Synthesis, characterization and activity of an immobilized photocatalyst : natural porous diatomite supported titania nanoparticles

Diatomite, a porous non-metal mineral, was used as support to prepare TiO2/diatomite composites by a modified sol–gel method. The as-prepared composites were calcined at temperatures ranging from 450 to 950 _C. The characterization tests included X-ray powder diffraction (XRD), scanning electron microscopy (SEM) with an energy-dispersive X-ray spectrometer (EDS), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption/desorption measurements. The XRD analysis indicated that the binary mixtures of anatase and rutile exist in the composites. The morphology analysis confirmed the TiO2 particles were uniformly immobilized on the surface of diatom with a strong interfacial anchoring strength, which leads to few drain of photocatalytic components during practical applications. In further XPS studies of hybrid catalyst, we found the evidence of the presence of Ti–O–Si bond and increased percentage of surface hydroxyl. In addition, the adsorption capacity and photocatalytic activity of synthesized TiO2/diatomite composites were evaluated by studying the degradation kinetics of aqueous Rhodamine B under UV-light irradiation. The photocatalytic degradation was found to follow pseudo-first order kinetics according to the Langmuir–Hinshelwood model. The preferable removal efficiency was observed in composites by 750 _C calcination, which is attributed to a relatively appropriate anatase/rutile mixing ratio of 90/10.

Fabrication of macro–mesoporous titania/alumina core–shell materials in oil/water interface

A series of macro–mesoporous TiO2/Al2O3 nanocomposites with different morphologies were synthesized. The materials were calcined at 723 K and were characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Transmission electron microscope (TEM), N2 adsorption/desorption, Infrared Emission Spectroscopy (IES), X-ray photoelectron spectroscopy (XPS) and UV–visible spectroscopy (UV–visible). A modified approach was proposed for the synthesis of 1D (fibrous) nanocomposite with higher Ti/Al molar ratio (2:1) at lower temperature (<100 °C), which makes it possible to synthesize such materials on industrial scale. The performance–morphology relationship of as-synthesized TiO2/Al2O3 nanocomposites was investigated by the photocatalytic degradation of a model organic pollutant under UV irradiation. The samples with 1D (fibrous) morphology exhibited superior catalytic performance than the samples without, such as titania microspheres.

Cyclic Salinity Model for deposition of large-scale coal deposits

Existing field data for Rangal coals (Late Permian) of the Bowen Basin, Queensland, Australia, are inconsistent with the depositional model generally accepted in the current geological literature to explain coal deposition. Given the apparent unsuitability of the current depositional model to the Bowen Basin coal data, a new depositional model, here named the Cyclic Salinity Model, is proposed and tested in this study.

The largest Au deposits in the St Ives Goldfield (Yilgarn Craton, Western Australia) may be located in a major Neoarchean volcano-sedimentary depo-centre

The largest Neoarchean gold deposits in the world-class St Ives Goldfield, Western Australia, occur in an area known as the Argo-Junction region (e.g. Junction, Argo and Athena). Why this region is so well endowed with large deposits compared with other parts of the St Ives Goldfield is currently unclear, because gold deposits at St Ives are hosted by a variety of lithologic units and were formed during at least three different deformational events. This paper presents an investigation into the stratigraphic architecture and evolution of the Argo-Junction region to assess its implications for gold metallogenesis. The results show that the region's stratigraphy may be subdivided into five regionally correlatable packages: mafic lavas of the Paringa Basalt; contemporaneously resedimented feldspar-rich pyroclastic debris of the Early Black Flag Group; coarse polymictic volcanic debris of the Late Black Flag Group; thick piles of mafic lavas and sub-volcanic sills of the Athena Basalt and Condenser Dolerite; and the voluminous quartz-rich sedimentary successions of the Early Merougil Group. In the Argo-Junction region, these units have an interpreted maximum thickness of at least 7,130 m, and thus represent an unusually thick accumulation of the Neoarchean volcano-sedimentary successions. It is postulated that major basin-forming structures that were active during deposition and emplacement of the voluminous successions later acted as important conduits during mineralisation. Therefore, a correlation exists between the location of the largest gold deposits in the St Ives Goldfield and the thickest parts of the stratigraphy. Recognition of this association has important implications for camp-scale exploration.

