Fly Ash Soil Stabilization for Non-Uniform Subgrade Soils, Volume I: Engineering Properties and Construction Guidelines, TR-461, 2005

Soil treated with self-cementing fly ash is increasingly being used in Iowa to stabilize fine-grained pavement subgrades, but without a complete understanding of the short- and long-term behavior. To develop a broader understanding of fly ash engineering properties, mixtures of five different soil types, ranging from ML to CH, and several different fly ash sources (including hydrated and conditioned fly ashes) were evaluated. Results show that soil compaction characteristics, compressive strength, wet/dry durability, freeze/thaw durability, hydration characteristics, rate of strength gain, and plasticity characteristics are all affected by the addition of fly ash. Specifically, Iowa selfcementing fly ashes are effective at stabilizing fine-grained Iowa soils for earthwork and paving operations; fly ash increases compacted dry density and reduces the optimum moisture content; strength gain in soil-fly ash mixtures depends on cure time and temperature, compaction energy, and compaction delay; sulfur contents can form expansive minerals in soil–fly ash mixtures, which severely reduces the long-term strength and durability; fly ash increases the California bearing ratio of fine-grained soil–fly ash effectively dries wet soils and provides an initial rapid strength gain; fly ash decreases swell potential of expansive soils; soil-fly ash mixtures cured below freezing temperatures and then soaked in water are highly susceptible to slaking and strength loss; soil stabilized with fly ash exhibits increased freeze-thaw durability; soil strength can be increased with the addition of hydrated fly ash and conditioned fly ash, but at higher rates and not as effectively as self-cementing fly ash. Based on the results of this study, three proposed specifications were developed for the use of self-cementing fly ash, hydrated fly ash, and conditioned fly ash. The specifications describe laboratory evaluation, field placement, moisture conditioning, compaction, quality control testing procedures, and basis of payment.

Fly Ash Soil Stabilization for Non-Uniform Subgrade Soils, Volume II: Influence of Subgrade Non-Uniformity on PCC Pavement Performance, TR-461, 2005

To provide insight into subgrade non-uniformity and its effects on pavement performance, this study investigated the influence of non-uniform subgrade support on pavement responses (stress and deflection) that affect pavement performance. Several reconstructed PCC pavement projects in Iowa were studied to document and evaluate the influence of subgrade/subbase non-uniformity on pavement performance. In situ field tests were performed at 12 sites to determine the subgrade/subbase engineering properties and develop a database of engineering parameter values for statistical and numerical analysis. Results of stiffness, moisture and density, strength, and soil classification were used to determine the spatial variability of a given property. Natural subgrade soils, fly ash-stabilized subgrade, reclaimed hydrated fly ash subbase, and granular subbase were studied. The influence of the spatial variability of subgrade/subbase on pavement performance was then evaluated by modeling the elastic properties of the pavement and subgrade using the ISLAB2000 finite element analysis program. A major conclusion from this study is that non-uniform subgrade/subbase stiffness increases localized deflections and causes principal stress concentrations in the pavement, which can lead to fatigue cracking and other types of pavement distresses. Field data show that hydrated fly ash, self-cementing fly ash-stabilized subgrade, and granular subbases exhibit lower variability than natural subgrade soils. Pavement life should be increased through the use of more uniform subgrade support. Subgrade/subbase construction in the future should consider uniformity as a key to long-term pavement performance.

Genesis of the Jurassic carbonate-hosted Pb-Zn deposits of Jebel Ressas (North-eastern Tunisia): Evidence from mineralogy, petrography and trace metal contents and isotope (O, C, S, Pb) geochemistry

