The levels of CO2 emissions generated by the cement industry and the growth in demand for its products have led to a search for ways to reduce these emissions. The use of supplementary cementitious materials has become one of the solutions proposed for this problem. Illite, which is found all over the world, is a possible supplementary cementitious material. Before illite can be used, it must be milled and treated thermally in order to activate it, so that the alkalis (Na+ and K+) are free and available to react. Alkalis in cement participate in deleterious reactions (alkali-silica reaction) or have a beneficial effect (alkaline activation). The alkalis present in the rocks can play an active role in these phenomena, however. In addition, the material could be influenced by the alkaline environment produced by the cement. The current study was aimed at analyzing whether an alkali release occurs and if so, how it is affected when a milled and thermally treated illitic rock is in contact with water or an alkaline solution. The material was characterized by X-ray fluorescence, polarizing microscopy, and X-ray diffraction (XRD). The sample was treated thermally at 300, 600, and 900°C, and the thermal activation was evaluated through XRD, density, and Atterberg limits. The evolution of alkali release was studied by determining the sodium and potassium concentration of contact water obtained by mixing the samples with different pH solutions for various lengths of time. In addition, the calcium concentration was determined. The concentrations of sodium and potassium in the contact water were determined by flame photometry, and of calcium by EDTA (ethylenediaminetetraacetic acid) titration. The results showed that with increasing age, increasing solution pH, and higher treatment temperatures, alkali release occurred and increased, whereas Ca2+ concentration decreased.

Polycarboxylate superplasticizer (PCE) is sensitive to the clay present in concrete aggregates. In particular, Montmorillonite (Mnt), an impurity inevitably contained in the aggregate, can significantly influence the performance of concrete. In an effort to improve the compatibility of PCE, a zwitterionic PCE with cationic amide groups and shorter side-chain lengths was synthesized via free radical copolymerization. The optimal synthesis condition was verified via Box-Behnken design. In addition to characterizing the PCE, the performance of PCE in cement pastes with or without Na-Mnt was examined and the underlying mechanism was explored. The results show that, compared with commercially available PCE, the required dosage of PCE for cements containing Na-Mnt decreased. Unlike commercially available PCE, no intercalation occured on the newly manufactured clay-tolerant PCE within the layers of Mnt, resulting in a greater sorption thickness and improved dispersion of the cements containing Na-Mnt.

The use of natural pozzolans in concrete applications is gaining more attention because of the associated environmental, economic, and technical benefits. In this study, reference cemented mine backfill samples were prepared using Portland cement, and experimental samples were prepared by partially replacing Portland cement with 10 or 20 wt.% fly ash as a byproduct (artificial) pozzolan or pumice as a natural pozzolan. Samples were cured for 7, 14, and 28 days to investigate uniaxial compressive strength development. Backfill samples containing 10 wt.% pumice had almost a similar compressive strength as reference samples. There is strong potential for pumice to be used in cemented backfill to minimize costs, improve backfill properties, and promote the sustainability of the mining industry.

The Yaylayolu kaolin deposit is situated in the vicinity of Tavşanlı, Kütahya, western Turkey. Mineral identification and characterization studies were conducted using powder X-ray diffraction (XRD), differential thermal analyses (DTA), scanning electron microscopy with an energy dispersive X-ray spectrometer (SEM-EDX), X-ray fluorescence (XRF) and Fourier transform infrared spectroscopy (FTIR) techniques. The degree of crystallinity, Hinckley's index (HI) and the Stoch index (SI) values were determined for kaolinite from the deposit.

Five representative samples from the kaolin deposit were used for ceramic technological tests. Particle size distribution, pH value, loss on ignition, A12O3, Fe2O3 and TiO2 contents were determined, drying shrinkage, firing shrinkage, dry bend strength, fired bend strength, water absorption, pfefferkorn plasticity index, whiteness of the fired and unfired samples (L* value) and bulk density were measured. The kaolin was found to be suitable for making white cement and wall tiles, floor tiles, and tableware items which are shaped by dry pressing and extrusion.

Rheological, porosimetric, and SEM studies of cements with additions of natural zeolites (chabazite, mordenite and clinoptilolite) were investigated. The addition of 5% zeolite to cement pastes had a plastifying effect. The increase in the rheological parameters of aqueous cement–zeolite suspensions began after additions of more than 10% zeolite. At a water/solid ratio (w/s) = 0.5 all compositions exhibited similar rheological behaviour for yield stress and maximum shear stress values. At lower w/s values the rheology depended on the zeolite used, decreasing in the order Sl (clinoptilolite, Nižny Hrabovec deposit, Slovakia), M (mordenite, Philipines), Bp (clinoptilolite, Beli Plast deposit, Bulgaria), NM (clinoptilolite, Saint Cloud deposit, New Mexico) and Ch (chabazite, Nasm Yan deposit, Korea).