A new approach to kimberlite facies terminology using a revised general approach to the nomenclature of all volcanic rocks and deposits: Descriptive to genetic

Although kimberlite pipes/bodies are usually the remains of volcanic vents, in-vent deposits, and subvolcanic intrusions, the terminology used for kimberlite rocks has largely developed independently of that used in mainstream volcanology. Existing kimberlite terminology is not descriptive and includes terms that are rarely used, used differently, and even not used at all in mainstream volcanology. In addition, kimberlite bodies are altered to varying degrees, making application of genetic terminology difficult because original components and depositional textures are commonly masked by alteration. This paper recommends an approach to the terminology for kimberlite rocks that is consistent with usage for other volcanic successions. In modern terrains the eruption and emplacement origins of deposits can often be readily deduced, but this is often not the case for old, variably altered and deformed rock successions. A staged approach is required whereby descriptive terminology is developed first, followed by application of genetic terminology once all features, including the effects of alteration on original texture and depositional features, together with contact relationships and setting, have been evaluated. Because many volcanic successions consist of both primary volcanic deposits as well as volcanic sediments, terminology must account for both possibilities.

A preliminary OSL chronology for coastal dunes on Moreton island, Queensland, Australia – Marginal deposits of A large-scale quaternary shelf sediment system

Moreton Island and several other large siliceous sand dune islands and mainland barrier deposits in SE Queensland represent the distal, onshore component of an extensive Quaternary continental shelf sediment system. This sediment has been transported up to 1000 km along the coast and shelf of SE Australia over multiple glacioeustatic sea-level cycles. Stratigraphic relationships and a preliminary Optically Stimulated Luminance (OSL) chronology for Moreton Island indicate a middle Pleistocene age for the large majority of the deposit. Dune units exposed in the centre of the island and on the east coast have OSL ages that indicate deposition occurred between approximately 540 ka and 350 ka BP, and at around 96±10 ka BP. Much of the southern half of the island has a veneer of much younger sediment, with OSL ages of 0.90±0.11 ka, 1.28±0.16 ka, 5.75±0.53 ka and <0.45 ka BP. The younger deposits were partially derived from the reworking of the upper leached zone of the much older dunes. A large parabolic dune at the northern end of the island, OSL age of 9.90±1.0 ka BP, and palaeosol exposures that extend below present sea level suggest the Pleistocene dunes were sourced from shorelines positioned several to tens of metres lower than, and up to few kilometres seaward of the present shoreline. Given the lower gradient of the inner shelf a few km seaward of the island, it seems likely that periods of intermediate sea level (e.g. ~20 m below present) produced strongly positive onshore sediment budgets and the mobilisation of dunes inland to form much of what now comprises Moreton Island. The new OSL ages and comprehensive OSL chronology for the Cooloola deposit, 100 km north of Moreton Island, indicate that the bulk of the coastal dune deposits in SE Queensland were emplaced between approximately 540 ka BP and prior to the Last Interglacial. This chronostratigraphic information improves our fundamental understanding of long-term sediment transport and accumulation on large-scale continental shelf sediment systems.

Multiple sulfur isotope analyses support a magmatic model for the volcanogenic massive sulfide deposits of the Teutonic Bore volcanic complex, Yilgarn Craton, Western Australia

