Pozzolanic activity of oil-refining catalyst: evaluation by electron and atomic microscopy

The reuse of waste fluid catalytic cracking (FCC) catalyst as partial surrogate for cement can reduce the environmental impact of both the oil-refinery and cement production industries [1,2]. FCC catalysts can be considered as pozzolanic materials since in the presence of water they tend to chemically react with calcium hydroxide to produce compounds possessing cementitious properties [3,4]. In addition, partial replacement of cement with FCC catalysts can enhance the performance of pastes and mortars, namely by improving their compressive strength [5,6]. In the present work the reaction of waste FCC catalyst with Ca(OH)2 has been investigated after a curing time of 28 days by scanning electron microscopy (SEM) with electron backscattered signal (BSE) combined with X-ray energy dispersive spectroscopy (EDS) carried out with a JEOL JSM 7001F instrument operated at 15 kV coupled to an INCA pentaFetx3 Oxford spectrometer. The polished cross-sections of FCC particles embedded in resin have also been evaluated by atomic force microscopy (AFM) in contact mode (CM) using a NanoSurf EasyScan 2 instrument. The SEM/EDS results revealed that an inward migration of Ca occurred during the reaction. A weaker outward migration of Si and Al was also apparent (Fig. 1). The migration of Ca was not homogeneous and tended to follow high-diffusivity paths within the porous waste FCC catalyst particles. The present study suggests that the porosity of waste FCC catalysts is key for the migration/reaction of Ca from the surrounding matrix, playing an important role in the pozzolanic activity of the system. The topography images and surface roughness parameters obtained by atomic force microscopy can be used to infer the local porosity in waste FCC catalyst particles (Fig. 2).

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Low-Carbon Cement with Waste Oil-Cracking Catalyst Incorporation

The present paper shows preliminary results of an ongoing project which one of the goals is to investigate the viability of using waste FCC catalyst (wFCC), originated from Portuguese oil refinery, to produce low carbon blended cements. For this purpose, four blended cements were produced by substituting cement CEM I 42.5R up to 20% (w/w) by waste FCC catalyst. Initial and final setting times, consistency of standard paste, soundness and compressive strengths after 2, 7 and 28 days were measured. It was observed that the wFCC blended cements developed similar strength, at 28 days, compared to the reference cement, CEM I 42.5R. Moreover, cements with waste FCC catalyst incorporation up to 15% w/w meet European Standard EN 197-1 specifications for CEM II/A type cement, in the 42.5R strength class.

Waste Marble Dust Blended Cement

Marble processing activities generates a.significant amount of waste in dust form. This waste, which is nowadays one of the environmental problems worldwide, presents great potential of being used as mineral addition in blended cements production. This paper shows preliminary results of an ongoing project which ultimate goal is to investigate the viability of using waste marble dust (WMD), produced by marble Portuguese industry, as cement replacement material. In order to evaluate the effects of the WMD on mechanical behaviour, different mortar blended cement mixtures were tested. These mixtures were prepared with different partial substitution level of cement with WMD. Strength results of WMD blended cements were compared to control cements with same level of incorporation of natural limestone used to produce commercial Portland-limestone cements. The results obtained show that WMD blended cements perform better than limestone blended cements for same replacement level up to 20% w/w. Therefore, WMD reveals promising attributes for blended cements production.

Development of an injectable grout for concrete repair and strengthening

This paper deals with the coupled effect of temperature and silica fume addition on rheological, mechanical behaviour and porosity of grouts based on CEMI 42.5R, proportioned with a polycarboxylate-based high range water reducer. Preliminary tests were conducted to focus on the grout best able to fill a fibrous network since the goal of this study was to develop an optimized grout able to be injected in a mat of steel fibers for concrete strengthening. The grout composition was developed based on criteria for fresh state and hardened state properties. For a CEMI 42.5R based grout different high range water reducer dosages (0%, 0.2%, 0.4%, 0.5%, 0.7%) and silica fume (SF) dosages (0%, 2%, 4%) were tested (as replacement of cement by mass). Rheological measurements were used to investigate the effect of polycarboxylates (PCEs) and SF dosage on grout properties, particularly its workability loss, as the mix was to be injected in a matrix of steel fibers for concrete jacketing. The workability behaviour was characterized by the rheological parameters yield stress and plastic viscosity (for different grout temperatures and resting times), as well as the procedures of mini slump cone and funnel flow time. Then, further development focused only on the best grout compositions. The cement substitution by 2% of SF exhibited the best overall behaviour and was considered as the most promising compared to the others compositions tested. Concerning the fresh state analysis, a significant workability loss was detected if grout temperature increased above 35 degrees C. Below this temperature the grout presented a self-levelling behaviour and a life time equal to 45 min. In the hardened state, silica fumes increased not only the grout's porosity but also the grout's compressive strength at later ages, since the pozzolanic contribution to the compressive strength does not occur until 28 d and beyond. (C) 2012 Elsevier Ltd. All rights reserved.

