Utilizing Fly Ash Cenosphere and Aerogel for Lightweight Thermal Insulating Cement-Based Composites

Thermal insulating composites help to reduce the total power consumption in a building by creating a barrier between external and internal environment. Such composites can be used in the roofing tiles or wall panels for exterior surfaces. This study purposes to develop lightweight cement-based composites for thermal insulating applications. Waste materials like silica fume (an industrial by-product) and fly ash cenosphere (FAC) (hollow micro-spherical shells obtained as a waste residue from coal fired power plants) were used as partial replacement of cement and lightweight filler, respectively. Moreover, aerogel, a nano-porous material made of silica, was also used in different dosages for improved thermal insulating behavior, while poly vinyl alcohol (PVA) fibers were added for enhanced toughness. The raw materials including binders and fillers were characterized by X-Ray Diffraction (XRD), X-Ray Fluorescence spectroscopy (XRF), and Brunauer–Emmett–Teller (BET) analysis techniques in which various physical and chemical properties of the raw materials were evaluated like specific surface area, chemical composition (oxide form), and pore size distribution (if any). Ultra-lightweight cementitious composites were developed by varying the amounts of FAC and aerogel with 28-day unit weight ranging from 1551.28 kg/m3 to 1027.85 kg/m3. Excellent mechanical and thermal insulating properties of the resulting composites were obtained ranging from 53.62 MPa to 8.66 MPa compressive strength, 9.77 MPa to 3.98 MPa flexural strength, and 0.3025 W/m-K to 0.2009 W/m-K as thermal conductivity coefficient (QTM-500). The composites were also tested for peak temperature difference between outer and inner surfaces when subjected to heating (in a specially designed experimental set-up) by a 275W infrared lamp. The temperature difference up to 16.78 oC was achieved, which indicated outstanding properties of the developed composites to act as a thermal barrier for building envelopes. Microstructural studies were carried out by Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDS) for characterizing the inner structure of the composite specimen. Also, the hydration products were quantified using the surface area mapping and line scale technique in EDS. The microstructural analyses indicated excellent bonding of FAC and aerogel in the cementitious system. Also, selective reactivity of FAC was ascertained from the SEM imagery where the partially consumed FAC shells were observed. All in all, the lightweight fillers, FAC, and aerogel helped to produce the lightweight composites due to their physical characteristics, while exceptional mechanical properties, owing to FAC partial reactivity, were achieved.

Characterization and Geochemical Modeling of Cu and Zn Sorption Using Mixed Mineral Systems Injected with Iron Sulfide under Sulfidic-Anoxic Conditions I: Case Study of Cwmheidol Mine Waste Water, Wales, United Kingdom

This study investigates sorption of Cu and Zn contained in natural mine wastewater, using mixed mineral systems in sulfidic-anoxic condition. The mine wastewater was obtained from disused mine workings at Cwmheidol in Wales, United Kingdom. These contaminants flow into water courses. These water courses include River Rheidol. In this River fishing activities exist. In an attempt to reduce Cu-Zn levels of fish intake in the watercourses, single mineral systems and 1:1 mixed mineral systems of clay and goethite were tested with the mine waste water for copper and zinc removal at variable pH. Modelling of hydroxyl complexes was carried out using phreeqc method. Reactions using batch mode technique was conducted at room temperature. There was significant differences in the behaviour of copper and zinc removal using mixed mineral systems when compared  to single mineral systems. All mixed mineral systems sorb more Cu than Zn when tested with mine wastewater.