We report sensitive high mass resolution ion microprobe, stable isotopes (SHRIMP SI) multiple sulfur isotope analyses (32S, 33S, 34S) to constrain the sources of sulfur in three Archean VMS deposits—Teutonic Bore, Bentley, and Jaguar—from the Teutonic Bore volcanic complex of the Yilgarn Craton, Western Australia, together with sedimentary pyrites from associated black shales and interpillow pyrites. The pyrites from VMS mineralization are dominated by mantle sulfur but include a small amount of slightly negative mass-independent fractionation (MIF) anomalies, whereas sulfur from the pyrites in the sedimentary rocks has pronounced positive MIF, with ∆33S values that lie between 0.19 and 6.20‰ (with one outlier at −1.62‰). The wall rocks to the mineralization include sedimentary rocks that have contributed no detectable positive MIF sulfur to the VMS deposits, which is difficult to reconcile with the leaching model for the formation of these deposits. The sulfur isotope data are best explained by mixing between sulfur derived from a magmatic-hydrothermal fluid and seawater sulfur as represented by the interpillow pyrites. The massive sulfide lens pyrites have a weighted mean ∆33S value of −0.27 ± 0.05‰ (MSWD = 1.6) nearly identical with −0.31 ± 0.08‰ (MSWD = 2.4) for pyrites from the stringer zone, which requires mixing to have occurred below the sea floor. We employed a two-component mixing model to estimate the contribution of seawater sulfur to the total sulfur budget of the two Teutonic Bore volcanic complex VMS deposits. The results are 15 to 18% for both Teutonic Bore and Bentley, much higher than the 3% obtained by Jamieson et al. (2013) for the giant Kidd Creek deposit. Similar calculations, carried out for other Neoarchean VMS deposits give value between 2% and 30%, which are similar to modern hydrothermal VMS deposits. We suggest that multiple sulfur isotope analyses may be used to predict the size of Archean VMS deposits and to provide a vector to ore deposit but further studies are needed to test these suggestions.

Size-dependent elasticity of nanocrystalline titania

Synchrotron-based high-pressure x-ray diffraction measurements indicate that compressibility, a fundamental materials property, can have a size-specific minimum value. The bulk modulus of nanocrystalline titania has a maximum at particle size of 15 nm. This can be explained by dislocation behavior because very high dislocation contents can be achieved when shear stress induced within nanoparticles counters the repulsion between dislocations. As particle size decreases, compression increasingly generates dislocation networks hardened by overlap of strain fields that shield intervening regions from external pressure. However, when particles become too small to sustain high dislocation concentrations, elastic stiffening declines. The compressibility has a minimum at intermediate sizes.

Atheroma: Is calcium important or not? A modelling study of stress within the atheromatous fibrous cap in relation to position and size of calcium deposits

Atheromatous plaque rupture h the cause of the majority of strokes and heart attacks in the developed world. The role of calcium deposits and their contribution to plaque vulnerability are controversial. Some studies have suggested that calcified plaque tends to be more stable whereas others have suggested the opposite. This study uses a finite element model to evaluate the effect of calcium deposits on the stress within the fibrous cap by varying their location and size. Plaque fibrous cap, lipid pool and calcification were modeled as hyperelastic, Isotropic, (nearly) incompressible materials with different properties for large deformation analysis by assigning time-dependent pressure loading on the lumen wall. The stress and strain contours were illustrated for each condition for comparison. Von Mises stress only increases up to 1.5% when varying the location of calcification in the lipid pool distant to the fibrous cap. Calcification in the fibrous cap leads to a 43% increase of Von Mises stress when compared with that in the lipid pool. An increase of 100% of calcification area leads to a 15% stress increase in the fibrous cap. Calcification in the lipid pool does not increase fibrous cap stress when it is distant to the fibrous cap, whilst large areas of calcification close to or in the fibrous cap may lead to a high stress concentration within the fibrous cap, which may cause plaque rupture. This study highlights the application of a computational model on a simulation of clinical problems, and it may provide insights into the mechanism of plaque rupture.

