An SEM investigation of the pozzolanic activity of a waste catalyst oil refinery

The most active phase of the fluid catalytic cracking (FCC) catalyst, used in oil refinery, is zeolite-Y which is an aluminosilicate with a high internal and external surface area responsible for its high reactivity. Waste FCC catalyst is potentially able to be reused in cement-based materials - as an additive - undergoing a pozzolanic reaction with calcium hydroxide (Ca(OH)2) formed during cement hydration [1-3]. This reaction produces additional strength-providing reaction products i.e., calcium silicate hydrate (C-S-H) and hydrous calcium aluminates (C-A-H) which exact chemical formula and structure are still unknown. Partial replacement of cement by waste FCC catalyst has two key advantages: (1) lowering of cement production with the associated pollution reduction as this industry represents one of the largest sources of man-made CO2 emissions, and (2) improving the mechanical properties and durability of cement-based materials. Despite these advantages, there is a lack of fundamental knowledge on pozzolanic reaction mechanisms as well as spatial distribution of porosity and solid phases interactions at the microstructural level and consequently their relationship with macroscopical engineering properties of catalyst/cement blends. Within this scope, backscattered electron (BSE) images acquired in a scanning electron microscope (SEM) equipped with Energy-Dispersive Spectroscopy (EDS) and by X-ray diffraction were used to investigate chemical composition of hydration products and to analyse spatial information of the microstructure of waste FCC catalyst blended cement mortars. For this purpose mortars with different levels of cement substitution by waste catalyst as well as with different hydration ages, were prepared. The waste FCC catalyst used is produced by the Portuguese refinery company Petrogal S.A.

Electrochemical and analytical investigation of passive films formed on stainless steels in alkaline media

Passive films were grown in potentiodynamic mode, by cyclic voltammetry on AISI 316 and AISI 304 stainless steels. The composition of these films was investigated by X-ray photoelectron spectroscopy (XPS). The electrochemical behaviour and the chemical composition of the passive films formed by cyclic voltammetry were compared to those of films grown under natural conditions (by immersion at open circuit potential, OCP) in alkaline solutions simulating concrete. The study included the effect of pH of the electrolyte and the effect of the presence of chloride ions. The XPS results revealed important changes in the passive film composition, which becomes enriched in chromium and depleted in magnetite as the pH decreases. On the other hand, the presence of chlorides promotes a more oxidised passive layer. The XPS results also showed relevant differences on the composition of the oxide layers for the films formed under cyclic voltammetry and/or under OCP.

Repair mortars for rammed earth constructions

Proceedingsof the XII DBMC – 12th International Conference on Durability of Building Materials and Components, Vol.2, Porto, FEUP, March 2011, p.689-696

Physical and chemical assessment of lime–metakaolin mortars: Influence of binder:aggregate ratio

Cement & Concrete Composites 45 (2014) 264–271

Numerical simulation of blast effects on fibre grout RC panels

The main purpose of the present dissertation is the simulation of the response of fibre grout strengthened RC panels when subjected to blast effects using the Applied Element Method, in order to validate and verify its applicability. Therefore, four experimental models, three of which were strengthened with a cement-based grout, each reinforced by one type of steel reinforcement, were tested against blast effects. After the calibration of the experimental set-up, it was possible to obtain and compare the response to the blast effects of the model without strengthening (reference model), and a fibre grout strengthened RC panel (strengthened model). Afterwards, a numerical model of the reference model was created in the commercial software Extreme Loading for Structures, which is based on the Applied Element Method, and calibrated to the obtained experimental results, namely to the residual displacement obtained by the experimental monitoring system. With the calibration verified, it is possible to assume that the numerical model correctly predicts the response of fibre grout RC panels when subjected to blast effects. In order to verify this assumption, the strengthened model was modelled and subjected to the blast effects of the corresponding experimental set-up. The comparison between the residual and maximum displacements and the bottom surface’s cracking obtained in the experimental and the numerical tests yields a difference of 4 % for the maximum displacements of the reference model, and a difference of 4 and 10 % for the residual and maximum displacements of the strengthened model, respectively. Additionally, the cracking on the bottom surface of the models was similar in both methods. Therefore, one can conclude that the Applied ElementMethod can correctly predict and simulate the response of fibre grout strengthened RC panels when subjected to blast effects.

