Estudo da reciclagem de resíduos de fibras de vidro em geopolímeros, argamassas e telas de impermeabilização

Mestrado em Engenharia de MateriaisDesenvolveu-se uma parceria entre a Universidade de Aveiro, Ria Blades, S.A. e Saint-Gobain Weber Portugal, S.A. com objetivo de encontrar formas de aproveitamento dos resíduos de fibra de vidro produzidos na Ria Blades, S.A., que atualmente são depositados em aterro. O trabalho incidiu em três produtos-alvo: telas de impermeabilização, argamassas e geopolímeros. No que diz respeito às telas de impermeabilização, de base polimérica (poliuretano), os resíduos foram aplicados como agente de reforço. Estudou-se o efeito da incorporação das fibras na aderência, na resistência à tração e na durabilidade perante ciclos de gelo-degelo. Quando incorporadas fibras de vidro, registou-se um aumento na aderência ao suporte relativamente à amostra padrão e um crescimento (de cerca de 20 vezes) na resistência à tração. Na incorporação em argamassas bastardas, o objetivo foi perceber o efeito da substituição das fibras poliméricas atualmente usadas, pelas fibras de vidro residuais. Estudou-se o efeito na percentagem de ar incorporado e densidade do amassado, bem como a variação de massa e de dimensão, módulo de elasticidade, resistência à compressão e flexão do produto endurecido. A incorporação de fibra de vidro não aparenta prejudicar o desempenho das argamassas, sendo os resultados semelhantes nas amostras padrão. Apesar de as quantidades incorporadas serem apenas de 0,1%, é possível que a utilização destes resíduos tenha impactos economicamente positivos para as duas empresas. Nos geopolímeros, a incorporação das fibras de vidro pretendeu explorar dois efeitos distintos: (i) como ligante, em substituição parcial de metacaulino (até 40% em massa); (ii) como agente de reforço da mistura. Numa primeira fase, foi necessário caracterizar as matérias primas e os resíduos para respeitar as razões molares que asseguram uma maior extensão da reação. Foram avaliadas a densidade aparente, resistência à compressão, absorção de água ao longo do tempo de cura e ainda a resistência à flexão no caso de as fibras funcionarem como agente de reforço. Como substituto parcial do metacaulino verifica-se uma descida na resistência à compressão com o aumento de resíduo de fibra de vidro. No entanto com a otimização da formulação com 20% de fibras de vidro foi possível duplicar o valor da resistência à compressão (> 8MPa). Como agente de reforço, os resultados mostram ganhos de resistência à compressão de 4 vezes quando se incorporam fibras de 6mm de comprimento, relativamente a amostras sem reforço. O uso de fibras mais longas (20mm) é mais eficaz no aumento da resistência à flexão.A partnership has been developed between the University of Aveiro, Ria Blades, S.A. and Saint-Gobain Weber Portugal, S.A. in order to find a way to recycle the glass-fibre residues produced from Ria Blades, S.A. that are currently being send to landfill. Three possible target-products were exploited: waterproofing membrane, mortars and geopolymers. On the waterproofing membrane, based on polyurethane, the residues were incorporated as reinforcing agents and effects on adhesion, tensile strength and resistance to freeze-thaw cycles were determined. An increase of 20 times on the tensile strength has been registered, relatively to the standard sample. On mortars, the aim was to understand the effect of the substitution of the currently used reinforcing-fibres for the wasted glass-fibres. Fresh-state properties such as the entrained air content and density were evaluated. The effect on relevant hardened-state properties was then studied, including the variation of mass and dimensions, the compressive and flexural strengths, and elastic modulus. The behaviour of the mortars doesn’t seem to be affected by the incorporation of glass-fibres because the results from both the mortars with and without glass-fibres are similar. Although the quantity of incorporated glass-fibres is only around 0,1%, its use may have positive economic benefits for both companies. In geopolymers, the incorporation of wasted glass-fibres aimed to explore two distinct effects: (i) use as binder, partially substituting the metakaolin (up to 40 wt.%); (ii) use as reinforcing agent of common matrixes. On the first stage it was necessary to characterize both the raw materials and the glass-fibres, in order to achieve the desirable molar ratios that assure an extended reaction. Hardened samples were characterized in terms of density, compressive strength and water absorption. In the attempted reinforced geopolymers the flexural strength was additionally tested. When the glass-fibres were used as partial substitute of metakaolin, a drop of the compressive strength was observed for higher contents of glass-fibres. Optimizing the mixture for 20 % of glass-fibres allowed to duplicate the compressive strength (> 8 MPa). When 6 mm glass-fibres were used as a reinforcing agent, the compressive strength increased 4 times when compared to samples without reinforcement. Using 20 mm fibres is the most effective way of improving flexural strength

