Abstract Environmental friendliness and cost demand the development of lignin-modified phenolic (LPF) resins for application as a binder for carbon-containing refractories (CCRs) production. Moreover, the in-situ graphitization of such resins can produce crystalline carbon, which is an essential component of CCRs. Consequently, this study investigated LPF resins graphitization using ferrocene, boron oxide and boric acid. The modified resins were synthesized using thermally treated kraft lignin based on 1.5 formaldehyde to phenol molar ratio and with up to 30 wt.% lignin as phenol replacement. The resins chemical composition and the structural organization and oxidation resistance of carbons derived from the plain resins and those containing the graphitizing additives were determined. The results showed that ferrocene and the boron compounds could induce graphitic carbon generation when carbonizing LPF resins at 1500 °C for 5 hours. The best graphitization level (73%) was achieved when 10 wt.% boric acid was added to the resin produced with 20 wt.% lignin. Regarding the formulations containing ferrocene, the highest amount of graphitic carbon (48%) was generated when 5 wt.% of this additive was added to the resin synthesized with 10 wt.% lignin. The carbons derived from the formulations containing boron oxide presented the best oxidation resistance.

The radiopacity of CAC-based compositions containing additives (ZnO, Ag and Bi2O3) was evaluated by optical density measurements, cold crushing strength, apparent porosity, pore size distribution, in vitro apatite-formation ability (bioactivity) and cell viability. The bioactivity was assessed via pH and calcium concentration measurements in simulated body fluid (SBF) for samples previously treated or not with sodium silicate (SS) solution. The surface of the samples after treatment was analyzed by scanning electron microscopy, energy dispersive X-ray analysis and confocal Raman spectroscopy. Cell viability was evaluated by MTT and alkaline phosphatase (ALP) activity. Radiopacity results confirmed that compositions containing ZnO-Ag (25:1 wt%) and ZnO-Bi2O3 (15:10 wt%) presented suitable values of radiopacity (> 3 mmAl). The identification of calcium and mainly phosphorus by EDX, highlighted the generation of an apatite-like layer on the compositions' surface after immersion in SBF or SBF/SS. CAC-blend containing 25 wt% ZnO, ZnO-Ag and ZnO-Bi2O3 presented slightly lower cell viability compared to the positive control.

Recent studies involving the use of calcium aluminate cement (CAC) as a biomaterial are based on commercial products. Improvements can be attained by investigating the properties of their crystalline phases in order to better design the material's composition. Therefore, calcium aluminate phase samples immersed in simulated body fluid (SBF) solutions prepared according to Kokubo’s (KSBF) and Rigo’s (RSBF) methodology had their pH evaluated. The surfaces of these samples were analyzed by SEM, EDX and XRD techniques. The treatment with KSBF did not favor the precipitation of calcium phosphate phases on the surface of CAC phases. On the other hand, in RSBF solution, the pH value attained was higher than for the KSBF one and magnesium phosphate was identified on the surface of CA, C3A and C12A7 samples. Only for CA2, the optimal precipitation condition was attained in RSBF and a surface layer of the hydroxyapatite was detected. Based on its ability of stimulating hydroxyapatite deposition in SBF and other properties, CA2 can be eligible as the most suitable composition for biomedical purposes.

The aim of this study was to determine the best radiopaque additive to be incorporated to calcium aluminate cement (CAC) to promote radiopacity. Measurements of optical density were carried out on white MTA and CAC with and without additives such as: polymeric dispersant, plasticizer and various radiopacifiers. The effects of the radiopacifying addition on some properties of CAC were also evaluated. The radiopacity value for CAC-Bi2O3 (25%) was higher than the other radiopacifying agents tested. The addition of ZnO (25%) and 15%ZnO:10%Bi2O3 increased the compressive strength of CAC, whereas for Bi2O3 (25%) containing samples the strength was lower than for the CAC. The ZnO (25%) and 15%ZnO:10%Bi2O3 additions also reduced the apparent porosity. CAC does not have sufficient radiopacity to be distinguished from adjacent anatomic structures, such as dental tissues and bone. The addition of 15%ZnO:10%Bi2O3 can be suggested as the most suitable one to obtain the best compromise between good physical and mechanical properties and ideal radiopacity for clinical purposes.

Portland cement-based materials are present in our everyday life. Over the last two decades, important developments have been made to improve their mechanical strength, mainly through microstructural design. In addition, another promising parameter still remains in the early stages of understanding: that of adhesion. Recently, interdisciplinary researchers have considered the issue of water confinement by the hydrated cementitious surfaces. It could contribute to increase the adhesion and strength in these materials. On the other hand, ionic and non-ionic chaotropic substances might be able to disorder the structure of such special water. The results presented in this paper show important effects of these chaotropic substances on the strength of cementitious materials. They highlight the role of the confined water on the adhesion, when the microstructural parameters are kept constant. More than contributing to the fundamental understanding of adhesion within cement paste, these results provide basic insights on in-situ nanotechnology.