Solar Photocatalysis of Methyl Orange Using Multi-Ion Doped TiO2 Catalysts

Solar-light activated titanium dioxide photocatalysts were prepared by hydrolysis of titanium (IV) isopropoxide with thiourea, followed by calcinations at 450 °C. The experiments demonstrated that methyl orange in aqueous solutions were successfully degraded under solar light using doped TiO2. The photocatalytic oxidation of a mono azo methyl-orange dye has been investigated in multi ion doped TiO2 and solar light. Solutions were irradiated by solar-light until high removal was achieved. It was found that there was no degradation of methyl orange in the dark and in the absence of TiO2. Varieties of laboratory prepared TiO2 catalysts both un-doped and doped using titanium (IV) isopropoxide and thiourea as a dopant were tested in order to compare their photoreactivity. As a result, it was found that the efficiency of the process strongly depends on the working conditions. The highest degradation rate of methyl orange was obtained at optimum dosage using commercially produced TiO2. Our work focused on laboratory synthesized catalyst and the maximum methyl orange removal was achieved at 81% with catalyst loading of 0.04 g/L, initial pH of 3 and methyl orange concentration of 0.005 g/L using multi-ion doped catalyst. The kinetics of photocatalytic methyl orange dye stuff degradation was found to follow a pseudo-first-order rate law. The presence of the multi-ion dopant (thiourea) enhanced the photoefficiency of the titanium dioxide catalyst.

Degradation of Amitriptyline Hydrochloride, Methyl Salicylate and 2-Phenoxyethanol in Water Systems by the Combination UV/Cl2

Three emerging contaminants (amitriptyline hydrochloride, methyl salicylate and 2-phenoxyethanol) frequently found in waste-waters were selected to be individually degraded in ultra-pure water by the combined advanced oxidation process constituted by UV radiation and chlorine. The influence of pH, initial chlorine concentration and nature of the contaminants was firstly explored. The trend for the reactivity of the selected compounds was deduced: amitriptyline hydrochloride > methyl salicylate > 2-phenoxyethanol. A later kinetic study was carried out and focused on the specific evaluation of the first-order rate constants and the determination of the partial contribution to the global reaction of the direct photochemical pathway and the radical pathway. A comparison between the rate constant values among photochemical experiments without and with the presence of Cl2 reveals a clear increase in the oxidation efficiency of the combined process with respect to the photochemical reaction alone. In a second stage, the simultaneous oxidation of mixtures of the selected contaminants in several types of water (ultrapure water, surface water from a reservoir, and two secondary effluents) was also performed by the same combination UV/Cl2 under more realistic operating conditions. The efficiency of this combined system UV/Cl2 was compared to other oxidants such as the UV/S2O82- and UV/H2O2 AOPs. Results confirmed that the UV/Cl2 system provides higher elimination efficiencies among the AOPs tested.

Co-Disposal of Coal Ash with Mine Tailings in Surface Paste Disposal Practices: A Gold Mining Case Study

The present paper describes the study of paste tailings prepared in laboratory using gold tailings, produced in a Finnish gold mine with the incorporation of coal ash. Natural leaching tests were conducted with the original materials (tailings, fly and bottom ashes) and also with paste mixtures that were prepared with different percentages of tailings and ashes. After leaching, the solid wastes were physically and chemically characterized and the results were compared to those selected as blank – the unleached samples. The tailings and the coal ash, as well as the prepared mixtures, were characterized, in addition to the textural parameters, by the following measurements: grain size distribution, chemical composition and pH. Mixtures were also tested in order to characterize their mechanical behavior by measuring the flexural strength, the compressive strength and the consistency. The original tailing samples presented an alkaline pH because during their processing they were previously submitted to pressure oxidation with destruction of the sulfides. Therefore, it was not possible to ascertain the effect of the coal ashes in the acid mine drainage. However, it was possible to verify that the paste reactivity was affected mostly by the bottom ash and that the tailings blended with bottom ash present lower mechanical strength than when blended with a combination of fly and bottom ash. Surface paste disposal offer an attractive alternative to traditional methods in addition to the environmental benefits of incorporating large-volume wastes (e.g. bottom ash). However, a comprehensive characterization of the paste mixtures is crucial to optimize paste design in order to enhance engineer and environmental properties.