Innovative application for bauxite residue: red mud-based inorganic polymer spheres as pH regulators

In this study, and for the first time, red mud (RM)-based geopolymer spheres were synthesised, with varying porosity and RM content, and then their use as pH regulators was evaluated. The aluminosilicate sources of these inorganic polymers were 100% waste-based, consisting of a mixture of RM and fly ash wastes. Geopolymer spheres containing up to 60 wt.% RM were successfully produced, while higher RM contents distorted the specimens' spherical shape. Results showed that alkalis leaching from the spheres over time can be controlled by their porosity, while the RM content induces only minor changes to leaching. The RM-based spheres leached up to 0.0237 mol/dm3g of OH- ions from their structure, this being among the highest values ever reported for geopolymers. This allowed a continuous and prolonged pH buffer capacity with narrow pH decay over the 28 days (2.4 pH units), suggesting the use of the RM-based spheres as pH buffering materials in wastewater treatment and anaerobic digestion systems.publishe

In-depth investigation of the long-term strength and leaching behaviour of inorganic polymer mortars containing green liquor dregs

Green liquor dregs are the most challenging waste stream coming from the pulp and paper industry. Despite tremendous efforts, there are not currently any viable recycling alternatives for this massively produced waste (2 Mt/year), which inevitably ends up in landfills. Urgent actions must be undertaken to tackle this. In this work, a substantial amount of dregs was incorporated into eco-friendly, waste-based inorganic polymer (geopolymer) mortars as fine filler. Then, and for the first time, the long-term strength performance (up to 270 days) and heavy metals leaching behaviour of the dregs-containing mortars was evaluated. The effect of the mixture composition and dregs incorporation content on the fresh- and hardened-state properties of the mortars was also studied. Dregs were found to increase the initial and final setting time of the slurries, thus extending the open time before their in-situ application. The use of dregs as fine filler effectively enhances the compressive strength of the mortars, and decreases their water absorption levels. These eco-friendly building materials showed excellent long-term performance, as their strength continuously increases up to the 270th day (after mixture), and no signs of efflorescence formation were detected. Moreover, the heavy metals leaching levels of the mortars were well below the contamination limits in soil, which demonstrates the feasibility of this recycling methodology.publishe

Synthesis of red mud derived M-type barium hexaferrites with tuneable coercivity

Hexagonal ferrites can be employed in a multitude of applications, the most common hexaferrites are the M ferrites such as BaFe12O19 (barium hexaferrite, BaM). It is known that if Fe3+ is substituted with a combination of Ti4+/Co2+ the coercivity of BaM can be reduced to produce soft M ferrites with easily switchable magnetisation. They can be utilised as powders, films or bulk ceramics, and can be manufactured from a wide variety of synthesis methods. The production of hexaferrites usually requires commercial raw materials, but if an industrial waste can be utilised, this will help to ease waste disposal and storage costs, valorise a waste material and encourage circular economy. In this study, bauxite residue (red mud) from the production of alumina was used to synthesise M-type hexaferrites, using a simple ceramic process. BaCO3, or BaCO3+Co3O4, were added to the red mud, blended and heated at 1000 °C to produce the M-type hexaferrites. Without cobalt addition up to 81.1 wt% M ferrite was produced, and with Co addition up to 74.3 wt% M ferrite was formed. Without cobalt, the M ferrite phase closely resembled BaFe9Al3O19, and was a hard ferrite with a magnetisation of 12–19 A m2/kg for the whole powder (up to 23.6 A m2/kg for the M ferrite phase) and a coercivity of ~290 kA/m. When cobalt was added, secondary titanate phases vanished, and Ti4+/Co2+ partially substituted very soft M ferrite was formed with a low coercivity of ~16 kA/m but a higher magnetisation of 24.5 A m2/kg for the whole powder (up to 34.9 A m2/kg for the M ferrite phase). Therefore, not only can good quality magnetic materials be easily produced from this common waste material, but its magnetic properties can be tuned by varying the 2 + ions added during the process.publishe

