O fosfogesso é um resíduo da indústria de fertilizantes fosfatados que concentra radionuclídeos naturais. Neste trabalho foi estudada a taxa de exalação de 222Rn em placas e tijolos de fosfogesso, visando sua utilização na construção de residências. Para tanto, foram determinadas a taxa de exalação de 222Rn por meio da técnica da câmara de acumulação com detectores sólidos de traços nucleares (SSNTD) inseridos em uma câmara de difusão e a dose efetiva para um indivíduo habitando uma residência construída com esses materiais. A título de comparação foi também determinada a taxa de exalação teórica, por meio do modelo proposto pela UNSCEAR, a partir da concentração de 226Ra nas placas e tijolos de fosfogesso. A contribuição do revestimento na superfície dos materiais para a diminuição da taxa de exalação de radônio foi também avaliada. Foram estudados placas e tijolos fabricados com fosfogesso das empresas Bunge Fertilizantes, Ultrafertil e Fosfertil e tijolos fabricados com gesso comum. Os valores médios obtidos foram 0,19 0,06 Bq m-2 h-1, 1,3 0,3 Bq m-2 h-1 e 0,41 0,07 Bq m-2 h-1 para as placas fabricadas com fosfogesso proveniente das empresas Bunge, Ultrafertil e Fosfertil, respectivamente. Já para os tijolos de fosfogesso, os valores foram 0,11 0,01 Bq m-2 h-1, 1,2 0,6 Bq m-2 h-1, 0,47 0,15 Bq m-2 h-1, para o fosfogesso da Bunge, Ultrafertil e Fosfertil. O tijolo fabricado com gesso comum apresentou valor médio de 0,18 0,08 Bq m-2 h-1. As doses efetivas anuais para um indivíduo habitando uma residência construída como os tijolos ou placas de fosfogesso de qualquer uma das procedências ficaram abaixo do limite de dose efetiva para indivíduos do público de 1 mSva-1 estabelecido pela Comissão Internacional de Proteção Radiológica. / Phosphogypsum is a waste of the fertilizer industry that concentrates radionuclides. In this work, the 222Rn exhalation rate from phosphogypsum paltes and blocks from different origins used at dwellings construction was studied. The 222Rn exhalation rate was determined through the accumulation chamber technique with solid state nuclear track detectors (SSNTD). The effective dose for an individual living in a residence built with phosphogypsum based materials was evaluated. It also was calculated the 222Rn exhalation rate through the UNSCEAR model, from the 226Ra concentration in the materials, in order to compare the experimental results. It was evaluated the contribution of building component (paint) to the reduction of 222Rn exhalation rate. The plates and blocks were manufactured with phosphogypsum from Bunge Fertilizantes, Ultrafertil and Fosfertil. Blocks manufactured with ordinary gypsum was also evaluated. The average results obtained were 0.19 ± 0.06 Bq m-2 h-1, 1.3 ± 0.3 Bq m-2 h-1 and 0.41 ± 0.07 Bq m-2 h-1for plates manufactured with phosphogypsum from Bunge Fertilizer, Ultrafertil and Fosfertil, respectively. For the phosphogypsum blocks the values were 0.11 ± 0.01 Bq m-2 h-1, 1.2 ± 0.6 Bq m-2 h-1, 0.47 ± 0.15 Bq m-2 h-1, for Bunge, Ultrafertil and Fosfertil. The blocks manufactured with ordinary gypsum presented average value of 0.18 ± 0.08 Bq m-2 h-1. All phosphogypsum plates and blocks evaluated in this study presented effective dose for radon inhalation lower than the recommended value of 1mSv y1, the annual effective dose limit for public exposure by International Commission on Radiological Protection.

