Reduced thermal conductivity by nanoscale intergrowths in perovskite like layered structure La2Ti2O7

The effect of substitution and oxidation-reduction on the thermal conductivity of perovskite-like layered structure (PLS) ceramics was investigated in relation to mass contrast and non-stoichiometry. Sr (acceptor) was substituted on the A site, while Ta (donor) was substituted on the B site of La2Ti2O7. Substitution in PLS materials creates atomic scale disorders to accommodate the non-stoichiometry. High resolution transmission electron microscopy and X ray diffraction revealed that acceptor substitution in La2Ti2O7 produced nanoscale intergrowths of n = 5 layered phase, while donor substitution produced nanoscale intergrowths of n = 3 layered phase. As a result of these nanoscale intergrowths, the thermal conductivity value reduced by as much as ∼20%. Pure La2Ti2O7 has a thermal conductivity value of ∼1.3 W/m K which dropped to a value of ∼1.12 W/m K for Sr doped La2Ti2O7 and ∼0.93 W/m K for Ta doped La2Ti2O7 at 573 K.

Proposed structures for poorly characterized phases in C2M carbonaceous chondrite meteorites

Structure and chemistry of poorly characterized phases (PCP). We suggest here that approximately 10 angstrom PCP, a dominant matrix variety, has a structure equivalent to iron-rich tochilinite [6Fe (sub 0.9) S 5(Fe, Mg) (OH) (sub 2) ] which consists of coherently interstratified mackinawite and brucite sheets. approximately 17 angstrom PCP, previously described as an SBB-type mixed-layer structure, is a commensurate intergrowth of serpentine and tochilinite layers. A wide range of cation substitutions is possible within both tochilinite and serpentine-tochilinite structural types. Various forms of PCP observed in carbonaceous chondrites are intergrowths of tochilinite, serpentine, serpentine-tochilinite and/or valleriite-type minerals.--Modified journal abstract.

Bismuth tungsten-oxide bronzes - a study of intergrowth phases and related aspects

Reaction of bismuth metal with WO$_3$ in the absence of oxygen yields interesting bronze-like phases. From analytical electron microscopy and X-ray photoelectron spectroscopy, the product phases are found to have the general composition Bi$_x$ WO$_3$ with bismuth in the 3+ state. Structural investigations made with high resolution electron micrscopy and cognate techniques reveal that when x < 0.02, a perovskite bronze is formed. When x $\geqslant$ 0.02, however, intergrowth tungsten bronzes (i.t.b.) containing varying widths of the WO$_3$ slab are formed, the lattice periodicity being in the range 2.3-5.1 nm in a direction perpendicular to the WO$_3$ slabs. Image-matching studies indicate that the bismuth atoms are in the tunnels of the hexagonal tungsten bronze (h.t.b.) strips and the h.t.b. strips always remain one-tunnel wide. Annealed samples show a satellite structure around the superlattice spots in the electron diffraction patterns, possibly owing to ordering of the bismuth atoms in the tunnels. The i.t.b. phases show recurrent intergrowths extending up to 100 nm in several crystals. The periodicity varies considerably within the same crystal wherever there is disordered intergrowth, but unit cell dimensions can be assigned from X-ray and electron diffraction patterns. The maximum value of x in the i.t.b. phases is ca. 0.07 and there is no evidence for the i.t.b. phase progressively giving way to the h.t.b. phase with increase in x. Hexagonal tungsten bronzes that contain bismuth with x up to 0.02 can be formed by starting from hexagonal WO$_3$, but the h.t.b. phase seems to be metastable. Optical, magnetic and electron transport properties of the i.t.b. phases have been measured and it appears that the electrons become itinerant when x > 0.05.

The world of perovskite oxides: From dielectrics to superconductors

Some aspects of the properties of oxides of perovskite and K2 NiF4 structures are presented. Some of the interesting aspects discussed are intergrowths, orthorhombicity of superconducting cuprates and importance of holes on oxygen.