Alkali Silica Reaction Mitigation and Prevention Measures for Arkansas Local Aggregates

The objective of this research is to mitigate and prevent the alkali silica reactivity (ASR) in highway construction projects. ASR is a deleterious reaction initiated when the silica content of the aggregate reacts with alkali hydroxides in cement in the presence of relatively high moisture content. The ASR results in the formation of an expansive white colored gel-like material which forms the destructive tensile stresses inside hardened concrete. In this research, different types of local aggregates available in the State of Arkansas were mixed and mortar bars were poured according to the ASTM specifications. Mortar bars expansion was measured versus time and aggregates with potential ASR problems were detected. Different types of supplementary cementitious materials (SCMs) were used in remixing mortar bars with highly reactive aggregates. Length changes for remixed bars proved that different types of SCMs can be successfully used in reducing the expansive effect of ASR. SCMs percentage by weight is highly dependent on the SCM type. The result of this study will help avoiding future losses due to ASR cracking in construction project and reduce the maintenance, repair, and replacement budgets required for highways network.

Non-Methane Hydrocarbons Emission during the Photocopying Process

Prosperity of electronic equipment in photocopying environment not only has improved work efficiency, but also has changed indoor air quality. Considering the number of photocopying employed, indoor air quality might be worse than in general office environments. Determining the contribution from any type of equipment to indoor air pollution is a complex matter. Non-methane hydrocarbons are known to have an important role on air quality due to their high reactivity. The presence of hazardous pollutants in indoor air has been detected in one photocopying shop in Novi Sad, Serbia. Air samples were collected and analyzed for five days, during 8-hr working time in three time intervals, whereas three different sampling points were determined. Using multiple linear regression model and software package STATISTICA 10 the concentrations of occupational hazards and microclimates parameters were mutually correlated. Based on the obtained multiple coefficients of determination (0.3751, 0.2389 and 0.1975), a weak positive correlation between the observed variables was determined. Small values of parameter F indicated that there was no statistically significant difference between the concentration levels of nonmethane hydrocarbons and microclimates parameters. The results showed that variable could be presented by the general regression model: y = b0 + b1xi1+ b2xi2. Obtained regression equations allow to measure the quantitative agreement between the variables and thus obtain more accurate knowledge of their mutual relations.

Effect of Fly Ash Fineness on Sorption Properties of Geopolymers Based On Liquid Glass

Fly ash (FA) thanks to the significant presence of SiO2 and Al2O3 as the main components is a potential raw material for geopolymers production. Mechanical activation is a method for improving FA reactivity and also the porosity of final mixture; those parameters can be analysed through sorption properties. They have direct impact on the durability of fly ash based geopolymer mortars. In the paper, effect of FA fineness on sorption properties of geopolymers based on sodium silicate, as well as relationship between fly ash fineness and apparent density, compressive and flexural strength of geopolymers are presented. The best results in the evaluated area reached the sample H1, which contents the highest portion of particle under 20μm (100% of GFA). The interdependence of individual tested properties was confirmed for geopolymer mixtures corresponding to those in the cement based mixtures: higher is portion of fine particles < 20μm, higher is strength, density and lower are sorption properties. The compressive strength as well as sorption parameters of the geopolymer can be reasonably controlled by grinding process and also ensured by the higher share of fine particle (to 20μm) in total mass of the material.

Properties of Cement Pastes with Different Particle Size Fractions of Metakaolin

Properties of Portland cement mixtures with various fractions of metakaolin were studied. 10% of Portland cement CEM I 42.5 R was replaced by different fractions of high reactivity metakaolin with defined chemical and mineralogical properties. Various fractions of metakaolin were prepared by jet mill classifying system. There is a clear trend between fineness of metakaolin and hydration heat development. Due to metakaolin presence in mixtures the compressive strength development of mortars is rather slower for coarser fractions but 28-day flexural strengths are improved for all fractions of metakaoline used in mixtures compared to reference sample of pure Portland cement. Yield point, plastic viscosity and adhesion of fresh pastes are considerably influenced by fineness of metakaolin used in cement pastes.

