Rheological behavior of fresh inorganic polymer paste: Polymer bridging effect of the alkali silicate solution

Inorganic polymers (IP), produced by alkali activation of a glassy precursor, have been mainly investigated on their microstructure and mechanical strength properties. However, it is important to understand how the IP flow behaves under shear conditions, in particular when pumping is required. The activating solution is one of the main parameters influencing rheology. Therefore, the physical effect of the silicate structure on the rheology was investigated by varying the SiO2/Na2O molar ratio from 1.4 to 2.0 in the activator. The elastic and rheological properties of the IP were measured with a rheometer. In order to investigate the activator silicate structure and IP polymerisation development, Fourier Transform Infrared Spectroscopy (FTIR) and Nuclear Magnetic Resonance Spectroscopy (NMR) were performed. A decrease in elasticity was monitored for IP with a low SiO2/Na2O ratio as a result of the dissolved species, which can be correlated to NMR. The FTIR spectra implied that an activating solution with a higher SiO2/Na2O ratio resulted in the formation of a 3D silicate network with Q3 and Q4 crosslinks. The presence of a network modifier in the activating solution, such as Na, resulted in more Q1 and Q2 crosslinks. A higher stress, at a shear rate of 0.1 s-1; was observed in IP which consisted of a 3D silicate network as a result of the polymer bridging effect between the particles. A stronger shear thinning was observed in an IP with a higher SiO2/Na2O ratio, due to the steric hindrance from the entangled silicates. The rheological data of the IP can be fitted with the Herschel-Bulkley model

Mixture optimization of an alkali-activated steel slag to maximize binder strength using optimal design of experiments

The diversity of precursors suitable for alkali activation demands a flexible methodology to study the properties of alkali-activated binders. Optimal design of experiments (ODOE) [1] allows a systematic and efficient exploration of effects and interactions among mix components and processing conditions, a situation commonly found during proportioning studies. Moreover, the ODOE algorithms provide sets of experiments of an optimized size that consider all the factors studied at the same time, a key feature to detect absolute maximums (or minimums) of a response. In this case, the strength-optimized proportioning for basic-oxygen-furnace (BOF) slag specimens activated with NaOH solutions was determined. The impact of solution molarity ranging from 0M (only water) to 0.5M and the additions of gypsum (2 to 6 wt%), Portland cement (0 to 10 wt%) and 0.2 wt% of a commercial plasticizer (polycarboxylate-based dispersant) were mapped. Proportions tested were selected running ODOE software using an I-optimality criteria algorithm, which minimizes the average variance of model prediction. A response surface model (RSM) for 28-day strength was defined. Paste and mortar specimens were produced with the predicted proportioning of highest strength and its binding matrix was characterized and compared with low-strength samples using X-ray diffraction (XRD), secondary electron microscopy (SEM) and infrared spectrometry (FTIR). The results obtained confirm that the methodology generates a model able to predict mechanical response, detecting general trends, high impact factors and interactions. More important, the optimal experimental design can be used to effectively study changes in the binding matrices and link them to the binder’s mechanical performance. Please click Additional Files below to see the full abstract

Influence of the type of alkaline activator on the reactions and mechanical properties of autoclaved bauxite residue-based monoliths

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Inorganic polymer cement from Fe-Silicate glasses: Varying the activating solution to glass ratio

Large volumes of Fe-silicate glasses - slags - are produced as residues of metal production and waste treatment processes. It would be interesting if these materials could become an alternative group of precursors for the synthesis of inorganic polymer (IP) cements. This paper investigates the polymerisation of Fe-silicate glasses of composition (in wt%) SiO2: 40; FeO: 30; CaO: 15; Al2O3: 8 and an activating solution of composition (in wt%) Na2O: 15; SiO2: 13; H2O: 72. The mass ratio of the activating solution to the glass (L/S) was varied from 0.3 to 1.0 and the effect on the IP chemistry, microstructure and properties was investigated. Despite the high Fe and low Al contents of the glass, an IP cement could be synthesised, resistant to water dissolution and delivering mortars of compressive strength >52 MPa after 28 days curing at room temperature when using a L/S ratio of 0.45. Lowering the ratio from 1.00 to 0.45 results in a significant improvement in compressive strength, a lower porosity and when immersed in water, Na dissolution is decreased and water pH is lower. Microstructural investigation indicates that when the amount of activating solution is decreased, the degree of glass dissolution is lower resulting in less IP formation and a more homogeneous IP chemistry. Compared to higher L/S ratios, the IP mortar has a more densely packed microstructure of partially dissolved glass and sand aggregates bound by the IP matrix. At lower L/S ratios, the formation of micro scale shrinkage cracks in the IP matrix is strongly reduced, while at higher L/S ratios, shrinkage cracking is more pronounced and individual micro-cracks connect to form more pronounced large scale cracks. At a L/S ratio of 0.45, the IP cement is composed of 90 wt% Fe-silicate glass and only 10 wt% Na-silicate (% of powder mix) and it is indicated that this percentage can still be reduced. As 90 wt% of this IP cement is composed of a waste material and as curing is performed at ambient temperatures, its production is expected to have important ecological and economic benefits.status: publishe