Preparation, structure, microwave absorption and other properties of the 125K superconductor Tl2Ca2Ba2Cu3O10+δ*1

It is shown that Tl2Ca2Ba2Cu3O10+δ (2223), the n=3 member of the Tl2O2. Can�1Ba2CunO2n+2 family shows a Tc (zero-resistance) of 125K (onset 140K) only when it is prepared by the sealed tube ceramic method starting from the 1313 composition. The structure is orthorhombic (Image compared to 30� of 2122), but electron diffraction patterns show two possible orthorhombic structures. Lattice images show the expected local structure and also the presence of dislocations and intergrowths. Both 2223 and 2122 oxides absorb microwaves (9.1GHz) intensely in the superconducting state, with some hysteresis. XPS measurements show Cu mainly in the 1+ state, suggesting the important role of oxygen holes.

Structural adaptability in the system Bi2O3 - WO3 : Higher members of the homologous series Bi2WnO3n+3

The ultramicrostructure of phases with n = 1, 2 and 3 in the hypothetical series Bi2WnO3n+3 has been investigated by high resolution electron microscopy and energy dispersive X-ray emission spectroscopy. For n = 1 and 2, well ordered phases with the predicted compositions have been obtained, but for n = 3, a severely disordered assemblage containing intergrowths of the two known structures and strips of the n = 3 member is produced. No evidence for ordered structures with n > 2 has yet been obtained.

Structural adaptability in the system Bi2O3 --- WO3 : Higher members of the homologous series Bi2WnO3n+3

The ultramicrostructure of phases with n = 1, 2 and 3 in the hypothetical series Bi2WnO3n+3 has been investigated by high resolution electron microscopy and energy dispersive X-ray emission spectroscopy. For n = 1 and 2, well ordered phases with the predicted compositions have been obtained, but for n = 3, a severely disordered assemblage containing intergrowths of the two known structures and strips of the n = 3 member is produced. No evidence for ordered structures with n > 2 has yet been obtained.

Metastable phase relations and europium(II) luminescence of barium hexa-aluminates prepared by gel to crystallite conversion

Wet chemical reaction of hydrated alumina gels, Al2O3.yH(2)O(80intergrowths. The metastable Ba-hexa-aluminates doped with Eu(II), exhibit predominantly the 436nm emission band for all the 'x' values. No deterioration in emission intensity is noticed on long term preservation of the phosphors. Differences prevailing in literature on the phase relations in Ba-hexa-aluminates can be attributed to preparative route dependent metastability.

Ultrahigh-temperature metamorphism from an unusual corundum plus orthopyroxene intergrowth bearing Al-Mg granulite from the Southern Marginal Zone, Limpopo Complex, South Africa

The Southern Marginal Zone of the Limpopo Complex is composed of granite-greenstone cratonic rocks reworked by a Neoarchean high-grade tectono-metamorphic event. Petrographic and mineral chemical characterization of an Al-Mg granulite from this zone is presented here. The granulite has a gneissic fabric with distinct Al-rich and Si-rich layers, with the former preserving the unusual lamellar (random and regular subparallel) intergrowths of corundum and symplectic intergrowth of spinel with orthopyroxene. The Al-rich layer preserves mineral assemblages such as rutile with orthopyroxene + sillimanite +/- A quartz, Al-rich orthopyroxene (similar to 11 wt%), spinel + quartz, and corundum in possible equilibrium with quartz, while the Si-rich layer preserves antiperthites and orthopyroxene + sillimanite +/- A quartz, all considered diagnostic of ultrahigh-temperature metamorphism. Application of Al-in-opx thermometry, ternary feldspar thermometry and construction of suitable pressure-temperature phase diagrams, compositional and model proportion isopleth results indicate P-T conditions as high as similar to 1,050-1,100 A degrees C, and similar to 10-12 kbars for the Al-Mg granulite. Our report of ultrahigh-temperature conditions is significant considering that the very high temperature was reached during decompression of an otherwise high-pressure granulite complex (clockwise P-T path), whereas most other ultrahigh-temperature granulites are linked to magma underplating at the base of the crust (counterclockwise P-T path).