Microbial life and deposits in paper machine circuits

Väitöskirjani käsittele mikrobien ja erilaisten kemikaalien rooleja saostumien ja biofilmien muodostumisessa paperi- ja kartonkikoneilla. "Saostuma" tässä työssä tarkoittaa kiinteän aineen kertymää konepinnoille tai rajapinnoille konekierroissa, jotka on tarkoitettu massasulppujen, lietteiden, vesien tai ilman kuljetukseen. Saostumasta tulee "biofilmi" silloin kun sen oleellinen rakennekomponentti on mikrobisolut tai niiden tuotteet. Väitöstyöni työhypoteesina oli, että i. tietämys saostumien koostumuksesta, sekä ii. niiden rakenteesta, biologisista, fysikaalis-kemiallisista ja teknisistä ominaisuuksista ohjaavat tutkijaa löytämään ympäristöä säästäviä keinoja estää epätoivottujen saostumien muodostus tai purkaa jo muodostuneita saostumia. Selvittääkseni saostumien koostumista ja rakennetta käytin monia erilaisia analytiikan työkaluja, kuten elektronimikroskopiaa, konfokaali-laser mikroskopiaa (CLSM), energiadispersiivistä röntgenanalyysiä (EDX), pyrolyysi kaasukromatografiaa yhdistettynä massaspektrometriaan (Py-GCMS), joninvaihtokromatografiaa, kaasukromatografiaa ja mikrobiologisia analyysejä. Osallistuin aktiivisesti innovatiivisen, valon takaisinsirontaan perustuvan sensorin kehittämistyöhön, käytettäväksi biofilmin kasvun mittaukseen suoraan koneen vesikierroista ja säiliöistä. Työni osoitti, että monet paperinvalmistuksessa käytetyistä kemikaaleista reagoivat keskenään tuottaen orgaanisia tahmakerroksia konekiertojen teräspinnoille. Löysin myös kerrostumia, jotka valomikroskooppisessa tarkastelussa oli tulkittu mikrobeiksi, mutta jotka elektronimikroskopia paljasti alunasta syntyneiksi, alumiinihydroksidiksi joka saostui pH:ssa 6,8 kiertokuitua käyttävän koneen viiravesistä. Monet paperintekijät käyttävät vieläkin alunaa kiinnitysaineena vaikka prosessiolot ovat muuttuneet happamista neutraaleiksi. Sitä pidetään paperitekijän "aspiriinina", mutta väitöstutkimukseni osoitti sen riskit. Löysin myös orgaanisia saostumia, joiden alkuperä oli aineiden, kuten pihkan, saippuoituminen (kalsium saippuat) niin että muodostui tahmankasvua ylläpitävä alusta monilla paperi- ja kartonkikoneilla. Näin solumuodoiltaan Deinococcus geothermalista muistuttavia bakteereita kasvamassa lujasti teräskoepalojen pintaan kiinnittyneinä pesäkkeinä, kun koepaloja upotettiin paperikoneiden vesikiertoihin. Nämä deinokokkimaiset pesäkkeet voivat toimia jalustana, tarttumisalustana muiden mikrobien massoille, joka selittäisi miksi saostumat yleisesti sisältävät deinokokkeja pienenä, muttei koskaan pääasiallisena rakenneosana. Kun paperikoneiden käyttämien vesien (raakavedet, lämminvesi, biologisesti puhdistettu jätevesi) laatua tutkitaan, mittausmenetelmällä on suuri merkitys. Koepalan upotusmenetelmällä todettu biofilmikasvu ja viljelmenetelmällä mitattu bakteerisaastuneisuus korreloivat toisiinsa huonosti etenkin silloin kun likaantumisessa oli mukana rihmamaiseti kasvavia bakteereja. Huoli ympäristöstä on pakottanut paperi- ja kartonkikoneiden vesikiertojen sulkemiseen. Vesien kierrätys ja prosessivesien uudelleenkäyttö nostavat prosessilämpötilaa ja lisäävät koneella kiertävien kolloidisten ja liuenneiden aineiden määriä. Tutkin kiertovesien pitoisuuksia kolmessa eriasteisesti suljetussa tehtaassa, joiden päästöt olivat 0 m3, 0,5 m3 ja 4 m3 jätevettä tuotetonnia kohden, perustuen puhdistetun jäteveden uudelleen käyttöön. Nollapäästöisellä tehtaalla kiertovesiin kertyi paljon orgaanisesti sidottua hiiltä (> 10 g L-1), etenkin haihtuvina happoina (maito-, etikka-, propioni- ja voi-). Myös sulfaatteja, klorideja, natriumia ja kalsiumia kertyi paljon, > 1 g L-1 kutakin. Pääosa (>40%) kaikista bakteereista oli 16S rRNA geenisekvenssianalyysien tulosten perusteella sukua, joskin etäistä (< 96%) ainoastaan Enterococcus cecorum bakteerille. 4 m3 päästävältä tehtaalta löytyi lisäksi Bacillus thermoamylovorans ja Bacillus coagulans. Tehtaiden saostumat sisälsivät arkkeja suurina pitoisuuksina, ≥ 108 g-1, mutta tunnistukseen riittävää sekvenssisamanlaisuutta löytyi vain yhteen arkkisukuun, Methanothrix. Tutkimustulokset osoittivat että tehtaan vesikiertojen sulkeminen vähensi rajusti mikrobiston monimuotoisuutta, muttei estänyt liuenneen aineen ja kiintoaineen mineralisoitumista.