Low-carbon cement with waste oil-craking catalyst incorporation

The present paper shows preliminary results of an ongoing project which one of the goals is to investigate the viability of using waste FCC catalyst (wFCC), originated from Portuguese oil refinery, to produce low carbon blended cements. For this purpose, four blended cements were produced by substituting cement CEM I 42.5R up to 20% (w/w) by waste FCC catalyst. Initial and final setting times, consistency of standard paste, soundness and compressive strengths after 2, 7 and 28 days were measured. It was observed that the wFCC blended cements developed similar strength, at 28 days, compared to the reference cement, CEM I 42.5R. Moreover, cements with waste FCC catalyst incorporation up to 15% w/w meet European Standard EN 197-1 specifications for CEM II/A type cement, in the 42.5R strength class.

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.

(E)xperimental study of the porosity and microstructure of self-compacting concrete (SCC) with binary and ternary mixes of fly ash and limestone filler

Self-compacting concrete (SCC) can soon be expected to replace conventional concrete due to its many advantages. Its main characteristics in the fresh state are achieved essentially by a higher volume of mortar (more ultrafine material) and a decrease of the coarse-aggregates. The use of over-large volumes of additions such as fly ash (FA) and/or limestone filler (LF) can substantially affect the concrete's pore structure and consequently its durability. In this context, an experimental programme was conducted to evaluate the effect on the concrete's porosity and microstructure of incorporating FA and LF in binary and ternary mixes of SCC. For this, a total of 11 SIX mixes were produced; 1 with cement only (C); 3 with C + FA in 30%, 60% and 70% substitution (fad); 3 with C + LF in 30%, 60% and 70% fad; 4 with C + FA + LF in combinations of 10-20%, 20-10%, 20-40% and 40-20% f(ad), respectively. The results enabled conclusions to be established regarding the SCC's durability, based on its permeability and the microstructure of its pore structure. The properties studied are strongly affected by the type and quantity of additions. The use of ternary mixes also proves to be extremely favourable, confirming the beneficial effect of the synergy between these additions. (C) 2015 Elsevier Ltd. All rights reserved.

Experimental study of the mechanical properties and durability of self-compacting mortars with nano materials (SiO2 and TiO2)

Resumo: Cement, as well as the remaining constituents of self-compacting mortars, must be carefully selected, in order to obtain an adequate composition with a granular mix as compact as possible and a good performance in the fresh state (self-compacting effect) and the hardened state (mechanical and durability-related behavior). Therefore in this work the possibility of incorporating nano particles in self-compacting mortars was studied. Nano materials are very reactive due mostly to their high specific surface and show a great potential to improve the properties of these mortars, both in mechanical and durability terms. In this work two nano materials were used, nano silica (nano SiO2) in colloidal state and nano titanium (nano TiO2) in amorphous state, in two types of self-compacting mortars (ratio binder:sand of 1:1 and 1:2). The self-compacting mortar mixes have the same water/cement ratio and 30% of replacement of cement with fly ashes. The influence of nano materials nano-SiO2 and nano-TiO2 on the fresh and hardened state properties of these self-compacting mortars was studied. The results show that the use of nano materials in repair and rehabilitation mortars has significant potential but still needs to be optimized. (C) 2015 Elsevier Ltd. All rights reserved.

