Ana Paula Kirchheim

Real-time high-resolution X-ray imaging and nuclear magnetic resonance study of the hydration of pure and Na-doped C3A in the presence of sulfates

This study details the differences in real-time hydration between pure tricalcium aluminate (cubic C(3)A or 3CaO·Al(2)O(3)) and Na-doped tricalcium aluminate (orthorhombic C(3)A or Na(2)Ca(8)Al(6)O(18)), in aqueous solutions containing sulfate ions. Pure phases were synthesized in the laboratory to develop an independent benchmark for the reactions, meaning that their reactions during hydration in a simulated early age cement pore solution (saturated with respect to gypsum and lime) were able to be isolated. Because the rate of this reaction is extremely rapid, most microscopy methods are not adequate to study the early phases of the reactions in the early stages. Here, a high-resolution full-field soft X-ray imaging technique operating in the X-ray water window, combined with solution analysis by (27)Al nuclear magnetic resonance (NMR) spectroscopy, was used to capture information regarding the mechanism of C(3)A hydration during the early stages. There are differences in the hydration mechanism between the two types of C(3)A, which are also dependent on the concentration of sulfate ions in the solution. The reactions with cubic C(3)A (pure) seem to be more influenced by higher concentrations of sulfate ions, forming smaller ettringite needles at a slower pace than the orthorhombic C(3)A (Na-doped) sample. The rate of release of aluminate species into the solution phase is also accelerated by Na doping.

Role of Adsorption Phenomena in Cubic Tricalcium Aluminate Dissolution

The workability of fresh Portland cement (PC) concrete critically depends on the reaction of the cubic tricalcium aluminate (C3A) phase in Ca- and S-rich pH >12 aqueous solution, yet its rate-controlling mechanism is poorly understood. In this article, the role of adsorption phenomena in C3A dissolution in aqueous Ca-, S-, and polynaphthalene sulfonate (PNS)-containing solutions is analyzed. The zeta potential and pH results are consistent with the isoelectric point of C3A occurring at pH ∼12 and do not show an inversion of its electric double layer potential as a function of S or Ca concentration, and PNS adsorbs onto C3A, reducing its zeta potential to negative values at pH >12. The S and Ca K-edge X-ray absorption spectroscopy (XAS) data obtained do not indicate the structural incorporation or specific adsorption of SO42- on the partially dissolved C3A solids analyzed. Together with supporting X-ray ptychography and scanning electron microscopy results, a model for C3A dissolution inhibition in hydrated PC systems is proposed whereby the formation of an Al-rich leached layer and the complexation of Ca-S ion pairs onto this leached layer provide the key inhibiting effect(s). This model reconciles the results obtained here with the existing literature, including the inhibiting action of macromolecules such as PNS and polyphosphonic acids upon C3A dissolution. Therefore, this article advances the understanding of the rate-controlling mechanism in hydrated C3A and thus PC systems, which is important to better controlling the workability of fresh PC concrete.

Aplicação da Avaliação do Ciclo de Vida na análise de impactos ambientais de materiais de construção inovadores: estudo de caso da pegada de carbono de clínqueres alternativos

O setor da construcao civil e reconhecido como um grande consumidor de recursos, e responsavel por diversas emissoes que causam impactos substanciais ao ambiente. Muitos destes impactos estao diretamente relacionados a producao de materiais de construcao. Por isso, mundialmente cresce a tendencia de se propor o uso de materiais de construcao inovadores, que considerem a mitigacao de seus impactos ambientais no processo produtivo. Para avaliar todos os impactos ambientais relacionados a estes materiais, e necessario que se avalie todas as fases de seu ciclo de vida. Para isso, propoe-se a aplicacao da Avaliacao do Ciclo de Vida (ACV), metodologia internacionalmente consagrada na avaliacao ambiental de produtos, processos e servicos, sendo tambem normatizada para o calculo de declaracoes ambientais de produtos da construcao civil. Sabe-se que a producao cimento emite quantidade pronunciadas de gases do efeito estufa. Por isso, neste trabalho, a ACV e aplicada para o calculo da pegada de carbono de clinqueres alternativos produzidos em laboratorio. Os resultados obtidos demonstram uma reducao em 22% da pegada de carbono do clinquer alternativo em relacao ao clinquer Portland, indicando as etapas do processo produtivo que mais colaboram para estes valores. Ainda, evidencia-se a ampla aplicabilidade da ferramenta ACV ao setor da construcao.

A Scanning Transmission X-ray Microscopy Study of Cubic and Orthorhombic C3A and Their Hydration Products in the Presence of Gypsum

This paper shows the microstructural differences and phase characterization of pure phases and hydrated products of the cubic and orthorhombic (Na-doped) polymorphs of tricalcium aluminate (C3A), which are commonly found in traditional Portland cements. Pure, anhydrous samples were characterized using scanning transmission X-ray microscopy (STXM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) and demonstrated differences in the chemical and mineralogical composition as well as the morphology on a micro/nano-scale. C3A/gypsum blends with mass ratios of 0.2 and 1.9 were hydrated using a water/C3A ratio of 1.2, and the products obtained after three days were assessed using STXM. The hydration process and subsequent formation of calcium sulfate in the C3A/gypsum systems were identified through the changes in the LIII edge fine structure for Calcium. The results also show greater Ca LII binding energies between hydrated samples with different gypsum contents. Conversely, the hydrated samples from the cubic and orthorhombic C3A at the same amount of gypsum exhibited strong morphological differences but similar chemical environments.

