Orientadores: Antonio Ludovico Beraldo, Holmer Savastano Júnior / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Agrícola / Made available in DSpace on 2018-08-21T10:15:51Z (GMT). No. of bitstreams: 1 Rodrigues_MichelleSantos_D.pdf: 5803870 bytes, checksum: c6cbc3e5bb60178760286846f51dffb6 (MD5) Previous issue date: 2012 / Resumo: Neste trabalho produziram-se cinzas de palha de cana-de-açúcar por queima controlada para avaliar a sua aplicação como adição mineral em matrizes cimentícias. As palhas foram submetidas a quatro diferentes temperaturas de queimas: 600 °C, 700 °C, 800 °C e 900 °C, e as cinzas foram denominadas CPCA600, CPCA700, CPCA800 e CPCA900, respectivamente. Após a queima cada cinza passou por um processo de moagem e foi submetida a análises de fluorescência de raios X, difração de raios X, microscopia eletrônica de varredura, granulometria a laser, massa específica real por picnometria a gás e superfície específica por B.E.T (Brunauer-Emmett-Teller). A reatividade das cinzas foi avaliada por meio de medições de condutividade elétrica em soluções insaturadas de Ca(OH)2/cinzas. Foram analisadas pastas com cimento Portland ou hidróxido de cálcio em função da idade de cura úmida (7, 28, 63 e 91 dias) por meio das técnicas de termogravimetria, compressão simples, compressão diametral, absorção de água, porosidade aparente, massa específica aparente, porosimetria por intrusão de mercúrio, microscopia eletrônica de varredura, calorimetria e difração de raios X de alta resolução, realizada no Laboratório Nacional de Luz Síncrotron. As cinzas CPCA600 e CPCA700 foram consideradas mais reativas e foram aplicadas em compósitos de fibrocimento. As caracterizações das cinzas mostraram que a CPCA600 e a CPCA700 contêm composição química de material pozolânico, partículas com elevada nano e microporosidade e elevadas áreas de superfície específica, assim como foi observado um halo de amorficidade nos difratogramas de ambas as cinzas. O ensaio de condutividade elétrica no sistema hidróxido de cálcio/cinzas mostrou elevada reatividade dessas cinzas. Na avaliação das pastas, as cinzas CPCA600 e CPCA700 apresentaram maior consumo de hidróxido de cálcio, maior resistência à compressão simples e menor volume de poros. As caracterizações físicas (absorção de água, porosidade aparente e massa específica aparente) e mecânicas (módulo de ruptura, energia específica, módulo de elasticidade e limite de proporcionalidade) dos compósitos mostrou que aqueles produzidos com a CPCA700 apresentaram características físicas e mecânicas similares àquelas do controle, o que viabiliza a substituição parcial do cimento Portland pela mesma / Abstract: This research work produced sugarcane straw ashes by controlled burning and evaluates its application as mineral admixture in cementitious matrices. Straws were subjected to four different burning temperatures. Straws were dried and burned at 600 °C, 700 °C, 800 °C and 900 °C that were named SCSA600, SCSA700, SCSA800 and SCSA900, respectively. After firing the material passed through a milling process and it was subjected to analysis of X ray fluorescence, X ray diffraction, scanning electron microscopy (SEM), particle size laser, real density and specific surface area by B.E.T (Brunauer-Emmett-Teller). The reactivity evaluation of the ashes was performed by measuring the electrical conductivity of insaturated solutions of Ca(OH)2/ash. Pastes with Portland cement or calcium hydroxide were evaluated according to the curing hydration age (7, 28, 63 and 91 days) by means of thermogravimetry, compressive strength, splitting test, water absorption, apparent porosity and bulk density, mercury intrusion porosimetry, scanning electron microscopy, calorimetry and high-resolution X-ray diffraction, at the National Laboratory of Synchrotron Light. The ashes SCSA600 and SCSA700 were considered more reactive and have been applied in cement composite. The characterizations show that SCSA600 and SCSA700 ashes contain chemical composition of pozzolanic material, and nano particles with high microporosity, and consequently, with high specific surface areas, as has been observed halo amorphicity in both diffractograms ashes. Electrical conductivity obtained at the system calcium hydroxide/ashes showed high reactivity for these ashes. In the pastes evaluation, the ashes SCSA600 and SCSA700 showed higher consumption of calcium hydroxide, higher compressive strength and reduced volume of pores. The physical characterizations (water absorption, apparent porosity and bulk density) and mechanical (modulus of rupture, specific energy, elastic modulus and proportionality limit) of the composites showed that those produced with the ash SCSA700 were similar to the control ones, which enables the partial replacement of Portland cement by this kind of ash / Doutorado / Construções Rurais / Doutora em Engenharia Agrícola

