–hisingerite solid solutions after primary olivine may be attributed to appropriate values of thermodynamic parameters such as elevated a S i O 2 ( a q ) and decreased a H 2 ( a q ) at low temperatures (~200 °C). Importantly, recent observations of Martian rocks have indicated that they are evolved magmatically like the ferroan peridotites analyzed here, which, in turn, suggests that the processes and phyllosilicate assemblages recorded here are more directly relevant to those occurring on Mars than are traditional terrestrial serpentinites.

A structure hierarchy for silicate minerals: sheet silicates

The structure hierarchy hypothesis states that structures may be ordered hierarchically according to the polymerisation of coordination polyhedra of higher bond-valence. A hierarchical structural classification is developed for sheet-silicate minerals based on the connectedness of the two-dimensional polymerisations of (TO4) tetrahedra, where T = Si4+ plus As5+, Al3+, Fe3+, B3+, Be2+, Zn2+ and Mg2+. Two-dimensional nets and oikodoméic operations are used to generate the silicate (sensu lato) structural units of single-layer, double-layer and higher-layer sheet-silicate minerals, and the interstitial complexes (cation identity, coordination number and ligancy, and the types and amounts of interstitial (H2O) groups) are recorded. Key aspects of the silicate structural unit include: (1) the type of plane net on which the sheet (or parent sheet) is based; (2) the u (up) and d (down) directions of the constituent tetrahedra relative to the plane of the sheet; (3) the planar or folded nature of the sheet; (4) the layer multiplicity of the sheet (single, double or higher); and (5) the details of the oikodoméic operations for multiple-layer sheets. Simple 3-connected plane nets (such as 63, 4.82 and 4.6.12) have the stoichiometry (T2O5)n (Si:O = 1:2.5) and are the basis of most of the common rock-forming sheet-silicate minerals as well as many less-common species. Oikodoméic operations, e.g. insertion of 2- or 4-connected vertices into 3-connected plane nets, formation of double-layer sheet-structures by (topological) reflection or rotation operations, affect the connectedness of the resulting sheets and lead to both positive and negative deviations from Si:O = 1:2.5 stoichiometry. Following description of the structural units in all sheet-silicate minerals, the minerals are arranged into decreasing Si:O ratio from 3.0 to 2.0, an arrangement that reflects their increasing structural connectivity. Considering the silicate component of minerals, the range of composition of the sheet silicates completely overlaps the compositional ranges of framework silicates and most of the chain-ribbon-tube silicates.

Generating functions for stoichiometry and structure of single- and double-layer sheet-silicates

Two-dimensional nets may be used to generate the stoichiometry and structure of single-layer and double-layer sheet-silicate minerals. Many sheet-silicate minerals are based on the 3-connected plane nets 63, 4.82, (4.6.8)2(6.82)1and (52.8)1(5.82)1, and some more complicated nets, e.g. (5.6.7)4(5.72)1(62.7)1, (4.122)2(42.12)1, (52.8)1(5.62)1(5.6.8)2(62.8)1,have one or two representative structures. Many complicated sheet-silicate minerals are based on sheets of 2-, 3- and 4-connected tetrahedra that may be developed from 3- and 4-connected plane nets by a series of oikodoméic operations on 3- or 4-connected nets that change the topologyof the parent net. There are three classes of oikodoméic operations: (1) insertion of 2- and 3-connected vertices into 3- and 4-connected plane nets; (2,3) replication of single-layer sheets by topological mirror or two-fold-rotation operators, and condensation of the resulting twosingle-layer sheets to form double-layer sheets. The topological aspects of these sheet structures may be described by functions that express stoichiometry in terms of tetrahedron connectivities (formula-generating functions) and functions that associate these formula-generating functionswith specific two-dimensional nets. Using these functions, we may generate formulae and structural arrangements of single-layer and double-layer silicate structures with specific local and long-range topological features.