Modelo para calcular a contribuição da fibra na resistência à punção de lajes em concreto reforçado com fibra de aço

Neste artigo, formulações analíticas são desenvolvidas para calcular a resistência à punção de lajes lisas de concreto reforçado com fibras de aço (CRFA) e que também são reforçadas à flexão por barras de aço (reforço convencional). A partir de análises estatísticas sobre um banco de dados que reúne resultados experimentais de caracterização do comportamento pós-fissuração do CRFA, equações são estabelecidas para avaliar parâmetros da resistência residual à tração na flexão (fRi) a partir de informações fundamentais que caracterizam a fibra de aço. O parâmetro de resistência fRi, proposto pelo ModelCode10 foi usado para definir a lei tensão-abertura da fissura (σ-w) que simula o mecanismo de reforço da fibra em um material cimentício. A segunda parte do artigo descreve uma formulação analítica baseada nos conceitos propostos por Muttoni e Ruiz, onde a lei σ-w é convenientemente integrada para simular a contribuição da fibra de aço na resistência à punção de lajes em CRFA. A partir de um banco de dados, composto de 154 ensaios de punção, o bom desempenho da proposta apresentada é demonstrado. O desempenho do modelo também é evidenciado comparando-se os seus resultados a outros modelos.

Tensile stress–crack width law for steel fibre reinforced self-compacting concrete obtained from indirect (splitting) tensile tests

In this work, the fracture mode I parameters of steel fibre reinforced self-compacting concrete (SFRSCC) were derived from the numerical simulation of indirect splitting tensile tests. The combined experimental and numerical research allowed a comparison between the stress-crack width (σ - w) relationship acquired straightforwardly from direct tensile tests, and the σ - w response derived from inverse analysis of the splitting tensile tests results. For this purpose a comprehensive nonlinear 3D finite element (FE) modeling strategy was developed. A comparison between the experimental results obtained from splitting tensile tests and the corresponding FE simulations confirmed the good accuracy of the proposed strategy to derive the σ – w for these composites. It is concluded that the post-cracking tensile laws obtained from inverse analysis provided a close relationship with the ones obtained from the experimental uniaxial tensile tests.

Assessment of the performance of steel fibre reinforced self-compacting concrete in elevated slabs

The reinforcement mechanisms at the cross section level assured by fibres bridging the cracks in steel fibre reinforced self-compacting concrete (SFRSCC) can be significantly amplified at structural level when the SFRSCC is applied in structures with high support redundancy, such is the case of elevated slab systems. To evaluate the potentialities of SFRSCC as the fundamental material of elevated slab systems, a ¼ scale SFRSCC prototype of a residential building was designed, built and tested. The extensive experimental program includes material tests for characterizing the relevant properties of SFRSCC, as well as structural tests for assessing the performance of the prototype at serviceability and ultimate limit conditions. Three distinct approaches where adopted to derive the constitutive laws of the SFRSCC in tension that were used in finite element material nonlinear analysis to evaluate the reliability of these approaches in the prediction of the load carrying capacity of the prototype.

Recycled steel fibre reinforced concrete failing in bending and in shear

Recent research is showing that the addition of Recycled Steel Fibres (RSF) from wasted tyres can decrease significantly the brittle behaviour of cement based materials, by improving its toughness and post-cracking resistance. In this sense, Recycled Steel Fibre Reinforced Concrete (RSFRC) seems to have the potential to constitute a sustainable material for structural and non-structural applications. To assess this potential, experimental and numerical research was performed on the use of RSFRC in elements failing in bending and in beams failing in shear. The values of the fracture mode I parameters of the developed RSFRC were determined by performing inverse analysis with test results obtained in three point notched beam bending tests. To assess the possibility of using RSF as shear reinforcement in Reinforced Concrete (RC) beams, three point bending tests were executed with three series of RSFRC beams flexurally reinforced with a relatively high reinforcement ratio of longitudinal steel bars in order to assure shear failure for all the tested beams. By performing material nonlinear simulations with a computer program based on the finite element method (FEM), the applicability of the fracture mode I crack constitutive law derived from the inverse analysis is assessed for the prediction of the behaviour of these beams. The performance of the formulation proposed by RILEM TC 162 TDF and CEB-FIP 2010 for the prediction of the shear resistance of fibre reinforced concrete elements was also evaluated.

Influence of casting condition on the anisotropy of the fracture properties of Steel Fibre Reinforced Self-Compacting Concrete (SFRSCC)

Identification of the tensile constitutive behaviour of Fibre Reinforced Concrete (FRC) represents an important aspect of the design of structural elements using this material. Although an important step has been made with the introduction of guidance for the design with regular FRC in the recently published fib Model Code 2010, a better understanding of the behaviour of this material is still necessary, mainly for that with self-compacting properties. This work presents an experimental investigation employing Steel Fibre Self-Compacting Concrete (SFRSCC) to cast thin structural elements. A new test method is proposed for assessing the post-cracking behaviour and the results obtained with the proposed test method are compared with the ones resulted from the standard three-point bending tests (3PBT). Specimens extracted from a sandwich panel consisting of SFRSCC layers are also tested. The mechanical properties of SFRSCC are correlated to the fibre distribution by analysing the results obtained with the different tests. Finally, the stress-crack width constitutive law proposed by the fib Model Code 2010 is analysed in light of the experimental results.

