Calcium aluminate cement (CAC) is a rapid hardening cementitious material often used in niche concrete repairs where high early-age strength and robust durability are required. This research project characterized the implications of the additions of various mineral and chemical admixtures to plain CAC to mitigate strength reductions associated with conversion, an inevitable strength reduction associated with the densification of metastable hydrates (CAH10 and C2AH8) to stable hydrates (C3AH6 and AH3). The effect of these admixtures on early-age strength development, volume change, and the correlation to macro-scale performance were reported in this dissertation. Various mixtures of CAC were investigated including: pure CAC, binary blends of CAC with fly ash (Class C) or CaCO3, and ternary blends of CAC with slag and silica fume. Characterization of the influence of these admixtures on hydration was completed using x-ray diffraction, isothermal calorimetry, and chemical shrinkage. Investigations on the implications of early-age volume change were conducted for autogenous deformation. In addition to laboratory testing, the final phase of the project was to correlate and elucidate the data generated in the laboratory to real-world field performance. Field trials were conducted to evaluate and monitor the behavior of CAC systems and investigate the link between laboratory generated research and actual large scale behavior. / text

Made available in DSpace on 2014-06-11T19:23:42Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-02-24Bitstream added on 2014-06-13T20:48:19Z : No. of bitstreams: 1 burger_cp_me_jabo.pdf: 769968 bytes, checksum: 7766d90823dbf5c423709325e1af199c (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / O tratamento de não união e união retardada é um desafio constante na rotina do ortopedista veterinário. A dificuldade de se conseguir repouso adequado dos pacientes submetidos à osteossíntese, frequentemente, resulta em consolidações mal sucedidas. Com o objetivo de se avaliar o comportamento do cimento de aluminato de cálcio, foram induzidos defeitos ósseos de 3,57mm de diâmetro nos fêmures de 12 coelhos, sendo os do lado direito preenchidos com o referido biomaterial e os do esquerdo permaneceram vazios. Aos 15, 30 e 60 dias de pós-operatório, realizaram-se avaliações clínico-cirúrgicas, radiográficas e histológicas, a fim de se observar o potencial osteoindutor e osteocondutor do biomaterial no defeito ósseo, e se houve osteointegração. Os resultados evidenciaram que o cimento aluminoso, nesta formulação, não possui esses potenciais e nem poder de osteointegração, possivelmente por possuir porosidade reduzida / The treatment of non union and delayed union is a constant challenge for veterinary orthopedists. The difficulty in achieving adequate rest for patients which have undergone osteosynthesis results in unsuccessful bone consolidations. With the aim of evaluating the behavior of a calcium aluminate cement, bone defects of 3,57 mm of diameter were induced in femurs of 12 rabbits. The defects on the right side were filled with the biomaterial and the ones on the left side remained unfilled. The evaluation periods occurred at 15, 30 and 60 days after surgery. Clinical, surgical, radiographic and histological evaluations were performed in order to observe the osteoinductive and osteocondoctive potential of the biomaterial on the bone defects, as well to verify if there was osteointegration. The results showed that the aluminate cement does not have these potencial and nor cause osteointegration in the formulation used in this study

Resumo: O tratamento de não união e união retardada é um desafio constante na rotina do ortopedista veterinário. A dificuldade de se conseguir repouso adequado dos pacientes submetidos à osteossíntese, frequentemente, resulta em consolidações mal sucedidas. Com o objetivo de se avaliar o comportamento do cimento de aluminato de cálcio, foram induzidos defeitos ósseos de 3,57mm de diâmetro nos fêmures de 12 coelhos, sendo os do lado direito preenchidos com o referido biomaterial e os do esquerdo permaneceram vazios. Aos 15, 30 e 60 dias de pós-operatório, realizaram-se avaliações clínico-cirúrgicas, radiográficas e histológicas, a fim de se observar o potencial osteoindutor e osteocondutor do biomaterial no defeito ósseo, e se houve osteointegração. Os resultados evidenciaram que o cimento aluminoso, nesta formulação, não possui esses potenciais e nem poder de osteointegração, possivelmente por possuir porosidade reduzida / Abstract: The treatment of non union and delayed union is a constant challenge for veterinary orthopedists. The difficulty in achieving adequate rest for patients which have undergone osteosynthesis results in unsuccessful bone consolidations. With the aim of evaluating the behavior of a calcium aluminate cement, bone defects of 3,57 mm of diameter were induced in femurs of 12 rabbits. The defects on the right side were filled with the biomaterial and the ones on the left side remained unfilled. The evaluation periods occurred at 15, 30 and 60 days after surgery. Clinical, surgical, radiographic and histological evaluations were performed in order to observe the osteoinductive and osteocondoctive potential of the biomaterial on the bone defects, as well to verify if there was osteointegration. The results showed that the aluminate cement does not have these potencial and nor cause osteointegration in the formulation used in this study / Orientador: Cíntia Lucia Maniscalco / Coorientadora: Paola Castro Moraes / Banca: Julio Carlos Canola / Banca: Gustavo Garkalns de Souza Oliveira / Mestre