High-resolution imaging of biotite using focal series exit wavefunction restoration and the graphene mechanical exfoliation method

We have applied mechanical exfoliation for the preparation of ultra-thin samples of the phyllosilicate mineral biotite. We demonstrate that the 'scotch tape' approach, which was made famous as an early method for production of single-atom-thick graphene, can be used for production of sheet-silicate specimens that are sufficiently thin to allow high-resolution transmission electron microscope (HRTEM) imaging to be achieved successfully while also being free from the specimen preparation artefacts that are often caused by ion-beam milling techniques. Exfoliation of the biotite parallel to the (001) planes has produced layers as thin as two structural TOT units thick (∼2 nm). The minimal specimen thickness enabled not only HRTEM imaging but also the application of subsequent exit wavefunction restoration to reveal the pristine biotite lattice. Exit wavefunction restoration recovers the full complex electron wave from a focal series of HRTEM images, removing the effects of coherent lens aberrations. This combination of methods therefore produces images in which the observed features are readily interpreted to obtain atomic resolution structural information.

Crystal structure and revised chemical formula for burckhardtite, Pb2(Fe3+Te6+)[AlSi3O8]O6: a double-sheet silicate with intercalated phyllotellurate layers

The crystal structure of burckhardite from the type locality, Moctezuma, Sonora, Mexico, has been refined to R1 = 0.0362 and wR2 = 0.0370 for 215 reflections with I > 2σ(I). Burckhardtite is trigonal, space group P3̄ 1m, with the unit-cell parameters a = 5.2566(5) Å , c = 13.0221(10) Å , V = 311.62(5) Å3 and Z = 1 for the ideal formula unit Pb2(Fe3+Te6+)[AlSi3O8]O6. There is no long-range order of (Fe3+, Te6+) or (Al3+, Si4+). New microprobe data were used to estimate site scattering factors, and Raman spectroscopic data showed no evidence of O–H stretching bands. Burckhardtite is not closely related to the micas, as supposed previously, but is a double-sheet silicate in which the aluminosilicate anion resembles that of minerals such as cymrite and kampfite. The [(Fe3+Te6+)O6]3– part of the structure is not bonded directly to the aluminosilicate layer, but forms a discrete anionic phyllotellurate layer that alternates with the [AlSi3O8]– double sheets. Similar phyllotellurate layers are known from several synthetic phases. In burckhardtite, Pb2+ cations intercalate between phyllosilicate and phyllotellurate layers, forming a Pb2[FeTeO6] module that is topologically similar to a slab of the structure of rosiaite, Pb[Sb2O6]. The crystal symmetry, structure, classification as a double-sheet silicate and chemical formula, including the determination of the 6+ valence of Te and absence of essential H2O, are all new findings for the mineral.

Connectivity and formula-generating functions for sheet-silicate minerals

Silicate sheets may be described by two-dimensional nets in which the vertices of the net are occupied by tetrahedra, and the edges of the net represent linkages between tetrahedra. A plane net must contain 3-connected vertices, but not all vertices need to be 3-connected. Simple silicate structures may thus be generated from simple 3-connected plane nets (e.g. 63, 4.82, 4.6.8, (4.6.8)2(6.82)1, etc.). More complicated silicate nets may be generated by various "building operations": (1) Insertion: insertion of 2- and 4-connected vertices into 3-connected plane nets; (2) Repetition: generation of double (or triple) nets by topological symmetry operations that retain transitivity at the junction between the repeated elements. Diversity is also introduced within the sheets of tetrahedra by [1] adjacent apical tetrahedron vertices pointing in the same or different directions, and [2] by folding of the sheets. For simple structures, net type strongly affects the stoichiometry of the resultant structure as the unit cells of the various nets are of different sizes (and shapes), although the stoichiometry may also be affected by non-tetrahedral components. Building operations strongly affect the stoichiometry of the resultant sheet, and this effect may be quantified. We define a formula-generating function F(k,l,...) that generates the formula of a sheet with specific topological features denoted by the indices k,l,... . A simple 3-connected net results in sheets of the form (T2O5)n where n denotes the number of (T2O5)n in the unit cell of the underlying net (for 63, n = 1; for 4.82, n = 2; for (4.6.8)2(6.82)1, n = 3, etc). Plane nets with k 3-connected vertices and l inserted 2-connected vertices result in sheets of the form [T(k+l) O(2.5k+3l)], where (...) are subscripted. Single- and double-sheet structures may be generated from the function F(k,l) = T(N{k+l}) O(N{3k+2.5l}-n{N-1}) where N = 1 and 2 for single- and double-sheets, respectively, and (...) are subscripted.