The Jebel Ressas Pb-Zn deposits in North-Eastern Tunisia occur mainly as open-space fillings (lodes, tectonic breccia cements) in bioclastic limestones of the Upper Jurassic Ressas Formation and along the contact of this formation with Triassic rocks. The galena-sphalerite association and their alteration products (cerussite, hemimorphite, hydrozincite) are set within a calcite gangue. The Triassic rocks exhibit enrichments in trace metals, namely Pb, Co and Cd enrichment in clays and Pb, Zn, Cd, Co and Cr enrichment in carbonates, suggesting that the Triassic rocks have interacted with the ore-bearing fluids associated with the Jebel Ressas Pb-Zn deposits. The delta(18)O content of calcite associated with the Pb-Zn mineralization suggests that it is likely to have precipitated from a fluid that was in equilibrium with the Triassic dolostones. The delta(34)S values in galenas from the Pb-Zn deposits range from -1.5 to +11.4%, with an average of 5.9% and standard deviation of 3.9%. These data imply mixing of thermochemically-reduced heavy sulfur carried in geothermal- and fault-stress-driven deep-seated source fluid with bacterially-reduced light sulfur carried in topography-driven meteoric fluid. Lead isotope ratios in galenas from the Pb-Zn deposits are homogenous and indicate a single upper crustal source of base-metals for these deposits. Synthesis of the geochemical data with geological data suggests that the base-metal mineralization at Jebel Ressas was formed during the Serravallian-Tortonian (or Middle-Late Miocene) Alpine compressional tectonics.