Red mud-based inorganic polymer spheres: innovative and environmentally friendly anaerobic digestion enhancers

Red mud-based inorganic polymer spheres were used as alternative pH regulators and process enhancers in sequencing batch anaerobic reactors treating cheese whey. This byproduct tends to quickly acidify under anaerobic conditions, and the common route to control pH and ensure suitable conditions for methane production involves the use of commercial alkaline raw materials. The spheres were synthesized using significant amounts of hazardous and toxic waste, red mud (50 wt% of solid components), whose recycling is challenging. The inorganic polymeric spheres, when compared to virgin alkaline raw materials, improved organic matter removal by 44%, prevented VFA accumulation (acidification degree less than 20%), maintained pH values in a range (6.5-7.2) to ensure maximum methanogenic activity by archaea microorganisms, and boosted the methane volume by ~90%. These promising results demonstrate the feasibility and performance advantages of using these innovative spheres instead of virgin raw materials, which is an important tool towards sustainable development.publishe

Immobilization of Hazardous Wastes on One-Part Blast Furnace Slag-Based Geopolymers

: The immobilization of hazardous wastes in ordinary Portland cement (OPC)-based materials has been widely studied and implemented. OPC-based materials have a high carbon footprint associated with their production and geopolymer materials are a sustainable and eco-friendly alternative. Therefore, this work aimed to immobilize two hazardous industrial wastes: copper wastewater sludge and phosphogypsum in one-part geopolymer materials. For that purpose, the precursor was partially substituted by these wastes (5, 10 and 20 wt.%) in the formulations. The geopolymer fresh and hardened state properties were evaluated, and the immobilisation of pollutants was determined through leaching tests. In phosphogypsum pastes (PG5, PG10 and PG20) it was observed that the compressive strength decreased with the increase in its amount, varying between 67 MPa and 19 MPa. In copper sludge pastes, the compressive strength of the specimens (CWS5 and CWS10) reached ~50 MPa. The mortars, MPG10 and MCWSs10, had compressive strengths of 13 MPa and 21 MPa, respectively. Leaching tests showed that pastes and mortars immobilise the hazardous species of the wastes, except for As from copper sludge, whose the best result was found in the compact paste (CWSs10) that leached 2 mg/kg of As. Results suggest that optimized compositions are suitable for the construction sectorThis research was funded by Ministerio de Ciencia e Innovación (MICINN), grant number PID2020-116461RB-C21 and Agencia de Innovación y Desarrollo de Andalucía (IDEA) grant number UHU-1255876. This work was done in the scope of the project CICECO- Aveiro Institute of Materials, UIDB/50011/2020 & UIDP/50011/2020, co-financed by national funds through the FCT/MEC. This research was funded by FCT (Portuguese Foundation for Science and Technology), grant number 2020.01135.CEECIND (R.M.N.) and SFRH/BD/144562/2019 (J.C.

Evaluation of the Nature and Concentration of the Surfactant on the Properties of Red Mud/Metakaolin Porous Geopolymers Foamed with Aluminium

The chemical foaming technique is possibly the most common method of producing porous geopolymers. Despite this, to date, the role of the content and type of surfactant on the pore size distribution of porous geopolymers is not fully perceived, as constant surfactant dosages are usually employed. In addition, the comparison of literature studies is challenging since a distinct mixture of designs is employed. This investigation intends to provide additional insights on the topic, focusing on synthesizing red mud/metakaolin geopolymer foams and envisioning their use in thermal insulating applications. Various mixtures were prepared using three commercially available surfactants, namely Hostapur OSB, sodium dodecyl sulfate (SDS), and Triton X114. The content of the surfactant (0.025, 0.05, and 0.075 wt.%) and the amount of the foaming agent (aluminum powder, Al; 0.05, 0.075, and 0.10 wt.%) was modified, keeping the binder composition constant and the physical properties of the produced geopolymers were characterized. Results show that the combination between sodium dodecyl sulfate (0.025 wt.%) and aluminum (0.10 wt.%) leads to the strongest reduction in the foam density, the lowest value here reported being −400 kg/m3. On the other hand, samples produced with Hostapur OSB have much higher open porosity (up to 47.7%) and water absorption (up to 80.4%) values, showing that this surfactant leads to a pore network with higher connectivity. In addition, the microstructure of the foams, particularly pore morphology (size and shape) and connectivity between the produced pores are highly dependent on the type of surfactant, sodium dodecyl sulfate generating coarser pore size distribution with round, but mostly closed pores, while a narrower pore size distribution coupled with smaller size pores is seen with the Hostapur. These results suggest the feasibility of tuning the foams’ properties (porosity and mechanical performance) according to the application by the proper combination of the type of surfactant and their concentration, enabling their use as thermal and acoustic insulators or as filters/membranes in wastewater treatment systems

