The ageing of alumina hydrolysates synthesized from sec-butoxyaluminium(III)

A combination of X-ray diffraction, thermal analysis and Raman spectroscopy was employed to characterise the ageing of alumina hydrolysates synthesised from the hydrolysis of anhydrous tri-sec-butoxyaluminium(III). X-Ray diffraction showed that the alumino-oxy(hydroxy) hydrolysates were pseudoboehmite. For boehmite the lamellar spacings are in the b direction and multiple d(020) peaks are observed for the un-aged hydrolysate. After 4 h of ageing, a single d(020) peak is observed at 6.53 Å. Thermal analysis showed five endotherms at 70, 140, 238, 351 and 445°C. These endotherms are attributed to the dehydration and dehydroxylation of the boehmite-like hydrolysate. Raman spectroscopy shows the presence of bands for the washed hydrolysates at 333, 355, 414, 455, 475, 495, 530 and 675 cm–1. These bands are attributed to pseudoboehmite. Ageing of the hydrolysates results in an increase in the crystallite size of the pseudoboehmite.

Evaluation of the in vitro bioactivity of bioceramics

Two common methods have been used to evaluate the in vitro bioactivity of bioceramics for the application of bone repair. One is to evaluate the ability of apatite formation by soaking ceramics in simulated body fluids (SBF); the other method is to evaluate the effect of ceramics on osteogenic differentiation using cell experiments. Both methods have their own drawbacks in evaluating the in vitro bioactivity of bioceramics. In this commentary paper we review the application of both methods in bioactivity of bioceramics and conclude that (i) SBF method is an efficient method to investigate the in vitro bioactivity of silicate-based bioceramics, (ii) cellular bioactivity of bioceramics should be investigated by evaluating their stimulatory ability using standard bioceramics as controls; and (iii) the combination of these two methods to evaluate the in vitro bioactivity of bioceramics can improve the screening efficiency for the selection of bioactive ceramics for bone regeneration.

In search of a hidden long-term isolated sub-chondritic 142Nd/144Nd reservoir in the deep mantle : implications for the Nd isotope systematics of the Earth

Here we search for evidence of the existence of a sub-chondritic 142Nd/144Nd reservoir that balances the Nd isotope chemistry of the Earth relative to chondrites. If present, it may reside in the source region of deeply sourced mantle plume material. We suggest that lavas from Hawai’i with coupled elevations in 186Os/188Os and 187Os/188Os, from Iceland that represent mixing of upper mantle and lower mantle components, and from Gough with sub-chondritic 143Nd/144Nd and high 207Pb/206Pb, are favorable samples that could reflect mantle sources that have interacted with an Early-Enriched Reservoir (EER) with sub-chondritic 142Nd/144Nd. High-precision Nd isotope analyses of basalts from Hawai’i, Iceland and Gough demonstrate no discernable 142Nd/144Nd deviation from terrestrial standards. These data are consistent with previous high-precision Nd isotope analysis of recent mantle-derived samples and demonstrate that no mantle-derived material to date provides evidence for the existence of an EER in the mantle. We then evaluate mass balance in the Earth with respect to both 142Nd/144Nd and 143Nd/144Nd. The Nd isotope systematics of EERs are modeled for different sizes and timing of formation relative to ε143Nd estimates of the reservoirs in the μ142Nd = 0 Earth, where μ142Nd is ((measured 142Nd/144Nd/terrestrial standard 142Nd/144Nd)−1 * 10−6) and the μ142Nd = 0 Earth is the proportion of the silicate Earth with 142Nd/144Nd indistinguishable from the terrestrial standard. The models indicate that it is not possible to balance the Earth with respect to both 142Nd/144Nd and 143Nd/144Nd unless the μ142Nd = 0 Earth has a ε143Nd within error of the present-day Depleted Mid-ocean ridge basalt Mantle source (DMM). The 4567 Myr age 142Nd–143Nd isochron for the Earth intersects μ142Nd = 0 at ε143Nd of +8 ± 2 providing a minimum ε143Nd for the μ142Nd = 0 Earth. The high ε143Nd of the μ142Nd = 0 Earth is confirmed by the Nd isotope systematics of Archean mantle-derived rocks that consistently have positive ε143Nd. If the EER formed early after solar system formation (0–70 Ma) continental crust and DMM can be complementary reservoirs with respect to Nd isotopes, with no requirement for significant additional reservoirs. If the EER formed after 70 Ma then the μ142Nd = 0 Earth must have a bulk ε143Nd more radiogenic than DMM and additional high ε143Nd material is required to balance the Nd isotope systematics of the Earth.

Vibrational spectroscopic studies of laboratory scale polymer melt processing : application to a thermoplastic polyurethane nanocomposite

A laboratory scale twin screw extruder has been interfaced with a near infrared (NIR) spectrometer via a fibre optic link so that NIR spectra can be collected continuously during the small scale experimental melt state processing of polymeric materials. This system can be used to investigate melt state processes such as reactive extrusion, in real time, in order to explore the kinetics and mechanism of the reaction. A further advantage of the system is that it has the capability to measure apparent viscosity simultaneously which gives important additional information about molecular weight changes and polymer degradation during processing. The system was used to study the melt processing of a nanocomposite consisting of a thermoplastic polyurethane and an organically modified layered silicate.