O fosfogesso (FG), um subproduto da indústria de fosfato, é classificado como Material Radioativo de Ocorrência Natural Tecnologicamente Aumentado (TENORM) ou como um resíduo NORM. Ele é obtido durante o ataque da rocha fosfática com ácido sulfúrico para a produção de ácido fosfórico. O FG apresenta em sua composição radionuclídeos das séries de decaimento natural do U e Th: principalmente 226Ra, 228Ra, 232Th, 210Pb e 210Po. Os produtores brasileiros estocam o FG em pilhas secas, o que representa riscos para o meio ambiente. Sendo assim, estudos foram realizados para avaliar meios de sua reutilização. Uma possível solução para este problema é o emprego do FG na agricultura como um condicionador do solo. A entidade reguladora brasileira (CNEN) estabeleceu limites de isenção para o uso de FG na agricultura ou na indústria cimenteira: a concentração de atividade de 226Ra e 228Ra deve ser inferior a 1 Bq g-1. No entanto, para a sua aplicação segura, ainda é necessário assegurar que os radionuclídeos presentes no PG não estarão disponíveis para o ambiente. Este estudo tem como objetivo verificar a disponibilidade de 238U e 232Th em amostras de solos com FG através de percolação com água, por meio do cálculo da fração disponível. Esta fração foi obtida pela relação entre a concentração dos radionuclídeos no lixiviado (pelo emprego de um procedimento radioquímico adaptado, publicado pela Agência Internacional de Energia Atômica - IAEA) sobre a concentração total das amostras (obtida por Análise por Ativação com Nêutrons Instrumental e espectrometria gama). Os resultados demonstraram que a fração disponível dos radionuclídeos foi em todos os casos inferior a 0,2%. Isto indica que a utilização de fosfogesso como insumo agrícola não contribui para o aumento da disponibilidade de 238U e 232Th na água de lixiviação. / Phosphogypsum (PG), a byproduct of the phosphate industry, is classified as Technologically Enhanced Naturally Occurring Radioactive Material (TENORM) or as a NORM waste. It is obtained during the attack of the phosphate rock with sulphuric acid for the production of phosphoric acid. PG presents in its composition radionuclides of the natural U and Th decay series: mainly 226Ra, 228Ra, 232Th, 210Pb and 210Po. The Brazilian producers stock the PG in dry stacks, posing risks to the surrounding environment. Therefore, several studies were undertaken to evaluate viable ways of its reuse. One possible solution to this problem is to reuse PG in agriculture as a soil conditioner. The Brazilian regulatory body (CNEN) established exemption limits for the use of PG in agriculture or cement industry: the 226Ra and 228Ra activity concentration should be below 1.0 Bq g-1. However, for its safe application, it is still necessary to ensure that the radionuclides present in the PG will not be available to the environment. This study aims to determine the availability of 238U and 232Th in samples of soils amended with PG through percolation with water, by calculating the available fraction. This fraction was obtained by the ratio of the concentration of the radionuclides in the leachate (by a radiochemical procedure based on a publication from International Atomic Energy Agency - IAEA) over the total concentration in the samples (by Instrumental Neutron Activation Analysis and gamma spectrometry). The results demonstrated that the available fraction of the radionuclides were in all cases lower than 0.2%. This indicates that the use of phosphogypsum as agricultural input does not contribute to increase the availability of 238U and 232Th to the leaching water.

Fosfogesso é um resíduo sólido poluente resultante da produção de ácido fosfórico, principal componente de fertilizantes fosfatados. Esse resíduo é gerado no mundo a uma taxa de 180 milhões de toneladas por ano, originando problemas sérios de armazenagem em vários países. As restrições de leis ambientais e o aumento do custo de espaço para a armazenagem do fosfogesso têm estimulado pesquisadores a encontrarem aplicações para este resíduo. Uma delas é a sua utilização como material de construção de bases rodoviárias. O objetivo principal deste trabalho é avaliar a influência do tipo de cimento Portland na resistência e deformabilidade das misturas de fosfogesso e cimento, com vistas à sua utilização em construção rodoviária. O comportamento mecânico foi analisado através de ensaios de compressão simples de corpos de prova compostos de fosfogesso e cimento, variando-se o tipo de cimento (CP III 40, CP V ARI e CP II-E 32), o teor de cimento (5%, 10% e 15%), a energia de compactação (normal e modificada), a condição de ensaio dos corpos de prova (sem imersão e após imersão em água por 4 horas) e o período de cura (1, 3, 7, 28, 84 e 210 dias). Realizou-se também uma comparação entre os desempenhos das misturas de fosfogesso e cimento e de