INCREASING THE DIMENSIONAL STABILITY OF CAO-FEOX-AL2O3-SIO2 ALKALI-ACTIVATED MATERIALS: ON THE SWELLING POTENTIAL OF CALCIUM OXIDE-RICH ADMIXTURES

Advanced thermochemical conversion processes are emerging technologies for materials\u2019 recovery and energetic conversion of wastes. During these processes, a (semi-)vitreous material is also produced, and as these technologies get closer to maturity and full-scale implementation, significant volumes of these secondary outputs are expected to be generated. The production of building materials through the alkali activation of such residues is often identified as a possible large-scale valorization route, but the high susceptibility of alkali-activated materials (AAM) to shrinkage limits their attractiveness to the construction sector. Aiming to mitigate such a phenomenon, an experimental study was conducted investigating the effect of calcium oxide-rich admixtures on the dimensional stability of CaO-FeOx-Al2O3-SiO2 AAMs. This work describes the impacts of such admixtures on autogenous and drying shrinkage, porosity, microstructure, and mineralogy on AAMs. Drying shrinkage was identified as the governing mechanism affecting AAM volumetric stability, whereas autogenous shrinkage was less significant. The reference pastes presented the highest drying shrinkage, while increasing the dosage of shrinkage reducing agent (SRA) was found to reduce drying shrinkage up to 63%. The reduction of drying shrinkage was proportional to SRA content; however, elevated dosages of such admixture were found to be detrimental for AAM microstructure. On the other hand, small dosages of calcium oxide-rich admixtures did not induce significant changes in the samples\u2019 mineralogical evolution but promoted the formation of denser and less fractured microstructures. The results presented here show that calcium oxide-rich admixtures can be used to increase AAM\u2019s volumetric stability and an optimal dosage is prescribed

In-situ measurements of high-temperature dielectric properties of municipal solid waste incinerator bottom ash

[EN] Microwave heating is a potential green technology demonstrating many advantages over conventional heating methods. Prior to designing an industrial microwave process, however, a fundamental knowledge of the dielectric properties of the material to be thermally treated is imperative, as these properties determine the response of the material to an applied electromagnetic field. In this study, the fundamental interactions between microwave energy and municipal solid waste incinerator (MSWI) bottom ash (BA) are investigated through in situ complex permittivity measurements. Using an enhanced version of the cavity perturbation method, the dielectric properties were determined from room temperature up to 1100 degrees C at a frequency close to the industrial 2.45 GHz. The results demonstrated that BA is a low-loss microwave absorber up to 320 degrees C, above which microwave flash pyrolysis of the organic matter abruptly enhances the dielectric loss of BA, resulting in a thermal runaway. The addition of water and graphite to BA induces a higher dielectric constant and loss factor. The evolution of the dielectric properties as a function of temperature is correlated to changes in the material as determined by Simultaneous Differential Scanning Calorimetry, Thermogravimetric Analysis and High Temperature X-ray Diffraction. The reported results form a baseline for the assessment of the MSWI BA response under microwave irradiation.This work was supported by the European Community's Horizon 2020 Programme under Grant Agreement No. 721185 (MSCA-ETN NEW-MINE). This publication reflects only the authors' view, exempting the Community from any liability. Project website: http://new-mine.eu/.Flesoura, G.; García-Baños, B.; Catalá Civera, JM.; Vleugels, J.; Pontikes, Y. (2019). In-situ measurements of high-temperature dielectric properties of municipal solid waste incinerator bottom ash. Ceramics International. 45(15):18751-18759. https://doi.org/10.1016/j.ceramint.2019.06.101S1875118759451

A new approach for the vitrification of municipal solid waste incinerator bottom ash by microwave irradiation