Bi-Layered Porous/Cork-Containing Waste-Based Inorganic Polymer Composites: Innovative Material towards Green Buildings

Reduction of the energy consumption and CO2 emissions by the building sector might be a huge driver to mitigate climate change. One promising approach to mitigate energy consumption is the use of lightweight and low thermal-conductivity materials that could reduce the energy losses inside buildings and at the same time the use of heating and cooling devices that generate associated CO2 emissions. In this study, different strategies to produce lightweight and low thermal conductivity inorganic polymers were evaluated and compared, including the first ever production of bi-layered porous/cork-containing waste-based inorganic polymer composites. The bi-layered composites showed the lowest density (461 kg/m3) and thermal conductivity (94.9 mW/m K) values and reasonable compressive strength (0.93 MPa) demonstrating their interesting potential for enhancing the energy efficiency of buildings. Moreover, these composites were produced at room temperature, using an industrial waste (biomass fly ash) as precursor and a highly sustainable and renewable resource as light aggregate (cork), preventing the depletion of natural resources and the use of fossil-fuel derivates, respectively

Sustainable and efficient cork - inorganic polymer composites: an innovative and eco-friendly approach to produce ultra-lightweight and low thermal conductivity materials

In this investigation cork was used as a low density aggregate in the production of ultra-lightweight and low thermal conductivity inorganic polymer (geopolymer) composites. This novel and highly sustainable material, synthesised at room temperature (23 °C), may decrease the energy losses inside buildings, thus contributing to the United Nations development goals regarding energy and climate change. The ultra-low density (260 kg/m3) and low thermal conductivity (72 mW/m K) shown by the cork-composites are the second lowest ever reported for inorganic polymer composites, only being surpassed by that of polystyrene-inorganic polymer composites. However, cork is a fully renewable and sustainable resource, while polystyrene is manufactured from non-renewable fossil fuels, and for that reason our strategy has an additional sustainability advantage. Moreover, the cork-inorganic polymer composites do not release any toxic fume when under fire conditions, which is a major advantage over polymeric-based foams.R. M. Novais wishes to thank FCT project H2CORK (PTDC/CTMENE/6762/2014), and R. C. Pullar wishes to thank FCT (Portuguese Fundation for Science and Technology) grant IF/00681/2015, for supporting this work. This work was developed in the scope of the project CICECO - Aveiro Institute of Materials UID/CTM/50011/2013 (Compete Reference: POCI-01-0145-FEDER-007679), Associated Laboratory of University of Aveiro, financed by national funds through the FCT/MEC and when appropriate co-financed by FEDER under the PT2020 Partnership Agreement.publishe

Technical, Environmental, and Cost Assessment of Granite Sludge Valorisation

The granite sludge (GS) produced during block sawing can be exploited as alternative raw material in ceramic and concrete industries. Based on the case study of a Portuguese granite processing plant, this work analysed, by experimental tests and Environmental and Cost Life Cycle analyses, the feasibility of GS valorisation as a substitute (i) for feldspar in a ceramic paste and (ii) fine–medium inert filler in structural concrete. The results demonstrated that both the valorisation pathways are more advantageous than GS landfilling. Due to granulometric, mineralogical composition and shrinkage, GS can substitute feldspar in sandstone tiles or tableware products, although its tinting effect can limit noble whitish ceramic applications. In structural concrete mixes, 5% w/w GS instead of fine inert filler reduces the compressive strength and increases the water:cement ratio. The GS generates lower environmental impacts as a substitute for inert filler than as a substitute for feldspar in most of the impact categories analysed, even though the latter valorisation pathway provides higher benefits in Climate Change and the Depletion of Fossil resources, Water, and Ozone. If no monetary value is recognised for GS valorisation by the market, the sustainability of GS life cycle cost decreases when compared to its landfilling