Tesi sul tema "Ash reaction"

Published Article
Fly Ash is a by-product at thermal power stations, also otherwise known as residues of fine particles that rise with flue gases. An industrial by-product may be inferior to the traditional materials used construction applications, but, the lower the cost of these inferior materials make it an attractive alternative if adequate performance can be achieved. The objective of this study is to evaluate the chemical and physical effectiveness of self-cementing fly ashes derived from thermal power stations for construction applications with combined standards. Using laboratory testing specimens, suitable types of Fly Ashes namely: Kendal Dump Ash, Durapozz and Pozzfill, were tested to the required standards to evaluate the potential properties. All three Fly Ashes have been classified as a Class F Fly Ash, which requires a cementing agent for reactions to take place and for early strength gains in the early stages of the reaction processes. The Fly Ashes conformed to the combination of standards and have shown that the proper reactions will take place and will continue over period of time. The use of fly ash is accepted worldwide due to saving in cement, consuming industrial waste and making durable materials, especially due to improvement in the quality fly ash products.

Philosophiae Doctor - PhD
The catalytic support materials used in the present study are zeolite HBEA and MCM-41. These high silica zeolites were synthesised from coal fly ash (CFA) waste via a novel approach that involved a fusion step, acid assisted silica extraction and removal of Al, Ca and Na from the silica by treatment with oxalic acid. The generated silica was converted to HBEA and MCM-41 via conventional hydrothermal treatment. The metal incorporation onto HBEA was done via two approaches namely; liquid phase ion exchange (LIE) and wet impregnation (WI) while the loading on MCM-41 was only done via WI since the material does not possess exchange sites. The metal solution precursors were AMD and Fe extracted from CFA (FeAsh) via acid leaching followed by pH regulation by concentrated NaOH. This is the first time these solutions were tested as possible metal precursors in catalyst synthesis.
2021-08-30

An investigation was undertaken to determine the gasification and combustion characteristics of chars derived from an inertinite-rich coal discard sample with a high ash content. Fundamental knowledge of the reaction rate kinetics for char conversion at reactions conditions used in fluidised bed gasification and combustion was obtained. For this purpose, characterisation of the parent coal and derived chars, reactivity determinations of the chars and detailed reaction rate modelling was undertaken. The characterisation performed consisted of standard coal analytical methods. petrographic techniques, CCSEM image analysis and a surface adsorption method. The parent coal consists of 32% by volume of inertinite, 7% of vitrinite, 13% of biand tri-macerite, 30% of maceral/mineral mixtures (carbominerite) with 18% of mineral-rich material. Reflectances obtained from measurements taken on vitrinites and total maceral reflectance scans increased dramatically on charring at 900°C and is accompanied by an extension of vitrinite-class distribution. Volatiles were liberated essentially from the original parent vitrinites, creating fine pores. Inertinites increased in reflectance but not in porosity and are characterised as dense char fractions in the final charred product, which was established according to a coal form analysis. Structural change due to low temperature thermal stress fracturing ("passive deflagration") occurred early on in the temperature regimes, creating increased surface areas and porosity. The chars consist of a high proportion (52%) of extraneous rock fragments together with minerals mainly as fine inclusions in carbon rich particles. The chars have very low porosities and surface areas created by devolatisation of maceral associations and deflagration. Combustion and gasification reactivity experiments were carried out in a thermogravimetric analyser at 87.5 and 287.5 kPa pressures between 700 and 900'C and with varying mixtures of oxygen/nitrogen and carbon dioxide/nitrogen mixtures respectively. The effects of temperature, pressure, gas composition and particle size on reactivity were found to confirm well-established trends. The effect of temperature in the high temperature range was, however, strongly affected by pore and film diffusion during combustion. Models based on the random pore model without and with pore diffusion incorporating the properties of the char (porosity. ash content, and derived structural parameter) and structural mechanisms concerning carbon removal, were successfully solved and validated against experimental results. As a result of the complexity of the models consisting of many unknown parameters, a procedure consisting of step-wise regression was developed and applied successfully. This procedure uses a unified carbon conversion versus a reduced time parameter plot with the latter defined as real time/time for 90% conversion. It was found that for char panicles with a mean diameter of 1mm prepared at 900°C. the random pore model (chemical reaction controlling) was applicable for predicting the gasification reaction rate with carbon dioxide-nitrogen mixtures at temperatures up to 9OO'C, whereas for the combustion reactions with oxygen-nitrogen mixtures an adapted chemical reaction-pore diffusion model was found to be applicable in the temperature range 450 to 600°C. The model is characterised by a variable Thiele modulus which can account for pore- diffusion and can undergo a transition to a chemically controlled reaction as a result of the depletion of carbon in the carbon/mineral matrix. Intrinsic reaction rate parameters for gasification and combustion are reported and compared with published results, and were Sound to be slightly different. Diffusion coefficients were also evaluated from the combustion reaction results and found to compare very well with predictions with the Knudsen diffusion model.
Thesis (Ph.D. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2007.

Thesis (MScAgric)--University of Stellenbosch, 2003.
ENGLISH ABSTRACT: Coal mining in South Africa is estimated to produce 200 Ml of acid mine drainage (AMD) per day in the Pretoria-Witwatersrand-Vereeniging (PWV) area alone, while electricity production resulted in approximately 27 Mt of ash in 2001. A large number of collieries in South Africa are tied to power stations where these two waste streams, acid mine drainage and fly ash, have the capacity to neutralize each other and provide an opportunity for co-disposal. The aim of this study was to investigate the reactions that occur during the co-disposal of fly ash leachate (FAL) and AMD and to examine the precipitates that result from the neutralisation reactions. Potentiometric titration was employed to investigate the neutralisation of Al-Fe salt solutions, simulating acid mine drainage (AMD), with alkaline solutions of Ca or Na hydroxide as well as fresh alkaline leachate from fly ash (FAL). The effectiveness of fly ash in removing metals and other salts from acid mine water was examined by analysing the neutralised water and modelling the results thermodynamically. Precipitates, prepared from large scale synthetic AMD and FAL co-disposal at various pH levels and Fe:Al ratios, were characterised according to composition, mineralogy and surface properties. The experimental neutralisation of synthetic acid mine drainage was achieved through titrating the components of SAMD (Fe and Al salt solutions) and solutions of various Fe:Al mole ratios with different bases in air and N2, and comparing the SAMD-FAL system with these simple acids and bases. The FAL used in all experiments was produced from fresh fly ash collected at Arnot power station. The SAMD was prepared as a solution with a pH of 2.5 and containing 12.7 mmol/L Al, 10.9 mmol/L Fe and 40.8 mmol/L SO4. The characterisation of reaction solids was achieved by collecting the precipitates formed from the co-disposal of FAL and SAMD with Fe:Al ratios of 7.3, 0.8 and 2.5. From the titration experiments it was found that upscale potentiometric titrations of SAMD show buffer zones at pH values of 3.5, 4, 6 and 10 corresponding to Fe(III)precipitation, Al precipitation, Fe(II) hydrolysis and oxidation, and Al redissolution, respectively, while downscale potentiometric titrations with SAMD show buffer zones at pH values 12 – 11, 9 and 4.5, which correspond to Fe oxidation and precipitation, Al precipitation and Al re-dissolution, respectively. A high concentration of Al in the simulated AMD inhibited the crystallinity of the precipitates and resulted in a large quantity of SO4 being removed from solution, which suggests that an aluminium sulphate phase is precipitating, but it is not crystalline and cannot be identified by XRD. Titrations performed up-scale by adding FAL to AMD showed near-complete metal and substantial SO4 removal from solution. The characterisation of reaction solids by x-ray diffraction, infrared spectroscopy, thermal gravimetric and differential thermal analysis revealed that the precipitates consist of poorly crystalline, highly Al-substituted goethite and ferrihydrite with large amounts of SO4 included in the structure. Poorly crystalline bayerite appears at a high pH and high Al concentration, and calcite is present in precipitates made by adding SAMD to FAL. High surface charges of between 330 cmolc/kg positive and 550 cmolc/kg negative charge and potentially large specific surface areas between 7 and 236 m2/g suggest a strong potential for the precipitates to function as low-grade adsorbents in wastewater treatment. The similarity of these ochre precipitates to soil minerals implies that land disposal of the neutralised solids is also viable.
AFRIKAANSE OPSOMMING: Steenkool mynbou in SA produseer na benaming 200 ML suur mynwater per dag in die PWV area alleenlik, terwyl opwekking van elektrisiteit naastenby 27 Mt vliegas geproduseer het in 2001. ’n Groot aantal steenkoolmyne in SA word verbind met kragsentrales, waar hierdie twee strome afval, suur mynwater en vliegas, die kapasiteit het om mekaar te neutraliseer en die weg te baan vir gesamentlike wegdoening. Die doel van hierdie studie was om die reaksies wat plaasvind gedurende gesamentlike wegdoening van vliegas loog (VAL) en suur mynwater (SMW) te ondersoek, asook die neerslae wat mag vorm as gevolg van neutralisasie reaksies. Potensiometriese titrasies was gebruik om die neutralisering tussen Al:Fe-sout oplossings te ondersoek as nabootsing van SMW met gebruikmaking van alkaliese oplossings van Ca of Na hidroksied asook vars loog van VA. Die effektiwiteit van VA om metale en soute uit SMW te verwyder was getoets deur outleding van die geneutraliseerde water en modellering van die termodinamika. Neerslae berei uit groot-skaal sintetiese SMW en VAL en met gelyktydige storting by verskeie pH vlakke en Fe:Al verhoudings, was gekarakteriseer volgens samestelling, mineralogie en oppervlak eienskappe. Die eksperimentele neutralisering van sintetiese suur mynwater (SSMW) was gedoen deur titrering van die SSMW komponente en oplossings van verskeie Fe:Al molêre verhoudings met verskillende basisse in lug en N2, en vergelyking van SSMW-VAL sisteem met hierdie eenvoudige sure en basisse. Die VAL gebruik in alle eksperimente was geproduseer van vliegas verkry van die Arnot kragsentrale. Die SSMW was berei as ’n oplossing met ’n pH van 2.5 en bevat 12.7 mmol/L Al, 10.9 mmol/L Fe en 40.8 mmol/L SO4. Die karakterisering van vastestowwe uit die reaksie was gedoen deur die bemonstering van neerslae gevorm as gevolg van die gelyktydige wegdoening van VAL en SSMW met Al:Fe verhoudings van 7.3, 0.8 en 2.5.Die was waargeneem in die titrasie eksperimente dat hoër-skaal potensiometriese titrasie van SSMW buffersones, by pH waardes 3.5, 4, 6 en 10, ooreenstem met Fe(III) presipitasie, Al presipitasie, Fe(II) hidrolise en oksidasie, en Al her oplossing, terwyl laer skaal potensiometriese titrasie met SSMW buffer sones by pH waardes 12 - 11, 9 en 4.5 ooreenstem met Fe(III) presipitasie en oksidasie, Al presipitasie en heroplossing respektiewelik. ’n Hoë konsentrasie Al in die sintetiese SMW het kristalliniteit van die neerslae geïnhibeer en veroorsaak dat ’n hoeveelheid SO4 uit oplossing verwyder is, wat suggereer dat die AlSO4 fase neerslaan maar nie kristallyn is en gevolglik nie opgetel word met x-straal diffraksie nie. Titrasies gedoen by hoërskaal deur byvoeging van VAL tot SSMW, het feitlik volledige metaal en SO4 verwydering uit oplossing getoon. Die karakterisering deur x-straal diffraksie, infrarooispektroskopie, termies gravimetries en differentiële termiese analise, het getoon dat die presipitate bestaan uit swak kristallyne, hoë Al-gesubstitueerde goethiet en ferrihidriet met groot hoeveelhede SO4 vasgevang in die struktuur. Swak kristallyne bayeriet verskyn by hoë pH en hoë Al-konsentrasies en kalsiet is teenwoordig in neerslae gevorm deur byvoeging van SSMW tot VAL. Hoë oppervlakladings van tussen 330 cmolc/kg positief en 550 cmolc/kg negatiewe lading en ook potensieel groot spesifieke oppervlak van tussen 7 en 236 m2/g, dui op ’n sterk potensiaal vir neerslae om as laegraadse adsorbeermiddels in afvalwaterbehandeling gebruik te word. Die ooreenstemming in hierdie geelbruin neerslae met grond minerale, impliseer dat die land storting van geneutraliseerde vastestowwe ook lewensvatbaar is.