solo-cimento. Os resultados mostram que o tipo de cimento não tem efeito predominante no comportamento da mistura, se comparado com os efeitos das outras variáveis. Entretanto, observou-se que, a longo prazo, os cimentos CP II-E 32 e CP V ARI, com teores elevados de aluminato tricálcico (C3A) em sua composição, 5% e 7,5%, respectivamente, conduzem à diminuição de resistência e rigidez da mistura; ao contrário do cimento CP III 40, com baixo teor de C3A, 2,4%, que forneceu, até os 210 dias, o aumento das mesmas. Além disto, o aumento do teor de cimento, da energia de compactação e do tempo de cura conduz ao crescimento, e a imersão dos corpos de prova em água a uma queda, da resistência e rigidez das misturas. No estudo comparativo, as misturas de fosfogesso e cimento apresentam resistência e rigidez, respectivamente, da ordem de ¼ e ½ da resistência e rigidez das misturas de solo-cimento. Finalmente, conclui-se que as misturas de fosfogesso e cimento têm potencial para serem usadas em construção rodoviária. / Phosphogypsum is a pollutant solid by-product resulting from the production of phosphoric acid, a major constituent of phosphate fertilizers. The annual worldwide production of this by-product is approximately 180 millions tons a year, causing serious problems in several countries due to its disposal. Environmental pressures as well as increased land costs associated with stockpiling phosphogypsum have stimulated researchers to find applications for this material. One of them is its use as road base material. The main objective of this research is to evaluate the influence of Portland cement type on the strength and deformability of cement-stabilized phosphogypsum mixtures for use in road construction. Thus the mechanical behavior of the mixtures was analyzed through unconfined compression testing of specimens composed by phosphogypsum and cement, varying the cement type (CP III 40, CP V ARI and CP II-E 32), the cement content (5%, 10% and 15%), the compaction energy (standard and modified Proctor), the testing conditions (without immersion and after immersion in water) and the curing time (1, 3, 7, 28, 84 and 210 days). A comparative study of performance between cement-stabilized phosphogypsum and cement-soil mixtures was also carried out. The laboratory results indicated the cement type has no significant effect in the mechanical behavior of the mixtures, if compared with the effects of the other parameters. However, it was observed in long-term periods that thecement types CP II-E 32 and CP V ARI, with 5% and 7,5% tricalcium aluminate (C3A) contents in their chemical composition, respectively, lead to decreasing strength and stiffness of the mixture; unlike the cement type CP III 40, with lower C3A content, 2,4%, that leads to increasing strength and stiffness of the mixture up to 210 day. In addition, the strength and stiffness of the mixtures increase with increasing cement content, compaction energy and curing period before testing, but decrease with immersion test condition. In the comparative study, the cement-stabilized phosphogypsum mixtures has strength and stiffness of about ¼ e ½ of the strength and stiffness of the cement-soil mixtures, respectively. Finally, it was concluded that the cement-stabilized phosphogypsum mixtures have potential application for road construction.

Este trabalho tem como objetivo estudar, a partir de ensaios de laboratório, o comportamento mecânico de misturas de fosfogesso e cal destinadas à construções de bases e sub-bases rodoviárias. O fosfogesso é um resíduo resultante da produção do ácido fosfórico, principal componente de fertilizantes fosfatados. O fosfogesso é gerado em grande escala, originando sérios problemas de armazenagem. Restrições de leis ambientais e o aumento do custo de espaço para a armazenagem do fosfogesso têm estimulado pesquisas para a aplicação desse material. Entre as pesquisas, encontra-se, o aproveitamento desse resíduo como material de construção de bases e sub-bases rodoviárias. As amostras destas misturas foram submetidas a ensaios de compressão simples, compressão diametral e CBR. Nos ensaios de compressão simples e compressão diametral, os corpos de prova foram ensaiados sem imersão e após imersão prévia em água por quatro horas. Para todos os teores de cal utilizados (0%, 3%, 5%, 7% e 10%) os corpos-de-prova foram compactados na energia equivalente ao Proctor modificado. Para cada teor de cal os corpos-de-prova passaram por processo de cura de 0, 3, 7 e 28 dias. Quatro réplicas foram moldadas para cada condição de ensaio, obtendo-se a média dos resultados pelo método estatístico de GRUBBS. Concluiu-se com esses ensaios que valores crescentes de tempo de cura e de teor de cal conduziram a maiores valores de resistência e de rigidez. Além disso, ensaios realizados após a imersão em água apresentaram