Low level nuclear waste arising from UK nuclear sites, research establishments, hospitals and industry is currently disposed of at the Drigg Disposal Facility in Cumbria. Waste is packed into steel canisters before being compacted and grouted into larger steel storage containers. The aqueous chemistry of wastes, especially radionuclides, in the presence of grout material is of major interest. The gout used at the Drigg site is a mixture of Ordinary Portland Cement and Pulverised Fly Ash additive, from which ingressing water will leach high levels of calcium, sodium and potassium and produce waters of a high pH. Aerobic environments are expected to dominate over the early period of the vault life, after which the combined effect of canister corrosion and microbial activity will lead to anaerobic conditions. After a much longer period (100,000 years) anaerobic conditions may cease and yield once again an aerobic environment where migration of radionuclides may be sorption-controlled rather than on hydroxide precipitation at high pH. Work has been performed under both aerobic and anaerobic conditions to study uranium solubility in the presence of complexing ligands that may be present in the waters of the nearfield of a low-level waste disposal vault. Eleven ligands have been investigated: carbonate, phosphate, chloride, sulphate, acetate, citrate, EDTA, NTA and organic matter- humic acid, fulvic acid and iso-sacchannic acid. Anaerobic conditions were achieved by two different procedures; the first used ferrous ions in hydroxide solution and the second used dithionite in hydroxide solution. Both methods produce reducing electrode potentials and high pH. Computer software has been used to model experimental results, thereby predicting uranium solubilities and speciation, and to propose new formation constants to fit the experimental results more closely. Studies have also been perforined to measure uranium sorption by grout material at high pH in the presence of the above ligands. This work makes a significant contribution to the understanding of uranium solubility and speciation in waters. at high pH and under conditions relevant to low level nuclear waste disposal.