Kinetic Rate Comparison of Methane Catalytic Combustion of Palladium Catalysts Impregnated onto γ-Alumina and Bio-Char

Catalytic combustion of methane is imperative due to stability of methane at low temperature. Methane (CH4), therefore, remains unconverted in vehicle exhausts thereby causing greenhouse gas GHG emission problem. In this study, heterogeneous catalysts of palladium with bio-char (2 wt% Pd/Bc) and Al2O3 (2wt% Pd/ Al2O3) supports were prepared by incipient wetness impregnation and then subsequently tested for catalytic combustion of CH4. Support-porous heterogeneous catalytic combustion (HCC) material were selected based on factors such as surface area, porosity, thermal stability, thermal conductivity, reactivity with reactants or products, chemical stability, catalytic activity, and catalyst life. Sustainable and renewable support-material of bio-mass char derived from palm shell waste material was compared with those from the conventional support-porous materials. Kinetic rate of reaction was determined for combustion of methane on Palladium (Pd) based catalyst with Al2O3 support and bio-char (Bc). Material characterization was done using TGA, SEM, and BET surface area. The performance test was accomplished using tubular quartz reactor with gas mixture ratio of 3% methane and 97% air. The methane porous-HCC conversion was carried out using online gas analyzer connected to the reactor that performed porous-HCC. BET surface area for prepared 2 wt% Pd/Bc is smaller than prepared 2wt% Pd/ Al2O3 due to its low porosity between particles. The order of catalyst activity based on kinetic rate on reaction of catalysts in low temperature was 2wt% Pd/Bc>calcined 2wt% Pd/ Al2O3> 2wt% Pd/ Al2O3>calcined 2wt% Pd/Bc. Hence agro waste material can successfully be utilized as an inexpensive catalyst support material for enhanced CH4 catalytic combustion.

Investigation of Minor Actinide-Contained Thorium Fuel Impacts on CANDU-Type Reactor Neutronics Using Computational Method

Currently, thorium fuel has been especially noticed because of its proliferation resistance than long half-life alpha emitter minor actinides, breeding capability in fast and thermal neutron flux and mono-isotopic naturally abundant. In recent years, efficiency of minor actinide burning up in PWRs has been investigated. Hence, a minor actinide-contained thorium based fuel matrix can confront both proliferation resistance and nuclear waste depletion aims. In the present work, minor actinide depletion rate in a CANDU-type nuclear core modeled using MCNP code has been investigated. The obtained effects of minor actinide load as mixture of thorium fuel matrix on the core neutronics has been studied with comparing presence and non-presence of minor actinide component in the fuel matrix. Depletion rate of minor actinides in the MA-contained fuel has been calculated using different power loads. According to the obtained computational data, minor actinide loading in the modeled core results in more negative reactivity coefficients. The MA-contained fuel achieves less radial peaking factor in the modeled core. The obtained computational results showed 140 kg of 464 kg initial load of minor actinide has been depleted in during a 6-year burn up in 10 MW power.

Efficient Compact Micro DBD Plasma Reactor for Ozone Generation for Industrial Application in Liquid and Gas Phase Systems

Ozone is well known as a powerful, fast reacting oxidant. Ozone based processes produce no by-product residual as non-reacted ozone decomposes to molecular oxygen. Therefore an application of ozone is widely accepted as one of the main approaches for a Sustainable and Clean Technologies development. There are number of technologies which require ozone to be delivered to specific points of a production network or reactors construction. Due to space constraints, high reactivity and short life time of ozone the use of ozone generators even of a bench top scale is practically limited. This requires development of mini/micro scale ozone generator which can be directly incorporated into production units. Our report presents a feasibility study of a new micro scale rector for ozone generation (MROG). Data on MROG calibration and indigo decomposition at different operation conditions are presented. At selected operation conditions with residence time of 0.25 s the process of ozone generation is not limited by reaction rate and the amount of ozone produced is a function of power applied. It was shown that the MROG is capable to produce ozone at voltage level starting from 3.5kV with ozone concentration of 5.28*10-6 (mol/L) at 5kV. This is in line with data presented on numerical investigation for a MROG. It was shown that in compare to a conventional ozone generator, MROG has lower power consumption at low voltages and atmospheric pressure. The MROG construction makes it applicable for both submerged and dry systems. With a robust compact design MROG can be used as an integrated module for production lines of high complexity.

