Introdução: O tratamento dos tumores ósseos benignos é frequentemente realizado por abordagem intralesional com curetagem do tumor e preenchimento da falha óssea com substâncias biológicas ou sintéticas. Entre as biológicas estão os vários tipos de enxertos e o maior representante das sintéticas é o cimento ósseo ou polimetilmetacrilato (PMMA). O uso do cimento ósseo compacto pode apresentar problemas devido à necrose térmica, ao afrouxamento asséptico, à incapacidade de remodelação e à elasticidade inadequada em relação ao osso normal. O desenvolvimento de um cimento ósseo esponjoso que atenda a estas demandas mecânicas e biológicas e que seja de fácil manipulação no ambiente cirúrgico tem estimulado alguns pesquisadores. Basicamente, é possível formar poros no interior do cimento por mistura de substâncias hidrossolúveis ou por reação química produtora de gás. Objetivo: Desenvolver e caracterizar fisicamente e mecanicamente um cimento ósseo com poros intercomunicantes de aspecto estrutural esponjoso. Material e métodos: A produção de cimento esponjoso foi realizada misturando-se o PMMA com bicarbonato de sódio e ácido cítrico. Foram confeccionados 90 corpos de prova com 40 mm de altura por 20 mm de diâmetro distribuídos em 6 grupos (n=15): G1 formado por cimento esponjoso em que antes da polimerização do cimento foram adicionados bicarbonato de sódio e ácido cítrico na proporção de 10% em relação ao componente sólido do cimento (polímero); G2 - cimento esponjoso na proporção de 20%; G3 - cimento esponjoso na proporção de 30%; G4 - cimento ósseo de PMMA compacto; G5 - formado por cimento de poliuretana de mamona (Bioósteo®) na proporção de 20%; G6 formado de corpos de prova cilíndricos de osso esponjoso extraído com trefina de côndilos tibiais proximais de bovinos. A qualidade do cimento esponjoso foi avaliada por macroscopia, cálculo de densidade, imersão em azul de metileno, tomografia computadorizada, microscopia eletrônica de varredura e ensaio mecânico de compressão. Resultados: A melhor forma de produção de cimento esponjoso foi pela mistura de PMMA e componentes efervescentes. O teste da imersão em azul de metileno mostrou que os G2 e G3 apresentaram melhor intercomunicabilidade. As análises com o microscópio eletrônico de varredura (MEV) mostraram uma ampla variação no tamanho e distribuição dos poros que medem de 50m a 3mm. Em relação aos ensaios mecânicos não houve diferenças significativas entres os grupos de cimento esponjoso G1, G2 e G3. Estes grupos apresentaram valores pouco inferiores aos do grupo G6 de osso esponjoso bovino. O grupo G4 (PMMA compacto) apresentou valores extremamente altos quando comparado ao osso esponjoso bovino e ao cimento esponjoso. O grupo G5 de cimento ósseo de mamona não atingiu os valores aceitáveis de resistência mecânica. Conclusão: Foi possível desenvolver um cimento esponjoso à base de polimetilmetacrilato pela mistura com os aditivos efervescentes, bicarbonato de sódio e ácido cítrico, que apresenta características físicas e