Cerâmicas porosas encontram um vasto campo de aplicações tecnológicas, tais como isolantes térmicos em equipamentos siderúrgicos, filtros de fluidos em altas temperaturas e biomateriais. A obtenção dessas estruturas por meio de moldagem direta de suspensões aquosas é uma interessante técnica de conformação, pois, peças com geometrias complexas e de grandes volumes podem ser produzidas. Neste caso, a consolidação ocorre, geralmente, pela ação de um ligante hidráulico, cuja função é garantir níveis mínimos de resistência mecânica à verde. Em sistemas refratários, os ligantes mais utilizados são o cimento de aluminato de cálcio (CAC) e alumina hidratável (AH), devido à alta refratariedade e custos competitivos destes materiais. Nas estruturas porosas à base de alumina, particularmente, eles podem proporcionar valores distintos de porosidade e diferentes tipos de microestruturas. Este trabalho teve como objetivo entender como o CAC e a AH interagem com a alumina. Foram avaliados a evolução microestrutural e os efeitos do teor (10 até 40% em volume de ligante hidráulico) e do tamanho das partículas da matriz (alumina fina e grossa) nas amostras à verde e durante o aquecimento inicial até 1500°C. De modo geral, maiores volumes de ligantes permitiram a obtenção de estruturas à verde mais rígidas e resistentes, porém menos porosas. Além da porosidade total (PT), as microestruturas decorrentes das transformações de fases cristalinas ou amorfas também influenciaram os resultados mecânicos. No caso do CAC, as fases formadas durante as reações in situ ajudaram a melhorar as propriedades mecânicas das amostras, mesmo que acompanhado por um acréscimo em porosidade. Em proporções estequiométricas, os cristais de hexaluminato de cálcio (CA6) formados após tratamento a 1500°C inibiram a densificação, ajudando na manutenção da PT (36,7-46,5%), ainda com boa resistência (acima de 20 MPa em compressão diametral). Nos sistemas ligados com AH, observou-se grandes perdas em propriedades mecânicas antes da sinterização, as quais foram relacionadas ao aumento de densidade real dos precipitados do ligante e à perda de conexão entre as partículas da matriz. Em altas temperaturas, os precipitados de AH auxiliaram a sinterização e garantiram a obtenção de peças porosas quando se utilizou alumina grossa (PT: 44,3-47,7%). / Porous ceramics have a wide range of technological applications, such as thermal insulation in steelmaking furnaces, filter for high temperature fluids and as biomaterials. Obtaining these structures through the direct casting of aqueous suspensions is an interesting conformation method since pieces with complex geometries and large volumes can be produced. In this case, the consolidation usually occurs by the action of a hydraulic binder, which provides the minimum levels of mechanical strength in green samples. In refractory systems, the most used binders are calcium aluminate cement (CAC) and hydratable alumina (HA), due to the high refractoriness and competitive costs of these materials. Particularly, in porous alumina-based structures, they can provide distinct values of porosity and different types of microstructures. The purpose of the present work is to understand how CAC and HA interact with alumina. The effects of the binder content (from 10 up to 40% in volume) and the particle size of the matrix (fine and coarse) during initial heating up to 1500°C were studied. In general, larger volumes of binders provided green samples with less porosity but higher mechanical strength. Besides total porosity (TP), the microstructures generated from the transformations of crystalline or amorphous phases also influenced the mechanical results. In the case of CAC, the phases formed by in situ reactions improved the mechanical properties of the samples, despite the increase in porosity. In stoichiometric proportions, the crystals of calcium hexaluminate (CA6) formed after treatment at 1500°C inhibited the densification, favoring to maintain total porosity (36.7-46.5%), even with acceptable mechanical properties (above 20 MPa under diametric compression). In HA-bonded systems, before the sintering begins, a decrease in mechanical properties was noted and related to the increase in density of the precipitates and loss of connection between the matrix particles. At high temperature, the precipitates from HA aided the sintering and guaranteed porous samples in coarse alumina composition (TP: 44.3- 47.7%).

