John L. Provis

Geopolymers for immobilization of Cr6+, Cd2+, and Pb2+

Alkali activation of fly ash by sodium silicate solutions, forming geopolymeric binders, provides a potential means of treating wastes containing heavy metals. Here, the effects on geopolymer structure of contamination of geopolymers by Cr(VI), Cd(II) and Pb(II) in the forms of various nitrate and chromate salts are investigated. The addition of soluble salts results in a high extent of dispersal of contaminant ions throughout the geopolymer matrix, however very little change in geopolymer structure is observed when these materials are compared to their uncontaminated counterparts. Successful immobilization of these species will rely on chemical binding either into the geopolymer gel or into other low-solubility (silicate or aluminosilicate) phases. In the case of Pb, the results of this work tentatively support a previous identification of Pb(3)SiO(5) as a potential candidate phase for hosting Pb(II) within the geopolymer structure, although the data are not entirely conclusive. The addition of relatively low levels of heavy metal salts is seen to have little effect on the compressive strength of the geopolymeric material, and in some cases actually gives an increase in strength. Sparingly soluble salts may undergo some chemical conversion due to the highly alkaline conditions prevalent during geopolymerization, and in general are trapped in the geopolymer matrix by a simple physical encapsulation mechanism. Lead is in general very effectively immobilized in geopolymers, as is cadmium in all except the most acidic leaching environments. Hexavalent chromium is problematic, whether added as a highly soluble salt or in sparingly soluble form.

Generalized Structural Description of Calcium–Sodium Aluminosilicate Hydrate Gels: The Cross-Linked Substituted Tobermorite Model

Structural models for the primary strength and durability-giving reaction product in modern cements, a calcium (alumino)silicate hydrate gel, have previously been based solely on non-cross-linked tobermorite structures. However, recent experimental studies of laboratory-synthesized and alkali-activated slag (AAS) binders have indicated that the calcium-sodium aluminosilicate hydrate [C-(N)-A-S-H] gel formed in these systems can be significantly cross-linked. Here, we propose a model that describes the C-(N)-A-S-H gel as a mixture of cross-linked and non-cross-linked tobermorite-based structures (the cross-linked substituted tobermorite model, CSTM), which can more appropriately describe the spectroscopic and density information available for this material. Analysis of the phase assemblage and Al coordination environments of AAS binders shows that it is not possible to fully account for the chemistry of AAS by use of the assumption that all of the tetrahedral Al is present in a tobermorite-type C-(N)-A-S-H gel, due to the structural constraints of the gel. Application of the CSTM can for the first time reconcile this information, indicating the presence of an additional activation product that contains highly connected four-coordinated silicate and aluminate species. The CSTM therefore provides a more advanced description of the chemistry and structure of calcium-sodium aluminosilicate gel structures than that previously established in the literature.

Microscopy and microanalysis of inorganic polymer cements. 2: the gel binder

By scanning electron microscopy and microanalysis of fly ash-based and mixed fly ash-slag inorganic polymer cement (i.e., “fly ash geopolymer”) binders, a more detailed understanding of the gel structure and its formation mechanism have been developed. The binder is predominantly an aluminosilicate gel charge balanced by alkali metal cations, although it appears that calcium supplied by slag particles becomes relatively well dispersed throughout the gel. The gel itself is comprised of colloidal-sized, globular units closely bonded together at their surfaces. The microstructure of the binder resulting from hydroxide activation of fly ash is much less uniform than that which forms in a corresponding silicate-activated system; this can be rationalized in terms of a newly developed explanation for the differences in reaction mechanisms between these two systems. In hydroxide activation, the newly formed gel phase nucleates and grows outwards from the ash particle surfaces, whereas the high silica concentration in a silicate-activated system enables a more homogeneous gelation process to take place throughout the inter-particle volume.

Microscopy and microanalysis of inorganic polymer cements. 1: remnant fly ash particles

Accurate and precise electron microscopic analysis of the remnant solid precursor (fly ash and blast furnace slag) particles embedded in an inorganic polymer cement (or “fly ash geopolymer”) provides critical information regarding the process of gel binder formation. Differential solubility of phases in the fly ash is seen to be important, with insoluble mullite crystals becoming exposed by the retreat of the surrounding glassy phases. High-iron particles appear to remain largely unreacted, and the use of sectioned and polished specimens provides a view of the inside of these particles, which can show a wide variety of phase separation morphologies and degrees of intermixing of high iron and other phases. Calcium appears to be active in the process of alkali activation of ash/slag blends, although the competitive and/or synergistic effects of ash and slag particles during the reaction process remain to be understood in detail.

Characterization of Aged Slag Concretes

Slag concretes, activated by carbonates or carbonate/hydroxide mixtures and cast between 1964 and 1982, are examined. These concretes have served for prolonged periods under conditions in which portland cements would have deteriorated rapidly, and yet have remained sound and actually increased in strength over their service life. By a combination of microscopic and nuclear magnetic resonance (NMR) analysis, this durability is attributed to the combination of a highly polymerized, relatively low-Ca, amorphous C-S-H outer product, with an inner product that undergoes continuing hydration via a cyclic process involving carbonate anions. The relatively consistent Ca/Si ratio across all phases is believed to contribute to durability, as is the low Al content of the C-S-H phases formed in systems using hydroxide activators. The low permeability of the concretes also appears to have contributed to their durability.