Effect of pH and Ionic Exchange on the Reactivity of Bioglass/Chitosan Composites Used as a Bone Graft Substitute

Chitosan (CH) material reinforced by bioactive glass (46S6) was fabricated. 46S6 containing 17% wt% CH was studied in vitro and in vivo. Physicochemical techniques, such as Fourier transform infrared spectroscopy (FT-IR), coupled plasma optical emission spectrometry (ICP-OES) analysis were used. The behavior of 46S6CH17 was studied by measuring the in situ pH in a SBF solution. The 46S6CH17 was implanted in the rat femoral condyl. In vitro 46S6CH17 gave an FTIR - spectrum in which three absorption bands with the maxima at 565, 603 and 1039cm-1 after 3 days of soaking in physiological solution. They are assigned to stretching vibrations of PO4^3- group in phosphate crystalline. Moreover, the pH measurement was decreased in the SBF solution. The stability of the calcium phosphate precipitation depended on the pH value. In vivo, a rise in the Ca and phosphate P ions concentrations in the implanted microenvironment was determined.

The Effect of Saturates on Rheological and Aging Characteristics of Bitumen

According to Rostler method (ASTM D 2006), saturates content of bitumen is determined based on its reactivity to sulphuric acid. While Corbett method (ASTM D 4124) based on its polarity level. This paper presents results from the study on the effect of saturates content determined by two different fractionation methods on the rheological and aging characteristics of bitumen. The result indicated that the increment of saturates content tended to reduce all the rheological characteristics concerned. Bitumen became less elastic, less viscous, and less resistant to plastic deformation, but became more resistant to fatigue cracking. After short and long term aging process, the treatment effect coefficients of saturates decreased, saturates became thicker due to aging process. This study concludes that saturates is not really stable or reactive in aging process. Therefore, the reactivity of saturates should be considered in bitumen aging index

The MUST ADS Concept

The presented work is motivated by a French law regarding nuclear waste management. A new conceptual Accelerator Driven System (ADS) designed for the Minor Actinides (MA) transmutation has been assessed by numerical simulation. The MUltiple Spallation Target (MUST) ADS combines high thermal power (up to 1.4 GWth) and high specific power. A 30 mA and 1 GeV proton beam is divided into three secondary beams transmitted on three liquid lead-bismuth spallation targets. Neutron and thermalhydraulic simulations have been performed with the code MURE, based on the Monte-Carlo transport code MCNPX. A methodology has been developed to define characteristic of the MUST ADS concept according to a specific transmutation scenario. The reference scenario is based on a MA flux (neptunium, americium and curium) providing from European Fast Reactor (EPR) and a plutonium multireprocessing strategy is accounted for. The MUST ADS reference concept is a sodium cooled fast reactor. The MA fuel at equilibrium is mixed with MgO inert matrix to limit the core reactivity and improve the fuel thermal conductivity. The fuel is irradiated over five years. Five years of cooling and two years for the fuel fabrication are taken into account. The MUST ADS reference concept burns about 50% of the initial MA inventory during a complete cycle. In term of mass, up to 570 kg/year are transmuted in one concept. The methodology to design the MUST ADS and to calculate fuel composition at equilibrium is precisely described in the paper. A detailed fuel evolution analysis is performed and the reference scenario is compared to a scenario where only americium transmutation is performed.

Neutronic Study of Two Reactor Cores Cooled with Light and Heavy Water Using Computation Method

Most HWRs currently use natural uranium fuel. Using enriched uranium fuel results in a significant improvement in fuel cycle costs and uranium utilization. On the other hand, reactivity changes of HWRs over the full range of operating conditions from cold shutdown to full power are small. This reduces the required reactivity worth of control devices and minimizes local flux distribution perturbations, minimizing potential problems due to transient local overheating of fuel. Analyzing heavy water effectiveness on neutronic parameters such as enrichment requirements, peaking factor and reactivity is important and should pay attention as primary concepts of a HWR core designing. Two nuclear nuclear reactors of CANDU-type and hexagonal-type reactor cores of 33 fuel assemblies and 19 assemblies in 1.04 P/D have been respectively simulated using MCNP-4C code. Using heavy water and light water as moderator have been compared for achieving less reactivity insertion and enrichment requirements. Two fuel matrixes of (232Th/235U)O2 and (238/235U)O2 have been compared to achieve more economical and safe design. Heavy water not only decreased enrichment needs, but it concluded in negative reactivity insertions during moderator density variations. Thorium oxide fuel assemblies of 2.3% enrichment loaded into the core of heavy water moderator resulted in 0.751 fission to absorption ratio and peaking factor of 1.7 using. Heavy water not only provides negative reactivity insertion during temperature raises which changes moderator density but concluded in 2 to 10 kg reduction of enrichment requirements, depend on geometry type.