valores de resistência à compressão simples, resistência à compressão diametral e rigidez menores do que os obtidos sem imersão. Observou-se também que as misturas de fosfogesso e cal, no geral, apresentaram melhores resultados de resistência à compressão simples, resistência à compressão diametral e coesão do que as misturas de solo cal. Entretanto as misturas compostas por fosfogesso e cimento obtiveram valores superiores de resistência e rigidez se comparada com as misturas de fosfogesso e cal. / This work has the aim of study, considering laboratory experiments, the mechanical behavior of a mixture of phosphogypsum and lime to be used in bases and sub-bases of road construction. The phosphogypsum is a solid waste result of the phosphoric acid production, main component of phosphor fertilizers. The phosphogypsum is generated in large scale, causing serious problems of storage. Restriction of environment laws and the increasing cost of the area needed for the phosphogypsum storage have stimulated researches to this material application. Among these researches, there is the reutilization of this waste as construction material of road bases and sub-bases. The samples of theses mixtures were submitted to tests of unconfined compressive strength, indirect tensile strength and California bearing ratio. In the tests of unconfined compressive strength and indirect tensile strength, the specimens were submitted to two test conditions: without immersion and with immersion in water for four hours. It was used 0%, 3%, 5%, 7% e 10% of lime in the mixtures. All specimens were compacted in the energy modified Proctor. Each specimens get through to a process of curing time of the 0, 3, 7 and 28 days. For each condition test 4 copies were molded and the result got by the statistic method of GRUBBS. With this tests, it was concluded that higher values of time of cure and the line content led to higher strength and stiffness values. Besides, test performed after immersion in water presented strength values for the unconfined compressive, diametral compression strength and stiffness lower than those obtained without immersion. It also can be observed that phosphogypsum and lime mixtures got better results of unconfined compressive strength and diametral compression strength than soil and lime mixtures. However, phosphogypsum and cement mixtures got better results of strength and stiffness than phosphogypsum and lime mixtures.

No description available.

Orientador: Prof. Dr. Sérgio Ricardo Lourenço / Tese ( doutorado)- Universidade Federal do ABC. Programa de Pós-Graduação em Energia, 2016.

Submitted by Luciana Ferreira (lucgeral@gmail.com) on 2015-05-05T14:45:17Z No. of bitstreams: 4 Dissertação - Juliana Verônica Ribeiro das Chagas - 2014 - (1).pdf: 1793681 bytes, checksum: ac64ee69a56f065f9eede650ce8286c0 (MD5) Dissertação - Juliana Verônica Ribeiro das Chagas - 2014 - (2).pdf: 2858658 bytes, checksum: 1274a997059f25141f2f6c339f2fa71d (MD5) Dissertação - Juliana Verônica Ribeiro das Chagas - 2014 - (3).pdf: 1859876 bytes, checksum: 4b38928fd5a6be491dc707a495e0bf73 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2015-05-05T15:14:24Z (GMT) No. of bitstreams: 4 Dissertação - Juliana Verônica Ribeiro das Chagas - 2014 - (1).pdf: 1793681 bytes, checksum: ac64ee69a56f065f9eede650ce8286c0 (MD5) Dissertação - Juliana Verônica Ribeiro das Chagas - 2014 - (2).pdf: 2858658 bytes, checksum: 1274a997059f25141f2f6c339f2fa71d (MD5) Dissertação - Juliana Verônica Ribeiro das Chagas - 2014 - (3).pdf: 1859876 bytes, checksum: 4b38928fd5a6be491dc707a495e0bf73 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Made available in DSpace on 2015-05-05T15:14:24Z (GMT). No. of bitstreams: 4 Dissertação - Juliana Verônica Ribeiro das Chagas - 2014 - (1).pdf: 1793681 bytes, checksum: ac64ee69a56f065f9eede650ce8286c0 (MD5) Dissertação - Juliana Verônica Ribeiro das Chagas - 2014 - (2).pdf: 2858658 bytes, checksum: 1274a997059f25141f2f6c339f2fa71d (MD5) Dissertação - Juliana Verônica Ribeiro das Chagas - 2014 - (3).pdf: 1859876 bytes, checksum: 4b38928fd5a6be491dc707a495e0bf73 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Previous issue date: 2014-07-02 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The phosphogypsum, a by-product from the production of phosphoric acid, requires the availability of large areas for its storage, representing a problem for the industries of fertilizers, both economically and environmentally. Therefore, there is a need to search for alternative applications of phosphogypsum in order to minimize the impacts of its deposition. Several studies were performed to verify the possibility of using phosphogypsum in geotechnical works, which showed promising results. However, the deformability of this material can be a limiting factor for their use. Thus, one of the main objectives of