Cerâmicas porosas encontram um vasto campo de aplicações tecnológicas, tais como isolantes térmicos em equipamentos siderúrgicos, filtros de fluidos em altas temperaturas e biomateriais. A obtenção dessas estruturas por meio de moldagem direta de suspensões aquosas é uma interessante técnica de conformação, pois, peças com geometrias complexas e de grandes volumes podem ser produzidas. Neste caso, a consolidação ocorre, geralmente, pela ação de um ligante hidráulico, cuja função é garantir níveis mínimos de resistência mecânica à verde. Em sistemas refratários, os ligantes mais utilizados são o cimento de aluminato de cálcio (CAC) e alumina hidratável (AH), devido à alta refratariedade e custos competitivos destes materiais. Nas estruturas porosas à base de alumina, particularmente, eles podem proporcionar valores distintos de porosidade e diferentes tipos de microestruturas. Este trabalho teve como objetivo entender como o CAC e a AH interagem com a alumina. Foram avaliados a evolução microestrutural e os efeitos do teor (10 até 40% em volume de ligante hidráulico) e do tamanho das partículas da matriz (alumina fina e grossa) nas amostras à verde e durante o aquecimento inicial até 1500°C. De modo geral, maiores volumes de ligantes permitiram a obtenção de estruturas à verde mais rígidas e resistentes, porém menos porosas. Além da porosidade total (PT), as microestruturas decorrentes das transformações de fases cristalinas ou amorfas também influenciaram os resultados mecânicos. No caso do CAC, as fases formadas durante as reações in situ ajudaram a melhorar as propriedades mecânicas das amostras, mesmo que acompanhado por um acréscimo em porosidade. Em proporções estequiométricas, os cristais de hexaluminato de cálcio (CA6) formados após tratamento a 1500°C inibiram a densificação, ajudando na manutenção da PT (36,7-46,5%), ainda com boa resistência (acima de 20 MPa em compressão diametral). Nos sistemas ligados com AH, observou-se grandes perdas em propriedades mecânicas antes da sinterização, as quais foram relacionadas ao aumento de densidade real dos precipitados do ligante e à perda de conexão entre as partículas da matriz. Em altas temperaturas, os precipitados de AH auxiliaram a sinterização e garantiram a obtenção de peças porosas quando se utilizou alumina grossa (PT: 44,3-47,7%). / Porous ceramics have a wide range of technological applications, such as thermal insulation in steelmaking furnaces, filter for high temperature fluids and as biomaterials. Obtaining these structures through the direct casting of aqueous suspensions is an interesting conformation method since pieces with complex geometries and large volumes can be produced. In this case, the consolidation usually occurs by the action of a hydraulic binder, which provides the minimum levels of mechanical strength in green samples. In refractory systems, the most used binders are calcium aluminate cement (CAC) and hydratable alumina (HA), due to the high refractoriness and competitive costs of these materials. Particularly, in porous alumina-based structures, they can provide distinct values of porosity and different types of microstructures. The purpose of the present work is to understand how CAC and HA interact with alumina. The effects of the binder content (from 10 up to 40% in volume) and the particle size of the matrix (fine and coarse) during initial heating up to 1500°C were studied. In general, larger volumes of binders provided green samples with less porosity but higher mechanical strength. Besides total porosity (TP), the microstructures generated from the transformations of crystalline or amorphous phases also influenced the mechanical results. In the case of CAC, the phases formed by in situ reactions improved the mechanical properties of the samples, despite the increase in porosity. In stoichiometric proportions, the crystals of calcium hexaluminate (CA6) formed after treatment at 1500°C inhibited the densification, favoring to maintain total porosity (36.7-46.5%), even with acceptable mechanical properties (above 20 MPa under diametric compression). In HA-bonded systems, before the sintering begins, a decrease in mechanical properties was noted and related to the increase in density of the precipitates and loss of connection between the matrix particles. At high temperature, the precipitates from HA aided the sintering and guaranteed porous samples in coarse alumina composition (TP: 44.3- 47.7%).