Origin of needle fibre calcite (NFC) : a geochemical approach

ABSTRACTNeedle fibre calcite (NFC) is one of the most widespread habits of pedogenic calcite. It is a monocrystal of calcite, in the shape of a needle, with a diameter of one micron and a length between 4 and 103 times its width. NFC occurs in soils with different macroscopic and microscopic morphologies. Macroscopically, two main habits of NFC exist: "cotton ball'Mike clusters and as "powder" coating on pebbles inside the soil. It can also act as nucleation sites for precipitation of calcite cements of purely physicochemical origin (LCC - Late Calcitic Cement). Although many studies have been conducted on needle fibre calcite, its origin remains a subject of debate. The NFC having never been reproduced in the laboratory whatever the considered approach, the processes responsible for its precipitation as a so particular morphology remain unexplained. The shift between the length orientation of the needle crystal and the normal axis of calcite growth (c-axis) is also unresolved.Samples taken in two soils observed in quarries (Villiers and Savagnier) in the Swiss Jura Mountains are used to investigate the processes involved in the formation of these calcite crystals in pedogenic environments. Three groups of microscopic morphologies are distinguished: (i) simple needles (SN), (ii) simple needles with overgrowths (SNO), and (iii) simple needles with nanofibres (SNN), nanofibres being either organic or mineral in nature. These groups correspond to different stages in the formation and evolution of NFC.Comparison of carbon and oxygen isotope compositions of NFC with LCC, in relationship with the composition of the carbonate host rock (CHR), and the carbon isotope signature of dissolved inorganic carbon (DIC) from the soil waters, indicates that both NFC and LCC are precipitated in isotopic equilibrium with the soil solution. Similar Ô13C and Ô180 values of the elongated NFC and the rhombohedral calcite crystals of the LCC suggest that the precipitation of these different calcite habits is not due to changes in physicochemical conditions. The growth of NFC crystals inside an organic mould formed by the fungal hyphae could explain the formation of calcite ciystals in the shape of a needle in isotopic equilibrium with the local environment.Strontium and calcium isotope compositions of the three microscopic groups of NFC and LCC were also studied, in order to determine the origin of calcium (Ca2+) entrapped in the calcite lattice and to elucidate the processes responsible for the precipitation of NFC. The 87Sr/86Sr ratio of the SN is closer to the 87Sr/86Sr ratio of the carbonate host rock than the LCC, SNO, and SNN. This could be another clue for the formation of SN inside fungal hyphae, because fungi are known to dissolve the rocks to release and translocate through their hyphae nutrients necessary for their growth. SN and SNN are depleted in Sr and enriched in ^Ca compared to the LCC. In the context of Villiers quarry, where the two ciystal shapes precipitate at similar temperature (in a range of 0,6°C), such variations are the result of a slower precipitation rate of NFC, which is inconsistent with a purely physicochemically precipitated elongate crystal.Finally, NFC is enriched in major and trace elements (i.e. Fe, Zn, Cu, and Mo) compared to the LCC. This enrichment is ascribed to modification in precipitation processes between the NFC and LCC. Right now, it is not possible to preclude the influence of the particular shape of NFC or the biological influence. REEs are not fractionated in NFC, contrary to LCC. Thus, NFC does not precipitate from a percolation solution circulating downward the soil, which should lead to the fractionation of the REEs. As explained above, fungi, are able to dissolve and translocate nutrients. This kind of processes allows releasing elements in the soil solution without fractionation and could explain the particular chemical signature of NFC regarding the REEs.The geochemical approach to investigate the origin of NFC presented in this study does not allow providing direct clues to the fungal origin of NFC, but brings several new insights in the understanding of the formation of such a particular mineral, calcite needles, by precluding definitively their physicochemical origin.RESUMELa calcite en aiguilles (NFC) est l'une des formes les plus ubiquiste de calcite pédogénique. Il s'agit d'un monocrystal de calcite d'un diamètre d'un micron et d'une longueur 4 à 102 fois supérieure à sa largeur. A l'échelle macroscopique, la NFC a été observée sous deux principaux aspects : l'une « cotonneuse » et l'autre formant un mince croûte autour des graviers du sol. La NFC peut également servir de support à la nucléation de ciments secondaires précipités de manière purement physico-chimique (LCC). Malgré les nombreuses études menées sur la NFC, son origine demeure encore inconnue. A ce jour, aucune expérience en laboratoire n'a permis de créer de la calcite en aiguilles, et ce, quelque soit l'approche abordée. Par conséquent, les processus précis responsables de la précipitation calcite avec une telle morphologie restent inconnus. Le décalage existant entre l'axe d'allongement des aiguilles de calcite et l'axe normal de croissance de la calcite (axe c) reste inexpliqué.Des échantillons de NFC, LCC, roche mère, eau de pluie des différents horizons du sol ont été prélevés principalement au front de deux carrières de graviers, ainsi que dans un profil de sol adjacent à ces carrières, dans le but de mieux comprendre les processus à l'origine de la précipitation de calcite en forme d'aiguille. Trois micro-morphologies ont été distinguées: les aiguilles simples (SN), les aiguilles simples avec surcroissances calcitiques (SNO) et enfin les aiguilles simples avec nanofibres (SNN), celles-ci pouvant être de minérales ou organiques. Ces groupes, d'après nos résultats et les études antérieures pourraient correspondre à différentes étapes de formation de la calcite en aiguilles.Dans un premier temps, la comparaison des signatures isotopiques de la calcite en aiguilles, du LCC, de la roche mère et du carbone inorganique dissout dans la solution du sol (CID) indique que la NFC, tout comme le LCC, précipite en équilibre avec la solution du sol. Les valeurs similaires en Ô13C et δ180 de cristaux de calcite allongés (NFC) et rhombohédriques (LCC) formés dans un même milieu suggère que ces différences morphologiques ne peuvent pas être attribuées à des modifications purement physico-chimiques. La croissance de NFC à l'intérieur d'un moule organique comme les hyphes de champignons semble être la seule hypothèse plausible permettant d'expliquer la formation de monocrystaux allongés de calcite en équilibre avec leur environnement.La composition isotopique en strontium (Sr) et calcium (Ca) des LCC et des trois micro¬morphologies de la NFC ont été étudiées également, afin de déterminer l'origine du Ca2+ présent dans le réseau cristallin de la calcite en aiguilles, ainsi que les processus responsables de la formation de NFC. Les valeurs du rapport 87Sr/86$r de la forme SN sont les plus proches de celles de la roche mère par rapport aux formes SNN et SNO et du LCC. Ceci pourrait être un nouvel indice de l'implication des champignons dans la précipitation de calcite en aiguilles, puisqu'ils sont connus pour avoir la capacité de dissoudre les roches afin de libérer les nutriments nécessaires à leur croissance, ainsi que de les transloquer par leurs hyphes. De plus, les formes SN et SNN sont appauvries en Sr et enrichies en "Ca, comparativement au LCC. Dans le sol étudié, tous les carbonates de calcium précipitent à la même température, par conséquent, de telles variations sont dues à un taux de précipitation plus lent de SN et SNN, ce qui est contradictoire avec l'hypothèse physico-chimique. Pour finir, la NFC est enrichie en certains éléments majeurs et traces (i.e. Fe, Zn, Cu et Mo) par rapport au LCC. Ceci peut être attribué à différents processus de formation entre la NFC et le LCC. Pour le moment il est impossible d'exclure l'influence de la forme particulière de la NFC ou celle du champignon. Les terres rares (REEs) ne sont pas fractionnées dans la NFC, contrairement au LCC. Ceci peut être expliqué par le fait que la NFC précipite à partir d'une solution qui n'a pas percolé à travers le sol. Les champignons en dissolvant les roches mettent en solution éléments sans les fractionner. L'approche géochimique de l'étude de la calcite en aiguilles ne permets pas de produire des preuves directes sur sa potentielle origine fongique, mais permet de mieux comprendre comment un minéral aussi singulier que la NFC peut se former. D'autre pare cette étude permets d'exclure définitivement l'hypothèse physico-chimique de l'origine de la calcite en aiguilles