mecânicas desejadas como substituto ósseo esponjoso nas curetagens para tratamento de tumores ósseos benignos. O cimento de mamona esponjoso na forma testada mostrou-se inadequado para os fins pretendidos. / Introduction: Benign bone tumors are usually treated by intralesional curettage. The bone defect may be filled with synthetic or biological substitutes. Polymetylmethacrylate (PMMA) is the most popular synthetic substitute and the solid form is associated to thermal necrosis, aseptic loosening, bone remodeling prevention and distinct elasticity. Research of porous cement that solves these drawbacks and can be molded intraoperatively has encouraged many authors. For surgical purposes, porosity can be achieved by mixing hydrosoluble substances or by gas-foaming reactions. Objective: Development and physical and mechanical characterization of a bone cement with interconnecting pores and cancellous bone like structural aspect. Methods: Porous cement was produced by adding the effervescent components sodium bicarbonate and citric acid to PMMA. Six groups of fifteen cylindrical samples (40 mm height, 20 mm diameter) were compared. G1, G2 and G3 groups consisted of porous cement specimens of PMMA with 10%, 20% and 30% of effervescent components respectively. G4 consisted of solid PMMA cement specimens. G5 group consisted of porous ricinic polyurethane cement (Bioósteo®) with 20% effervescent components specimens. The control group G6 consisted of bovine cancellous bone samples. The porous cements were characterized in terms of porosity, density, pore interconnectivity and compressive strength. Macroscopic evaluation and measuring, methylene blue immersion, Scanning Electron Microscopy (SEM), mechanical testing and a special computed tomography reading software were employed for these evaluations. Results: The pilot study showed that adding effervescent components to PMMA was the best solution for porous cement production. The methylene blue immersion test showed that G2 and G3 groups had better pore interconnection. Scanning electron microscopy (SEM) showed a wide variation in pore size, from 50m to 3mm, and pore distribution. No significant differences between G1, G2 and G3porous cement groups were found regarding to mechanical strength and Young Modulus. Cancellous bovine bone, G6, was slightly stronger and less elastic than these groups. This property is potentially beneficial considering osteointegration as a consequence of Wolfs law. Solid PMMA is extremely strength and inelastic. These properties do not match with cancellous bone. The porous ricinic polyurethane cement (Bioósteo®) is unacceptably weak. Conclusion: Porous cement was developed by adding effervescent components, sodium bicarbonate and citric acid, to polymethylmetacrylate. Physical and mechanical properties are very similar to cancellous bone. Further investigations to evaluate its bone substitute potential should be encouraged. The porous ricinic polyurethane cement (Bioósteo®) is inadequate these purpose.