Investigation of the Synthesis of Alcohols Byproducts in Fischer-Tropsch Synthesis on Modified Fe-Cu Catalyst: Reactivity and Mechanism

The influence of copper promoters and reaction conditions on the formation of alcohols byproducts of a common Fischer-Tropsch synthesis used iron-based catalysts were investigated. A good compromise of 28%Cu/FeKLaSiO2 can lead to the optimization of an improved Fischer-Tropsch catalyst. The product distribution shifts towards hydrocarbons with increasing the reaction temperature, while pressure promotes the formation of alcohols. It was found that the production of either alcohols or hydrocarbons followed A-S-F distributions, and their α parameters were essentially different which indicated a competition in the growing chain between the two species. TPD after acetaldehyde adsorption gave strong evidence of the insertion of a C1 oxygen-containing species into an alkyl chain.

Comparing Spontaneous Hydrolysis Rates of Activated Models of DNA and RNA

This research project aims to investigate difference in relative rates concerning phosphoryl transfer relevant to biological catalysis of DNA and RNA in the pH-independent reactions. Activated Models of DNA and RNA for alkyl-aryl phosphate diesters (with 4-nitrophenyl as a good leaving group) have successfully been prepared to gather kinetic parameters. Eyring plots for the pH– independent hydrolysis of 1 and 2 were established at different temperatures in the range 100–160 °C. These measurements have been used to provide a better estimate for the difference in relative rates between the reactivity of DNA and RNA cleavage. Eyring plot gave an extrapolated rate of kH2O = 1 × 10-10 s -1 for 1 (RNA model) and 2 (DNA model) at 25°C. Comparing the reactivity of RNA model and DNA model shows that the difference in relative rates in the pH-independent reactions is surprisingly very similar at 25°. This allows us to obtain chemical insights into how biological catalysts such as enzymes may have evolved to perform their current functions.

Global and Local Structure of Supported Pd Catalysts

The supported Pd catalysts were analyzed by X-ray diffraction and X-ray absorption spectroscopy in order to determine their global and local structure. The average particle size of the supported Pd catalysts was determined by X-ray diffraction method. One of the main purposes of the present contribution is to focus on understanding the specific role of the Pd particle size determined by X-ray diffraction and that of the support oxide. Based on X-ray absorption fine structure spectroscopy analysis we consider that the whole local structure of the investigated samples are distorted concerning the atomic number but the distances between atoms are almost the same as for standard Pd sample. Due to the strong modifications of the Pd cluster local structure, the metal-support interface may influence the electronic properties of metal clusters and thus their reactivity for absorption of the reactant molecules.

Preparation and Characterization of MoO3/Al2O3 Catalyst for Oxidative Desulfurization of Diesel using H2O2: Effect of Drying Method and Mo Loading

The mesoporous MoO3/γ-Al2O3 catalyst was prepared by incipient wetness impregnation method aiming to investigate the effect of drying method and molybdenum content on the catalyst property and performance towards the oxidation of benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyle dibenzothiophene (4,6-DMDBT) with H2O2 for deep oxidative desulfurization of diesel fuel. The catalyst was characterized by XRD, BET, BJH and SEM method. The catalyst with 10wt.% and 15wt.% Mo content represent same optimum performance for DBT and 4,6-DMDBT removal, but a catalyst with 10wt.% Mo has higher efficiency than 15wt.% Mo for BT conversion. The SEM images show that use of rotary evaporator in drying step reaches a more homogenous impregnation. The oxidation reactivity of different sulfur compounds was studied which followed the order of DBT>4,6-DMDBT>>BT.