Changes in the isoflavone profile and in the chemical composition of tempeh during processing and refrigeration

The objective of this work was to analyze changes in the isoflavone profile, determined by high performance liquid chromatography, at different processing stages and after refrigeration of tempeh. For tempeh production, clean soybean grains from cultivars BR 36 (low isoflavone content) and IAS 5 (high) were dehulled, and the separated cotyledons were hydrated and then cooked in boiling water for 30 min. Spores of the fungus Rhizopus microsporus var. oligosporus were inoculated in the cooked and cooled cotyledons, and incubated at 32ºC for 6, 12, 18, and 24 hours in perforated polypropylene bags, for fermentation. The resulting tempeh was stored at 4ºC for 6, 12, 18, and 24 hours. After 24-hour fermentation, isoflavone glucosides were 50% reduced, and the aglycone forms in the tempeh from both cultivars was increased. The malonyl forms reduced 83% after cooking. Less than 24 hours of refrigeration did not affect the isoflavone profile of tempeh from either cultivar, which is a good indicator of its quality. The tempeh maintains the high and low isoflavone content of the cultivars, which indicates that cultivar differences in this trait should be considered when processing tempeh.

Construction mechanisms and thermal evolution of upper crustal intrusions : the Saint-Jean-du-Doigt bimodal intrusion (Brittany, France)