Raman spectroscopic study of the multi-anion mineral dixenite CuMn2+14Fe3+(AsO3)5(SiO4)2(AsO4)(OH)6

The mixed anion mineral dixenite has been studied by Raman spectroscopy, complimented with infrared spectroscopy. The Raman spectrum of dixenite shows bands at 839 and 813 cm-1 assigned to the (AsO3)3- symmetric and antisymmetric stretching modes. The most intense Raman band of dixenite is the band at 526 cm-1 and is assigned to the ν2 AsO33- bending mode. DFT calculations enabled the position of AsO22- symmetric stretching mode at 839 cm-1, the antisymmetric stretching mode at 813 cm-1, and the deformation mode at 449 cm-1 to be calculated. Raman bands at 1026 and 1057 cm-1 are assigned to the SiO42- symmetric stretching vibrations and at 1349 and 1386 cm-1 to the SiO42- antisymmetric stretching vibrations. Both Raman and infrared spectra indicate the presence of water in the structure of dixenite. This brings into question the commonly accepted formula of dixenite as CuMn2+14Fe3+(AsO3)5(SiO4)2(AsO4)(OH)6. The formula may be better written as CuMn2+14Fe3+(AsO3)5(SiO4)2(AsO4)(OH)6•xH2O.

Deposition of hydroxyapatite and calcium oxalate dihydrate on a heat exchanger tube

Most studies on the characterisation of deposits on heat exchangers have been based on bulk analysis, neglecting the fine structural features and the compositional profiles of layered deposits. Attempts have been made to fully characterise a fouled stainless steel tube obtained from a quintuple Roberts evaporator of a sugar factory using X-ray diffraction and scanning electron microscopy techniques. The deposit contains three layers at the bottom of the tube and two layers on the other sections and is composed of hydroxyapatite, calcium oxalate dihydrate and an amorphous material. The proportions of these phases varied along the tube height. Energy-dispersive spectroscopy and XRD analysis on the surfaces of the outermost and innermost layers showed that hydroxyapatite was the major phase attached to the tube wall, while calcium oxalate dihydrate (with pits and voids) was the major phase on the juice side. Elemental mapping of the cross-sections of the deposit revealed the presence of a mineral, Si-Mg-Al-Fe-O, which is probably a silicate mineral. Reasons for the defects in the oxalate crystal surfaces, the differences in the crystal size distribution from bottom to the top of the tube and the composite fouling process have been postulated.

Volcanic stratigraphy, alteration zoning, and vein paragenesis of the Sascha-Pelligrini low-sulphidation epithermal system, Santa Cruz, Argentina

The Sascha-Pelligrini low-sulphidation epithermal system is located on the western edge of the Deseado Massif, Santa Cruz Province, Argentina. Outcrop sampling has returned values of up to 160g/t gold and 796g/t silver, with Mirasol Resources and Coeur D.Alene Mines currently exploring the property. Detailed mapping of the volcanic stratigraphy has defined three units that comprise the middle Jurassic Chon Aike Formation and two units that comprise the upper Jurassic La Matilde Formation. The Chon Aike Formation consists of rhyodacite ignimbrites and tuffs, with the La Matilde Formation including rhyolite ash and lithic tuffs. The volcanic sequence is intruded by a large flow-banded rhyolite dome, with small, spatially restricted granodiorite dykes and sills cropping out across the study area. ASTER multispectral mineral mapping, combined with PIMA (Portable Infrared Mineral Analyser) and XRD (X-ray diffraction) analysis defines an alteration pattern that zones from laumontite-montmorillonite, to illite-pyritechlorite, followed by a quartz-illite-smectite-pyrite-adularia vein selvage. Supergene kaolinite and steam-heated acid-sulphate kaolinite-alunite-opal alteration horizons crop out along the Sascha Vein trend and Pelligrini respectively. Paragenetically, epithermal veining varies from chalcedonic to saccharoidal with minor bladed textures, colloform/crustiform-banded with visible electrum and acanthite, crustiform-banded grey chalcedonic to jasperoidal with fine pyrite, and crystalline comb quartz. Geothermometry of mineralised veins constrains formation temperatures from 174.8 to 205.1¡ÆC and correlates with the stability field for the interstratified illite-smectite vein selvage. Vein morphology, mineralogy and associated alteration are controlled by host rock rheology, permeability, and depth of the palaeo-water table. Mineralisation within ginguro banded veins resulted from fluctuating fluid pH associated with selenide-rich magmatic pulses, pressure release boiling and wall-rock silicate buffering. The study of the Sascha-Pelligrini epithermal system will form the basis for a deposit-specific model helping to clarify the current understanding of epithermal deposits, and may serve as a template for exploration of similar epithermal deposits throughout Santa Cruz.