As carbon dissolution rates have been determined for a few chars only, a systematic and comprehensive study was undertaken in this project on the dissolution behaviour of carbon from non-graphitic materials into liquid iron. In addition to measuring the kinetics of carbon dissolution from a number of coal chars into liquid iron as a function of parent coal and coal ash composition, the influence of chemical reactions between solute/solid carbon and ash oxides was also investigated. These studies were supplemented with investigations on one metallurgical coke for the sake of comparison. The wettability of coal chars and coke with liquid iron at 1550 degrees C was measured as a function of time. Being essentially non-wetting, only a marginal improvement in contact angles was observed with time. The accumulation of alumina at the interface was detected for all materials and was seen to increase with time in all cases. Calcium and sulphur also appeared to preferentially accumulate at the interface, concentrating at levels in excess of those expected from the ash composition alone. Despite the high levels of silica in the ash initially, very little silica was detected in the interfacial region, implying ongoing silica reduction reactions. A small amount of silicon was however detected in the iron droplets, indicating silica reduction with solute carbon. It was identified that the reduction reactions can also consume solute carbon in the liquid iron. As this is occurring simultaneously with carbon dissolution into liquid iron, the interdependency of silica reduction and carbon dissolution could potentially limit the observed carbon dissolution rate. A theoretical model was developed for estimating the interfacial contact area between chars and liquid iron. Wettability was found to have a very significant effect on the area of contact. A two-step behaviour was observed in the carbon dissolution of two chars and coke. Slow rates of carbon dissolution in stage II were attributed to very high levels of interfacial blockage by reaction products leading to much reduced areas of contact between carbonaceous material and liquid iron. The first order dissolution rate constants for four chars/coke and the observed trend in first order dissolution rate constants were calculated. These dissolution results compare well with the previously measured dissolution rate constants. The trends in dissolution can be adequately explained on the basis of carbon structure, silica reduction, sulphur concentration in the metal and ash impurities.

With the increasing global energy demand and the decreasing availability of good quality coals, a better understanding of the important properties that control the behaviour of low–grade coals and the subsequent chars in various utilisation processes, becomes pertinent. An investigation was therefore undertaken, to study the effects of chemical and physical properties imparted on chars during pyrolysis on the subsequent gasification reaction kinetics of typical South African inertinite–rich, high ash Highveld coals. An attempt was made at following these changes in the transition from coals to chars by a detailed characterisation of both the parent coals and the respective chars. These changes were determined using various conventional and advanced techniques, which included among others, carbon crystallite analysis using XRD and char carbon forms analysis using petrography. Three of the four original coals were characterised as Bituminous Medium rank C (coals B, C and C2), while coal D2 was found to be slightly lower in rank (Bituminous Medium rank D). The coals were rich in inertinites (> 54 vol. %, mmb with coal C2 having as high as 79 vol. %, mmb) and high in ash content (> 26.7 wt. %, db) and cabominerite and minerite contents (26 – 39 vol. %, mmb). The inertinitevitrinite ratios of the coals were found to range from 1.93 to 26.3. Characterization results show that both volatile matter and inherent moisture content decreased, while ash, fixed carbon and elemental carbon contents increased from coals to chars, indicating that the pyrolysis process was efficient. Elemental hydrogen, oxygen and nitrogen contents decreased, whereas total sulphur contents increased from coals to chars. This reveals that the total sulphur contained in the char samples was associated with the char carbon matrix and the minerals. Hydrogen–carbon and oxygen–carbon ratios decreased considerably from coals to chars showing that the chars are more aromatic and denser products than the original coals. Despite the fact that mineral matter increased from coals to chars, the relative abundance of the different mineral phases and ash components did not exhibit significant variation amongst the samples. The alkali index was, however, found to vary considerably among the subsequent chars. Petrographic analysis of the coals and char carbon forms analysis of the chars reveal that total reactive components (TRC) decrease while the total inert components (TIC) increase from coals to chars. The 0% gain in TIC observed in char C2 was attributed to its relatively high partially reacted maceral char carbon forms content. Total maceral reflectance shifted to higher values in the chars (4.43 – 5.28 Rsc%) relative to the coals (1.15 – 1.63 Rsc%) suggesting a higher structural ordering in the chars. Carbon crystallite analyses revealed that the chars were condensed (smaller in size) relative to the parent coals. Lattice parameters: interlayer spacing, d002, increased, while the average crystallite height, Lc, crystallite diameter, La, and number of aromatic layers per crystallite, Nave, decreased from coals to chars. Carbon aromaticity generally increased whereas the fraction of amorphous carbon and the degree of disorder index decreased from parent coals to the respective chars. Both micropore surface area and microporosity were observed to increase while the average micropore diameter decreased from coals to chars. This shows that blind and closed micropores were “opened up” during the charring process. Despite the original coal samples not showing much variation in their properties (except for their maceral content), it was generally observed that the subsequent chars exhibited substantial differences, both amongst themselves and from the parent coals. The increasing orders of magnitude of micropore surface area, microporosity, fraction of amorphous carbon and structural disorderliness were found to change in the transition, a good indication that the chars’ properties varied from that of the respective parent coals. Isothermal CO2 gasification experiments were conducted on the chars in a Thermax 500 thermogravimetric analyser in the temperature range of 900 – 950 °C with varying concentrations of CO2 (25 – 100 mol. %) in the CO2–N2 reaction gas mixture at ambient pressure (0.875 bar in Potchefstroom). The effects of temperature and CO2 concentration were observed to be in conformity with established trends. The initial reactivity of the chars was found to increase in the order: chars C2 < C < B < D2, with char D2 reactivity greater than the reactivity of the other chars by a factor > 4. Gasification reactivity results were correlated with properties of the parent coals and chars. Except for the rank parameter (the vitrinite reflectance), no significant trend was observed with any other coal petrographic property. Correlations with char properties gave more significant and systematic trends. Major factors affecting the gasification reactivity of the chars as it pertains to this investigation are: parent coal vitrinite reflectance, and: aromaticity, fraction of amorphous carbon, degree of disorder and alkali indices, micropore surface area, microporosity and average micropore diameter of the chars. The random pore model (chemical reaction controlling) was found to adequately describe the gasification reaction experimental data (both conversions and conversion rates). The determined activation energy ranged from 163.3 kJ·mol–1 for char D2 to 235.7 kJ·mol–1 for char B; while the order of reaction with respect to CO2 concentration ranged between 0.52 to 0.67 for the four chars. The lower activation energy of char D2 was possibly due to its lower rank, lower coal vitrinite reflectance and higher alkali index. The estimated kinetic parameters of the chars in this study correspond very well with published results in open literature. It was possible to express the intrinsic reactivity, rs, of the chars (rate of carbon conversion per unit total surface area) using kinetic results, in empirical Arrhenius forms.
Thesis (M.Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2011.

The aim of this master thesis is study of possibilities of processing energy by-products, especially coal fly ash and fluidized bed ash, by hydrothermal treatment. Thanks to hydrothermal conditions and proper alkali activation of ashes we can obtain zeolites. Zeolites are microporous crystalline aluminosilicates which are use in many industrial sectors as catalysts, adsorbents and very good ion exchangers. The results of hydrothermal synthesis are influenced by many variable factors. This thesis mainly focused on influence of chosen alkali activator and the concentration of the activator together with a temperature of hydrothermal process. Other factor that is studied is choice of starting materials and solution/ash ratio. Phase composition of prepared samples was characterized by XRD and scanning electron microscopy (SEM). Also cation exchange capacity of prepared samples was determined.

This diploma thesis deals with the study of high-strength, high-volume fly ash concrete. The theoretical part of this thesis focuses on the detailed characteristic and main principles of high-strength concrete, high-volume fly ash concrete. In addition, according to the findings, the technology of high-strength and high-volume fly ash concrete, including principles of high strength, has been described. On the basis of the findings, high-strength, high-volume fly ash concrete for specific compressive strengths has been designed and created in the experimental section. These concretes were then subjected to a number of tests.

Alguns materiais, constituídos quase que exclusivamente por sílica, são empregados, de forma suplementar ao cimento Portland, por promoverem melhorias ao concreto, devido aos seus efeitos físicos e pozolânicos, além de atenderem a questões ambientais. No entanto, essa sílica pode gerar produtos indesejados na presença de álcalis, sendo este fenômeno conhecido como reação álcali sílica (RAS). Na presença de água, esses produtos são capazes de expandir no interior da massa de concreto, provocando fissuras internas e externas e, em casos mais graves, a degradação do elemento estrutural. Com a finalidade de evitar essa manifestação patológica, o presente trabalho propõe-se avaliar o potencial reativo frente à RAS da sílica ativa e dois tipos de cinzas da casca do arroz (CCA), uma comercial e outra residual. Nessa investigação foram adotados os teores de 5 a 50 %, utilizados como substituição parcial ao cimento Portland padrão. Os métodos de ensaio adotados nesta pesquisa foram o método acelerado em barras de argamassa segundo a NBR 15577 - 4/5, e dois novos métodos acelerados (cubos de pasta e prismas). O métodos acelerado em cubos de pasta avaliou a resistência à compressão, enquanto o método em prismas de pasta avaliou a variação dimensional. Os resultados obtidos em barras de argamassa apontaram que ambas as CCA investigadas, foram reativos frente à RAS. No entanto, o teor de 50 %, em ambas as CCA, se mostrou inócuo para essa reação. A sílica ativa foi considerada inócua em todos os teores avaliados. O aditivo superplastificante empregado não foi eficiente em reduzir a expansão provocada pela CCA. Os ensaios que avaliaram a expansão em prismas de pasta apresentaram uma ótima correlação positiva com o método normalizado em barras de argamassa. Nos prismas de pasta com 25 % de CCA industrial foram identificados os compostos franzinite, chessexite e thaumasite. Estes compostos apresentaram morfologia de acículas ora tortuosas ora delgadas e retilíneas compondo todas as amostras coletadas dessa pasta. A análise termogravimétrica apontou o alto poder adsorvente de água dessa pasta. Em conclusão, o ensaio em prismas de pastas a 48°C com 1,25 % de Na2Oeq demonstrou ser um método prático laboratorialmente e apresentou um grande potencial para avaliar os materiais suplementares ao cimento Portland frente a RAS, além de facilitar identificação dos produtos que provocaram expansão.
Some materials, consisting almost exclusively for silica, are employed, supplementary form to Portland cement, for promoting improvements to concrete, due to their physical and pozzolanic effects and environmental issues. However, this silica may generate unwanted products in presence of alkalis. This phenomenon is known as alkali-silica reaction (ASR). In the presence of water, these products are able to expand inside concrete, generating internal and external cracks and, in severe cases, structural element degradation. In order to prevent this pathologic manifestation, the aim of the present study was to evaluate reactive potential in ASR of fume silica and two types of rice husk ash (RHA), a manufacturing and residual. Levels of 5 to 50 % were used as partial replacement to standard Portland cement. In the present study, accelerated method in mortar bars according to NBR 15577 - 4/5 and two new accelerated methods (pastes cubes and prisms) were used. Accelerated method in paste cubes evaluated compressive strength, while method in paste prims evaluated dimensional change. Results in mortar bars demonstrated, both RHA, were reactive to ASR. However, level of 50 %, both RHA, was innocuous to ASR. Fume silica was innocuous to ASR at all levels evaluated. Superplasticizer additive was not effective to reduce to expansion caused by RHA. In the cubes assay was possible to evaluate the reactive potential to ASR by analysis of variation coefficient. Results demonstrated a positive correlation between expansion in paste prism and standard method in mortar bars. In the paste prism with 25 % of RHA manufacturing were identified compounds of franzinite, chessexite and thaumasite. These compounds presented morphology of needles sometimes tortuous and sometimes thin and straight in all samples. Thermogravimetric analysis showed the high adsorbent power of water in this paste. In conclusion, paste prims assay at 48ºC with Na2Oeq 1.25 % demonstrated to be a practical laboratory method and presented a great potential to evaluate additional material to Portland cement in front of ARS, and this assay facilitates the identifications of products that cause expansion.