Understanding the emplacement and growth of intrusive bodies in terms of mechanism, duration, ther¬mal evolution and rates are fundamental aspects of crustal evolution. Recent studies show that many plutons grow in several Ma by in situ accretion of discrete magma pulses, which constitute small-scale magmatic reservoirs. The residence time of magmas, and hence their capacities to interact and differentiate, are con¬trolled by the local thermal environment. The latter is highly dependant on 1) the emplacement depth, 2) the magmas and country rock composition, 3) the country rock thermal conductivity, 4) the rate of magma injection and 5) the geometry of the intrusion. In shallow level plutons, where magmas solidify quickly, evi¬dence for magma mixing and/or differentiation processes is considered by many authors to be inherited from deeper levels. This work shows however that in-situ differentiation and magma interactions occurred within basaltic and felsic sills at shallow depth (0.3 GPa) in the St-Jean-du-Doigt (SJDD) bimodal intrusion, France. This intrusion emplaced ca. 347 Ma ago (IDTIMS U/Pb on zircon) in the Precambrian crust of the Armori- can massif and preserves remarkable sill-like emplacement processes of bimodal mafic-felsic magmas. Field evidence coupled to high precision zircon U-Pb dating document progressive thermal maturation within the incrementally built ioppolith. Early m-thick mafic sills (eastern part) form the roof of the intrusion and are homogeneous and fine-grained with planar contacts with neighboring felsic sills; within a minimal 0.8 Ma time span, the system gets warmer (western part). Sills are emplaced by under-accretion under the old east¬ern part, interact and mingle. A striking feature of this younger, warmer part is in-situ differentiation of the mafic sills in the top 40 cm of the layer, which suggests liquids survival in the shallow crust. Rheological and thermal models were performed in order to determine the parameters required to allow this observed in- situ differentiation-accumulation processes. Strong constraints such as total emplacement durations (ca. 0.8 Ma, TIMS date) and pluton thickness (1.5 Km, gravity model) allow a quantitative estimation of the various parameters required (injection rates, incubation time,...). The results show that in-situ differentiation may be achieved in less than 10 years at such shallow depth, provided that: (1) The differentiating sills are injected beneath consolidated, yet still warm basalt sills, which act as low conductive insulating screens (eastern part formation in the SJDD intrusion). The latter are emplaced in a very short time (800 years) at high injection rate (0.5 m/y) in order to create a "hot zone" in the shallow crust (incubation time). This implies that nearly 1/3 of the pluton (400m) is emplaced by a subsequent and sustained magmatic activity occurring on a short time scale at the very beginning of the system. (2) Once incubation time is achieved, the calculations show that a small hot zone is created at the base of the sill pile, where new injections stay above their solidus T°C and may interact and differentiate. Extraction of differentiated residual liquids might eventually take place and mix with newly injected magma as documented in active syn-emplacement shear-zones within the "warm" part of the pluton. (3) Finally, the model show that in order to maintain a permanent hot zone at shallow level, injection rate must be of 0.03 m/y with injection of 5m thick basaltic sills eveiy 130yr, imply¬ing formation of a 15 km thick pluton. As this thickness is in contradiction with the one calculated for SJDD (1.5 Km) and exceed much the average thickness observed for many shallow level plutons, I infer that there is no permanent hot zone (or magma chambers) at such shallow level. I rather propose formation of small, ephemeral (10-15yr) reservoirs, which represent only small portions of the final size of the pluton. Thermal calculations show that, in the case of SJDD, 5m thick basaltic sills emplaced every 1500 y, allow formation of such ephemeral reservoirs. The latter are formed by several sills, which are in a mushy state and may interact and differentiate during a short time.The mineralogical, chemical and isotopic data presented in this study suggest a signature intermediate be¬tween E-MORB- and arc-like for the SJDD mafic sills and feeder dykes. The mantle source involved produced hydrated magmas and may be astenosphere modified by "arc-type" components, probably related to a sub¬ducting slab. Combined fluid mobile/immobile trace elements and Sr-Nd isotopes suggest that such subduc¬tion components are mainly fluids derived from altered oceanic crust with minor effect from the subducted sediments. Close match between the SJDD compositions and BABB may point to a continental back-arc setting with little crustal contamination. If so, the SjDD intrusion is a major witness of an extensional tectonic regime during the Early-Carboniferous, linked to the subduction of the Rheno-Hercynian Ocean beneath the Variscan terranes. Also of interest is the unusual association of cogenetic (same isotopic compositions) K-feldspar A- type granite and albite-granite. A-type granites may form by magma mixing between the mafic magma and crustal melts. Alternatively, they might derive from the melting of a biotite-bearing quartz-feldspathic crustal protolith triggered by early mafic injections at low crustal levels. Albite-granite may form by plagioclase cu¬mulate remelting issued from A-type magma differentiation.