this study was to analyse the evolution of deformation over time of the phosphogypsum, soil and a mixture containing 10% of phosphogypsum and 90% of soil (mixture A). Furthermore, this study also analysed the deformability of these materials when they are not saturated, which is the natural condition in which they are used. The phosphogypsum was collected in a phosphate fertilizers industry, called Anglo American, in the city of Catalão, Goiás, and the soil was collected in Aparecida de Goiânia, Goiás. For the analysis of deformation over time, consolidation tests were performed with different loading times (48 hours, 7 days and 15 days) on samples in saturated condition. After the consolidation tests, others tests were conducted in order to give a better understanding of the results, such as: X-Ray diffraction, permeability, scanning electron microscopy (SEM) and tests to obtain the water retention curve using the equipment WP4C (Dewpoint PotentiaMeter). For the analysis of the deformation in unsaturated condition, consolidation tests in unsaturated conditions and tests of water content control were performed in the soil, phosphogypsum and mixture A (10% phosphogypsum + 90% soil). The results show no stabilizing of the deformation over time of the mixture A and the phosphogypsum. Furthermore, the increase of the deformation due only to the secondary compression expected for a period of five years is approximately 0.5% for the soil, 1.4% for the mixture A and 15.5% for the phosphogypsum. It has been found by granulometry tests that the deformations occur due to the breakage of the grains of phosphogypsum. It is noteworthy that no mineralogical change occurs, as observed by X-ray diffraction. Furthermore, it was verified with the unsaturated consolidation tests that a slight variation of suction occurs during the test, but this variation influenced more the deformability of the phosphogypsum than of the soil and mixture A. Thus, it was concluded that the deformation limits the use of phosphogypsum or mixtures of phosphogypsum and soil in geotechnical works. / O fosfogesso, subproduto da fabricação do ácido fosfórico, necessita da disponibilidade de grandes áreas para ser estocado, representando um problema para as indústrias de fertilizantes tanto do ponto de vista econômico quanto ambiental. Diante disso, surge a necessidade de buscar alternativas de aplicação do fosfogesso de forma a minimizar os impactos decorrentes de sua deposição. Diversos trabalhos foram realizados para verificar a possibilidade de utilização do fosfogesso em obras geotécnicas, os quais apresentaram resultados promissores. No entanto, a deformabilidade deste material pode ser um limitante para o seu uso. Dessa forma, um dos objetivos deste trabalho foi analisar a evolução da deformabilidade ao longo do tempo do fosfogesso, do solo e de uma mistura contendo 10% de fosfogesso e 90% de solo (mistura A). Além disso, foi analisado também a deformabilidade desses materiais quando estão não saturados, que é a condição natural em que eles serão utilizados. O fosfogesso foi coletado na indústria de fertilizantes fosfatados Anglo American na cidade de Catalão, Goiás, e o solo foi coletado em Aparecida de Goiânia, Goiás. Para a análise da deformabilidade ao longo do tempo, foram executados ensaios de adensamento com diferentes tempos de carregamento (48 horas, 7 dias e 15 dias) nas amostras em condição saturada. Após os ensaios de adensamento foram realizados ensaios complementares visando uma melhor compressão dos resultados como: difração de raios-X, permeabilidade, microscopia eletrônica de varredura (MEV) e ensaios para obtenção da curva de retenção de água, utilizando o equipamento WP4C (Dewpoint PotentiaMeter). Para a análise da deformabilidade na condição não saturada, foram executados ensaios de adensamento não saturados e ensaios de controle de umidade no solo, no fosfogesso e na mistura A (10 % fosfogesso + 90 % solo). Os resultados mostram que não houve estabilização das deformações da mistura A e do fosfogesso ao longo do tempo. Além disso, o aumento da deformação volumétrica devido apenas ao adensamento secundário prevista para um período de cinco anos é de aproximadamente 0,5% para o solo, 1,4% para a Mistura A e 15,5 % para o fosfogesso. Foi verificado por meio de ensaios de granulometria, que as deformações ocorrem devido a quebra dos grãos de fosfogesso. Vale ressaltar que não ocorre alteração mineralógica, fato verificado através da difração de raios-X. Além disso, foi visto com os ensaios de adensamento não saturados que ocorre uma pequena variação de sucção ao longo do ensaio, mas que essa variação influenciou mais a deformabilidade do fosfogesso do que do solo e da mistura A. Portanto, concluiu-se que a deformação limita o uso do fosfogesso ou de misturas solo e fosfogesso em obras geotécnicas.

