Environmental assessment of alkali-activated materials based on agro-industrial waste as alkaline activators through leaching tests.

Global circular economy drives the development of sustainable alkali activated materials (AAM) for use as construction material from industrial by-products and wastes. The assessment of the potentially hazardous substances release of these new material combinations into the soil and groundwater over time is essential. In this study, the aim is the environmental assessment of three AAMs based on blast furnace slag (BFS), activated with almond shell biomass ash (ABA) as potassium source and three solid sources of silica from the agricultural industry, rice husk ash (RHA), spent diatomaceous earth (SDE) and bamboo leaf ash (BLA), using European horizontal leaching tests proposed for construction materials, for monolithic form, Dynamic Surface Leaching Test (DSLT) and for granular form, Up-flow Percolation Test and the Compliance leaching test, by simulating different scenarios of their entire life cycle. The leaching results of the AAM showed the effectiveness of the inertization of all the recycled materials studied, which exceeded some inert materials limits, by means of the activation process. Despite the absence of significant differences in the leaching mechanisms of the oxyanions As, Cr, Mo, Sb, Se and V between the three AAMs developed, they presented different long-term leaching behavior depending on their form, monolithic, or granular, and therefore in their different life cycle stages. Therefore, it is concluded that although the incorporation of agro-industrial waste as alternative activators in BFS based AAM according to the Dutch Soil Quality Decree (for unrestricted use of monolithic and granular materials) is an environmentally acceptable option, the design of waste derived AAMs should be assessed by means of a combination of leaching tests that cover their expected life cycle.

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.

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.

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.

Auto-Combustion of Corn Straw: Production and Characterization of Corn Straw Ash (CSA) for Its Use in Portland Cement Mortars.

Agricultural waste availability implies the possibility of recovering energy as biomass. The collateral effect is the production of ashes that, in some cases, have the potential to be reused in the manufacture of cement, mortar, and concrete. This article presents the study of the auto-combustion (unlike all previous studies) of corn (maize) straw (stems and leaves). The auto-combustion temperature was monitored, and the obtained corn straw ash (CSA) was characterized by means of X-ray fluorescence, X-ray diffraction, thermogravimetry, and scanning electron microscopy. Finally, the behavior of ground CSA was analyzed in both the fresh state by measurement of workability on the spreading table and the hardened state by compressive strength measurement on mortars in which 10% of ordinary Portland cement (OPC) was replaced with CSA. These values were compared to both a control mortar (OPC) and a mortar in which OPC was partially replaced with 10% limestone filler. Ashes showed adequate pozzolanic reactivity because, at 90 curing days, the compressive strength of the mortars with 10% replacement of OPC with CSA was practically equal (98% of the strength) to the control mortar without pozzolan replacement. The auto-combustion of biomass is a process that can be easily available, and the results on pozzolanic reactivity of CSA are satisfactory. The auto-combustion could be used by low-income communities to reduce Portland cement clinker use and to recover waste.

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.

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.

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.

Preliminary Study of the Fresh and Hard Properties of UHPC That Is Used to Produce 3D Printed Mortar.

Three-dimensional printed concrete (3DPC) is a relatively recent technology that may be very important in changing the traditional construction industry. The principal advantages of its use are more rapid construction, lower production costs, and less residues, among others. The choice of raw materials to obtain adequate behavior is more critical than for traditional concrete. In the present paper a mixture of cement, silica fume, superplasticizer, setting accelerator, filler materials, and aggregates was studied to obtain a 3DPC with high resistance at short curing times. When the optimal mixture was found, metallic fibers were introduced to enhance the mechanical properties. The fresh and hard properties of the concrete were analyzed, measuring the setting time, workability, and flexural and compressive strength. The results obtained demonstrated that the incorporation of fibers (2% in volume) enhanced the flexural and compressive strength by around 163 and 142%, respectively, compared with the mixture without fibers, at 9 h of curing. At 28 days of curing, the improvement was 79.2 and 34.7% for flexural and compressive strength, respectively.

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.

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.

Characterization of Glass Powder from Glass Recycling Process Waste and Preliminary Testing.

This work studies the possibility of incorporating different proportions of glass powder from the waste glass (rejected material called fine cullet) produced during the glass recycling process into the manufacturing of mortar and concrete. For this purpose, the material is characterized by its chemical composition and pozzolanic activity, and the shape and size of its particles are studied. It is then incorporated as a substitute for cement into the manufacturing of mortar and concrete at 25% and 40% of cement weight, and its effect on setting times, consistency, and mechanical strength is analyzed. Its behavior as a slow pozzolan is verified, and the possibility of incorporating it into concrete is ratified by reducing its cement content and making it a more sustainable material.

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.

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.