Carbon-isotope stratigraphy of the Liesberg Beds Member (Oxfordian, Swiss Jura) using echinoids and crinoids

The Liesberg Beds form the transition between the lower Oxfordian dark coloured marls (Renggeri Member and the Terrain a Chailles Member) and the middle Oxfordian reefal limestones (St-Ursanne Formation). Both lithofacies and biofacies are diverse and evolve rapidly up-section. Stable isotope studies of whole-rock samples are therefore excluded. In search for a convenient isotopic marker, we measured carbon isotope compositions of several fossil groups and chose crinoid stems of Millericrinus spp and echinoid spines of Paracidaris spp because of their abundance throughout the section and the small variations of delta(13)C within one fossil and between fossils from the same stratigraphic level. The delta(13)C values of echinoderms largely reflect earliest diagenetic conditions at the seawatersediment interface. The porous stereome structure secreted of high Mg-calcite by echinoderms has a high reactive surface/volume ratio, which triggers the precipitation of very early syntaxial cements. In the four studied sections reproducible carbon isotope shifts were observed both for Millericrinus spp stems and Paracidaris spp spines. A negative delta(13)C shift of 1-1.5 parts per thousand was observed near the base of the section, just above the transition from Terrain a Chailles Member, where the first corals occur. In the middle and upper part of the four sections, characterised by a stepwise increase of corals and the macrofossils, a positive delta(13)C Shift of about 2 parts per thousand was observed. Despite the highly variable lithologic composition of the Liesberg Beds;Member, carbon isotope shifts seem to be consistent and warrant an interpretation as an original signal, controlled by the isotopic composition of dissolved carbonic acid in seawater. We explain the heavy delta(13)C values (approximate to 2-2.3 parts per thousand) in the lower Liesberg Beds as a transition from an oxygen-limited environment (Terrain a Chailles Member) to the Liesberg Beds Member. The lowest delta(13)C values (approximate to 1-1.5 parts per thousand) correspond to a large input of dissolved nutrients to the platform under oxidizing conditions. The ensuing positive shift (between 2.5 and 3.5 parts per thousand), however, seems to correspond to a general trend of opening up of the platform and connection to open marine waters. Positive delta(13)C values in the upper Liesberg Beds is interpreted as a result of important accelareted extraction of organic carbon from the ocean reservoir, that occurred possibly during periods of warm and humid climate.

Fibre-reinforced composites as root canal posts

Fibre-reinforced composite (FRC) root canal posts are suggested to have biomechanical benefits over traditional metallic posts, but they lack good adhesion to resin composites. The aim of this series of studies was to evaluate the adhesion of individually formed fibre-reinforced composite material to composite resin and dentin, as well as some mechanical properties. Flexural properties were evaluated and compared between individually formed FRC post material and different prefabricated posts. The depth of polymerization of the individually formed FRC post material was evaluated with IR spectrophotometry and microhardness measurements, and compared to that of resin without fibres. Bonding properties of the individually formed FRC post to resin cements and dentin were tested using Pull-out- and Push-out-force tests, evaluated with scanning electron microscopy, and compared to those of prefabricated FRC and metal posts. Load-bearing capacity and microstrain were evaluated and failure mode assessment was made on incisors restored with individually formed FRC posts of different structures and prefabricated posts. The results of these studies show that the individually polymerized and formed FRC post material had higher flexural properties compared to the commercial prefabricated FRC posts. The individually polymerized FRC material showed almost the same degree of conversion after light polymerization as monomer resin without fibres. Moreover, it was found that the individually formed FRC post material with a semiinterpenetrating polymer network (IPN) polymer matrix bonded better to composite resin luting cement, than did the prefabricated posts with a cross-linked polymer matrix. Furthermore, it was found that, contrary to the other posts, there were no adhesive failures between the individually formed FRC posts and composite resin luting cement. This suggests better interfacial adhesion of cements to these posts. Although no differences in load-bearing capacity or microstrain could be seen, the incisors restored with individually formed FRC posts with a hollow structure showed more favourable failures compared to other prefabricated posts. These studies suggest that it is possible to use individually formed FRC material with semi-IPN polymer matrix as root canal post material. They also indicate that there are benefits especially regarding the bonding properties to composite resin and dentin with this material compared to prefabricated FRC post material with a cross-linked matrix. Furthermore, clinically more repairable failures were found with this material compared to those of prefabricated posts.