Resource recovery is an attractive alternative to the waste disposal problem. The chief by-product of this process, refuse derived fuel (RDF) can be co-fired in traditional coal burning facilities. The cement industry is a potential user of RDF. This study, based on a test burn done at Texas Industries Inc. in Midlothian, Texas, demonstrated the technical, environmental, and economic feasibility of using RDF fuel in a cement kiln. Technically, the cement showed no deleterious effects when RDF was substituted for coal/natural gas at 20% by Btu content. Environmentally, acid rain gases were reduced. Economically, RDF was shown to be a cost effective fuel substitute if a resource recovery facility was erected on site.

Les résines échangeuses d’ions (REI) sont largement utilisées dans l’industrie nucléaire pour décontaminer certains effluents radioactifs. Après utilisation, elles sont généralement enrobées dans des matériaux cimentaires. Cependant, leur cimentation est compliquée par la forte expansion de certains enrobés de résines. L’origine de cette expansion reste mal connue, de même que les conditions qui la favorisent. Au cours de ce travail, les interactions entre des résines échangeuses d’ions cationiques sous forme Na+ ou Ca2+ et du silicate tricalcique (C3S), du ciment Portland (CEM I) ou du ciment au laitier (CEM III/C) ont été étudiées au jeune âge afin d’améliorer la compréhension de cette instabilité dimensionnelle.Les résultats montrent que lors de l’hydratation d’une pâte de C3S ou de CEM I incorporant des REI sous forme Na+, celles-ci subissent transitoirement une phase d’expansion par suite de la diminution de la pression osmotique de la solution interstitielle. Cette expansion de faible amplitude qui se produit juste après la prise est suffisante pour dégrader l’enrobé par ailleurs fragilisé par un ensemble de processus : faible degré d’avancement de l’hydratation, précipitation de C-S-H moins cohésifs car fortement enrichis en sodium, microstructure hétérogène avec des zones de forte porosité et la précipitation de gros cristaux de portlandite facilement clivables à l’interface REI/matrice.Cette expansion peut être empêchée en réalisant un prétraitement calcique des résines ou en les enrobant avec un ciment au laitier dont la cinétique d’hydratation est plus lente que celle du ciment Portland. / Ion exchange resins (IERs) are widely used by the nuclear industry to decontaminate radioactive effluents. After use they are usually encapsulated in cementitious materials. However, the solidified waste forms can exhibit a strong expansion, possibly leading to cracking. Its origin is not well understood as well as the conditions when it occurs.In this work, the interactions between cationic resins in the Na+ or Ca2+ form and tricalcium silicate (C3S), Portland cement (CEM I) or Blastfurnace slag cement (CEM III/C) are investigated at an early age in order to gain a better understanding of the expansion process.The results show that during the hydration of a paste of C3S or CEM I containing IERs in the Na+ form, the resins exhibit a transient expansion of small magnitude due to the decrease in the osmotic pressure of the interstitial solution. This expansion, which occurs just after cement setting, is sufficient to damage the material which is poorly consolidated for several reasons: small hydration degree, precipitation of less cohesive sodium bearing C-S-H, heterogeneous microstructure with highly porous zones and lastly clivable crystals of portlandite at the interface between resins and paste.This expansion can be prevented by performing a calcium pretreatment of the resins or by using a CEM III/C cement with a slower rate of hydration than that of Portland cement.