Density functional modeling of the local structure of kaolinite subjected to thermal dehydroxylation.

Understanding the atomic-level changes that occur as kaolinite is converted (thermally dehydroxylated) to metakaolin is critical to the optimization of this large-scale industrial process. Metakaolin is X-ray amorphous; therefore, conventional crystallographic techniques do not reveal the changes in local structure during its formation. Local structure-based experimental techniques are useful in understanding the atomic structure but do not provide the thermodynamic information which is necessary to ensure plausibility of refined structures. Here, kaolinite dehydroxylation is modeled using density functional theory, and a stepwise methodology, where several water molecules are removed from the structure, geometry optimization is carried out, and then the process is repeated. Hence, the structure remains in an energetically and thermodynamically feasible state while transitioning from kaolinite to metakaolin. The structures generated during the dehydroxylation process are validated by comparison with X-ray and neutron pair distribution function data. Thus, this study illustrates one possible route by which dehydroxylation of kaolinite can take place, revealing a chemically, energetically, and experimentally plausible structure of metakaolin. This methodology of density functional modeling of the stepwise changes in a material is not limited in application to kaolinite or other aluminosilicates and provides an accurate representation of the local structural changes occurring in materials used in industrially important processes.

Magnesia-Based Cements: A Journey of 150 Years, and Cements for the Future?

This review examines the detailed chemical insights that have been generated through 150 years of work worldwide on magnesium-based inorganic cements, with a focus on both scientific and patent literature. Magnesium carbonate, phosphate, silicate-hydrate, and oxysalt (both chloride and sulfate) cements are all assessed. Many such cements are ideally suited to specialist applications in precast construction, road repair, and other fields including nuclear waste immobilization. The majority of MgO-based cements are more costly to produce than Portland cement because of the relatively high cost of reactive sources of MgO and do not have a sufficiently high internal pH to passivate mild steel reinforcing bars. This precludes MgO-based cements from providing a large-scale replacement for Portland cement in the production of steel-reinforced concretes for civil engineering applications, despite the potential for CO2 emissions reductions offered by some such systems. Nonetheless, in uses that do not require steel reinforcement, and in locations where the MgO can be sourced at a competitive price, a detailed understanding of these systems enables their specification, design, and selection as advanced engineering materials with a strongly defined chemical basis.

Activating solution chemistry for geopolymers

Abstract: This chapter discusses the different solutions that are used as activators in geopolymer synthesis: alkali metal hydroxides and silicates. The phase behaviour, speciation and physical properties of different potential activating solutions are discussed. The use of alternative activators is also briefly mentioned.

Quantitative study of the reactivity of fly ash in geopolymerization by FTIR

Fourier transform infrared (FTIR) spectroscopy has been applied to analyse the environments of Al–O and Si–O bonds in fly ash, which are used as raw materials of geopolymer synthesis. It is noted that the relative intensities of the bands at around 1000, 910 and 700 cm−1 are much higher in fly ash with higher reactivity, as reflected by the compressive strength of geopolymer. Deconvolution analysis of the band from 400 to 1400 cm−1 shows that the cumulative area of these three resolved bands, together with the band at ∼1090 cm−1, which is assigned to the asymmetric stretching of Si(Al)–O–Si, is proportional to the reactivity of fly ash. If it is assumed that the area of the resolved bands is proportional to the concentration of the corresponding bonds, a general indication is therefore that fly ash containing more reactive bonds will exhibit higher reactivity in geopolymerisation. FTIR spectroscopy in combination with particle size analysis provides a fast approach to predict the reactivity of fly ash, from the perspective of aluminosilicate glass chemistry.

What is the structure of kaolinite? Reconciling theory and experiment.

Density functional modeling of the crystalline layered aluminosilicate mineral kaolinite is conducted, first to reconcile discrepancies in the literature regarding the exact geometry of the inner and inner surface hydroxyl groups, and second to investigate the performance of selected exchange-correlation functionals in providing accurate structural information. A detailed evaluation of published experimental and computational structures is given, highlighting disagreements in space groups, hydroxyl bond lengths, and bond angles. A major aim of this paper is to resolve these discrepancies through computations. Computed structures are compared via total energy calculations and validated against experimental structures by comparing computed neutron diffractograms, and a final assessment is performed using vibrational spectra from inelastic neutron scattering. The density functional modeling is carried out at a sufficiently high level of theory to provide accurate structure predictions while keeping computational requirements low enough to enable the use of the structures in large-scale calculations. It is found that the best functional to use for efficient density functional modeling of kaolinite using the DMol3 software package is the BLYP functional. The computed structure for kaolinite at 0 K has C1 symmetry, with the inner hydroxyl group angled slightly above the a,b plane and the inner surface hydroxyls aligned close to perpendicular to that plane.