Experimental study of the porosity and microstructure of self-compacting concrete (SCC) with binary and ternary mixes of fly ash and limestone filler

Abstract Self-compacting concrete (SCC) can soon be expected to replace conventional concrete due to its many advantages. Its main characteristics in the fresh state are achieved essentially by a higher volume of mortar (more ultrafine material) and a decrease of the coarse-aggregates. The use of over-large volumes of additions such as fly ash (FA) and/or limestone filler (LF) can substantially affect the concrete's pore structure and consequently its durability. In this context, an experimental programme was conducted to evaluate the effect on the concrete's porosity and microstructure of incorporating FA and LF in binary and ternary mixes of SCC. For this, a total of 11 SCC mixes were produced: 1 with cement only (C); 3 with C + FA in 30%, 60% and 70% substitution (fad); 3 with C + LF in 30%, 60% and 70% fad; 4 with C + FA + LF in combinations of 10-20%, 20-10%, 20-40% and 40-20% fad, respectively. The results enabled conclusions to be established regarding the SCC's durability, based on its permeability and the microstructure of its pore structure. The properties studied are strongly affected by the type and quantity of additions. The use of ternary mixes also proves to be extremely favourable, confirming the beneficial effect of the synergy between these additions. © 2015 Elsevier Ltd. All rights reserved.

Fresh-state properties of self-compacting mortar and concrete with combined use of limestone filler and fly ash

This paper presents the results of a study on the behaviour of self-compacting concrete (SCC) in the fresh and hardened states, produced with binary and ternary mixes of fly ash (FA) and limestone filler (LF), using the method proposed by Nepomuceno. His method determines the SCC composition parameters in the mortar phase (self-compacting mortar - SCM) easily and efficiently, whilst guaranteeing the SCC properties in both the fresh and hardened states. For this, 11 SCMs were studied: one with cement (C) only; three with FA at 30%, 60% and 70% C substitution; three with LF at 30%, 60% and 70% C substitution; four with FA + LF in combinations of 10-20%, 20-10%, 20-40% and 40-20% C substitution. Once the composition of these mortars was defined, 18 SCC mixes were produced: 14 binary SCC mixes were produced with the seven binary mortar mixes, and four ternary SCC mixes were produced with the four ternary mortar mixes. In addition to the methodology proposed by Nepomuceno, the combined use of FA and LF in ternary mixtures was tested. The results confirmed that the method could yield SCC with adequate properties in both the fresh and hardened states. It was also possible to determine the SCC composition parameters in the mortar phase (self-compacting mortar - SCM) that will guarantee the SCC properties in both the fresh and hardened states, as confirmed through the optimized behaviour of the SCC in the fresh state and the promising results in the hardened state (compressive strength). The potential demonstrated by the joint use of LF and FA through the synergetic interaction of both additions is emphasized.

Durability performance of self-compacting concrete (SCC) with binary and ternary mixes of fly ash and limestone filler

The basic objective of this work is to evaluate the durability of self-compacting concrete (SCC) produced in binary and ternary mixes using fly ash (FA) and limestone filler (LF) as partial replacement of cement. The main characteristics that set SCC apart from conventional concrete (fundamentally its fresh state behaviour) essentially depend on the greater or lesser content of various constituents, namely: greater mortar volume (more ultrafine material in the form of cement and mineral additions); proper control of the maximum size of the coarse aggregate; use of admixtures such as superplasticizers. Significant amounts of mineral additions are thus incorporated to partially replace cement, in order to improve the workability of the concrete. These mineral additions necessarily affect the concrete’s microstructure and its durability. Therefore, notwithstanding the many well-documented and acknowledged advantages of SCC, a better understanding its behaviour is still required, in particular when its composition includes significant amounts of mineral additions. An ambitious working plan was devised: first, the SCC’s microstructure was studied and characterized and afterwards the main transport and degradation mechanisms of the SCC produced were studied and characterized by means of SEM image analysis, chloride migration, electrical resistivity, and carbonation tests. It was then possible to draw conclusions about the SCC’s durability. The properties studied are strongly affected by the type and content of the additions. Also, the use of ternary mixes proved to be extremely favourable, confirming the expected beneficial effect of the synergy between LF and FA. © 2015 RILEM.

Research progress on reuse of fluid catalytic cracking waste from oil refinery in cement-based materials

Present paper present the main results obtained in the scope of an ongoing project which aims to contribute to the valorization of a waste generated by the Portuguese oil company in construction materials. This waste is an aluminosilicate with high pozzolanic reactivity. Several different technological applications had already been tested with success both in terms of properties and compliance with the corresponding standards specifications. Namely, this project results already demonstrated that this waste can be used in traditional concrete, self-compacted concrete, mortars (renders, masonry mortar, concrete repair mortars), cement main constituent as well as alkali activated binders.