Les ciments phosphomagnésiens sont des ciments inorganiques de la famille des ciments activés par des acides. Malgré le fait qu'ils soient connus depuis le début du XXème siècle, leur utilisation reste assez limitée dans le génie civil. Ces matériaux sont utilisés dans le cadre de réparation notamment pour des réparations routières qui nécessitent un développement rapide des résistances en compression. Plus récemment, ces ciments ont été utilisés pour des applications de stabilisation/solidification (S/S) des déchets et notamment de certains types de déchets chimiquement incompatibles avec le ciment Portland. Toutefois, les défis de mise en œuvre de ce type de ciment sont liés à la nature même de la réaction, très exothermique et très rapide. La phase liante de ces ciments, la k-struvite (MgKPO4.6H2O), est obtenue par un mélange de magnésie (MgO) et de dihydrophosphate de potassium (KH2PO4) en présence d'eau. MgO + KH2PO4 + 5H2O  MgKPO4.6H2OLes mécanismes qui régissent la prise de ce ciment sont encore mal connus et plusieurs théories, mettant en jeu ou non la formation de produits secondaires, ont été proposées. Nos travaux de recherche ont porté sur la compréhension des mécanismes de prise des ciments phosphomagnésiens ainsi que sur l'influence des paramètres de formulation sur les propriétés de ces ciments. L'étude a montré que la formation de la k-struvite passe par une réaction de précipitation-dissolution d'un produit intermédiaire, la newberyite (MgHPO4.3H2O). Les réactions de formation de ces deux produits sont contrôlées par le taux de sursaturation des espèces en solution et le pH du milieu réactionnel. L'étude met également en lumière la forte sensibilité de ces ciments à la quantité d'eau introduite. Avec un rapport E/C très faible comparativement à un ciment Portland (rapport E/C compris entre 0,1 et 0,25), une faible variation (0,02) entraine la ségrégation de la pâte de ciment et une hétérogénéité à la surface du matériau. Parmi les paramètres de formulation, le rapport molaire MgO/KH2PO4 (Mg/P) est le plus important. En effet, il influe sur la quasi-totalité des propriétés du ciment : résistance en compression, temps de prise, chaleur de réaction, fluidité de la pâte, …. L'utilisation de faibles rapports Mg/P entraine une mauvaise tenue à l'eau du ciment, la formation de cristaux à l'intérieur de la microstructure et visibles à la surface de l'échantillon (apparition d'une efflorescence) ainsi qu'un gonflement important de la pâte de ciment (pouvant aller jusqu'à la fissuration des échantillons). A l'issue de l'étude paramétrique une formulation d'une pâte a pu être définie. Des mesures de variations dimensionnelles, ainsi que des mesures de retrait chimique ont été effectuées, afin de mieux comprendre les mécanismes mis en jeu pour induire les phénomènes de gonflement. En support, des analyses de la microstructure (MEB, DRX, ATG) ainsi que des essais de lixiviation viennent compléter la campagne expérimentale. Ces résultats viennent confirmer l'influence d'un rapport Mg/P faible sur le gonflement et la tenue à l'eau du ciment phosphomagnésien. Pour finir, une étude sur l'influence des divers ajouts, dans le but d'améliorer ses performances, a montré que les fillers inertes (sable siliceux ou cendres volantes) retardent le temps de prise et réduisent la chaleur d'hydratation / Magnesium phosphate cements are the most representative cements of the activated-by-acid cements family. Despite the fact that they are known since the early 20th century, their use in civil engineering is fairly limited. These materials are used for road repairs where the fast compressive strength development is an advantage. Recently they have also been used in wastes stabilization/solidification (S/S), especially with wastes incompatible with Portland cement. The challenges of the use of these cements are related to the nature of their formation reaction: fast, very exothermic, with a very short setting time (only a few minutes).The bonding phase, k-struvite (MgKPO4.6H2O), is obtained from magnesium oxide mixed in water with monopotassium phosphate (KH2PO4).MgO + KH2PO4 + 5H2O  MgKPO4.6H2OThe setting mechanisms are still poorly known and various theories, involving or not secondary product formation, have been suggested. Our researches have aimed to understand the setting mechanisms, as well as the influence of the formulation parameters on the properties of the magnesium phosphate cement. Results show that the formation of k-struvite involved a precipitation-dissolution reaction of an intermediate product, the newberyite (MgHPO4.3H2O). Formation reactions of these two products are controlled by the supersaturation rate and the pH of the solution. The study highlights the strong effect of water on the properties of fresh cement paste. With a low mass ratio e/c in comparison of Portland cement (ratio e/c between 0,1 and 0,25), a slight modification of the ratio (0,02) leads to a segregation and a surface heterogeneity of the cement paste. Among the formulation parameters, the molar ratio MgO/KH2PO4 (Mg/P) seems the most important parameter. Indeed, it impacts most of the properties of the magnesium phosphate cement (compressive strength, setting time, reaction heat, paste fluidity …). Low Mg/P ratios lead to poor water resistance, to crystals formation inside the microstructure that can be seen on the surface of the sample (an efflorescence appearance), and to important swelling of the paste, leading to the cracking of the samples. After the parametric study, a magnesium phosphate cement paste has been defined. Dimensional changes and chemical shrinkage measurement were conducted to understand the mechanisms involved in this swelling phenomenon. In support, microstructural analyses (SEM, XRD, TGA) and leaching tests complete the experimental campaign. The results confirm the influence of a low Mg/P ratio on cement swelling and water resistance. Finally, a study on various additions to the paste has been conducted, with the purpose of improving the cement paste performances. It shows that the addition of an inert filler (siliceous sand or fly ashes) has a retarding effect and reduced the reaction heat