Optimum geometry for uniform deposits on a rotating substrate from a point source

The application of an algorithm shows that maximum uniformity of film thickness on a rotating substrate is achieved for a normalized source-to-substrate distance ratio, h/r =1.183.

High Lithium Storage in Mixed Crystallographic Phase Nanotubes of Titania and Carbon-Titania

Morphology and electrochemical performance of mixed crystallographic phase titania nanotubes for prospective application as anode in rechargeable lithium ion batteries are discussed. Hydrothermally grown nanotubes of titania (TiO2) and carbon-titania (C-TiO2) comprise a mixture of both anatase and TiO2 (B) crystallographic phases. The first cycle capacity (at Current rate = 10 mAg(-1)) for bare TiO2 nanotubes was 355 mAhg(-1) (approximately 1.06 Li), which is higher than both the theoretical capacity (335 mAhg(-1)) and the reported values for pure anatase and TiO2 (B) nanotubes. Higher capacity is attributed to it combination of the presence of mixed crystallographic phases of titania and trivial size effects. The surface area of bare TiO2 nanotubes was very high at 340 m(2) g(-1). C-TiO2 nanotubes showed a slightly lower first-cycle specific capacity of 307 mAhg(-1), but the irreversible capacity loss in the first cycle decreased by half compared to bare TiO2 nanotubes. The C-TiO2 nanotubes also showed a better rate capability, that is, higher capacities compared to bare TiO2 nanotubes in the Current range 0.1-2 Ag-1. Enhanced rate capability in the case of C-TiO2 is attributed to the efficient percolation of electrons as well its to the decrease in the anatase phase.

High lithium storage in micrometre sized mesoporous spherical self-assembly of anatase titania nanospheres and carbon

Composite of anatase titania (TiO2) nanospheres and carbon grown and self-assembled into micron-sized mesoporous spheres via a solvothermal synthesis route are discussed here in the context of rechargeable lithium-ion battery. The morphology and carbon content and hence the electrochemical performance are observed to be significantly influenced by the synthesis parameters. Synthesis conditions resulting in a mesoporous arrangement of an optimized amount carbon and TiO2 exhibited the best lithium battery performance. The first discharge cycle capacity of carbon-titania mesoporous spheres (solvothermal reaction at 150 degrees C at 6 h, calcination at 500 degrees C under air, BET surface area 80 m(2)g(-1)) was 334 mAhg(-1) (approximately 1 Li) at current rate of 0.066 Ag-1. High storage capacity and good cyclability is attributed to the nanostructuring of TiO2 (mesoporosity) as well as due to formation of a percolation network of carbon around the TiO2 nanoparticles. The micron-sized mesoporous spheres of carbon-titania composite nanoparticles also show good rate cyclability in the range (0.066-6.67) Ag-1.

The Influence of Titania on Creep in Superplastic Zirconia

Detailed high-temperature compression creep experiments on a pure 3 mol% yttria-stabilized tetragonal zirconia (3YTZ) and 3YTZ doped with 4.8 wt% TiO2 revealed that both materials exhibit a similar transition in stress exponents from n similar to 1 to n similar to 2 with a decrease in stress. The stress exponent of 1 and the inverse grain size dependence p of similar to 3 are consistent with the Coble diffusion creep at high stresses; the increase in stress exponent at low stresses is attributed to an interface-controlled diffusion creep process. Measurements revealed that grain-boundary sliding contributes to >similar to 50% of the total strain in both regions with n similar to 1 and n similar to 2, indicating the operation of the same fundamental deformation process in both regions. The creep data indicate that doping with TiO2 leads to an increase in the grain-boundary diffusion coefficients. The increase observed in the dihedral angle with doping is also consistent with the increase in grain boundary diffusion coefficient and the reported enhanced ductility in such materials.