A reação álcali-agregado é uma manifestação patológica diretamente ligada à seleção dos materiais (cimento, agregados miúdo e graúdo, água e aditivos) que pode comprometer a durabilidade das estruturas de concreto, uma vez que a interação desses materiais e as condições ambientais é que vão conferir ao concreto determinadas propriedades ligadas à sua vida útil. A reação entre os hidróxidos alcalinos solubilizados na fase líquida dos poros dos concretos e alguns agregados reativos é lenta e resulta em um gel que, ao se acumular em vazios do concreto e na interface pasta-agregado, na presença de água, se expande, exercendo pressão interna no concreto. Ao exceder a resistência à tração do concreto, a pressão interna pode promover fissurações. A reação álcali-agregado requer a atuação conjunta de água, agregado reativo e álcalis. Sua prevenção pode ser feita a partir da eliminação de um dos fatores, ou seja, a partir do emprego de agregados inertes ou de cimentos com baixos teores de álcalis ou isolamento da umidade. Na impossibilidade de eliminar um dos fatores, medidas preventivas devem ser tomadas para o emprego de agregados reativos em obras de construção civil. Entre essas, destacam-se a utilização de cimentos com baixos teores de álcalis ou a de cimentos com adições ativas mitigadoras da reação álcali-agregado: escória de alto-forno, cinza volante, metacaulim e sílica ativa, que foi o objeto de pesquisa do presente trabalho. No programa experimental foram analisados dois tipos de agregado potencialmente reativos com os hidróxidos alcalinos: EDVDOWR e PLORQLWR_ JUDQtWLFR. O primeiro, proveniente de rocha ígnea, tem como constituintes deletérios vidro, clorofeíta, calcedônia (sílica criptocristalina), que dará origem à reação do tipo iOFDOL_VtOLFD. O agregado milonito granítico provém de rocha metamórfica, tem como constituintes deletérios quartzo microgranular, quartzo recristalizado, quartzo com extinção ondulante e quartzo e feldspato deformados, que dará origem ao tipo de reação iOFDOL_VLOLFDWR. Com o objetivo de avaliar a eficiência de adições ativas em mitigar as reações, os agregados foram combinados com 16 cimentos com adições ativas. Escória de alto-forno foi adicionada a 15%, 30%, 45% e 60% e cinza volante, a 10%, 15%, 25% e 35%, teores normalmente encontrados nos cimentos brasileiros. Metacaulim foi adicionada a 5%, 10%, 15% e 20%, e sílica ativa, a 5%, 10% e 15%, teores representativos da faixa normalmente adicionada diretamente a concretos. Todos os materiais utilizados foram caracterizados química, física e mineralogicamente, incluindo a análise petrográfica dos agregados. As barras de argamassa foram analisadas ao MEV, microscópio óptico de luz transmitida, realizaram-se ensaios de porosimetria por intrusão de mercúrio e análises térmicas para quantificar a teor de portlandita residual, e determinou-se o teor de álcalis dentro das barras após a realização dos ensaios para verificar a migração de íons de sódio. Os resultados indicam que a eficiência das adições ativas varia de acordo com a composição química e mineralógica das adições, da proporção desse material no cimento, e do grau de reatividade do agregado.
The alkali-aggregate reaction is a pathologic manifestation that can induce the premature distress and loss in serviceability of concrete structures affected. It is directly associated to the selection of materials (cement, coarse and fine aggregates, water and additives), as the interaction between these materials and environmental condition will grant the concrete some of the properties related to its service life. The slow reaction between alkali hydroxides soluble in the liquid phase within concrete pores and reactive aggregates gives rise to a gel that piles up within concrete voids and the aggregate-paste interface. In presence of water, the gel expands and exerts internal pressure in the concrete. When the internal pressure exceeds the tensile strength, cracking may come up as result. The alkali-aggregate reaction requires the action of water, reactive aggregate and alkalis altogether. Prevention can be carried out by eliminating one of these factors, i.e. employing either inert aggregates or lowalkali cements, or keeping the concrete away from moisture. Otherwise, preventive measures must be taken when reactive aggregates are used in civil construction works, such as the use of low-alkali cements or composite cements bearing alkaliaggregate- reaction mitigating admixtures: blast-furnace slag, fly ash, metakaolin and silica fume, which are the object of the present research. The experimental work included the analysis of two potentially reactive aggregates to alkali hydroxides: basalt and granite milonite. The igneous basalt carries deleterious constituents such as glass, chloropheite (cryptocrystalline silica), that will give rise to the DONDOL_VLOLFD type reaction while the metamorphic granite milonite carries micro granular, recrystallized, undulate-extinction-bearing quartz and deformed feldspar grains, that give rise to DONDOL_VLOLFDWH type reaction. Aiming at evaluating how efficient in mitigating these reactions the active admixtures are, these aggregates were mixed with 16 composite cements. The contents of admixtures followed those usually found in Brazilian industrial cements for blast-furnace slag (15%, 30%, 45%, 60%) and fly ash (10%, 15%, 25%, 35%), and those generally added directly to concrete for metakaolin (5%, 10%, 15%, 20%) and silica fume (5%, 10%, 15%). All materials were characterized for their chemical composition, physical properties and mineralogy. Petrography was carried out on the aggregates. The mortar bars were analyzed at the scanning electronic and transmitted-light optical microscopes. Mercury-intrusion porosimetry and thermal analyses were carried out to quantify residual portlandite. The alkali content within the bars was determined in order to verify migration of Na+ ions. The results show that the efficiency of active admixtures varies according to their chemical and mineralogical composition and proportioning in cement, and to the aggregate reactivity.

A reação álcali-agregado no concreto é um fenômeno que tem como causa uma reação química que ocorre entre os hidróxidos alcalinos provenientes do cimento e alguns minerais reativos presentes no agregado. Esta reação pode causar a deterioração do concreto, pois os seus subprodutos podem tornar-se expansivos na presença de umidade, originando fissuração, diminuição da resistência, aumento da permeabilidade e, eventualmente, a ruptura da estrutura. O uso de adições minerais em concretos suscetíveis à reação álcali-agregado tem sido apontado como uma alternativa eficiente na prevenção da reação expansiva, juntamente com o uso de agregados não reativos e a limitação dos teores de álcalis no cimento ou concreto. Neste contexto, o presente trabalho teve como objetivo principal a investigação do processo de deterioração do concreto devido à reação álcali-sílica, principalmente no que se refere ao tipo ou mineralogia do agregado e à utilização de cinza de casca de arroz, como substituição parcial do cimento Portland. Desta forma, o programa de pesquisa compreendeu, a realização de ensaios de expansão acelerada em barras de argamassa (ASTM C1260/94) moldadas com cimento Portland tipo CP-I S 32, com teores de 12,5; 25 e 50% de dois tipos de cinza de casca de arroz, em substituição parcial ao cimento, e quatro diferentes tipos de agregados (basalto B, basalto BGO, granito e riodacito). A microestrutura dos materiais utilizados e das barras submetidas ao ensaio acelerado foi avaliada através de técnicas analíticas e experimentais, tais como, petrografia, difração de raios x, porosimetria por intrusão de mercúrio, microscopia eletrônica de varredura e de transmissão (MEV e MET), com microanálise por detecção de energia dispersiva (EDS). Os resultados obtidos no ensaio acelerado comprovaram a potencialidade reativa das rochas analisadas e identificaram uma correlação entre o tipo de rocha e o teor de cinza de casca de arroz. A análise da microestrutura indicou que existe uma reação química da CCA com o meio alcalino utilizado no ensaio que acaba interferindo na formação e na relação C/S dos produtos expansivos resultantes da reação álcali-sílica.
The alkali-aggregate reaction in concretes is a phenomenon caused by a chemical reaction that occurs between alkaline hydroxides from Portland cement and some reactive minerals from aggregates. Such reaction can cause severe concrete deterioration, as its by-products can become expansive in the presence of water, originating fissuration, strength reduction, permeability increase, and eventually, the failure of concrete structures. The use of mineral admixtures in concretes susceptible to the alkali-aggregate reaction has been pointed out as an efficient alternative to prevent concrete expansion, along with the use of non-reactive aggregates and the limitation of the alkali amount in cement or concrete composition. In this context, the main purpose of the present work was the investigation of concrete deterioration due to the alkali-silica reaction, focusing the aspects related to the type or mineralogy of the aggregate and the utilization of rice husk ash as partial substitution of Portland cement. The research program comprised initially accelerated expansion tests carried out in mortar bars (ASTM C 1260/94), which were molded using CP-I S 32 Portland cement, 12.5, 25, and 50% contents of two types of rice husk ash, as partial replacement to the cement, and four different types of rock aggregates (basalt B, Basalt BGO, granite, and rhyodacite). Also, the microstructure of the concrete mixtures investigated, after being submitted to expansion in the accelerated tests, were evaluated through experimental and analytical techniques such as petrography, mercury intrusion porosimetry, x-ray diffraction, scanning and transmission electron microscopy (SEM and TEM), and energy dispersive detection (EDS). The results obtained have proved the reactivity potential of the investigated rock aggregates and identified a correlation between type of aggregate and rice husk ash content. The microstructure analysis indicated that the occurrence of a chemical reaction involving the rice husk ash in the alkaline environment established in the tests, had a significant effect on the amount of expansive by-products as C/S relation resulting from alkali-silica reactions.

