Binary and Ternary Blended Portland Cements Containing Different Types of Rice Husk Ash.

Rice husk ash (RHA) is agricultural waste with high silica content that has exhibited proven technical feasibility as a pozzolanic material since the 1970s. Notwithstanding, its use in mortars and concrete is limited by the standards currently utilized in some countries where RHA production is high and the aforementioned pozzolanic material is not standardized. This is the case in Spain, one of the main rice producers in Europe. Nowadays, the high pressure placed on the Portland cement production sector to reduce its energy use and CO2 emissions has given rise to a keen interest in mineral admixtures for cement manufacturing. In this research, we intended to establish the contributions of different RHA types to the final blended Portland cement properties ("H" is used to identify RHA in standardized cements). The experimental results demonstrated that RHA with good pozzolanic properties (large specific surface and high amorphous silica content) had to be limited to 10% cement replacement because of the severe reduction in workability at higher replacement percentages. RHA with lower reactivity, such as crystalline RHA, or fly ash (FA) can be used to prepare binary and ternary blended cements with reactive RHA. It is possible to design the following cements: CEM II/A-H and CEM II/A-(H-V). It would also be possible to design cement (CEM II/B-(H-V) with replacement values of up to 30% and the same 28-day mechanical performance as observed for the Portland cement without mineral addition.

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.

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.

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.

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.