Sulfate anion templation of macrocycles, capsules, interpenetrated and interlocked structures

This review examines the potential of anions, in particular sulfate, to template the formation of complex molecular architectures. Until recently, sulfate has been largely overlooked in this area and the examples described herein demonstrate this anion’s versatility in templating the formation of a diverse range of molecular systems including macrocycles, helixes, molecular capsules, interpenetrated and interlocked assemblies such as catenanes. In addition sulfate has been shown to template the formation of interpenetrated structures on a range of solid surfaces including gold, polystyrene beads and silicate nanoparticles, highlighting the potential of this anion in the fabrication of functional sensory devices exhibiting highly selective binding behaviour.

Raman spectroscopic study of the mineral shattuckite Cu5(SiO3)4(OH)2

Shattuckite Cu5(SiO3)4(OH)2 is a copper hydroxy silicate and is commonly known as a ‘healing’ mineral. Three shattuckite mineral samples from three different origins were analysed by Raman spectroscopy. Some Raman bands are common in the spectra of the minerals. Raman bands at around 890, 1058 and 1102 are described as the ν3 –SiO3 antisymmetric stretching vibrations. The Raman band at 670 cm-1 is assigned to the ν4 bending modes of the -SiO3 units and the band at around 785 cm-1is due to Si-O-Si chain stretching mode. Raman (and infrared) spectroscopy proves that water is in the molecular structure of shattuckite; thus the formula is better written as Cu5(SiO3)4(OH)2•xH2O.

Controlling cell-material interactions with polymer nanocomposites by use of surface modifying additives

Polymer nanocomposites (NC) are fabricated by incorporating well dispersed nanoscale particles within a polymer matrix. This study focuses on elastomeric polyurethane (PU) based nanocomposites, containing organically modified silicates (OMS), as bioactive materials. Nanocomposites incorporating chlorhexidine diacetate as an organic modifier (OM) were demonstrated to be antibacterial with a dose dependence related to both the silicate loading and the loading of OM. When the non-antibacterial OM dodecylamine was used, both cell and platelet adhesion were decreased on the nanocomposite surface. These results suggest that OM is released from the polymer and can impact on cell behaviour at the interface. Nanocomposites have potential use as bioactive materials in a range of biomedical applications.

Vibrational spectroscopy and solubility study of the mineral stringhamite CaCuSiO4•H2O

Stringhamite CaCuSiO4·H2O is a hydrated calcium copper silicate and is commonly known as a significant ‘healing’ mineral and is potentially a semi-precious jewel. Stringhamite is a neosilicate with Cu2+ in square planar coordination. Vibrational spectroscopy has been used to characterise the molecular structure of stringhamite. The intense sharp Raman band at 956 cm−1 is assigned to the ν1 (A1g) symmetric stretching vibration. Raman bands at 980, 997, 1061 cm−1 are assigned to the ν3 (A2u, B1g) antisymmetric stretching vibrations. Splitting of the ν3 vibrational mode supports the concept that the stringhamite SiO4 tetrahedron is strongly distorted. The intense bands at 505 and 519 cm−1 and at 570 cm−1 are assigned to the ν2 and ν4 vibrational modes. The question arises as to whether the mineral stringhamite can actually function as a healing mineral. An estimation of the solubility product at pH < 5 shows that the cupric ion can be released. The copper ion is a very powerful antibiological agent and thus the mineral stringhamite may well function as a healing mineral.

Whelanite Ca5Cu2(OH)2CO3,Si6O17•4H2O – A vibrational spectroscopic study

Whelanite Ca5Cu2(OH)2CO3,Si6O17•4H2O is a hydrated hydroxy mixed anion compound with both silicate and carbonate anions in the formula. The structural characterisation of the mineral whelanite remains incomplete. Whelanite is probably a neosilicate with Cu2+ in square planar coordination. Two Raman bands at 1070 and 1094 cm-1 are assigned to the ν1 symmetric stretching modes of the CO32- units. The observation of two symmetric stretching modes supports the concept of two non-equivalent CO32- units in the whelanite structure. The intense sharp Raman band at 1006 cm-1 is assigned to the ν1 (A1g) symmetric stretching vibration of the Si6O17 units. The splitting of the ν3 vibrational mode offers support to the concept that the SiO4 tetrahedron in whelanite is strongly distorted. A very intense Raman band observed at 666 cm-1 with a shoulder at 697 cm-1 is assigned to the ν4 vibrational modes. Intense Raman bands at 3534, 3556, 3550 and 3595 cm-1 are assigned to the stretching vibrations of the OH units. Low intensity Raman bands at 2910, 3187 and 3453 cm-1 are assigned to water stretching modes. Thus, vibrational spectroscopy has been used to characterise the molecular structure of whelanite. Whelanite is a mineral that could be conceived as a healing mineral