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Dissertação (Mestrado)
IPEN/D
Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
Natural rice husk ash (RHA) used in concrete contributes to civil construction sustainability. In fact, RHA is considered a residual pollutant and then it is necessary to destine this material correctly. However, it is necessary to investigate the consequences of replacing part of cement by natural RHA to produce concrete for structural purposes. In this context, the aim of this study was to evaluate the concrete durability produced with 15 % of blinder partial replacement by natural RHA in the expansion due to alkali-silica reaction (ASR) and penetration of chloride ion, as well as to suggest preventive measures with the use of mineral additions. In the present study, natural RHA was used as partially replacement of Portland cement. This natural RHA has been obtained without temperature control burning and placed directly into the mixer to suffer self-grinding with aggregates. We investigated the RAS neutralization of natural RHA by the use of cement with mineral additions (CPIIZ, CPIII e CPIV), as well as, we performed additional replacements of part from CPIIZ cement by fly ash (10, 15, 20, 30 and 40 %). We employed accelerated expansion method at 80°C in mortar bars followed by scanning electron microscopy (SEM) and X-ray diffraction (XRD), and long term at 38 °C and accelerated at 60 °C methods in concrete prisms. To investigate concrete resistance in the chloride ion penetration, we used chloride ions penetration method by immersion in saline solution (CPT) of concrete produced with natural RHA and CPIIZ cement added of fly ash (0, 12.75 or 17 %) and water-binder ratios of 0.45, 0.55 and 0.65 were adopted. Analyses of results were based in slope (K ) obtained from the average depths of penetration. In this study, we verified that in mortar bars assay the natural RHA generated expansion above of results allowed by norm in mixtures with standard cement, while CPIIZ cement with addition from 20 % of fly ash showed to mitigate the ASR. These results demonstrated that effect of mitigation of RAS proportionally increased with fly ash addition. Moreover, CPIV cement demonstrated excellence in mitigate the expansive reaction. The SEM analysis identified the characteristic products of ASR in the samples containing natural RHA. XRD analysis showed that the samples of mixtures with higher content of mineral addition showed peaks of calcium hydroxide (CH) with less intensity and mixtures with natural RHA presented greater calcium carbonate content. In relation to concrete prisms molded at 60°C, results showed an increase in expansion for mixture of CPIIZ with natural RHA, but these results remained below of maximum expansion predicted by test. Mixtures of CPII-Z with natural RHA added of 10 and 15% fly ash demonstrated better efficiency in expansion mitigation. In relation to concrete prisms molded at 38°C, the results are not conclusive to 12 months, but mixtures that presented a great expansion were of CPII-Z with natural RHA and 15% fly ash, the CPII-Z with RHA natural and CPII-Z with natural RHA and 10% fly ash, respectively. However, all mixtures had expansion below the maximum limit suggested by the Brazilian standard at 24 months. Through of results CPT, we can conclude that mineral additions provided improvements to the concrete with higher ages due to pozzolanic effect. Moreover, the best results obtained were in trace with lowest water-binder ratios, probably due to increased consumption of cement, which increases the CH amount to interact with the RHA and the fly ash. Therefore, mixtures of Portland cement with fly ash and natural RHA meet the durability of concrete, and also the use of natural RHA would be an important contribution to sustainability and preservation of environment by civil construction.
O emprego de cinza de casca de arroz (CCA) natural no concreto visa contribuir para a sustentabilidade da construção civil, destinando de maneira adequada, esse material que antes seria considerado um resíduo poluente. Porém, é necessária a investigação das consequências em substituir parte do cimento por CCA natural para produzir concreto com finalidade estrutural. Neste sentido, o objetivo deste trabalho foi avaliar a durabilidade de concretos produzidos com teor de 15 % de substituição parcial do aglomerante por CCA natural, frente à expansão devido à reação álcali-sílica (RAS) e à penetração de íons cloretos, assim como, sugerir medidas preventivas através do uso de adições minerais. No presente estudo, a CCA natural foi utilizada em substituição parcial ao cimento Portland no estado em que se encontra ao sair dos fornos de queima (sem controle de temperatura), diretamente na betoneira para sofrer auto-moagem com os agregados. Foi investigada a neutralização das RAS da CCA natural pelo emprego de cimentos com adições minerais (CPIIZ, CPIII e CPIV), assim como foram realizadas as substituições adicionais de parte do cimento CPIIZ por cinza volante (10, 15, 20, 30 e 40 %). Na investigação da RAS foram empregados os métodos de expansão acelerado a 80 °C em barras de argamassa acompanhado pela microscopia eletrônica de varredura (MEV) e difração de raios-X (DRX), e os métodos de longa duração a 38 °C e acelerado a 60 °C em prismas de concreto. Na investigação da resistência a penetração de íons cloretos foi empregado o método de penetração de íons cloretos por imersão em solução salina (EPCI) dos concretos produzidos com CCA natural e cimento CPIIZ adicionados de cinza volante (0; 12,75 ou 17 %) e nas relações água/aglomerante(a/ag) de 0,45; 0,55 e 0,65. A análise dos resultados do EPCI foi realizada com base no coeficiente angular da equação da reta (K ) obtido a partir das profundidades médias de penetração dos períodos investigados. Neste trabalho verificou-se que, no ensaio em barras de argamassa a CCA natural gerou expansão acima do permitido por norma nas misturas com cimento padrão, enquanto o cimento CPIIZ com adição a partir de 20 % de cinza volante se mostrou mitigador da RAS. Através desses resultados pode-se verificar que o efeito mitigador da RAS aumentou proporcionalmente com a adição de cinza volante. Além disso, o cimento CPIV mostrou excelência em mitigar a reação expansiva. A análise de MEV identificou os produtos característicos da RAS nas amostras contendo CCA natural e a DRX verificou que as amostras retiradas das misturas com maior teor de adição mineral apresentaram picos de hidróxido de cálcio (CH) com menor intensidade e ainda, que as misturas com CCA natural apresentaram maior quantidade de carbonato de cálcio. Em relação aos prismas de concreto moldados a 60 °C, os resultados mostraram maior expansão na mistura de CPIIZ com CCA natural, mas ela se manteve abaixo do limite máximo de expansão preconizado pelo ensaio. As misturas de CPII-Z com CCA natural adicionadas de 10 e 15 % de cinza volante mostraram melhor eficiência em mitigar a expansão. Em relação aos prismas de concreto moldados a 38 °C os resultados ainda não são conclusivos aos 12 meses, porém as misturas que apresentaram maior expansão em 12 meses foram as de CPII-Z com CCA natural e 15 % de cinza volante, de CPII-Z com CCA natural e CPII-Z com CCA natural e 10 % de cinza volante, respectivamente, entretanto, todas abaixo do limite máximo de expansão aos 24 meses, preconizado pela norma brasileira. Através das análises dos resultados do EPCI concluiu-se que as adições minerais proporcionaram melhorias ao concreto com maiores idades devido ao efeito pozolânico. Além disso, os melhores resultados obtidos foram nos traços com menor relação a/ag, provavelmente devido ao maior consumo de cimento que aumenta a quantidade de CH para interagir com a CCA e a cinza volante. Portanto, as misturas de cimento Portland com CCA natural e cinza volante atendem aos parâmetros de durabilidade do concreto, e com isso o uso da CCA natural seria um importante contribuinte na sustentabilidade e preservação do meio ambiente pela construção civil.

Biomass is increasingly used as a feedstock in global energy production. This may present operational challenges in energy conversion processes which are related to the inorganic content of these biomasses. As a larger variety of biomass is used the need for a basic understanding of ash transformation reactions becomes increasingly important. This is not only to reduce operational problems but also to facilitate the use of ash as a nutrient source for new biomass production. Ash transformation reactions were examined in the present work using the Lewis acid-base concept. The model presented in Paper I was further extended and discussed, including the definition of tertiary ash transformation reactions as reaction steps where negatively charged molecular ions, Lewis bases, other than hydroxides are present in the reactants. The effect of such reactions for bonding of various metal ions, Lewis acids, were discussed. It was found that the formation of various phosphates through secondary and tertiary ash transformation reactions is important for the behaviour of biomass ash in combustion. The suggested model was supported by findings in Papers II-VIII. The experimental findings in Papers II-VIII were discussed in terms of ash transformation reactions. The fuel design choices made to investigate the effect of phosphorus in particular on ash transformation reactions were high-lighted. Addition of phosphoric acid to woody-type and agricultural biomasses showed that phosphate formation has a large influence on the speciation of Si, S, and Cl. Co-combustion of a problematic agricultural residue with other biomasses showed that the relation between phosphorus, alkali and alkaline earth metal content is important. Co-combustion of biosolids with wheat straw was shown to greatly improve the combustion properties of wheat straw. It was suggested that fuel analyses should be presented using molar concentration (mole/kg) in diagrams based on ash transformation reactions and elements forming Lewis acids or bases. This may facilitate the assessment of the combustion behaviour of a fuel. Some comments were made on fuel design and additives, specifically pointing out that phosphorus content should always be carefully considered in relation to alkali and alkaline earth metals in fuels and fuel blends.

Thesis (M.S.) -- University of Maryland, College Park, 2008.
Thesis research directed by: Dept. of Civil and Environmental Engineering. Title from t.p. of PDF. Includes bibliographical references. Published by UMI Dissertation Services, Ann Arbor, Mich. Also available in paper.

Thesis (M.S.)--West Virginia University, 2001.
Title from document title page. Document formatted into pages; contains vii, 53 p. : ill. (some col.). Includes abstract. Includes bibliographical references (p. 48-53).

Alkali silica reaction (ASR), a reaction which occurs between reactive siliceous mineral components in the aggregate and the alkaline pore solution in concrete, is responsible for substantial damage to concrete structures in the U. S. and across the world. Lithium admixtures, including lithium nitrate (LiNO3), have been demonstrated to mitigate ASR damage, and are of particular interest for use in concrete airfield pavement construction, where ASR damage has been recently linked to the use of certain de-icing chemicals. Although the effectiveness of lithium admixtures at ASR-mitigation is well-researched, relatively less is known regarding the potential effects, including negative effects, on overall concrete behavior. The goal of this research is to better understand the influence of LiNO3 admixture on early age concrete behavior, and to determine if a maximum dosage rate for its use exists. Isothermal calorimetry, rheology and bleed water testing, time of setting, chemical shrinkage, autogenous shrinkage, free and restrained concrete shrinkage, and compressive and flexural strength were measured for pastes and concretes prepared with a range of LiNO3 dosages (i.e., 0, 50, 100, 200, and 400% of the recommended dosage). In addition, the interaction of LiNO3 with cement was evaluated by comparing results obtained with six cements of varying alkali and tricalcium aluminate (C3A) contents. Additionally, one of these cements, was examined alone and with 20% by weight Class F fly ash replacement. Results indicate that the hydration of the tricalcium silicate and tricalcium aluminate components of cement are accelerated by the use of LiNO3, and that low alkali cements (typically specified to avoid damage by ASR) may be particularly susceptible to this acceleration. However, inclusion of Class F fly ash at 20% by weight replacement of cement (also common in applications where ASR is a concern) appears to diminish these possibly negative effects of LiNO3 on early age hydration acceleration and heat generation. Dosages higher than the current standard dosage of LiNO3 may have minor effects on fresh concrete workability, causing slight decreases in Bingham yield stress, corresponding to slightly higher slump. Fresh concrete viscosity may also be affected, though more research is necessary to confirm this effect. LiNO3 had no effect on quantity of bleed water in the mixes tested. Generally, LiNO3 had no effect on initial and final setting times, although increasing dosages caused faster set times in the lowest alkali (Na2Oeq = 0.295%) cement examined. In shrinkage testing, higher LiNO3 dosages appeared to cause initial expansion in some sealed paste specimens, but in all cases the highest dosage led to greater autogenous shrinkage after 40 days. In concrete specimens, however, the restraining effect of aggregates diminished shrinkage, and no effect of the LiNO3 was apparent. In no cases, with any dosage of lithium tested, with or without fly ash replacement, did restrained shrinkage specimens show any cracking. Strength testing produced mixed results, with laboratory specimens increasing in 28-day compressive strength, but companion specimens cast in the field and tested by an outside laboratory, exhibited lower 28-day compressive strength, with increasing lithium dosages. Flexural specimens, also cast in the field and tested by an outside laboratory, appeared to show an increase in 28-day flexural strength with increasing lithium dosages. However, because of the conflicting results when comparing the various strength data, further research is necessary for conclusive evidence of LiNO3 effects on concrete strength.