Peraluminous sapphirine-cordierite pods in Mg-rich orthopyroxene granulite from southern India: Implications for lower crustal processes

Sapphirine-cordierite intergrowths occur as pods within garnet-absent, high-Mg orthopyroxene-granulite xenoliths in the Kambam valley, Madurai Block, southern India. Whereas the cores of the pods are composed of sapphirine (X-Mg = 0.871-0.897) - cordierite (X-Mg = 0.892-0.931) intergrowth along with rutile, zircon and monazite, the rims are characterized by cordierite, apatite, plagioclase, K-feldspar, quartz and minor calcite. The surrounding matrix comprises orthopyroxene (maximum Al2O3 4.1 wt.%, X-Mg 0.848-0.850), plagioclase, biotite and quartz, similar to the assemblage in the surrounding charnockites. Sapphirine in the Kambam rocks is characterized by high Al contents with an end-member composition in the range of 7:9:3 and 3:5:1. The occurrence of peraluminous sapphirine in association with cordierite and in the absence of phases such as sillimanite and garnet is distinct from ultrahigh-temperature assemblages in other localities within the Madurai Block. The peraluminous composition of the pods suggests that these domains could represent cryptic pathways through which aluminous melts migrated. The reaction of such peraluminous melts with Mg-rich orthopyroxene in the host granulite at temperatures of 1025 degrees C and pressures around 8 kbar as computed from phase equilibria modeling followed by an isobaric cooling is inferred to have generated the sapphirine-cordierite pods. The unusual high-Mg orthopyroxene granulite suggests interaction of supracrustal rocks with mafic magmas, which probably acted as the heat source for the partial melting of lower crust and UHT metamorphism.

Flotação por ar dissolvido para os minerais quartzo e feldspato utilizando coletores catiônicos

The pegmatite rocks in Rio Grande do Norte are responsible for much of the production of industrial minerals like quartz and feldspar. Quartz and feldspar are minerals from pegmatite which may occur in pockets with metric to centimetric dimensions or as millimetric to sub millimetric intergrowths. The correct physical liberation of the mineral of interest, in case of intergrowths, requires an appropriate particle size, acquired by size reduction operations. The method for treating mineral which has a high efficiency fines particles recovery is flotation. The main purpose of the present study is to evaluate the recovery of quartz and potassium feldspar using cationic diamine and quaternary ammonium salt as collectors by means of dissolved air flotation DAF. The tests were performed based on a central composite design 24, by which the influence of process variables was statistically verified: concentration of the quaternary ammonium salt and diamine collectors, pH and conditioning time. The efficiency of flotation was calculated from the removal of turbidity of the solution. Results of maximum flotation efficiency (60%) were found in the level curves, plotted in conditions of low concentrations of collectors (1,0 x 10-5 mol.L-1). These high flotation efficiencies were obtained when operating at pH 4 to 8 with conditioning time ranging from 3 to 5 minutes. Thus, the results showed that the process variables have played important roles in the dissolved air flotation process concerning the flotability of the minerals.

Geologia, geoquímica e petrologia magnética do magmatismo básico da área de Nova Canadá (PA), Província Carajás