Comportamento tribológico de biocompósitos de matriz de titânio

Dissertação de mestrado integrado em Engenharia de Materiais

Evaluation of the performance of steel fibre reinforced self-compacting concrete in elevated slab systems; from the material to the structure

Degree of Doctor of Philosophy of Structural/Civil Engineering

Fluência no betão desde as primeiras idades: um estudo experimental

Dissertação de mestrado integrado em Engenharia Civil

Evaluation of the Chemical Durability of Iowa Fly Ash Concretes, HR-327, 1993

The major objective of this research project was to investigate how Iowa fly ashes influenced the chemical durability of portland cement based materials. Chemical durability has become an area of uncertainty because of the winter application of deicer salts (rock salts) that contain a significant amount of sulfate impurities. The sulfate durability testing program consisted of monitoring portland cement-fly ash paste, mortar and concrete test specimens that had been subjected to aqueous solutions containing various concentrations of salts (both sulfate and chloride). The paste and mortar specimens were monitored for length as a function of time. The concrete test specimens were monitored for length, relative dynamic modulus and mass as a function of time. The alkali-aggregate reactivity testing program consisted of monitoring the expansion of ASTM C311 mortar bar specimens that contained three different aggregates (Pyrex glass, Oreapolis and standard Ottawa sand). The results of the sulfate durability study indicated that the paste and concrete test specimens tended to exhibit surface spalling but only very slow expansive tendencies. This suggested that the permeability of the test specimens was controlling the rate of deterioration. Concrete specimens are still being monitored because the majority of the test specimens have expanded less than 0.05%; hence, this makes it difficult to estimate the service life of the concrete test specimens or to quantify the performance of the different fly ashes that were used in the study. The results of the mortar bar studies indicated that the chemical composition of the various fly ashes did have an influence on their sulfate resistance. Typically, Clinton and Louisa fly ashes performed the best, followed by the Ottumwa, Neal 4 and then Council Bluffs fly ashes. Council Bluffs fly ash was the only fly ash that consistently reduced the sulfate resistance of the many different mortar specimens that were investigated during this study. None of the trends that were observed in the mortar bar studies have yet become evident in the concrete phase of this project. The results of the alkali-aggregate study indicated that the Oreapolis aggregate is not very sensitive to alkali attack. Two of the fly ashes, Council Bluffs and Ottumwa, tended to increase the expansion of mortar bar specimens that contained the Oreapolis aggregate. However, it was not clear if the additional expansion was due to the alkali content of the fly ash, the periclase content of the fly ash or the cristobalite content of the fly ash, since all three of these factors have been found to influence the test results.

Non-resorbable glass fibre-reinforced composite with porous surface as bone substitute material: Experimental studies in vitro and in vivo focused on bone-implant interface

The development of load-bearing osseous implant with desired mechanical and surface properties in order to promote incorporation with bone and to eliminate risk of bone resorption and implant failure is a very challenging task. Bone formation and resoption processes depend on the mechanical environment. Certain stress/strain conditions are required to promote new bone growth and to prevent bone mass loss. Conventional metallic implants with high stiffness carry most of the load and the surrounding bone becomes virtually unloaded and inactive. Fibre-reinforced composites offer an interesting alternative to metallic implants, because their mechanical properties can be tailored to be equal to those of bone, by the careful selection of matrix polymer, type of fibres, fibre volume fraction, orientation and length. Successful load transfer at bone-implant interface requires proper fixation between the bone and implant. One promising method to promote fixation is to prepare implants with porous surface. Bone ingrowth into porous surface structure stabilises the system and improves clinical success of the implant. The experimental part of this work was focused on polymethyl methacrylate (PMMA) -based composites with dense load-bearing core and porous surface. Three-dimensionally randomly orientated chopped glass fibres were used to reinforce the composite. A method to fabricate those composites was developed by a solvent treatment technique and some characterisations concerning the functionality of the surface structure were made in vitro and in vivo. Scanning electron microscope observations revealed that the pore size and interconnective porous architecture of the surface layer of the fibre-reinforced composite (FRC) could be optimal for bone ingrowth. Microhardness measurements showed that the solvent treatment did not have an effect on the mechanical properties of the load-bearing core. A push-out test, using dental stone as a bone model material, revealed that short glass fibre-reinforced porous surface layer is strong enough to carry load. Unreacted monomers can cause the chemical necrosis of the tissue, but the levels of leachable resisidual monomers were considerably lower than those found in chemically cured fibre-reinforced dentures and in modified acrylic bone cements. Animal experiments proved that surface porous FRC implant can enhance fixation between bone and FRC. New bone ingrowth into the pores was detected and strong interlocking between bone and the implant was achieved.