Heat of hydration is a property of Portland cement and a direct result of the chemical reaction between cement and water. The amount of heat released is dependent upon the cement mineralogical composition, curing temperature, water to cement ratio, and cement fineness. High temperature resulting from heat of hydration (thereon referred to as HOH) of cement can affect the hydration process, and consequently the kinetics of development of the mechanical properties of concrete. One of the main reasons triggering the interest in HOH of cement is its implication in thermal cracking of concrete. The high temperature gradient between the inner core and the outer surface of a concrete element is known to result in large tensile stresses that may exceed tensile strength, thus leading to early–age thermal cracking in mass concrete. This dissertation initially addresses accurately predicting the heat of HOH of Portland cement at seven days based on the heat flow data collected from isothermal calorimetry for a time interval of 0-84 h. This approach drastically reduces the time required to identify the seven day HOH of Portland cement. The second part of this study focuses on cement fineness and its critical role on the heat generated by Portland cement during hydration. Using a matrix of four commercially available Portland cements, representing a wide range of mineralogical composition, and subjecting each of the as-received cements to several grinding increments, a linear relationship was established between cement fineness and heat of hydration. The effect of cement fineness and mineralogical composition on HOH of Portland cement was then related through a mathematical expression to predict the HOH of Portland cement based on its mineralogical composition and fineness. Three expressions were proposed for the 1, 3 and 7 day HOH. The findings indicate that the equations developed, based on cement main phase composition and fineness, can be used to identify cements with high heat of HOH that may cause thermal cracking in mass concrete elements. Also, the equations can be used to correlate the HOH with the other properties of Portland cement for quality control and prediction of chemical and physical properties of manufactured Portland cement and concrete. Restrained shrinkage experiments results on mortar specimens prepared with cements of variable phase composition and fineness indicate that interaction of C3A and sulfate source is the prime phenomenon followed by cement fineness as the second main factor influencing concrete cracking. In order to minimize this effect, the third part of this study focused on studying alternatives that can lower the heat generated by concrete on hydration through the incorporation of nanomaterials; namely, graphene nanoparticles. The results indicate that incorporation of graphene a as replacement for Portland cement improves thermal diffusivity and electrical conductivity of the cement paste. Consequently, the use of graphene can trigger improvement of the thermal conductivity of concrete elements thus reducing the cracking potential of concrete. Measurements of HOH of graphene-cement paste, at w/c=0.5, using isothermal conduction calorimetry, indicate that incorporation of graphene up to 10% increases the length of the induction period while reduces the magnitude of the alite main hydration peak due to the filler effect. Furthermore, increasing the w/c ratio from 0.5 to 0.6 and graphene content from 1 % to 10% (as a partial replacement of cement) increases the 7 day HOH of Portland cement by 50 J/g. Isothermal conduction calorimetry heat flow curves show that incorporation of graphene particles up to 10% does not have significant effect on interaction of aluminates and sulfates sources since the time of occurrence of the C3A sulfate depletion peak is not affected by graphene substitution up to 10%. Full factorial statistical design and analysis conducted on compressive strength data of mortar specimens prepared at two w/c ratios, using cements of different finenesses and graphene content indicates that the quantity of graphene and the physical interaction due to variable w/c, graphene and cement fineness, have the smallest P-value among all the samples, representing the most significant impact on compressive strength of mortar samples. It appears that in graphene cement paste composites, addition of 1% graphene results in 21% reduction of Young’s modulus. Increasing the graphene content from 1% to 5% and/or 10% does not show significant effect on Young’s modulus. Similar trends can be observed in the hardness of graphene cement paste samples. In conclusion, partial replacement of Portland cement with graphene nanoparticles in concrete mixtures is a good alternative to lower the cracking potential in mass concrete elements.

Please read the abstract in the section 00front of this document. / Thesis (PhD (Chemistry))--University of Pretoria, 2008. / Chemistry / unrestricted

Please read the abstract in the front part of this document / Thesis (PhD (Chemistry))--University of Pretoria, 2007. / Chemistry / unrestricted

This thesis deals with the stopping of hydration of alkali activated slag by organic solvents and investigates to what extent the selected organic solvent affects the results of the analyses. The solvents used were acetone, diethyl ether, ethanol, isopropanol and methanol, and this is because these are the most commonly used organic solvents in practice. Thermogravimetric analysis along with differential thermal analysis was used to assess the degree of influence of organic solvents on the alkali activated slag and Portland cement samples. Methanol and acetone affected the samples the most and the longer the sample was stored in the solvent, the more it reacted with the organic solvent. The adverse interaction of organic solvent was greatest for the Portland cement samples. Samples that were rinsed with diethyl ether prior to analysis had lower mass losses than samples that were not rinsed. In the case of alkali activated slag, it was found that the way in which the thermogravimetric results were affected by organic solvents was highly dependent on the activator used, with the smallest effect observed for Na2CO3 activation, while the largest effect was observed for NaOH activation at temperatures below 600 °C, and for higher temperatures for water glass activation.

The project elaborated in frame of engineering studies branch N2332-00. The project is submitting design of technology production sand mixture with cement binder – Portland binder CEM I 42,5 N. Pursuant to of the literary pursuit a problem of the sand mixture with cement binder was tested few sand mixture. As optimal composition it turned out application sand mixture with 2 % CaCl2 content and 1 – 2 % Dextrin content. Sand mixture with cement has good moulder and regenerating.

This thesis deals with possibilities of using brick-grind-dust which is a secondary product from manufacturing of grinded bricks. A boom in this method of masonry is connected with an increase of production of these secondary materials. These secondary materials are partly returned to brick manufacturing and partly buried in a landfill site. Due to their composition and origin, these materials are potentially pozzolan active, making them interesting for applications in hydraulic binders. The aim of the work was to study the physical and chemical properties of several brick-grind-dust and brick sands. Subsequently, binders based on these materials and Portland cement were prepared. The properties of the binders were modified by means of adding a commercially available polycarboxylate superplasticizer. The development of mechanical properties of the prepared binders has been studied over time. Hydration of the selected binders was analyzed by isothermal calorimetry.