Concrete has proven to be, by far, one of the most reliable materials for the construction of critical infrastructure. However, despite its structural capacity, concrete members are susceptible to damage mechanisms that may decrease its performance and durability throughout its service life. One such mechanism is alkali-silica reaction (ASR), which takes place when unstable siliceous phases present in coarse or fine aggregates react with the alkali hydroxides from the concrete pore solution, generating a secondary product (i.e., ASR gel); this product swells upon moisture uptake from the surrounding environment, leading to cracking and expansion of the affected concrete. In severe cases of ASR-affected infrastructure, structural safety could become a problem, and thus requiring the demolition of affected members. It is, therefore, necessary to adopt effective protocols for the diagnosis and prognosis of aging infrastructure, to ensure its performance over time along with properly planning for rehabilitation strategies, whether required. This work presents a two-stage case study of the S.I.T.E. building at the University of Ottawa for the diagnosis and prognosis of ASR-affected members (i.e., columns) after nearly 20 years in service. The diagnosis phase was conducted with the aim of evaluating the cause and extent of distress and interpreting its impact on the performance of the affected structure. First, a visual inspection was conducted to evaluate potentially damaged members, in order to select the best location for core-drilling. Once ASR was confirmed through petrographic examination, specimens were evaluated through the multi-level assessment (i.e., coupling of microscopic and mechanical assessment). A range of damage was discovered among the examined columns (i.e., 0.03%, 0.05%, and 0.08% expansion). Moreover, evidence of developing freeze and thaw (FT) damage was discovered in columns with greater levels of expansion, raising future concerns regarding the durability and serviceability of members affected by this coupling of damage (i.e., ASR+FT). For the second stage of this project (i.e., prognosis), a novel ASR semi-empirical model was developed with the aim of predicting future ASR-induced expansion and damage in the S.I.T.E. building. The above model was developed and validated (using ASR exposure site data) through the coupling of existing chemo-mechanical macro-models, which were used to predict material behaviour on the structural scale, and novel mathematical relationships for the prediction of anisotropy in the columns. Moreover, the use of the multi-level assessment to predict the mechanical implications of predicted distress was found to enhance the model’s capacity for prognosis and demonstrated important potential for the accurate prediction of multi-level damage in the S.I.T.E. columns.

Coal ash deposits were collected in a 160 kWth, down-fired oxy-coal reactor under staged and unstaged conditions for four different coals (PRB, Gatling, Illinois #6, and Mahoning). Concentration measurements of carbon, oxygen, sodium, magnesium, aluminum, silicon, phosphorus, sulfur, chlorine, potassium, calcium, titanium, chromium, manganese, iron, nickel, strontium, and barium were gathered from each deposit sample using scanning electron microscopy and energy dispersive spectroscopy (SEM-EDS). Backscattered electron micrographs for each deposit sample were analyzed to gather morphological data. Particle size and shape were studied for each deposit collected. The average particle sizes of the particles in upstream deposits were much larger than the average particle sizes of the downstream deposits. The downstream deposits consisted primarily of spherical particles while the upstream deposits consisted of round, irregular polygonal, and porous particles. Deposit particles are believed to have deposited at all stages of burnout; those depositing early during pyrolysis may have continued to react after deposition. Element maps for the aforementioned elements were collected with SEM-EDS and analyzed to quantify both average composition and composition of individual particles. These values were compared to ASTM ash analyses performed for each coal and ash collected from the flue gas stream with a cyclonic particle separator. It was found that sulfur concentrations of deposits do not correlate with corresponding sulfur concentrations of the coal. Comparison of similar experiments performed with air-combustion show that oxy-combustion deposits contain about twice as much sulfur as air-combustion deposits when burning the same coal. Deposition propensity of each coal was also examined, and the PRB and Gatling coals were found to have a moderately high deposition propensity whereas the deposition propensity of the Mahoning and Illinois #6 coals was fairly low.

Thesis (MEng (Chemical Engineering))--Cape Peninsula University of Technology, 2020
Fly ash (FA) and acid mine drainage (AMD) are two undesirable materials generated from combustion of pulverized coal for energy and mining activity respectively. Both waste materials have serious, negative impacts on the environment. Fly ash storage leaches a variety of contaminants into surface and groundwater and AMD contains high amounts of toxic metals besides the already dominant 𝑆𝑂!"# concentrations. Many studies had investigated AMD treatment using FA and successfully removed significant amounts of sulphate, as well as minor and trace elements. Hence AMD can be treated using coal fly ash in an active or passive system without addition of any other chemicals. This study had as of objectives the evaluation of the neutralization capacity of FA from two South African’s power stations located in Mpumalanga which are Lethabo and Kendal with mine drainage water from the Mpumalanga coal fields using passive treatment. The research program simulated ex-situ neutralization of AMD in a fly ash slurry followed by continued AMD contact, representing the potential for using spent material as mine annulus fill to reduce air and water content and further AMD generation. Both the fly ash and AMD were obtained from the Mpumalanga province in Eastern South Africa. A 3:1 slurry ratio of AMD to fly ash was mixed until pH stabilized. After mixing, the slurry was packed in columns and left for a duration of 24 hours for a good settling time before the hydraulic treatment. Thereafter the AMD was continuously passed through the columns using gravity flow. Samples of effluent were collected at set time intervals during the hydraulic treatment. These samples were used to determine the flow rate, pH of the leachates and some sent for analysis by Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) and Ion Chromatography (IC) to determine the composition of the effluent water recovered. The X-ray diffraction done on both coal fly ash sources shown a dominance of quartz and mullites,on the other hand the X-ray fluorescence demonstrate that Kendal and Lethabo coal fly ash belong to class F ash due to fact that the total composition of SiO2, Al2O3 and Fe2O3 was exceeding 70% of the entire composition. Moreover, trace elements such as As, V, Ni, Mn, S, Sr, Cu, Y and Pb are found in the CFA used as well. The ICP-OES analysis showed that Eyethu AMD is very acidic with a pH of 2.23, with sulphate concentration of 2680 mg/L, displaying the existence of some metals some of which are Ca, Al and Fe. The neutralization process of Eyethu acid mine drainage using Kendal and Lethabo CFA was highlighted by the variation of pH from the time mine water was in contact with CFA, for the treatment with Lethabo CFA the treated water had its pH raised from 2.23 to 12.65 and from 2.23 to 8.37 using Lethabo and Kendal CFA respectively and this phenomena was explained by the dissolution and hydrolysis of the oxide components such as CaO. This neutralization process was characterized by a strong buffer zone around the pH of 12.83 to 8.37 from the Lethabo leachate and between 8.37 to 7.28 for the leachate from Kendal column. This buffer zone is explained by the hydrolysis of Al3+ which forms a hydroxide phase until all the aluminum ion was totally hydrolyzed. Electrical conductivity was also observed to vary. An amount of 1440 g of Kendal fly ash was used in the columns and treated 15 bed volumes of Eyethu AMD before the CFA was exhausted and lost its neutralizing power in the case of Lethabo CFA, 13 bed volumes of AMD were treated with 1280g CFA before breakthrough was observed. During treatment of Eyethu AMD with Lethabo and Kendal CFA the flow rate of the effluents water first increased during the first minutes of contact of AMD with CFA then started decreasing with time. The concentration of sulphate was reduced to up to 88% in the effluent from Lethabo CFA and 56% in the effluent from Kendal CFA. Some other metals such Fe, Mg, Mn, Al have been significantly removed from the AMD in the Lethabo and Kendal leachate. Furthermore, mass balance calculation were done around the columns in order to determine the moisture content and the % water recovery. From the calculation done it was shown that the column made of Kendal CFA can treat the AMD with a water recovery of 91.9% while Lethabo column could only recover 83.33% of the inlet water. In addition, Acid Base accounting tests were done in order to determine whether either Kendal or Lethabo CFA are from an acid generating or neutralizing rock. Test results have shown that both Kendal and Lethabo CFA are from an alkaline producing rock as their Net Neutralizing Potential and Neutralizing Potential Ratio were above 20 Kg/t CaCO3.

This research focuses on the characterization of damage accumulation in concrete specimens. Specifically, a nonlinear vibration technique is used to characterize the damage introduced by ongoing alkali-silica reactions (ASR). The nonlinear resonance testing consists of an analysis of the frequency response of concrete specimens subjected to impact loading. ASR introduces a third gel like phase, which can be expansive in the presence of moisture. The result of ASR is the formation of microcracks and debonding between aggregate and cement phases. Collectively, these changes act to increase the specimens' nonlinearity. As a result, it is found that the concrete samples exhibit nonlinear behavior; mainly a decrease in resonance frequency with an increasing level of excitation strain. The relationship between the amplitude of the response and the amount of frequency shift is used as a parameter to describe the nonlinearity of the specimen. The specimens used in this research are of varying reactivity with respect to ASR, which is induced in accordance with ASTM C 1293. The level of nonlinearity is used as a measure of damage caused by the progress of ASR throughout the one year test duration. These nonlinear resonance results are compared to the traditional measures of expansion described in the standard. The robustness and repeatability of the proposed technique is also investigated by repeated testing of samples assumed to be at a specific damage state. Finally, a petrographic staining technique is used to complement nonlinearity measurements and to further gain understanding of ASR. The results of this study show that the proposed nonlinear resonance methods are very sensitive to microstructural changes and have great potential for quantitative damage assessment in concrete.

This thesis examines the impact of the new revenue recognition standard, Accounting Standard Codification 606 (ASC 606), on the preparation and presentation of the financial statements. This thesis also inspects the impact of this change on the financial markets. This study begins with a qualitative examination of the impacts pertaining to ASC 606 through expert interviews and close examination of previously published reports. This paper later analyzes the financials of 10 specific companies and the effects attributed to ASC 606. And finally, this paper analyzes the effect of this change on the financials markets by examining the stock prices of each firm in the days surrounding the release of the updated financials.

Sizing (hydrophobization) is one of the most important process steps within the added-value chain of about 1/3rd of the worldwide produced paper & board products. Even though sizing with so-called reactive sizing agents, such as alkenyl succinic anhydride (ASA) was implemented in the paper industry decades ago, there is no total clarity yet about the detailed chemical and physical mechanisms that lead to their performance. Previous research was carried out on the role of different factors influencing the sizing performance, such as bonding between ASA and cellulose, ASA hydrolysis, size revision as well as the most important interactions with stock components, process parameters and additives during the paper making process. However, it was not yet possible to develop a holistic model for the explanation of the sizing performance given in real life application. This thesis describes a novel physico-chemical approach to this problem by including results from previous research and combining these with a wide field of own basic research and a newly developed method that allows tracing back the actual localization of ASA within the sheet structure. The carried out measurements and trial sets for the basic field of research served to evaluate the stock and process parameters that most dominantly influence the sizing performance of ASA. Interactions with additives other than retention aids were not taken into account. The results show that parameters, such as the content of secondary fibers, the degree of refining, the water hardness as well as the suspension conductivity, are of highest significance. The sample sets of the trials with the major impacting parameters were additionally analyzed by a newly developed localization method in order to better understand the main influencing factors. This method is based on optical localization of ASA within the sheet structure by confocal white light microscopy. In order to fulfill the requirements at magnification rates of factor 100 optical zoom, it was necessary to improve the contrast between ASA and cellulose. Therefore, ASA was pretreated with an inert red diazo dye, which does not have any impact on neither the sizing nor the handling properties of ASA. Laboratory hand sheets that were sized with dyed ASA, were analyzed by means of their sizing performance in correlation to measurable ASA agglomerations in the sheet structure. The sizing performance was measured by ultrasonic penetration analysis. The agglomeration behavior of ASA was analyzed automatically by multiple random imaging of a sample area of approx. 8650 µm² with a minimum resolution for particles of 500 nm in size. The gained results were interpreted by full factorial design of experiments (DOE). The trials were carried out with ASA dosages between 0% and 0.8% on laboratory hand sheets, made of 80% bleached eucalyptus short fiber kraft pulp and 20% northern bleached softwood kraft pulp, beaten to SR° 30, produced with a RDA sheet former at a base weight of 100 g/m² oven dry. The results show that there is a defined correlation between the ASA dosage, the sizing performance and the number and area of ASA agglomerates to be found in the sheet structure. It was also possible to show that the agglomeration behavior is highly influenced by external factors like furnish composition and process parameters. This enables a new approach to the explanation of sizing performance, by making it possible to not only examine the performance of the sizing agent, but to closely look at the predominant position where it is located in the sheet structure. These results lead to the explanation that the phenomenon of sizing is by far not a pure chemical process but rather a more physical one. Based on the gained findings it was possible so far to optimize the ASA sizing process in industrial-scale by means of ~ 50% less ASA consumption at a steady degree of sizing and improved physical sheet properties.