L’encrassement des façades d’immeuble est causé par un phénomène d’altération biologique essentiellement esthétique. Leur vieillissement naturel favorise la colonisation de micro-organismes. La cinétique de biodétérioration dépend de plusieurs paramètres, tels que la situation géographique, les conditions environnementales et les caractéristiques physico-chimiques du matériau. L’objectif de la présente étude est d’établir un lien entre la composition chimique de mortiers à base de ciments et leur cinétique de colonisation par des microorganismes. Deux bancs d’essais sont utilisés : un banc d’essai in situ et un banc d’essai de biodétérioration accélérée de laboratoire. Deux ciments Portland (OPC) et deux ciments alumineux (CAC) de minéralogies différentes ont été sélectionnés. L’effet de la porosité, de la rugosité et de la carbonatation a également été étudié. Le microorganisme sélectionné pour les essais de laboratoire est l’algue Klebsormidium flaccidum qui se développe de manière prépondérante sur les façades en France. Les résultats obtenus en laboratoire et in situ montrent que la biocolonisation des mortiers à base de CAC est plus lente que celle des mortiers à base d’OPC. Lorsque la porosité augmente, la vitesse de biocolonisation augmente et l’effet de la composition chimique est en grande partie masqué. La biocolonisation des mortiers carbonatés se réalise plus rapidement que celle des mortiers non carbonatés surtout dans le cas des mortiers à base d’OPC. Enfin, les mortiers de surface rugueuse sont colonisés plus rapidement quelle que soit la formulation testée. Cet effet est plus marqué pour les mortiers exposés in situ que pour ceux testés en laboratoire. / The fouling of building-facade is caused by a main aesthetic phenomenon of biological weathering. The natural weathering favors the micro-organisms development. The biofouling kinetics depends on several parameters such as geographical situation, environmental conditions and physicochemical parameters of substrates. The main objective of this study is to highlight the influence of the mortar chemistry in relationship with its physical properties on the algal growth. The biofouling kinetics was followed on samples exposed outdoor and on samples tested in a laboratory bench which consists in spraying an algal culture on mortar specimens. In order to characterize the influence of the mortar chemistry on biofouling, two Portland cements (OPC) and two calcium aluminate cements (CAC) were tested. The influence of roughness, porosity and carbonation was also studied. The green algae Klebsormidium flaccidum were chosen for the accelerated laboratory tests because of its representativeness. The results obtain in laboratory and in situ show that CAC based mortars slow down the colonization kinetics compared to OPC based mortars. When porosity increases the biofouling kinetics increases and the effect of the mortars chemical composition is largely hidden. The carbonated mortars biofouling is achieved more quickly than uncarbonated ones especially for OPC based mortars. Finally, the rough surfaces are colonized faster whatever formulation tested. This parameter is mostly highlighted for in situ tests.

Polymerem impregnované cementové materiály představují zajímavou a perspektivní alternativu klasických portlandských cementových past. Hlavním zástupcem těchto materiálů jsou macrodefect-free (MDF) kompozity, složené z anorganického pojiva a organického polymeru. I přes řadu vynikajících mechanických vlastností je plné zavedení MDF kompozitů na trh omezené především z důvodu jejich relativně nízké odolnosti vůči vlhkosti. Jednou z možností jak zvýšit odolnost výsledného MDF vůči vlhkosti je „in situ“ síťování polymeru. V této práci byla připravena počáteční série MDF kompozitů na bázi hlinitanového cementu a polyvinylalkoholu se třemi typy organo-titanátových síťovacích činidel (Tyzory). Efekt modifikace MDF kompozitů byl hodnocen na základě zkoušek pevnosti v tahu za ohybu po uložení materiálů v různých vlhkostních podmínkách.

When firing calcium ceramic materials creates a new crystalline phase anorthite. It can significantly improve the properties of ceramic body. This work deals with the possibilities of development anortitové ceramics using non-plastic raw materials, particularly alumina cement compared with conventional ceramics based on mullite.