Orientador: Gustava Paim Valença / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-24T00:06:11Z (GMT). No. of bitstreams: 1 Campos_Kurts_M.pdf: 1571455 bytes, checksum: be3e0b10fcf0076c5a292b9ff9f8e965 (MD5) Previous issue date: 2013 / Resumo: Em parques industriais produtores de ácido fosfórico, um grande problema é a quantidade de rejeito gerado, o fosfogesso (gesso com impurezas de ácido fosfórico e sulfúrico). A estocagem deste material no meio ambiente resulta em problemas graves para a fauna e flora nos locais onde é depositado. Neste trabalho, a viabilidade técnica de uma alternativa para o problema de descarte deste subproduto é discutida a partir da recuperação do dióxido de enxofre (SO2) de fosfogesso para utilização em plantas de ácido sulfúrico. Algumas simulações de processo das plantas de ácido sulfúrico serão apresentadas, apontando alternativas industriais para utilização de SO2 recuperado / Abstract: In industrial parks that produce phosphoric acid, the major problem is the amount of waste generated: the phosphogypsum (gypsum with impurities such as phosphoric and sulfuric acid). The storage of this material in the environment results in serious problems for wildlife and flora in places where it is deposited. An alternative to the problem of disposal of this waste as well as its technical feasibility is discussed, recovering sulfur dioxide SO2 from phosphogypsum for use in sulfuric acid plants. In this work, some simulations of sulfuric acid operation were made and the proposal is presented, pointing out the best alternative for SO2 reuse from phosphogypsum / Mestrado / Engenharia de Processos / Mestre em Engenharia Química

Fluoride ion is an accompanying impurity in a wide variety of chemical gypsum throughout the world. In this study, the Ion Selective Electrode (ISE) method, the Ion Chromatography (IC) method and the standard Willard and Winter method of fluoride analysis were adapted and compared for use in the quantification of fluoride in South African chemical gypsum. During the use of ISE, the pH of sample solutions was found to be a critical parameter for the results to be meaningful. An operating pH of approximately 5 was suitable for consistency of results. It was important to ensure the existence of the ionised form of fluorine in solution, because the detection was based on the sensitivity of the membrane electrode to this species. In the case of the Willard and Winter method, the traditional visual indicator titration was replaced by a more sensitive spectrophotometric detection, because of low fluoride levels in the chemical gypsum. The parameter sensitive reaction rate approach was adapted, and the reaction allowed to go to completion to enable measurement with a bench top spectrophotometer. The IC method required a good separator since fluoride ions usually eluted too early for detection on common ion exchange columns. The data handling of the chromatographic software was thoroughly examined and consistent integration of the chromatograms maintained. Sample preparation of the chemical gypsum involved particle size reduction through grinding. No trend between fluoride impurity and the particle size of the sample was observed. <p. The quantity of fluoride in Kynoch and Omnia phosphogypsum were found to be 0.10% and 0.04% respectively. The Tioxide chemical gypsum, titangypsum, was found to contain in the region of 0.02% fluoride. Generally, the level of fluorine (F) has to be reduced to about 0.2% before phosphogypsum can be used as substitute for natural gypsum in the cement industry. The aim of this study is to critically evaluate three analytical methods, namely, the Willard and Winter standard method of fluoride analysis, the ISE method, and IC as applied in the quantification of fluoride in chemical gypsum. Secondly, the efficiency of treatment of the chemical gypsum with water, lime and sulphuric acid was investigated. The ISE method was found to be faster and relatively simpler versus both Willard and Winter and the IC methods. The IC method was quite superior for indicating general complexity of the sample and it was faster than the Willard and Winter method. The standard Willard and Winter method was generally found to be long and tedious. The three methods validated one another as percentages of fluoride in the chemical gypsum samples were the same. The study indicated that a sulphuric acid pretreatment of the chemical gypsum was the most effective (90%) in the removal of fluoride impurity compared to the lime treatment and water washing (9%). However, the water washing would be inexpensive for practical treatment of chemical gypsum at plant level. / Thesis (PhD(Chemistry))--University of Pretoria, 2006. / Chemistry / unrestricted