Many highway and hydraulic structures in North America have been reported to be affected by alkali aggregate reaction (ASR). It is anticipated that most of these structures will be demolished as they approach the end of their service lives. Recycling demolished concrete as aggregates in new concrete is an option that not only reduces the amount of construction demolition waste (CDW) disposed in landfills but also lessens the consumption of non-renewable resources such as natural aggregates. However, the use of recycled concrete aggregate (RCA) in new concrete requires detailed research to make sure that the durability of the recycled material is not compromised, especially if the RCA had been previously affected by ASR. In this research project, coarse recycled concrete aggregate (RCA) is reclaimed and processed from distinct members (i.e. foundation blocks, bridge deck and columns) of an ASR-affected overpass after nearly 50 years of service. RCA concrete mixtures incorporating 50 and 100% replacement are manufactured and stored in conditions enabling further ASR development. Mechanical (i.e. Stiffness Damage Test - SDT) and microscopic (Damage Rating Index - DRI) analyses are performed at a fixed “secondary” induced expansion of 0.12%. Results show that the overall performance of the ASR-affected recycled mixtures depends upon the “past” condition of the RCA particles. Moreover, the DRI was able to capture the “past” and “secondary” induced expansion and damage of affected RCA while the SDT only detected the “secondary” distress development. Lastly, an adapted version of the DRI was proposed to further evaluate the overall damage of recycled concrete along with properly displaying “past” and “secondary” induced distress.

Předložená magisterská práce se zabývá možným použitím vitrifikovaného lignitového lóžového popele jako náhrada slinku v kompozitních cementech. Byly zkoumány vlivy přidaného vitrifikovaného lóžového popele, jeho jemnosti, alkalických roztoků a jejich koncentrací. Byly připraveny kompozitní cementy v souladu s normou DIN EN 197 – 1. V těchto cementech bylo nahrazeno 30 % slinku vitrifikovaným lóžovým popelem. Konkrétně byly připraveny kompozitní cementy s vitrifikovaným lóžovým popelem o jemnosti 5549 cm2/g a 8397 cm2/g. Dále byly přidány alkalické roztoky hydroxidů a síranů vždy o dvou různých koncentracích, za účelem stimulace pucolánové a/nebo geopolymerní reakce. Mechanické vlastnosti připravených vzorků byly charakterizovány mechanickým testováním na prizmách s rozměry 40×40×160 mm, jak je specifikováno v normě DIN EN 196 – 1. Byla provedena nedestruktivní měření dynamického elastického modulu a destruktivní testovaní na pevnosti v tlaku a v ohybu. Distribuce velikosti částic a chemická analýza vstupních materiálů byla vykonána pomocí laserové granulometrie a rentgenové fluorescence. U zatvrdlých kompozitů bylo dále zkoumáno po 2 a 28 dnech hydratace fázové složení s využitím metody rentgenové difrakce a mikrostruktura s využitím skenovací elektronové mikroskopie. Výsledky ukázaly, že mechanické vlastnosti jsou nezávislé na množství přidaných alkálií stejně jako na jemnosti přidaného vitrifikovaného lóžového popele. Nicméně, znatelně nižší mechanické pevnosti byly pozorovány pro vzorky, které byly aktivovány hydroxidy, pravděpodobně kvůli brzké tvorbě silikátového hydrogelu. Vzorky aktivované sírany nedosáhly pevností jako referenční malta.

Recycled concrete is among the rising eco-friendly construction materials which helps to reduce waste and the need for new natural resources. However, such concrete may present previous deterioration due to, for instance, alkali-silica reaction (ASR), which is an ongoing distress mechanism that may keep being developed in the recycled material. This work aims to evaluate the potential of further distress and crack development (i.e. initiation and propagation) of AAR-affected RCA concrete in recycled mixtures displaying distinct past damage degrees and reactive aggregate types. Therefore, concrete specimens incorporating two highly reactive aggregates (Springhill coarse aggregate and Texas sand) were manufactured in the laboratory and stored in conditions enabling ASR development. The specimens were continuously monitored over time and once they reached marginal (0.05%) and very high (0.30%) expansion levels, they were crushed into RCA particles and re-used to fabricate RCA concrete. The RCA specimens were then placed in the same previous conditions and the “secondary” ASR-induced development monitored over time. Results show that the overall damage in ASR-affected RCA concrete is quite different from affected conventional concrete, especially with regards to the severely damaged RCA particles, where ASR is induced by a reactive coarse aggregate, as the RCA particle itself may present several levels of damage simultaneously caused by past/ongoing ASR and newly formed ASR. Moreover, the influence of the original damage extent in such RCA concrete was captured by the slightly damaged RCA mixture eventually reaching the same damage level as the severely damaged mixture. Furthermore, the original extent of deterioration influence the “secondary” induced expansion and damage of RCA concrete since the higher the original damage level, the higher the cracks numbers and lengths observed in the RCA concrete for the same expansion level whereas wider cracks are generated by RCA having previously been subjected to slight damage thus indicating the difference in the distress mechanism as a function of original extent of damage. In addition, it has been found that distress on RCA containing a reactive sand generates and propagates from the residual mortar (RM) into the new mortar (NM) as opposed to RCA containing a reactive coarse aggregate, being generated and propagated from the original coarse aggregate (i.e. original virgin aggregate – OVA) into the NM. Likewise, RCA containing a reactive sand caused longer and higher number of cracks for the same “secondary” induced expansion than the RCA made of reactive coarse aggregate. Finally, novel qualitative and descriptive models are proposed in this research to explain ASR-induced distress generation and propagation on RCA mixtures made of reactive fine and coarse aggregates.

Equine encephalosis virus (EEV) is the cause of equine encephalosis. The disease is similar to mild forms of African horse sickness (AHS) and the two diseases are easily confused. Laboratory identification and serotyping of EEV is based on viral isolation in BHK-21 cells and a viral plaque inhibition neutralization test (Erasmus Dissertation (MSc)--University of Pretoria, 2011.
Veterinary Tropical Diseases
unrestricted