Diagenetic processes in a partially dolomitized carbonate reservoir: Casablanca oil field, Valencia Trough, offshore Spain.

Mesozoic and Neogene carbonates located in the Valencia Trough (offshore Spain, western Mediterranean Sea)are oil reservoirs. This paper investigates the diagenetic evolution of the Upper Jurassic limestones, currently dolomitized, that constitute the main reservoir of the Casablanca oil field. Core samples from Casablanca-1A well have been studied to determine the diagenetic products and their relation with porosity evolution, and to reconstruct the fluid flow history prior to and during oil emplacement. On the basis of petrological observations and geochemical analyses (major, minor and trace element composition and oxygen, carbon and strontium isotope composition), a major dolomitization event is recognized postdating subaerial exposure, erosion and karstification. The dolomitization event originated two replacive dolomites (RD1 and RD2) and two dolomite cements (saddle dolomite cement, SDC, and milky-white dolomite cement, MDC)which are partially cogenetic. RD1, RD2 and SDC precipitated at increasing temperatures (over 60ºC and below 110ºC), probably from meteoric water mixed with marine water. The last dolomite type milky-white dolomite cement) precipitated with increasing burial conditions and by arrival of hydrothermal fluids during the Miocene. The post-dolomitization sequence comprises precipitation of calcite cement and partial calcitization of all previous dolomites. The oxygen, carbon and strontium isotope compositions suggest that this calcite cementation occurred from meteoric waters mixed with Burdigalian - Langhian marine waters trapped in the sediments and expelled by compaction in the moderate to deep burial realm. Normal faults were the conduits for upward migration of these fluids as well as for later oil expulsion from the Burdigalian - Langhian source rocks. Late corrosion associated with organic acid-enriched fluids took place prior or simultaneously to oil migration during the Pliocene, enhancing porosity and increasing eservoir quality.

Kaivosteollisuudessa syntyvän kipsin hyödyntäminen

Diplomityön tarkoituksena oli tutkia ja kehittää käyttökohde kaivosteollisuudessa syntyvälle märälle kipsisivuvirralle, joka sisältää metalliepäpuhtauksina alumiinia, rautaa ja mangaania ja jonka määrä on noin 1 000 000 t/a. Kirjallisuuden pohjalta tutkittiin aluksi mahdollisuutta hyödyntää kipsiaines asfaltti- ja sementtiteollisuuden raaka-aineena. Sementin joukkoon lisätään tavallisesti noin 5 p-% kipsiä, mutta harvinaisimpiin sementtilaatuihin sitä voidaan lisätä jopa 30 p-%. Tästä huolimatta vain pieni osa tutkimuksen kohteessa syntyvästä kipsisivuvirrasta voitaisiin hyödyntää tässä sovelluksessa. Lisäksi kipsisivuvirran sisältämät epäpuhtaudet täytyisi poistaa tai saattaa inaktiiviseen muotoon. Myöskään sen kosteuspitoisuus ei saisi olla suuri. Näin ollen tämän kipsisivuvirran hyödyntäminen asfaltti- ja sementtiteollisuuden lisäaineena ei ole mahdollista Seuraavaksi harkittiin kipsin kierrättämistä, jolloin yhtenä vaihtoehtona oli hajottaa kipsi termisesti rikkioksideiksi ja valmistaa niistä rikkihappoa. Taloudellisista syistä hajoamistuotteen on oltava rikkitrioksidia, josta voitaisiin veteen imeyttämällä valmistaa rikkihappoa. Kipsin hajottaminen termovaa´alla osoitti, että kipsi vaatii noin 1400 ºC:n lämpötilan ja haihtuvat komponentit ovat H2O, SO ja SO2, muttei SO3. Alempien oksidien muuttaminen rikkihapoksi vaatisi katalyyttisen hapetuksen, mikä olisi käytännössä liian kallista. Toisena vaihtoehtona kipsin kierrättämiseksi tutkittiin sen biologista pelkistämistä rikkivedyksi ja kalsiumhydroksidilietteeksi. Laboratoriossa Ca(OH)2-lietteestä valmistettiin hiilidioksidin avulla kalsiumkarbonaattia, jolloin päästiin 90 %:n kalsiumhydroksidin konversiossa. Lisäksi alumiinihydroksidi saatiin erotettua kipsilietteestä kokeellisesti hydrosyklonin avulla. Diplomityössä päädyttiin siihen, että sulfaatin biologinen pelkistäminen ja alumiinihydroksidin mekaaninen erotus jatkuvatoimisesti on varteenotettava vaihtoehto kipsisivuvirran hyödyntämiseksi.