Combinar diversas matérias-primas (MP’s) para obter uma composição cerâmica é um procedimento composto por até cinco tarefas distintas e simultâneas: a) Controle da distribuição granulométrica; b) Composição Química; c) Área Superficial; d) Densidade; e) Custo. Considerar tais variáveis simultaneamente não é algo simples. Neste trabalho é apresentado um software desenvolvido em parceria com a empresa Alcoa Alumínio S.A., que realiza tal tarefa, permitindo que uma composição cerâmica seja desenvolvida de maneira simples levando em consideração as variáveis descritas. Este contém ainda, uma rotina computacional, baseada em otimização, que permite combinar um número ilimitado de matérias-primas (MP’s) obtendo a composição de melhor ajuste possível entre a distribuição gerada com a planejada, utilizando o critério de minimização da diferença quadrática. Para verificação da rotina foram realizados estudos de comportamento reológico em suspensões de alumina (compostas por nove faixas granulométricas distintas), formuladas de maneira automatizada e convencional, assumindo como curvas alvo as distribuições de Alfred e Andreasen, ambas com coeficiente de máxima densidade de empacotamento (q = 0.37). A eficácia da rotina foi comprovada pela superior velocidade de formulação no processo automatizado. Comparativamente, as precisões obtidas entre a rotina automatizada e convencional foram similares, resultando em comportamentos reológicos semelhantes.

Combining several raw materials to obtain a ceramic composition involves up to five different and simultaneous steps: a) control of particle size distribution; b) chemical composition; c) surface area; d) density; and e) cost. This work presents a software developed for Windows environment in partnership with Alcoa Aluminum S.A., which controls all five referred parameters. It also contains an optimized routine that allows automatically combination of an unlimited number of raw materials to achieve a designed distribution, based on the minimum square difference. Experimental verification of the routine involved preparation of alumina suspensions using nine different particle size ranges, combined both in a conventional and in an automated manner to provide designed distributions (Alfred and Andreasen, q = 0.37). The routines efficiency was verified by the high speed of the automated formulation process and the rheological results obtained. Close rheological behavior were found out, pointing out the accuracy of both approaches.

The fractals theory has been increasingly applied in the field of materials science and engineering. Models of fractal lines and surfaces have been generated to describe the microstructural features of materials. Special interest is placed upon a description of the fracture surface based on a fractal geometry in order to understand the crack path in materials. Several papers have demonstrated the relationship between the fractal dimension of a fracture surface and the values of roughness and fracture toughness. In this work an extension of the theory of fractals for ceramic materials is proposed, to which the crack deflection toughening mechanism is thought to be related. In order to accomplish this objective, a review describing the concept of fractals and its relationship with the fracture toughness is presented. In the following part, a correlation between fractal dimension, total energy of fracture and the average resistance to crack propagation is proposed; all these parameters being dependent on the history and on the complexity of crack propagation path.

A densidade de empacotamento de pós cerâmicos pode ser maximizada mediante o uso de modelos teóricos de distribuição de tamanho de partículas, o que pode resultar em importantes efeitos no comportamento reológico de suspensões, e em sensível aumento na densidade a verde dos compactos. Neste trabalho, foram estudadas propriedades de pós com distribuição de tamanho de partícula segundo os modelos de Alfred e de Andreasen em compactos obtidos por prensagem uniaxial, isostática e por colagem de barbotina. Verificou-se que embora o modelo de Alfred seja mais bem fundamentado que o de Andreasen, proporcionou compactos de menor densidade e pouca homogeneidade, nas amostras obtidas por colagem. Este comportamento foi atribuído à estrutura de poros do compacto, a qual possibilitou o arraste de partículas finas pelo fluxo de água. Nas amostras com distribuição segundo o modelo de Andreasen, isto não foi verificado.

The use of theoretical models of particle size distribution to maximise the packing density of a powder may result in significant improvement of the rheological behaviour of suspensions and compact's green density. In this work, Alfred and Andreasen models were studied, taking into account their effect on the characteristics of compacts obtained by uniaxial and isostatic pressing and by slip casting. It was noticed that although the Alfred model is considered more realistic than the Andreasen model, it has led to less dense and less homogeneous compacts in the samples obtained by slip casting. This behaviour, which hasn't been noticed in samples obtained by dry pressing, was attributed to the pore structure of the compacts, which allowed water flow to drag fine particles. In samples obtained according to the Andreasen model, that was not observed.