Die vorliegende Arbeit konnte im Rahmen des vom Bundesministerium für Bildung und Forschung (BMBF) geförderten Verbundprojektes „Zukunftsorientierte Waldwirtschaft (1998-2003)“ erstellt werden. Dieses Vorhaben hat die bundesweiten Forderungen und Zielvorstellungen der Landesforstverwaltungen aufgegriffen, die nicht standortsgemäßen, naturfernen und instabilen Nadelbaumreinbestände umzubauen und den Anteil an Mischbeständen in den Forstbetrieben deutlich zu erhöhen. Neben ökonomischen Zielen sollte der Waldumbau vor allem auch ökologische Belange berücksichtigen. Dies wurde durch entsprechende Forschungsschwerpunkte vom BMBF wissenschaftlich begleitet. Die Vogelbeere (Gemeine Eberesche, Sorbus aucuparia L.) ist aufgrund ihrer hohen klimatischen und standörtlichen Anpassungsfähigkeit in den Mittelgebirgslagen Europas eine der häufigsten Nebenbaumarten in Fichtenwaldgesellschaften und künstlichen Fichtenforsten. Mit der vorliegenden Arbeit sollte geprüft werden, wie einzelbaumweise eingemischte Vogelbeeren, welche sich natürlich angesamt haben, frühzeitig in die Behandlung von Fichtenjungbeständen einbezogen werden können. Die Vogelbeere wird somit für eine erhebliche Dauer des Bestandeslebens – mindestens aber bis zum Zeitpunkt ihrer möglichen natürlichen Verjüngung – als ein vitales Bestandesglied im Sinne eines ökologischen Waldumbauverfahrens angesehen. Ziel war dabei die optimale Einzelbaumentwicklung der Vogelbeere hinsichtlich ihrer Dimension und Qualität, vor allem aber ihrer Vitalität. Grundlegend ist durch eine Abfrage in der Forsteinrichtungsdatenbank (FESA) für den Landeswald Sachsens das Flächenpotential an Fichtenjungbeständen bis zum Alter 50 Jahre in den mittleren Lagen erfasst worden, in denen natürlich angesamte und einzelbaumweise eingemischte Vogelbeeren vorkommen. Mit Hilfe einer terrestrischen Inventur wurden die ausgewählten Bestände stichprobenartig aufgesucht und dabei die vorkommenden Vogelbeeren hinsichtlich Dimension, Qualität, Vitalität und Schäden untersucht. Für ein waldbauliches Experiment sind weiterhin Fichtenjungbestände im Alter 16, 19, 26 und 32 Jahre auf Standorten mäßiger Trophie in den mittleren Lagen des sächsischen Forstbezirkes Bärenfels ausgewählt worden. In diesen Beständen wurden einzelbaumweise eingemischte Vogelbeeren unterschiedlicher soziologischer Stellung in den drei Varianten „keine“, „mäßige“ und „starke“ Freistellung gefördert. Die Zuwachsreaktionen verschiedener Baumkompartimente der untersuchten Vogelbeeren wurden in Abhängigkeit der Faktoren Alter, Freistellungsvariante und Konkurrenzsituation analysiert. Für einige Messungen war es notwendig dem Versuchsdesign auch Bäume destruktiv zu entnehmen. Insgesamt wurden ca. 700 ha Fichtenjungbestände erfasst, in denen die Vogelbeere einzelbaumweise in den Oberstand eingemischt war oder als weitere Baumart erwähnt wurde. Das durchschnittliche Mischprozent der Vogelbeere im Oberstand betrug ca. 16%. Die terrestrische Inventur zeigte, dass in den sehr jungen und kleinflächigen Beständen (mit bis zu 4 ha Größe) das Vorkommen der der Vogelbeeren am höchsten ist. Die Bäume sind dort zwar vor allem durch Mehrstämmigkeit (Garbenwuchs) gekennzeichnet, dennoch konnte bei den untersuchten Bäumen überwiegend eine gerade Stammform angesprochen werden. In den älteren Beständen stieg dann der Anteil der einschnürigen Stämme und Gabelungszwiesel, und zunehmend wurde die soziologische Stellung als „beherrscht“ und „unterdrückt“ für die Vogelbeeren angesprochen. Die erfassten Schälschäden fielen entgegen den Erwartungen vergleichsweise gering aus. Merkliche Schälschäden wurden erst in den beiden ältesten Fichtenaltersklassen angesprochen und diese nur als gering eingestuft. Die Einschätzung der Vitalität der Vogelbeeren mit Hilfe des baumartenunabhängigen Kronenanspracheschlüssels nach ROLOFF (2001) ergab in allen betrachteten Fichtenaltersklassen überwiegend eine geschwächte bis merklich geschwächte Vitalität. Die Ergebnisse des waldbaulichen Experimentes zeigten, dass die Wachstumsreaktionen der Vogelbeeren je nach betrachteter Fichtenaltersstufe unterschiedlich sind. Je früher eine Förderung erfolgt, umso stärker sind die Reaktionen des Einzelbaumes. Die freigestellten Bäume reagierten deutlich mit gesteigertem relativem BHD-Zuwachs, wobei die Kategorie „mäßige Freistellung“ am Ende der Beobachtungsperiode tendenziell die höchsten Werte besaß und dieser Zuwachs mit zunehmender Fichtenaltersstufe abnahm. Jahrringanalysen an Stammscheiben von entnommenen Probebäumen zeigten, dass die gesteigerte Zuwachsrate des Dickenwachstums nach 3 Vegetationsperioden wieder nachlässt. Das Höhenwachstum wurde in jeder beobachteten Fichtenaltersstufe und Konkurrenzsituation nicht signifikant durch die angewendeten Maßnahmen beeinflusst. Insgesamt zeichneten sich alle Probebäume durch hohe HD-Werte (im Mittel 138) aus, nur die Vogelbeeren der Fichtenaltersstufe 19 besaßen vergleichsweise stabile Werte unter 100. Die freigestellten Vogelbeeren entwickelten in allen betrachteten Altersstufen deutlich erweiterte Kronenschirmflächen und einen signifikanten Kronenradiuszuwachs. Die Ergebnisse der Gesamtblattmasseschätzungen zeigten für Vogelbeeren der Fichtenaltersstufe 26 deutliche Tendenzen, die belegen, dass geförderte Bäume mehr Blattmasse pro Baum ausgebildet haben als nicht geförderte Bäume. Die Anzahl der fruktifizierenden Bäume stieg von 41 % im Jahr 2001 auf 81 % im Jahr 2003, wobei die Stichprobe im Jahr 2003 um 17 Bäume durch destruktive Beprobungen reduziert gewesen ist. Es zeichnete sich ein Trend zum Anstieg der Fruchttrockenmasse je Vogelbeere in Abhängigkeit von der Freistellungsvariante ab, wobei stärker freigestellte Bäume mehr Fruchtmasse produzierten, als mäßig freigestellte Bäume (p = 0,029). Für einen mittleren Probebaum von ca. 5 cm BHD wurde eine Gesamtfeinwurzelmasse von ca. 202 g (R² = 0,30) und eine maximale horizontale Feinwurzelausbreitung von etwa 8 m ermittelt. Die höchsten mittleren Biomasseanteile an der gesamten oberirdischen Biomasse der Bäume hatte jeweils das Kompartiment „Stamm“, mit Anteilen zwischen 67 und 86 % über alle betrachteten Versuchsvarianten. Darauf folgen bei fast allen Versuchsvarianten die Biomasseanteile der Äste aus der Lichtkrone (ca. 5,5 bis 15,5 %). Die Blattbiomasse nimmt am Gesamtbaum einen verhältnismäßig geringen Anteil ein (zwischen 3,1 und 12,4 % über alle Varianten). Die jüngeren Bäume der Fichtenaltersstufe 16 hatten über alle Versuchsvarianten verhältnismäßig hohe Blattmasseanteile im Vergleich zu den Bäumen der Fichtenaltersstufe 26. Insgesamt hat die starke Freistellung tendenziell das Allokationsverhältnis zugunsten der Astbiomasse verschoben. Die älteren Bäume bildeten weniger Blattbiomasse im Vergleich zur Stammbiomasse. Einzelbaumweise eingemischte Vogelbeeren können als ideale Mischbaumart für einen ökologischen Waldumbau, speziell in jungen Fichtenreinbeständen, angesehen werden. Die Vogelbeere findet sich auf natürlichem Wege in diesen Beständen ein, wenn eine ausreichende Präsenz an fruktifizierenden Altbäumen gewährleistet ist. Um sie als wertvolle Zeitmischung zu erhalten, muss sie aber als eigenständiger Z-Baum Eingang in die Waldbaustrategien der Fichtenjungbestände finden, indem sie frühzeitig und regelmäßig gefördert wird. Ein passendes Wildmanagement sollte dabei Schäden an den Bäumen weitestgehend vermeiden, welche die Qualität und Vitalität, und somit den Erhalt der Vogelbeeren, nachweislich gefährden. Aus ökologischem Blickwinkel erfahren Standort, Fauna und Flora der Fichtenreinbestände durch die Präsenz geförderter und somit vitaler Vogelbeeren eine Aufwertung. Die freigestellten Bäume produzieren höhere Blattbiomassen, die nachweislich zu einer Verbesserung der Humusauflage führen, und von gesteigerten Fruktifikationsraten können Insekten und Säugetiere profitieren. Eine erhöhte unterirdische Wurzelaktivität und entsprechende Bodenmelioration wird zudem angenommen. Wenn geeignete Verjüngungsnischen in näherer Umgebung der Einzelbäume existieren, kann mit einer konsequent und regelmäßig geförderten Vogelbeere auch dem Nachhaltsumbau für die Gestaltung von zukünftigen Bestandesgenerationen gedient werden. Weiterhin kann sie als eine geeignete Baumart hinsichtlich der Gestaltung eines Risikomanagements nach Störungen und Katastrophen angesehen werden, da sie aufgrund ihrer Eigenschaften für eine rasche Wiederbewaldung sorgt. Vor dem Hintergrund eines prognostizierten Klimawandels stellt sie zudem mit ihrer standörtlichen Anspruchslosigkeit eine geeignete Mischbaumart für zukünftige Bestockungen dar. Die vorliegende Arbeit konnte zeigen, dass das Wuchspotential der Vogelbeere in bisherigen Untersuchungen und daraus resultierenden Erkenntnissen unterschätzt wurde. Konsequent gepflegte Vogelbeeren ohne Wildschäden existieren kaum und konnten somit kaum untersucht werden. An dieser Stelle besteht weiterer Forschungsbedarf, welcher auf längerfristigen Versuchsaufbauten basieren sollte
The present work is part of the joint research program „Zukunftsorientierte Waldwirtschaft (1998-2003)“ which was funded by the German Federal Ministry of Education and Research (BMBF). The program acted on nationwide requests and formulated goals of federal forest administrations to convert artificial and instable conifer stands unsuited to the site and to significantly increase the portion of mixed populations. Besides economic goals the conversion measures primarily were to consider ecological needs. These were assured by scientific super-vision by the BMBF in respective focal programs. Rowan (Sorbus aucuparia L.) exhibits high climatic and habitational adoptability. Therefore, it is a major secondary tree species in Europe’s average mountain ranges both in natural and artificial spruce forests. This work aimed to investigate how naturally seeded single tree admixtures of rowan can precociously be integrated into the management of young spruce stands. By rowan is viewed as a vital member of stand for a considerable part of the stand`s lifecycle in the sense of natural forest conversion, at least until its potential natural rejuvenation. The major goal in this approach was an ideal single tree development of rowan with respect to dimension, quality and, above all, its vitality. As a basis, the areal potential of young spruce stands aged up to 50 years in the mid altitudinal ranges containing naturally seeded single tree admixtures of rowan was determined by querying the forest inventory system database of the Federal Forest of Saxony (FESA). Selected stands were visited at random in the frame of a terrestrial inventory and found rowans were examined with respect to dimension, quality, vitality and damage. Furthermore, young spruce stands in the age of 16, 19, 26 and 32 years at sites of moderate trophic level at midaltitude of the Saxon forestry district Bärenfels were selected for a silvicultural experiment. In these stands single tree admixtures of rowans differing in sociological situation were supported by either no, moderate or strong thinning. Growth responses of different tree compartments of the examined rowans were analyzed in relation to the factors age, thinning variant and competition. For some measurements destructive removal of trees from the experimental design became necessary. In total, approx.700 ha of young spruce stands containing rowan as single tree admixtures in the overstorey or as additional tree species records were registered. The average percentage of mountain as in the overstorey was approx. 16 %. The terrestrial inventory demonstrated that very young stands with small plot sizes (up to 4 ha) exhibit the highest occurrence of rowan. Even though trees are mainly characterized by several secondary trunks here, straightshaped stems could be found in the majority of examined individuals. In older stands the percentage of constricted and bifurcated stems raised and sociological position of the rowan trees was increasingly determined as “dominated” and “repressed”. Recorded stripping damage was low in contrast to expectations. Notable stripping damage was only found in the two oldest age classes of spruce and was determined as low. The vitality assessment of the rowans using the tree species independent crown assessment method according to ROLOFF (2001) resulted predominantly in a weakened to substantially weakened vitality. Results of the silvicultural experiment demonstrated the growth reactions of rowan differ depending on the age class of spruces under investigation. The earlier crown release is initiated the stronger are the reactions of a single tree. Released trees considerably reacted by enhanced increment of relative diameter at breast height with the category of “moderate thinning” in direction showed highest values at the end of the observation period while this increment decreased with increasing age class of the spruces. Treering analysis of stem disks from removed individuals revealed that the enhanced rate of diameter growth decreased again after 3 vegetation periods. Vertical growth was not significantly influenced by the taken measures in any of the spruce age classes or competitive situations under investigation. Overall, all trees under investigation were characterized by high height to diameter ratios (mean of 138) with only rowans of age category 19 exhibiting relatively stable values below 100. Released rowans developed markedly expanded crown areas in all investigated ageclasses and a significantly elevated increment in crown diameter. Results of the total leaf biomass estimations revealed clear tendencies for rowans in the spruce age category 26. These prove the supported trees having developed more leaf biomass per individual as nonsupported. The number of fructifying trees rose from 41 % in 2001 to 81 % in 2003 whereas the sample size was reduced by 17 in 2003 by destructive sampling. A tendency of increased dry fruit mass per rowan berry depending on the release variant could be seen with stronger released trees producing more fruit mass than moderately released ones (p=0.029). For an average sample tree of approx. 5 cm breast height diameter a total hair root mass of approx. 202 g (R² = 0.30) and a maximum horizontal hair root distribution of approx. 8 m was determined. Highest mean portions of overall aboveground biomass of the trees were assigned to the stem compartment with percentages ranging from 67 to 86 % throughout all experimental variants. These were followed by the biomass portions of branches from the light crown (approx. 5.5 to 15.5 %). The leaf biomass accounts for a comparatively low proportion of the tree (between 3.1 und 12.4 % throughout all variants). The younger trees of spruce age category 16 had relatively high portions of leaf biomass as compared to trees of spruce age category 26. Altogether the strong release shifted the allocation pattern in favor of the branches biomass. Older trees developed less leaf biomass compared to stem biomass. Single tree admixtures of rowan can be considered ideal for ecological forest conversion, especially in young spruce stands. Rowan naturally adapts to these stands if a sufficient presence of fructifying, old trees is ensured. To preserve it as valuable temporal mixture, it has to make its way into forestry planting strategies for young spruce stands as an autonomous future tree by being receiving early and regular support. Associated wildlife management should as far as possible avoid damage of the trees endangering quality and vitality and by that preservation of rowans. From an ecological perspective the site, fauna and flora of pure spruce stands experience a revaluation through the presence of supported and therefore vital rowans. The released trees produce higher amounts of leaf biomass demonstrably leading to an amelioration of the humus layer and insects and mammals can profit from enhanced fructification rates. Furthermore, an increased underground root activity and related soil melioration is assumed. If suitable regeneration niches exist nearby the single trees, consequently and regularly supported rowans can as well serve sustainable conversion for the design of future generations of tree populations. Furthermore it can be considered a suitable tree species in view of the creation of a risk management plan following disturbances and catastrophes as its characteristics ensure fast reforestation. Against the background of a predicted climate change the rowan with its habitational modesty constitutes a suitable species for future stockings. The present work could demonstrate a clear underestimation of the growth potential of rowan in studies to date and their resulting conclusions. Consequently maintained rowans without damage caused by game do rarely exist and could therefore rarely be examined. Here, additional research is needed which should be based on longerterm experimental setups

Today the use of resources in the industry are not complete to be considered as sustainable from the perspective of nutrient recovery. In the Swedish pulp and paper industry residual streams such as bark, fiber reject and sludge are returned for more sustainable use more frequently. Around 300 000-600 000 tons of sludge is generated every year from different cleaning processes in the pulp and paper industry. About 15 % of that sludge is so called biosludge that is a result from biological water treatment, where large amounts of phosphorus are used. After the cleaning process the total amount of biosludge generated in Sweden each year is estimated to contain approximately 2000 tons of phosphorus (P). The most common way to discard the biosludge today is by incineration, where aspects such as high content of moisture and ash have proven to be problematic. Besides phosphorus, other elements such as sulfur (S), chlorine (Cl) and calcium (Ca) are often found in the biosludge in larger amounts.   This study included co-combustion experiments of current residual streams from the pulp and paper mill SCA Obbola AB where the aim was to investigate how the ash transformation chemistry was affected. The residual streams comprised of bark, fiber reject and biosludge which were combusted together with stem wood in a bench scaled bubbling fluidized bed. To investigate if different ash related operating and technical problems could be reduced and if there was potential of phosphorus recycling from the ashes, produced ash and other samples were examined by SEM/EDS. The fuel mix from SCA Obbola consisted of large amounts of Ca, S and P relative to more ordinary biomass fuels like stem wood. These elements originated from the biosludge and was confirmed by the fuel analysis. Analysis made on collected samples showed that Ca and P together formed phosphates that either stayed in the bed or was collected in the cyclone which indicated that there could be a potential for recovering phosphorus. Although, the Ca/P ratio in the ashes was too high, which probably leads to that phosphates unsuitable for nutrient recovery are formed.   The fiber reject from SCA Obbola contained large amounts of chlorine according to the fuel analysis which was indicated from the results later in the study. During the combustion most of the Cl left the bottom ash via volatilization. It was true for both the fuel blends with and without fiber reject. When larger amounts of biosludge was added to the fuel mix less of the corrosive compound potassium chloride (KCl) was found in depositions and collected fine particulate matter (PM). This was due to that more sulfur was added in the system when the amount of biosludge was increased which lead to that K reacted with SO2 instead of Cl and formed K2SO4. The observed reduction of KCl resulted in; 1) lower amounts of fine particulate matter which means less loaded particulate filters 2) less risk of high temperature corrosion on heat transfer surfaces. The general conclusion that could be drawn from this study was that by increasing the amount of biosludge in the fuel blend at already high mixings of fiber reject, problems such as corrosion and fine particulate matter could be reduced. These advantages must be considered to the amount of lime stone needed to be added for reducing HCl from a cost perspective.