The use of electromagnetic waves as a nondestructive evaluation technique to evaluate Portland cement concrete (PCC) structures is based on the principle that a change in the structure, composition, or properties of PCC results in a change in its dielectric properties. The coaxial transmission line is one of the few devices that can measure the dielectric properties of PCC at a frequency range of 100-1000 MHz. A coaxial transmission line developed at Virginia Tech was used to study the effect of moisture, type of aggregate, water/cement ratio, curing period, admixture type (microsilica, superplasticizer, and shrinkage admixture), and chloride content on the dielectric properties of PCC. Measurements were conducted in the time domain and converted to the frequency domain using Fast Fourier Transform. The research found that an increase in the moisture content of PCC resulted in an increase in the dielectric constant. Mixes containing limestone aggregate had a greater dielectric constant than those containing granite. The dielectric constant decreased with curing period due to the reduction in free water availability. Mixes containing higher water/cement ratios exhibited a higher dielectric constant, especially in the initial curing period. The admixtures did not significantly affect the dielectric constant after one day of curing. After 28 days of curing, however, all three admixtures had an effect on the measured dielectric constant as compared to control mixes. Chloride content had a significant effect on the loss part of the dielectric constant especially during early curing. A relationship was also established between the chloride permeability (based on conductance measurements) of PCC and its dielectric constant after 75 days of moist curing. / Master of Science

Soft soil stabilization frequently uses cement, lime, fly ash, etc., but very limited studies were conducted on the long-term durability of stabilized soil. The present research work deals with the long-term durability of commercially available soil (i.e., EPK clay) stabilized with ordinary Portland cement and polypropylene fiber using a realistic approach, where the effect can be noticed in each weathering cycle. In the present study, two different tests (i.e., wetting-drying and freezing-thawing) were conducted to analyze the long-term durability of stabilized soil. Cycles of higher temperature followed by rainfall, which generally occurs in southern states of the US, were analyzed by the wetting-drying test; and on the other hand, cycles of freezing temperature followed by normal temperature, which generally occurs in northern states of the US and Canada, were analyzed by the freezing-thawing test. For the mid-continental region where freezing, normal, and higher temperature followed by rainfall are expected to occur, hence both the test method i.e., wetting-drying and freezing-thawing, were suggested. Laboratory experimental investigations were conducted to find the percentage loss of stabilized soil during wetting-drying and freezing-thawing tests, which were used as a durability indicator for cement and cement-fiber stabilized soil. Stabilized samples were subjected to harsh environmental conditions in a laboratory set up, and their deterioration was observed and studied after each wetting-drying and freezing-thawing cycle. In the real world, stabilized soil encounters seasonal cycles of monsoon and summer in long run of its service life which was simulated in rapid weathering cycles in laboratory setup. EPK clay samples were stabilized with different percentages of cement, and a mix of cement-fiber combination and were subjected to 12 cycles of wetting-drying and freezing-thawing cycles separately to determine the percentage loss of soil in accordance with the ASTM standards. Finally, based on percentage loss of soil of those stabilized samples which survived up to 12 cycles of weathering action, the optimum content of stabilizing agent was determined for wetting-drying and freezing-thawing tests. Results of wetting-drying tests indicate that EPK clay stabilized with ordinary Portland cement and fiber combination survived up to 12 cycles, but only 10% cement + 0.5% fiber was durable against wetting-drying based on percentage loss. For all the samples stabilized with 10% cement + 0.5% fiber combination, the percentage loss of soil when subjected to durability test was less than 7%, which satisfy the Portland Cement Association’s (PCAs) durability specification. The results of freezing-thawing tests indicate that the EPK clay stabilized with 10% cement, 5% cement + 0.5% fiber, and 10% cement + 0.5% fiber survived up to 12 cycles and were durable against freezing-thawing based on percentage loss of soil i.e., less than 7% which satisfy the Portland Cement Association’s durability specification.