Influence of Accelerators on Cement Mortars Using Fluid Catalytic Cracking Catalyst Residue (FCC): Enhanced Mechanical Properties at Early Curing Ages.

Supplementary cementitious materials (SCMs) have been used in the construction industry to mainly reduce the greenhouse gas emissions associated with Portland cement. Of SCMs, the petrochemical industry waste known as fluid catalytic cracking catalyst residue (FCC) is recognized for its high reactivity. Nevertheless, the binders produced using SCMs usually present low mechanical strength at early curing ages. This study aims to assess the effect of different accelerating additives (KOH, sodium silicate SIL, commercial additive SKR) on the mechanical strength of mortars containing FCC. The results show that after only 8 curing hours, the compressive strength gain of the FCC mortars containing SKR was over 100% compared to the FCC mortar with no additive (26.0 vs. 12.8 MPa). Comparing the compressive strength of FCC mortar containing SKR to the control mortar, the enhancement is spetacular (6.85 vs. 26.03 MPa). The effectiveness of the tested accelerators at 8-24 curing hours was KOH ≈ SIL < SKR, whereas it was KOH < SIL < SKR for 48 h-28 days. The thermogravimetric data confirmed the good compatibility of FCC and the commercial accelerator.

Study of the Pozzolanic Reactivity of Sugar Cane Straw Ashes (SCSA) Burned under Controlled Conditions.

The aims of this work were to evaluate the reactivity of sugarcane straw ashes (SCSA) burned under controlled conditions and to analyze their reactivity in blended cement and hydrated lime pastes by thermogravimetric analysis (TG) and calorimetry. Four different ashes were produced, and burned at 600 °C, 700 °C, 800 °C and 900 °C (SCSA600, SCSA700, SCSA800 and SCSA900, respectively). These ashes were characterized by X-ray fluorescence spectroscopy, X-ray diffractometry, particle size distribution by laser diffraction and specific area surfaces to assess their potential interest in the partial replacement of inorganic binders (Portland cement (OPC) and hydrated lime). The hydrated lime pastes were subjected to scanning electron microscopy (SEM) and TG. The blended cement pastes were analyzed by TG and calorimetry, compressive strength testing and mercury intrusion porosimetry. High lime fixation percentages were observed in the hydrated lime and OPC pastes and were higher than 75% and 50% for the ashes burned at 600 °C and 700 °C, respectively. Calorimetry showed a delay in the heat release of SCSA600 and SCSA700 compared to the control paste. These pastes also had higher compressive strength and a smaller total pore volume. The results indicate the positive response of preparing sugar cane ashes under controlled conditions (mainly for straw calcined within the 600-700 °C range) for their use as pozzolanic addition by partially replacing inorganic binders.

Evaluation of Thermochemical Treatments for Rice Husk Ash Valorisation as a Source of Silica in Preparing Geopolymers.

The use of geopolymers has revolutionized research in the field of construction. Although their carbon footprint is often lower than that of traditional mortars with Portland cement, activators such as sodium silicate have a high environmental impact in the manufacturing of materials. Employing alternative alkali sources to produce geopolymers is necessary to obtain materials with a lower carbon footprint. The present research explores the use of rice husk ash (RHA) as an alternative source of silica to produce alkaline activators by four methods: reflux; high pressure and temperature reaction; thermal bath at 65 °C; and shaking at room temperature. To evaluate the efficiency of these methods, two types of experiments were performed: (a) analysing silica dissolved by the filtering/gravimetric method; and (b) manufacturing mortars to compare the effectiveness of the treatment in mechanical strength terms. The percentages of dissolved silica measured by the gravimetric method gave silica dissolution values of 70-80%. The mortars with the best mechanical strength results were the mixtures prepared with the thermal bath treatment at 65 °C. Mortar cured for 1 day (at 65 °C), prepared with this activator, yielded 45 MPa versus the mortar with commercial reagents (40.1 MPa). It was generally concluded that utilising original or milled RHA in preparing activators has minimal influence on either the percentage of dissolved silica or the mechanical strength development of the mortars with this alternative activator.

Impedance Spectroscopy as a Methodology to Evaluate the Reactivity of Metakaolin Based Geopolymers.