Pozzolanic reactions play a key role in improving the compressive strengths of compacted fly ash-lime specimens. Based on studies performed with cement amended fly ash (FA), activation of fly ash-lime pozzolanic reactions should accelerate the rate of strength development and mobilize larger compressive strengths facilitating improved engineering performance of fly ash amended materials. Further, use of phosphogypsum (PG) is a cause of environmental concern as the material is acidic (pH < 3.0) and contains considerable amounts of fluoride (0.86%). The main research objectives of the thesis are to activate lime-fly ash reactions by thermal and chemical activation process and examine the efficacy of fly ash pozzolanic reactions in controlling fluoride release by phosphogypsum. A comprehensive laboratory experimental program was performed to examine the influence of curing temperature (thermal activation) and calcined PG addition (chemical activation) on lime-fly ash reactions. The kinetics of fly ash-lime reactions are examined by monitoring the reacted lime content as function of curing period and temperature. The influence of variations in fly ash/lime content and dry density on the compressive strength developed by specimens is evaluated. The thermodynamic parameters for the fly ash-lime (FA-L) reactions have been delineated. Fly ash-lime-phosphogypsum (FA-L-G) mixes in slurry and compacted states were monitored for fluoride released as function of curing period The influence of curing temperature in activating fly ash-lime reactions is first examined. Specimens were cured at 25°C (termed RTC or room temperature cured) and at 80° (termed SC or steam cured) to understand thermal activation of fly ash-lime reactions. The rate of lime consumption by SC specimens classified as 2 stage process. The robust increase during stage 2 of steam curing suggested that the lime-solidification reactions did not reach equilibrium even after 4 days of curing at the elevated temperature. While only 3.1 to 3.3 % of added lime was consumed after 28 days of curing at room temperature, much larger amounts of lime ( 8.6-9.3%) were consumed after 4 days of steam-curing. Further, the lime-fly ash reactions were accelerated by 6 to 7 folds on curing the specimens at elevated temperature. The results indicated that activation of lime-fly ash reactions by curing at elevated temperature besides accelerating the rate of strength development also facilitated development of larger strength. Analysis of the free energy change values (ΔG°) indicated that the lime solidification reaction alters from dis-favored (less spontaneous) to favoured (spontaneous) state on curing at 80oC. The positive ΔH° (enthalpy change) values for the fly ash-lime reactions indicated that the reactions are endothermic in nature and are facilitated by increase in curing temperature. Gypsum activation was achieved by addition of 2.5 to 5% calcined phosphogypsum to fly ash lime mixes and curing the compacted specimens at room temperature (FA-L-G specimens). The rate of lime consumption by FA-L-G specimens appeared to be three stage process. The mass of lime consumed by FA-L-G specimens was about 1.5 to 3 folds higher than values of the RTC and SC specimens. Additional lime is consumed by FA-L-G specimens in ettringite formation. A similarity existed between rate of lime consumed and rate of strength developed by the FA-L-G specimens. It is proposed that besides lime solidification reactions, densification of the matrix by filling up of voids by fine gypsum particles and compaction of matrix by the growth of ettringite crystals also contribute to compressive strength of FA-L-G specimens; this additional mechanism of strength development accounts for their higher compressive strength in comparison to the SC and RTC specimens despite similar initial lime addition values. The trend of results suggests that activation of FA-L reactions by calcined PG addition is more effective than steam curing. Comparison of ΔG° values of RTC, SC and FA-L-G specimens revealed that the spontaneity of the lime solidification reactions is least for RTC specimens and improves with addition of phosphogypsum and further improves on curing at elevated temperature. Fly ash-lime pozzolanic reactions substantially reduced the fluoride released from the FA-L-G specimens. The marked reduction in fluoride released by PG amended with fly ash and lime is ascribed to entrapment of PG particles in the cemented matrix formed by fly ash-lime pozzolanic reactions together with consumption of fluoride in formation of insoluble fluoride bearing compounds. The thesis brings out that activation of fly ash-lime reactions leading to quicker and larger compressive strength development is achieved by curing the compacted fly ash-lime specimens at 80°C for 24 hr or by addition of 2.5 to 5% of calcined PG to fly ash-lime mix and curing the compacted specimens at room-temperature. As larger strengths are developed by PG addition than by curing at 80oC, it is recommended that FA-L-G technique be adopted for manufacture of building materials in the civil engineering industry. This technique is also sustainable as it does not require energy for heating which is needed in the steam-curing technique.