Intercalação Eletroquímica de Cátions Hexilamínio na Matriz Lamelar 1T-TiS2

The electrochemical synthesis of a ternary compound obtained by the intercalation of hydrated hexilaminium cations into the layered compound 1T-TiS2 is reported. Two different compounds were detected by cyclovoltammetry and studied by X-ray diffractometry. Models showing the steric arrangement of the hydrated hexilaminium cations into the Van der Waals gaps were proposed.

Troca iônica no estado sólido de európio3+ em zeólita Y: influência do tempo de reação

Rare earth elements supported in zeolites are the most important catalysts in the fluid cracking of petroleum. The solid state ion exchange of Eu3+ in Y zeolite was investigated. First of all, the hydrated EuCl3 was well mixed in a ball mill and was then heated at 300ºC for different times. The quantitative determination of Eu3+ showed that the degree of ion exchange depends on the reaction time at constant temperature, being ~95% in 4 h. The X-ray study showed that the crystallinity of the zeolite is little affected by the exchange procedure. The study of spectroscopic properties of Eu3+, emission spectra and lifetime, give information about the migration and position of the ion in the zeolite cages.

Fontes, reatividade e quantificação de metanol e etanol na atmosfera

In the last two decades, the use of oxygenated fuels, like methanol and ethanol, pure or in mixture with gasoline, has been growing due to benefits introduced into the air quality. In Brasil, the fraction of light duty vehicles powered by pure hydrated ethanol is estimated at about 4 million, while the remaining vehicles actually utilize a mixture (22:78 v/v) of ethanol:gasoline. As a consequence, there's a need for the availability of methods that can provide the evaluation of possible impacts of alcohol emissions in the formation of chemical species in the atmosphere, as ozone, aldehydes, carboxylic acids and so on. In this paper, methanol and ethanol are discussed in their general aspects, as well as their atmospheric sources, chemical reactivity and available methods of analysis.

Preparation and thermal decomposition of copper(II), zinc(II) and cadmium(II) chelates with 8-hydroxyquinoline

When the compounds are heated in an inert atmosphere it can be verified the consecutive partial sublimation, fusion, partial volatilization and partial thermal decomposition of the anhydrous complexes. When in an oxidating atmosphere the above process is only verified to Cu(II) chelates. Anhydrous copper(II) complexes present a monoclinic structure in the b form and the volatilized compound in a a form. Zinc(II) and cadmium(II) hydrated complexes are isomorphous and they present different cell dimensions from those reported previously.

Esfoliação e hidratação da caulinita após intercalação com uréia

Well-ordered Georgia kaolinite (Kga-1b) obtained from the source Clay Repository of the Clay Minerals Society (USA) was intercalated with urea using grinding procedures. To achieve complete intercalation 20% of urea (in weight) was used, producing Al2Si2O5(OH)4 (N2H4CO)0,86 with an interplanar basal spacing of 1,08nm. After washing with water under ultrasound stirring at 363K, urea was completely removed and kaolinite was partially exfoliated. After drying under air, the material was converted to hydrated kaolinite with the composition Al2Si2O5(OH)4 (H2O)0,64 and an interplanar basal spacing of 0,84nm. In this compound, water molecules positioned between the layers of the silicate can be removed after calcination at 573K, regenerating structurally disordered kaolinite.