Clínquer Portland com reduzido impacto ambiental

Atualmente ha um expressivo aumento no consumo de cimento, aliado a crescente preocupacao ambiental inserida dentro do processo industrial. Com o intuito de amenizar impactos gerados pelo consumo de materia-prima e emissao de CO 2 para a atmosfera, foi realizado um estudo em laboratorio no qual a escoria do forno panela (EFP), um residuo da industria siderurgica, foi empregada para fabricacao do clinquer Portland. O objetivo e avaliar a qualidade do clinquer e a emissao de CO 2 gerada ao adicionar esse subproduto na farinha do clinquer. Foram realizadas analises termogravimetricas para quantificar as emissoes de CO 2 por farinhas sem e com EFP, a partir da avaliacao de sua decomposicao em elevadas temperaturas. Os clinqueres produzidos foram avaliados qualitativamente por difracao de raios X e microscopia optica. Os resultados demonstram que o clinquer produzido com EFP tem uma emissao de CO 2 16,51% mais baixa que o clinquer referencia, produzido apenas com reagentes quimicos puros. Os resultados dessa analise mineralogica por difracao de raios X e microscopia optica de luz refletida mostraram-se satisfatorios, observando-se uma melhor queimabilidade da farinha com EFP.

Avaliação da perda de massa de farinhas precursoras de clínquer CSAB compostas com lodo de anodização do alumínio

Portland cement science is well established in Brazil and in the world; however, the development of calcium sulfoaluminate belite (CSAB) cements, considered a low-environmental impact material, is still in its initial stages relative to cement Portland abroad and there are even fewer studies nationally. One concern regarding the production of CSAB cements is the high amount of sulfur in the raw materials. Excess sulfur in the feed-stock of Portland cement causes the increase of SO2 emissions, a dampening the efficiency of the pre-heater in the clinker factory, in addition to causing the formation of bonding rings inside the kiln. The viability of the production of CSAB cement depends on the availability of raw materials at low cost, preferably with the use of an alternative industrial waste. Thus, the aim of this work is to analyze the mass loss of lab-made CSAB mixtures up to a temperature of 1450oC, in order to verify the decomposition of sulfated compounds and to evaluate the possibility of replacing bauxite by an alternative source of Al2O3, namely by aluminum anodizing sludge (AAS) residue, which presents itself as an interesting raw-material for the production of CSAB clinker due to its high content of alumina. Mixtures made with pure chemicals, AAS residue and conventional materials were produced. Raw materials were proportioned based on equations formation of compounds synthetic from the mixture oxides composition. To check the mass loss, thermogravimetric analyzes were performed. It was concluded that the maximum temperature for CSAB clinker production should be close to 1250oC to avoid decomposition of sulfur-containing phases and their related SO2 emissions.

Álcalis incorporados ao aluminato tricálcico: efeitos na hidratação

Tricalcium aluminate (C3A) is the phase that reacts more quickly in the cement hydration when in contact with water. Generally, the crystalline form of C3A synthesized during clinkerization is cubic. However, Na+ can be incorporated into the crystalline lattice of C3A, replacing the Ca2+, leading to the formation of orthorhombic C3A (Na-C3A). Although some studies have investigated the influence of this polymorphous on cement hydration, some knowledge gaps still exist. This study uses pure phases synthesized in laboratory to analyze the reactions independently, isolating the reactions from the others phases. Hydration reactions of C3A in presence of gypsum were investigated by isothermal calorimetry, scanning electron microscopy (SEM), X-ray diffraction (XRD), and dynamic mode rheology. The results showed differences in the hydration of each aluminate, indicating that the orthorhombic phase is more reactive at early ages in the presence of gypsum, consuming them very quickly. The pastes mixed with orthorhombic C3A and gypsum presented a total heat released at least 10 times greater than the ones made with cubic C3A. The SEM images and the XRD patterns demonstrate that the pastes containing orthorhombic C3A reacted at a faster rate, and the ettringite crystals formed were also longer.

Effect of Gypsum on the Early Hydration of Cubic and Na-Doped Orthorhombic Tricalcium Aluminate

The tricalcium aluminate (C3A) and sulfate content in cement influence the hydration chemistry, setting time and rheology of cement paste, mortar and concrete. Here, in situ experiments are performed to better understand the effect of gypsum on the early hydration of cubic (cub-)C3A and Na-doped orthorhombic (orth-)C3A. The isothermal calorimetry data show that the solid-phase assemblage produced by the hydration of C3A is greatly modified as a function of its crystal structure type and gypsum content, the latter of which induces non-linear changes in the heat release rate. These data are consistent with the in situ X-ray diffraction results, which show that a higher gypsum content accelerates the consumption of orth-C3A and the subsequent precipitation of ettringite, which is contrary to the cub-C3A system where gypsum retarded the hydration rate. These in situ results provide new insight into the relationship between the chemistry and early-age properties of cub- and orth-C3A hydration and corroborate the reported ex situ findings of these systems.