Afin de répondre aux questions des propriétaires de structures atteintes de réaction alcali-silice (RAS), ce travail se concentre sur une partie d'une méthodologie globale, proposée initialement par le LMDC et EDF, et dont le but est l'étude du comportement mécanique des constructions endommagées par la RAS. Pour atteindre cet objectif, l'avancement chimique de la RAS des granulats récupérés dans les structures affectées doit être évalué. Ainsi, ce travail est consacré à la quantification de la silice potentiellement réactive des granulats, par l'utilisation de deux approches : une approche indirecte par un test d'expansion et une approche directe par des méthodes chimiques. La présentation du manuscrit s'articule autour des points suivants :• Un test d'expansion pertinent et rapide sur mortiers pour relier la quantité de silice réactive à l'expansion mesurée. Les conditions expérimentales suivantes ont été choisies pour tester différentes tailles et natures de granulats, ainsi que différentes tailles d'éprouvettes : solution de NaOH à 1 mol/l et température de conservation de 60°C.• Une méthode chimique rapide de dissolution sélective pour mesurer directement la quantité de silice réactive disponible pour la RAS. La méthode HF / HF+HCl a été trouvé comme étant la plus efficace.• Un modèle chemo-mécanique pour analyser les effets de la taille des granulats et des éprouvettes, et évaluer l'avancement chimique de la réaction.Finalement, une méthodologie est proposée pour calculer la constante cinétique de la réaction dans le cadre de la requalification des structures atteintes de RAS
In order to answer the questions of the ASR-affected structures owners, this work focused on a part of a global methodology, which is proposed originally by the LMDC and EDF, aiming to reassess the mechanical behavior of ASR-damaged constructions. To achieve this purpose, the chemical advancement of ASR in the aggregates recovered from the structure should be evaluated. Thus, this work focuses on the assessment of the potentially reactive silica content with two main methods: indirectly by expansion test and directly by chemical methods. The presentation of this manuscript is around the following points: • A relevant and rapid expansion test on mortars to link the reactive silica content to measured expansion. The experimental condition: 1 mol/l NaOH solution conserved at 60°C is chosen to test different aggregate sizes, specimen sizes and natures of aggregate. • A fast chemical method of selective dissolution to measure directly the silica available for ASR. Acid/basic methods are tested and compared; HF / HF+HCl method is found to be the most effective. • A chemo-mechanical model to analyze the effect of aggregate size and specimen size, and evaluate the chemical advancement of ASR. Finally, a methodology is proposed to calculate the kinetics constant in the framework of structural requalification. Key words: alkali-silica reaction (ASR), chemical advancement, reactive silica, expansion test, chemical test, chemo-mechanical model, kinetic constant, selective dissolution

In der vorliegenden Dissertation sollten die hydrogeochemischen Prozesse herausgearbeitet werden, die für die Wasserqualitätsänderung während eines ASR Experiments in Bolivar, Südaustralien und während der Versickerung in einem künstlichen Grundwasseranreicherungsbecken in Berlin von Bedeutung waren. Reaktive Stofftransportmodellierung des ASR Experiments in Bolivar, Südaustralien zeigte, dass die hydrochemischen Veränderungen in der direkten Umgebung des Injektionsbrunnens während der Speicherphase nur durch rapide Änderungen der Sauerstoff- und Nitrat reduzierenden Bakterienmasse erklärt werden können. Die hydrochemischen Veränderungen in größerer Distanz zum Injektionsbrunnen wurden überwiegend durch Ionenaustauschprozesse und Kalzitlösung verursacht. Geochemische und hydraulische Messungen unter einem Sickerbecken in Berlin zeigten, dass die beobachteten geochemischen Änderungen im Sickerwasser mit den periodisch auftretenden wassergesättigten/wasserungesättigen Bedingungen unter dem Becken einhergehen. Während der ungesättigten Periode wird Luft unter das Becken gezogen und führt zur plötzlichen Reoxidierung von bereits in der gesättigten Periode gebildeten Eisensulfiden und zur beschleunigten Mineralisation von sedimentärem organischem Kohlenstoff. Reaktive Stofftransportmodellierung auf größerer Skale zeigte, dass allein die saisonalen Temperaturunterschiede im Infiltrationswasser für die beobachtete zeitliche und räumliche Dynamik der Redoxzonen im weiteren Abstrom des Sickerbeckens verantwortlich sind. Das Abbauverhalten der Arzneimittelsubstanz Phenazon hängt ausschließlich von der Verfügbarkeit von gelöstem Sauerstoff und damit indirekt von der Wassertemperatur im Aquifer ab. In der vorliegenden Arbeit wird deutlich, dass ein adäquates Verständnis der wasserqualitätsändernden Prozesse in künstlichen Anreicherungsystemen nur dann erreicht werden kann wenn Strömung, Transport und reaktive Prozesse, im Feld als auch in der Modellierung, simultan betrachtet werden.
In this thesis, three major studies were carried out in order to understand the key factors controlling the water quality changes that occurred during a reclaimed water Aquifer Storage and Recovery (ASR) experiment at Bolivar, South Australia and during ponded infiltration in Berlin, Germany. Multi-component reactive transport modelling of the ASR experiment suggested that during the storage phase, dynamic changes in bacterial mass have a significant influence on the local geochemistry in the vicinity of the injection well. Water quality changes further away from the injection well were mainly driven by ion exchange and calcite dissolution. Geochemical and hydraulic measurements below an artificial recharge pond in Berlin, Germany, showed that the observed dynamic changes of the hydrochemistry within the seepage water are strongly linked to the periodic saturated/unsaturated hydraulic conditions below the pond. During unsaturated conditions, atmospheric oxygen penetrates from the pond margins to the centre below the pond, leading to (i) a sudden re-oxidation of sulphide minerals that have formed previously during saturated conditions and (ii) an enhanced mineralisation of sedimentary particulate organic carbon. Reactive transport modelling showed that at larger scale, seasonal temperature changes of the infiltration water are the key control for the observed temporal and spatial redox dynamics further downstream the recharge pond. Moreover, the degradation behaviour of the pharmaceutically residue phenazone solely depends on the availability of dissolved oxygen, and thus indirectly on the water temperature within the aquifer. Overall this thesis shows that a sound understanding and analysis of the key processes affecting the water quality changes during artificial recharge of groundwater could only be achieved when flow, transport and reactive processes are considered simultaneously, both in the field and during modelling.

The research presented in this thesis focuses on the study of the reaction between boronic acids and diols and its evaluation as a possible "click" reaction, possibly applicable in bioconjugation and drug delivery. A key feature of this reaction is its reversibility at acidic pH, which could allow the release of a diol-containing drug from a bioconjugate in the acidic environment of late endosome/lysosome, possibly after undergoing receptor mediated endocytosis. Over the last two decades various studies have focused on the study of the conjugation of boronic acids to diols using Alizarin Red S as a fluorescence reporter. In this research we have presented an alternative method based on the batochromic shifts of Alizarin Red S absorbance; this method is particularly advantageous in complex systems with an elevated scattering, such as colloidal dispersions or for binding to complexed active compounds. We have therefore demonstrated that this method allows the determination of equilibrium constants between diols (e.g. catecholamines) and boronic acids. We have also demonstrated that the method allows to follow the kinetics of enzymatic reactions involving catechols; in particular, we have focused on cytochrome P450-mediated reactions such as the conversion of estradiol to 2-hydroxyestradiol using CYP1A2, or the demethylation of 3-methoxytyramine to dopamine using CYP2D6. Once we have established a reliable method for following this reaction on low molecular weight compounds, we have applied it to polymeric bioconjugates. Specifically, we have selected hyaluronic acid (HA) as a biocompatible and biodegradable polymeric backbone and produced derivatives containing boronic acids, catechols and dimethylated catechols (as negative controls). The resulting polymers where characterised via UV-Vis, 1H NMR and SLS, also qualitatively evaluating their cytotoxicity and enzymatic degradability. The conjugates with boronic acids showed the lowest cytotoxicity, and the highest degradability. The complexation of HA-boronic derivatives was then studied; using the same library of diols previously used with low molecular weight compounds, evaluating the effect of the presence of the polysaccharidic macromolecular chain.

Alkali Silica Reaction (ASR) is a deleterious, expansive reaction in concrete. Several ASTM methods test potential aggregates for ASR risk. One method uses NaOH digestion, followed by spectroscopic methods, to estimate the amount of reactive silica present in an aggregate. NaOH, however, can digest both crystalline (i.e. quartz) and non-crystalline (e.g. opal), or poorly crystalline silica, potentially yielding falsely high estimates of reactive silica. Studies in soil and plant sciences have used Tiron, an alkaline chelating agent (C6H4S2O8Na2), as a method of digesting opaline silica for spectroscopic analysis. Here we test this approach by analyzing reactive silica in road aggregate. Tiron extraction of reactive silica is more selective, in some cases extracting only ~ 30% of the silica compared to the harsher NaOH extraction: variation is due to differences in aggregate mineralogy, specifically SiO2. In conducting chelation analyses, UV/VIS seems to be a better approach than AA.

The waste treatment, particularly the thermal treatment of waste has changed fundamentally in the last 20 years, i.e. from facilities solely dedicated to the thermal treatment of waste to facilities, which in addition to that ensure the safe plant operation and fulfill very ambitious criteria regarding emission reduction, resource recovery and energy efficiency as well. Therefore this contributes to the economic use of raw materials and due to the energy recovered from waste also to the energy provision. The development described had the consequence that waste and solid recovered fuels (SRF) has to be evaluated based on fuel criteria as well. Fossil fuels – coal, crude oil, natural gas etc. have been extensively investigated due to their application in plants for energy conversion and also due to their use in the primary industry. Thereby depending on the respective processes, criteria on fuel technical properties can be derived. The methods for engineering analysis of regular fuels (fossil fuels) can be transferred only partially to SRF. For this reason methods are being developed or adapted to current analytical methods for the characterization of SRF. In this paper the possibilities of the energetic utilization of SRF and the characterization of SRF before and during the energetic utilization will be discussed.

This thesis contains two main parts: theoretical and experimental. The theoretical part deals with summarization knowledge of high-volume fly ash (HVFA) concretes. Among others, there are mentioned processes of producing of fly ash, characteristic features and resistance to aggressive environments of HVFA concretes. The theoretical part ends with a suitable example of practical application. In the practical part were tested properties of nine different mixtures containing 40%, 50% and 60% replacement by weight of the cement by fly ash. They were compared with the reference mixtures without fly ash addition. The main endpoints were long-term compressive strength, resistance to aggressive environments, the influence of fly ash on consistency, hydratation temperatures, water absorption and volume changes.