The aim of this study was to use the electrical impedance spectroscopy technique (IS) to carry out a systematic study on the mechanism of metakaolin geopolymerization for up to 7 curing days. The study was developed on two batches of metakaolin (MK), and their reaction processes were compared. Interpretative fundamental elements were developed based on the effective electrical conductivity curves regarding the metakaolin geopolymerization. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) were previously carried out and used to interpret and validate the electrical behavior of the fresh and hardened MK-based geopolymer pastes. The results highlighted the sensibility of the impedance technique to the identification and description of the MK geopolymerization process, as well as the changes resulting from even slight variations in the metakaolin composition. Furthermore, this indicated that the geopolymerization process in highly alkaline solutions could be divided into seven stages, including the processes of dissolution, nucleation, precipitation and formation of the gel and, eventually, the retraction/microcracks constitution. Late dissolution processes could be observed during the more advanced stages and were attributed to particles not being fully hydrated.

Reusing Construction and Demolition Waste to Prepare Alkali-Activated Cement.

Large amounts of waste are derived not only from construction processes, but also the demolition of existing buildings. Such waste occupies large volumes in landfills, which makes its final disposal difficult and expensive. Reusing this waste type is generally limited to being employed as filler material or recycled aggregate in concrete, which limits its valorisation. The present work proposes reusing construction and demolition waste to manufacture alkali-activated cement to improve its sustainability and recovery. Construction and demolition waste (C&DW) from a demolition waste collection plant in Valencia (Spain) was physically and chemically characterised. This residue contained large fractions of concrete, mortar, bricks, and other ceramic materials. X-ray fluorescence (XRF) analysis showed that its chemical composition was mainly CaO, SiO2 and Al2O3. X-ray diffraction (XRD) analysis revealed that it presented some crystalline products, and quartz (SiO2) and calcite (CaCO3) were the main components. Blends of C&DW and blast furnace slag (BFS) were alkali-activated with mixtures of sodium hydroxide and sodium silicate. The corresponding pastes were characterised by techniques such as thermogravimetry and scanning electron microscopy (SEM). The alkali-activated mortars were prepared, and the resulting mortars' compressive strength was determined, which was as high as 58 MPa with the 50% C&DW-50% BFS mixture. This work concluded that it is possible to make new sustainable binders by the alkali activation of C&DW-BFS without using Portland cement.

Hybrid Lime-Pozzolan Geopolymer Systems: Microstructural, Mechanical and Durability Studies.

This work studies the possibility of using geopolymer materials to enhance the mechanical and durability properties of hydrated lime-pozzolan mixtures, which gave rise to the so-called "hybrid systems". Two different waste types were used as pozzolan in the lime-pozzolan system: rice husk ash (RHA) and spent fluid catalytic cracking (FCC). The geopolymer fabricated with FCC was activated with commercial reagents (NaOH and Na2SiO3), and also with alternative sources of silica to obtain a lower carbon footprint in these mixtures. The alternative silica sources were RHA and residual diatomaceous earth (RDE) from the beer industry. The geopolymer mixture substituted the lime-pozzolan mixture for 30% replacement in weight. The hybrid systems showed better mechanical strengths for the short and medium curing ages in relation to the lime-pozzolan mixtures. Thermogravimetric analyses were performed to characterise the types of products formed in these mixtures. In the durability studies, hybrid systems better performed in freeze-thaw cycles and obtained lower capillarity water absorption values.

Reuse of Industrial and Agricultural Waste in the Fabrication of Geopolymeric Binders: Mechanical and Microstructural Behavior.

Resource recovery from waste is one of the most important ways to implement the so-called circular economy, and the use of alkali activated materials can become an alternative for traditional PC-based materials. These types of materials are based on waste resources involving a lower carbon footprint and present similar or high properties and good durability compared to that Portland cement (PC). This research work proposes using new waste generated in different types of industries. Four waste types were employed: fluid catalytic cracking residue (FCC) from the petrochemical industry; ceramic sanitary ware (CSW) from the construction industry; rice husk ash (RHA); diatomaceous waste from beer filtration (DB) (food industry). FCC and CSW were employed as precursor materials, and mixtures of both showed good properties of the obtained alkali activated materials generated with commercial products as activators (NaOH/waterglass). RHA and DB were herein used as an alternative silica source to prepare the alkaline activating solution. Mechanical behavior was studied by the compressive strength development of mortars. The corresponding pastes were characterized by X-ray diffraction, thermogravimetric analysis, and microscopy studies. The results were satisfactory, and demonstrated that employing these alternative activators from waste produces alkali activated materials with good mechanical properties, which were sometimes similar or even better than those obtained with commercial reagents.

Concrete for Precast Blocks: Binary and Ternary Combination of Sewage Sludge Ash with Diverse Mineral Residue.