La nécessité de rénover les réseaux d'assainissement des grandes villes et les besoins de construire de nouvelles structures conduisent les gestionnaires de réseaux d'assainissement et les fabricants de canalisation à rechercher des solutions pour obtenir des installations d'assainissement durables. Parmi les détériorations rencontrées dans ces structures, 9% peuvent être attribués à la biodétérioration des matériaux cimentaires. Cette étude a deux objectifs principaux. Le premier est de développer un essai accéléré reproductible en laboratoire et qui donne des résultats proches de ceux obtenus sur site. Le second est d'étudier la biodétérioration des matériaux cimentaires pour mieux comprendre les mécanismes et plus spécifiquement la différence de comportement entre les matériaux à base de ciment d'aluminate de calcium (CAC) et de ciment Portland ordinaire (OPC). Dans ce cadre, différentes formulations cimentaires ont été exposées in situ afin de déterminer les paramètres influant sur la biodétérioration. En parallèle, des expériences en laboratoire ont été réalisées pour mieux comprendre chaque étape du mécanisme de biodétérioration. Les résultats des expositions sur site montrent que les matériaux à base de CAC ont une durabilité plus importante que les autres formulations cimentaires. Les études réalisées en laboratoire permettent d'attribuer ces meilleures performances à la teneur en aluminium qui inhibe la croissance des microorganismes tout en protégeant la matrice grâce à la précipitation d'une couche d'alumine hydratée dans la porosité et à la surface de ces matériaux et qui maintient le pH à 3,5-4. La chimie de surface a également un rôle important en favorisant ou non l'oxydation abiotique de l'H2S. Les résultats des expositions sur site et des différents essais de laboratoire ont été utilisés pour développer un essai accéléré donnant des résultats prometteurs / The need for renovation of sewer networks in major cities and the necessity to build new structures lead managers of sewer pipe and manufacturers to seek for solutions for sustainable sanitation. 9% of damages encountered in these structures can be attributed to the biodeterioration of cementitious materials. This study has two main objectives. The first one is to develop an accelerated reproducible laboratory test that gives results similar to those obtained on site. The second is to study the biodeterioration of cementitious materials in order to better understand mechanisms and more especially the difference in behavior between materials based on calcium aluminate cement (CAC) and ordinary Portland cement (OPC). Within this framework, different cement formulations were exposed in situ to identify the parameters influencing biodeterioration. Meanwhile, laboratory experiments were conducted to better understand each step of the mechanism of biodeterioration. Results of on site exposition show that materials based on CAC have a greater durability than other cement formulations. Laboratory studies assign these best performances to the aluminum content which inhibits the growth of microorganisms while protecting the matrix by precipitation of a hydrated alumina layer in the porosity and on the surface of these materials. This layer maintains the pH at 3.5-4. Surface chemistry was shown to play an important role in catalizing abiotic oxidation of H2S. The results of on-site exhibitions and various laboratory tests were used to develop an accelerated test giving promising results

In calcium aluminate cement (CAC) systems the hydration process is different than portland cement (PC) systems. The hydration products of CAC are subjected to conversion depending on temperature, moisture, water-cement ratio, cement content, etc. Consequently, strength of CAC system can be seriously reduced. However, presence of other inorganic binders or additives may alter the hydration process and improve various properties of CAC based composites. The objective of this study is to investigate the temperature effect on the behaviour of CAC based composite binders. Throughout this research, several combinations of CAC-PC, CAC-gypsum, CAC-lime, CAC-ground granulated blast furnace slag (CAC-GGBFS) were studied. These CAC based composite binders were subjected to seven different curing regimes and their strength developments were investigated up to 210 days. In addition, the mechanism of strength development was examined by XRD analyses performed at 28 and 210 days. Finally, some empirical relationships between strength-time-curing temperatures were formulated. Experimental results revealed that the increase in ambient temperature resulted in an increase in the rate of conversion, thereby causing drastic strength reduction, particularly in pure CAC mix. It has been observed that inclusion of small amount of PC, lime, and gypsum in CAC did not induce conversion-free CAC binary systems, rather they resulted in faster conversion by enabling rapid formation of stable C3AH6 instead of metastable, high strength inducing CAH10 and C2AH8. On the other hand, in CAC-GGBFS mixes, the formation of stable straetlingite (C2ASH8) instead of calcium aluminate hydrates hindered the conversion reactions. Therefore, CAC-GGBFS mixes, where GGBFS ratio was over 40%, did not exhibit strength loss due to conversion reactions that occurred in pure CAC systems.