Encouraging the transition to a circular economy, the valorization of municipal solid waste incinerator (MSWI) bottom ash (BA) has received considerable attention in many processes. In the present work, flash microwave vitrification was effectively realized in a single mode cavity operating at 2.45 GHz within 1.5 min. The closed-loop process was evaluated in terms of energy and power input, treatment time and vitrified bottom ash (VBA) yield rate. The required minimum energy consumption was ∼3300 kJ/kg. By conducting thermo-electromagnetic multiphysics simulations, the heating mechanism of BA by microwave irradiation was underpinned. This relied on the generation of microwave-induced hot spots inside the material and high power density, in the order of 3 × 107 W/m3, that triggered the onset of BA melting at high heating rates. The inherent cold environment of the microwave cavity, due to the absence of any insulation material, in conjunction with the high silica content of BA promoted the glass forming ability of the melt. This allowed a natural fast cooling of the melt and VBA production, avoiding the cost and environmental impact accompanying conventional quenching. Preliminary characterization of the highly amorphous VBA product was performed and its exothermal heat flow after alkali activation revealed the potential incorporation in the binder of novel building materials

Effect of Accelerated Carbonation on AOD Stainless Steel Slag for Its Valorisation as a CO2-sequestering Construction Material

Non-stabilized Argon Oxygen Decarburisation (AODNS) slag in powdered form was examined for its carbon dioxide sequestration capacity and for its potential utilization in the fabrication of high value building materials. The curing of the sample was carried out in two accelerated carbonation environments: i) in a carbonation chamber, maintained at atmospheric pressure, 22 °C, 5 vol.% CO2 and 80% RH; and ii) in a carbonation reactor, where the CO2 partial pressure (pCO2) and temperature could be further increased. In the carbonation chamber, an average compressive strength of over 20 MPa, on a 64 cm3 cubic specimen, was obtained after one week of curing, which is sufficient for many construction applications. Further carbonation resulted in a linear increase of strength up ~30 MPa after three weeks. The CO2 uptake followed a similar trend, reaching a maximum of 4.3 wt.%. In the reactor, the compressive strength improved with an increase in pCO2 up to 8 bar, temperature up to 80 °C, and duration up to 15 h where the maximum CO2 uptake was 8.1 wt%. The reduction in porosity in the carbonated specimens was approximately in line with the strength gain in the samples. Phase analysis by X-ray powder diffraction and inspection by scanning electron microscopy showed the precipitation of calcite and formation of significant amounts of amorphous material after carbonation. Infrared spectroscopy also pointed to the presence of aragonite and vaterite. In the carbonation chamber, the calcite morphology was uniform throughout the specimen. In the reactor, however, the calcite crystals near the outer edges of the cubes had different morphology than those near the core. Carbonation of the slag resulted in the reduction of basicity by up to one pH unit, and contributed to controlling the leaching of several heavy metals and metalloids

Confinement Effects in Lewis Acid-Catalyzed Sugar Conversion: Steering Toward Functional Polyester Building Blocks

We report the use of solid Lewis acid catalysts for the conversion of tetrose sugars to four-carbon α-hydroxy acid esters (C_4-AHA), which are useful as functional polyester building blocks. Sn-β was by far the most active and selective catalyst, yielding up to 80% methyl vinyl glycolate (MVG), methyl-4-methoxy-2-hydroxybutanoate (MMHB), and α-hydroxy-γ-butyrolactone (HBL) combined at 95% conversion. A very high turnover frequency (TOF) of 330 mol_(C4-AHA) mol_(Sn) h^(–1) was attained using Sn-β, a more than 6-fold increase compared with homogeneous SnCl_4·5H_2O. It is shown that, using different Sn-based catalysts with various pore sizes, the product distribution is strongly dependent on the size of the catalyst pores. Catalysts containing mainly mesopores, such as Sn-MCM-41 or Sn-SBA-15, prefer the production of the more bulky MMHB, whereas microporous catalysts such as Sn-β or Sn-MFI favor the production of MVG. This effect can be further enhanced by increasing the reaction temperature. At 363 K, only 20% MVG is attained using Sn-β, but at 433 K, this increases to 50%. Using a kinetic analysis, it was found that, in microporous catalysts, steric hindrance near the Sn active site in the catalyst pores plays a dominant role in favoring the reaction pathway toward MVG. Moreover, the selectivity toward both products is kinetically controlled