This paper proposes binary and ternary combinations of sewage sludge ash (SSA) with fly ash (FA), marble dust (MD) and rice husk ash (RHA) as partial replacements of Portland cement in concretes with a similar dosage to that used in precast blocks, with very dry consistency. Several physical-mechanical tests were carried out on concrete specimens with curing ages of 28 and 90 days: density, water absorption, capillary water absorption, ultrasonic pulse velocity and compressive strength. The combinations of residues significantly improve the properties of the cementitious systems: 30% replacement of Portland cement provides strength values similar to the reference sample, showing the synergetic effects of the combination of the mineral additions. The significance of this research relies on the combined use of the mineral additions as well as the use of them for the precast block industry. The results show synergies among the additions and even that some of them showed relevant improvements when they are used in combination, performing better than when used individually.

Comparative Study of Coupling Techniques in Lamb Wave Testing of Metallic and Cementitious Plates.

Lamb waves have emerged as a valuable tool to examine long plate-like structures in a faster way compared to conventional bulk wave techniques, which make them attractive in non-destructive testing. However, they present a multimodal and dispersive nature, which hinders signal identification. Oblique incidence is one of the most known methods to generate and receive Lamb waves and it is applied in different experimental arrangements with different types of sensors. In this work, several setups were conducted and compared to determine the optimal ones to launch and detect ultrasonic Lamb waves, especially in non-homogeneous specimens. The chosen arrangements were contact with angle beam transducers, immersion in a water tank, localised water coupling using conical containers and air coupling. Plates of two different materials were used, stainless steel and Portland cement mortar. Theoretical and experimental dispersion curves were compared to verify the existence of Lamb modes and good correspondence was achieved.

Microscopic Chemical Characterization and Reactivity in Cementing Systems of Elephant Grass Leaf Ashes.

Many agrowastes are being used for energy production by combustion in power plants. This process generates huge amounts of ash, which has a potential pozzolanic activity for blending with Portland cement or hydrated lime. In this paper, the ash obtained from elephant grass (Pennisetum purpureum Schum var. purple) leaves (EGLs) was studied, including the silicon content and its distribution, the presence of other compounds, and in addition, the presence of silica bodies (phytoliths). Combustion temperatures of 450 and 650°C produced an unaltered inorganic skeleton (spodogram), whereas at 850°C, there is a sintering process because of high potassium content in the ash. Phytoliths and different types of hairs were identified, and they contained high percentages of silica. Magnesium (mainly as periclase) was distributed in the most porous parts in the interior of the leaves. The silica can react with calcium hydroxide (pozzolanic reaction) forming calcium silicate hydrates (observed by field-emission scanning electron microscopy and thermogravimetric analysis). Fixed lime percentages at 28 curing days (63%) indicated the high reactivity of EGL ashes in calcium hydroxide pastes due to the pozzolanic reaction. This study demonstrates the possibility of the reuse of ashes from EGLs for the production of environmental-friendly cements.

Use of ancient copper slags in Portland cement and alkali activated cement matrices.

Some Chilean copper slag dumps from the nineteenth century still remain, without a proposed use that encourages recycling and reduces environmental impact. In this paper, the copper slag abandoned in landfills is proposed as a new building material. The slags studied were taken from Playa Negra and Púquios dumps, both located in the region of Atacama in northern Chile. Pozzolanic activity in lime and Portland cement systems, as well as the alkali activation in pastes with copper slag cured at different temperatures, was studied. The reactivity of the slag was measured using thermogravimetric analysis (TGA), scanning electron microscopy (SEM), X-ray diffraction (XRD), electrical conductivity and pH in aqueous suspension and Fourier Transform Infrared Spectroscopy (FTIR). Furthermore, copper slag-Portland cement mortars with the substitution of 25% (by weight) of cement by copper slag and alkali-activated slag mortars cured at 20 and 65 °C were made, to determine the compressive strength. The results indicate that the ancient copper slags studied have interesting binding properties for the construction sector.

Microscopy Characterization of Silica-Rich Agrowastes to be used in Cement Binders: Bamboo and Sugarcane Leaves.