O mapeamento geológico realizado na área de Nova Canadá, porção sul do Domínio Carajás, Província Carajás, possibilitou a individualização de duas unidades de caráter máfico e intrusivas nos granitoides do Complexo Xingu e, mais restritamente, na sequência greenstone belt do Grupo Sapucaia. São representadas por diques de diabásio isotrópicos e por extensos corpos de anfibolito, com os últimos descrevendo texturas nematoblástica e granoblástica, de ocorrência restrita à porção SW da área. Ambos apresentam assinatura de basaltos subalcalinos de afinidade toleítica, sendo que os diques de diabásio são constituídos por três variedades petrográficas: hornblenda gabronorito, gabronorito e norito, sendo essas diferenças restritas apenas quanto à proporção modal de anfibólio, orto- e clinopiroxênio, já que texturalmente, as mesmas não apresentam diferenças significativas. São formados por plagioclásio, piroxênio (orto- e clinopiroxênio), anfibólio, minerais óxidos de Fe-Ti e olivina, apresentam um padrão ETR moderadamente fracionado, discreta anomalia negativa de Eu, ambiente geotectônico correspondente a intraplaca continental, e assinaturas dos tipos OIB e E-MORB. Já os anfibolitos são constituídos por plagioclásio, anfibólio, minerais opacos, titanita e biotita, mostram um padrão ETR horizontalizado, com anomalia de Eu ausente, sendo classificados como toleítos de arco de ilha e com assinatura semelhante aos N-MORB. Os dados de química mineral obtidos nessas unidades mostram que, nos diques de diabásio, o plagioclásio não apresenta variações composicionais significativas entre núcleo e borda, sendo classificados como labradorita, com raras andesina e bytownita; o anfibólio mostra uma gradação composicional de Fe-hornblenda para actinolita, com o aumento de sílica. Nos anfibolitos, o plagioclásio mostra uma grande variação composicional, de oligoclásio à bytownita nas rochas foliadas, sendo que nas menos deformadas, sua classificação é restrita à andesina sódica. O piroxênio, presente apenas nos diabásios, exibe considerável variação em sua composição, revelando um aumento no teor de magnésio nos núcleos, e de ferro e cálcio, nas bordas, permitindo classificá-los em augita, pigeonita (clinopiroxênio) e enstatita (ortopiroxênio). Os diabásios apresentam titanomagnetita, magnetita e ilmenita como os principais óxidos de Fe-Ti, permitindo reconhecer cinco formas distintas de ilmenita nessas rochas: ilmenita treliça, ilmenita sanduíche, ilmenita composta interna/externa, ilmenita em manchas e ilmenita individual. Feições texturais e composicionais sugerem que a titanomagnetita e os cristais de ilmenita composta externa e individual foram originados durante o estágio precoce de cristalização. Durante o estágio subsolidus, a titanomagnetita foi afetada pelo processo de oxi-exsolução, dando origem a intercrescimentos de magnetita pobre em titânio com ilmenita (ilmenitas treliça, em mancha, sanduíche e composta interna). Os anfibolitos possuem a ilmenita como único mineral óxido de Fe e Ti ocorrendo, portanto, sob a forma de ilmenita individual, onde encontra-se sempre associada ao anfibólio e à titanita. Os valores mais elevados de suscetibilidade magnética (SM) estão relacionados aos gabronoritos e noritos, os quais exibem maiores conteúdos modais de minerais opacos e apresentam titanomagnetita magmática em sua paragênese. A variedade hornblenda gabronorito define as amostras com valores intermediários de SM. Os menores valores de SM são atribuídos aos anfibolitos, que são desprovidos de magnetita. A correlação negativa entre valores de SM com os conteúdos modais de minerais ferromagnesianos indica que os minerais paramagnéticos (anfibólio e piroxênio) não possuem influência significativa no comportamento magnético dos diabásios, enquanto nos anfibolitos a tendência de correlação positiva entre estas variáveis pode sugerir que estas fases são as principais responsáveis pelos seus valores de SM. Dados geotermobarométricos obtidos a partir do par titanomagnetita-ilmenita nos diabásios indicam que estes se formaram em condições de temperatura (1112°C) e Fo₂ (-8,85) próximas daquelas do tampão NNO.

Cerro Porã Batholith: post-orogenic A-type granite from the Amoguijá Magmatic Arc - Rio ApaTerrane - South of the Amazonian Craton

O Batólito Cerro Porã é um corpo de aproximadamente 30 por 4 km de extensão, localizado na região de Porto Murtinho, Mato Grosso do Sul. Situa-se nos domínios do Terreno Rio Apa, porção sul do Cráton Amazônico. Constitui-se pela Fácies sienogranítica rosa e Fácies monzogranítica cinza. A primeira é caracterizada por textura equi a, essencialmente, inequigranular xenomórfica e pela presença constante de intercrescimentos gráfico e granofíric; constitui-se por feldspatos alcalinos, quartzo e plagioclásio, tendo biotita como único máfico primário. A Fácies monzogranítica cinza apresenta textura porfirítica, com uma matriz de granulação fina gráfica a granofírica e consiste de quartzo, plagioclásio, feldspatos alcalinos e agregados máficos (biotita e anfibólio). Ambas foram metamorfizadas na fácies xisto verde e a Fácies sienogranítica rosa mostra-se milonitizada quando em zonas de cisalhamento. Foi identificado um evento deformacional dúctil-rúptil originado em regime compressivo, responsável pela geração de xistosidade e lineação de estiramento mineral. A Zona de Cisalhamento Esperança relaciona-se a esta fase e reflete a história cinemática convergente, reversa a de cavalgamento, com transporte de topo para NWW. Quimicamente, esses litotipos classificam-se como granitoides do tipo A2 da série alcalina potássica saturada em sílica. Determinação geocronológica obtida pelo método U-Pb (SHRIMP) em zircão, forneceu idade de 1749 ±45 Ma para sua cristalização. Do ponto vista geotectônico, admite-se que o Granito Cerro Porã corresponda a um magmatismo associado a um arco vulcânico desenvolvido no Estateriano e que sua colocação se deu no estágio tardi a pós-orogênico.