This thesis is focused on monitoring attributes of ettringite in long term horizon, especially on his thermodynamic stability. Ettringit was prepared in two ways. Firstly, it is a method of hydration of yeelimite, secondly, ettringit is prepared by addition of aluminium sulphate and calcium hydroxide.

Předložená diplomová práce se zabývá přípravou a charakterizací vzorků z kompozitního kostního cementu na bázi fosforečnanu vápenatého (CPC). V teoretické části jsou popsány vlastnosti a struktura fosforečnanů vápenatých, včetně jejich interakce s tělním prostředím. Experimentální část nejdříve popisuje stanovení optimální techniky přípravy vzorků pomocí experimentů prováděných v ultračisté vodě. Optimální technika pro vytvrzování zahrnuje použití formy z paměťové pěny, ukončení vytvrzovacích reakcí pomocí absolutního chladného etanolu a sušení vzorků ve vakuové sušárně. Následně je v práci popsána příprava vzorků a proces vytvrzování CPC jak v přirozeném (prasečí krev), tak v prostředí simulovaných tělních tekutin (fyziologický roztok, Hankův a Ringerův roztok). Byla provedena morfologická studie pomocí skenovací elektronové mikroskopie (SEM) pro vzorky vytvrzené 1 den, 1 týden, 2 týdny a 1 měsíc kvůli očekávané významné změně v jejich krystalické struktuře, která byla taktéž zkoumána pomocí rentgenové difrakce (XRD), stanovující přeměnu -fosforečnanu vápenatého na kalcium deficitní hydroxyapatit (CDHA). Porozita vzorků byla zkoumána rentgenovou mikrotomografií (-CT) a vzorky vytvrzené v krvi vykazovaly mírně vyšší porozitu. Mechanické vlastnosti CPC vzorků byly zkoumány pomocí mechanických kompresních testů. Výsledky testů ukázaly stabilní pevnost cementových vzorků vytvrzených ve fyziologickém roztoku už po jednom dni vytvrzování, zatímco vzorky vytvrzené v krvi vykazovaly nárůst pevností dokonce i po jednom měsíci vytvrzování. Naopak pevnost vzorků vytvrzených jak v Hankově, tak v Ringerově roztoku rychle klesla po 2 týdnech vytvrzování pravděpodobně důsledkem mírně kyselého pH vytvrzovacích roztoků, které urychluje rozpad CPC vzorků. Výsledky práce ukazují významný vliv vytvrzovacích prostředí na vlastnosti CPC kostních cementů. Vzorky vytvrzené v krvi oproti vzorkům vytvrzených v umělé tělní plazmě vykázaly lepší vlastnosti, protože krev imituje in vivo podmínky.

In modern point of view of waste management is desirable to effectively process the grates possible amount of wastes. Sediments from cleaning of mined lime stones contains a lot of clay components, but there is also indispensable share of soft calcite. This composition makes these sediments a promising material for preparation of hydraulic binders. Production of common hydraulic binders, especially Portland cement, is very energy-intensive plus loads environment with considerable amount of combustion gases, therefore it is necessary to explore possibilities of alternative low - energy binders production and usage.

The issue of Hexavalent chromium toxicity to Portland cement hydration is a very actual these days. It takes much effort to obtain a cement containing Cr(VI) less than 2 ppm. The primary objective of this diploma theses is to find appropriate reducing substances and specify their efficiency, as well as to make an attempt to optimize their dosage. As reducing substances there were plumbed sulphites and tin(II) salts. The influence of reducing substances applied to the hydration and cement properties were validated by strenght tests, the calorimetric measurement and the volume-variation measurement. And also the changes in hydration products microstructure of Portland clinker after the gypsum replacement by sulphite ions were plumbed. The study of microstructure is based on SEM and XRD methods.

The subject of the diploma thesis is the preparation of macro-defect-free (MDF) composites based on calcium-aluminate cement and organic polymer polyvinylalcohol. Attention focused on the optimization of the dose, the degree of hydrolysis and molecular weight of the polymer with respect to the heat resistance of the material. Thermal degradation of polyvinyl alcohol leads to changes in the structure of MDF composite. The study was mainly focused on the characteristics of polyvinyl alcohol dosage associated with the resultant mechanical properties of the material. During the work were monitored for changes in the mechanical properties of samples were cured at 60 °C and subsequently fired at 180 °C, 600 °C, 1000 °C and 1400 °C. It was tested in flexural strength, heat microscopy, TGA-DTA-EGA and SEM analysis.

The subject of the thesis is to improve the moisture resistance of MDF (macro-defect-free) composites prepared on the basis of aluminous cement and polyvinyl alcohol. These materials are characterized by the absence of defects in the structure and high mechanical performance. These features make MDF composites a promising type of material that could be used in the future for construction purposes. The basic deficiency of MDF composites is insufficient resistance to water or moisture, accompanied by a significant decrease in strength. Therefore, this work deals with increasing of moisture resistance using organotitanate agent and modification of the polymer. Two types of polyvinyl alcohols differing in hydrolysis degree and degree of the polymerization has been modified. Based on the results of the measurement the effect of storage conditions on the properties and structure of prepared MDF composites was observed. The characterization of MDF composites were realized by measurement of flexural strength in bending, scanning electron microscopy with EDS analysis, TG-DTA-EGA, water absorption and consequently the porosity of all prepared MDF composites.