Agrowastes are produced worldwide in huge quantities and they contain interesting elements for producing inorganic cementing binders, especially silicon. Conversion of agrowastes into ash is an interesting way of yielding raw material used in the manufacture of low-CO2 binders. Silica-rich ashes are preferred for preparing inorganic binders. Sugarcane leaves (Saccharum officinarum, SL) and bamboo leaves (Bambusa vulgaris, BvL and Bambusa gigantea, BgL), and their corresponding ashes (SLA, BvLA, and BgLA), were chosen as case studies. These samples were analyzed by means of optical microscopy, Cryo-scanning electron microscopy (SEM), SEM, and field emission scanning electron microscopy. Spodograms were obtained for BvLA and BgLA, which have high proportions of silicon, but no spodogram was obtained for SLA because of the low silicon content. Different types of phytoliths (specific cells, reservoirs of silica in plants) in the studied leaves were observed. These phytoliths maintained their form after calcination at temperatures in the 350-850°C range. Owing to the chemical composition of these ashes, they are of interest for use in cements and concrete because of their possible pozzolanic reactivity. However, the presence of significant amounts of K and Cl in the prepared ashes implies a limitation of their applications.

Assessment of Pozzolanic Activity Using Methods Based on the Measurement of Electrical Conductivity of Suspensions of Portland Cement and Pozzolan.

The use of methods based on measuring electrical conductivity to assess pozzolanic activity has recently been used primarily in aqueous suspensions of pozzolan: calcium hydroxide. However, the use of similar methods in suspensions of cement with pozzolans has not been widely studied. This paper proposes a new method for rapid assessment of the pozzolanic activity of mineral admixtures in aqueous cement suspensions. In this study, the conditions for the application of the method were optimized, such as time, temperature, w/c ratio and dosage procedure. Finally, results are presented from the application of this method for characterizing the pozzolanic activity of the spent catalytic cracking catalyst. These results corroborate as previously reported, namely the high reactivity of this pozzolan obtained by other methods, such as thermogravimetry or evolution of the mechanical strength. In addition, the pozzolanic activity of the catalyst was compared with other pozzolans such as metakaolin and silica fume.

Assessment of the Pozzolanic Activity of a Spent Catalyst by Conductivity Measurement of Aqueous Suspensions with Calcium Hydroxide.

The pozzolanic activity of the spent catalyst produced by fluid catalytic cracking (FCC) has been studied by various methods in recent years. However, no quick and easy method has been reported for this activity based on the associated studies. In this work, the pozzolanic activity of a spent catalyst was investigated by measuring its electrical conductivity in aqueous suspensions of pozzolan/calcium hydroxide. The behavior of the FCC catalyst residue was compared to that of reactive and inert materials of similar chemical compositions. Further, the influence of temperature on the suspension was studied, and also, a new method was proposed in which the pozzolan/calcium hydroxide ratio was varied (with the initial presence of solid Ca(OH)2 in the system). It was concluded that the method is effective, fast and simple for evaluating the high reactivity of the catalyst. Therefore, this method is an alternative for the evaluation of the reactivity of pozzolanic materials.

Use of Slag/Sugar Cane Bagasse Ash (SCBA) Blends in the Production of Alkali-Activated Materials.

Blast furnace slag (BFS)/sugar cane bagasse ash (SCBA) blends were assessed for the production of alkali-activated pastes and mortars. SCBA was collected from a lagoon in which wastes from a sugar cane industry were poured. After previous dry and grinding processes, SCBA was chemically characterized: it had a large percentage of organic matter (ca. 25%). Solutions of sodium hydroxide and sodium silicate were used as activating reagents. Different BFS/SCBA mixtures were studied, replacing part of the BFS by SCBA from 0 to 40% by weight. The mechanical strength of mortar was measured, obtaining values about 60 MPa of compressive strength for BFS/SCBA systems after 270 days of curing at 20 °C. Also, microstructural properties were assessed by means of SEM, TGA, XRD, pH, electrical conductivity, FTIR spectroscopy and MIP. Results showed a good stability of matrices developed by means of alkali-activation. It was demonstrated that sugar cane bagasse ash is an interesting source for preparing alkali-activated binders.

Increase of the reactivity of densified silica fume by sonication treatment.

Five silica fumes from different manufacturers were subjected to ultrasonic treatment in order to decrease particle agglomeration and improve particle dispersion. The effectiveness of the sonication was observed as a reduction in particle size distribution of sonicated silica fume (SSF) compared to non-sonicated silica fume. SSF was added to Portland cement, and then the hydrated paste was analysed by thermogravimetric analyses (TGA/DTG) and scanning electron microscopy (SEM/EDX). The results were compared with those of control pastes made with untreated densified silica fume (DSF), as well as a reference cement paste of ordinary Portland cement (OPC). A maximum grade of de-agglomeration by the sonication was obtained, with a high volume of particles of diameter less than 1 µm. Images obtained by transmission electron microscopy (TEM) of the SSF showed sintered particles that could not be fragmented by the treatment. Micro-structural characterisation results showed an increase in the reactivity of the silica fume after the treatment.