After 28 days of hydration the mixtures containing 10% Bp clinoptilolite, mordenite, and Sl clinoptilolite (up to 30%) had unchanged specific pore volumes but additions of 10% and 30% of chabazite and NM clinoptilolite and of 30% mordenite and Bp clinoptilolite lead to increases in the total specific pore volume compared to the neat cement paste. Between the 28th and 180th days of hydration the specific volume of the pores in all the cement-zeolite pastes decreased due to the filling of the pores with products from the pozzolanic reaction between the zeolites and the hydration products of the cement.

The pozzolanic reaction between zeolite and the hydration products of cement is enhanced by the zeolite content in the samples and depends on the Si/Al ratio (clinoptilolite (Si/Al >4.5), mordenite (Si/Al >5), chabazite (Si/Al <2.5)) and the surface area (clinoptilolite from Slovakia has the smallest crystallites and, hence, the greatest reactive surface area).

Turkey has a long tradition (starting with prehistoric civilizations) and experience in exploring for raw clay materials and processing them into ceramic products. Many of these products, such as tiles and sanitary ware, are manufactured for domestic and export markets. Kaolin is one of the raw materials of major importance for the ceramic and paper industry, as well as for a number of auxiliary applications. There is ongoing interest in applying kaolin in the construction industry as a raw material in the production of white cement clinker and as an artificial pozzolanic additive for concrete (in the form of metakaolin). This report presents results related to search, assessment and evaluation of available resources for advanced cement and concrete additives.

Cement mortars and concretes incorporating clinoptilolite, silica fume and fly ash were investigated for changes in their physical and mechanical properties. It was found that additions of 10% clinoptilolite and 10% Pozzolite (1:1 mixture of silica fume and fly ash) were optimal for improvement of the quality of the hardened products, giving 8% and 13% increases in flexural and compressive strength respectively. The specific pore volume of the mortars incorporating zeolite decreased between the 28th and 180th day to levels below the values for the control composition due to the fact that clinoptilolite exhibits its pozzolanic activity later in the hydration. In these later stages, pores with radii below 500 nm increased at the expense of larger pores. The change in the pore-size distribution between the first and sixth months of hydration occurs mostly in the mortars with added zeolite.

Large volumes of depleted natural and low-enriched uranium exist in the UK waste inventory. This work reports on initial investigations of the leaching performance of candidate glass and cement encapsulation matrices containing UO3 powder as well as that of uranium oxide powders. The surface areas of UO3 powder and the monolith samples of UO3 conditioned in the glass and cement matrices were very different making leaching comparisons difficult. The results showed that for both types of monolith conditioned samples a steady increase of uranium concentration in solution with time was generally not observed. The wt.% of uranium leached from UO3 conditioned in the lead borosilicate glass wasteform was approximately five orders of magnitude less than that leached from UO3 powder. Similarly, the quantities of uranium leached from UO3 conditioned in composite cement made with ordinary Portland cement, and from magnesium phosphate cement, were approximately four and three orders of magnitude, respectively, less than that leached from UO3 powder. The performance of a mixed oxide borosilicate glass wasteform was only slightly better than that of UO3 powder. This work shows that wasteforms based on encapsulation in lead borosilicate glass and cement matrices have the greatest potential for further development.

Cementitious matrices are being assessed for immobilization of radioactive wastes. This paper discusses some mineralogical aspects of cement chemistry and the uses of siliceous minerals as selective sorbants to enhance immobilization potential.

Studies of sorption and leaching of caesium from pulverized fuel ash (PFA), blast furnace slag, tobermorite, xonotlite, and clinoptilolite are reported. The role of incorporation of these additives in cement and the effect on the nature of the composite matrix on caesium behaviour has been investigated. Specific mechanisms of the interaction of additives with highly alkaline cement environment are described. While slags, PFA, and clinoptilolite undergo reaction at different rates, tobermorite and xonotlite appear to be stable in cement.

In the United Kingdom, disposal of radioactive waste may involve packages of grouted waste being placed in a geological disposal facility (GDF) and surrounded by a cementitious backfill. This paper describes modelling that has been carried out to develop an understanding of the possible spatial and temporal evolution within the GDF.

A single waste package is assumed to be filled with an encapsulation grout, placed in an underground vault and surrounded by a cementitious backfill. Groundwater from the host rock flows into the vault and through the backfill. A simplified model system examines the interactions between groundwater, cementitious backfill and grout.

In most cases the model predicts a reduction in the backfill porosity due to precipitation and dissolution reactions, particularly at the upstream edge of the vault. The degree to which this occurs depends on the groundwater composition. The model also predicts precipitation and dissolution reactions would occur in the grouts close to their interface with the backfill, reducing the local porosity significantly which may isolate the grouts from the backfill, so that the pH within the grouts would be unchanged over an extended period.

Hielscherite, ideally Ca3Si(OH)6(SO4)(SO3)·11H2O, (IMA 2011-037) is the first ettringite-group mineral with essential sulfite. We have identified a continuous natural solid-solution series from endmember thaumasite, Ca3Si(OH)6(SO4)(CO3)·12H2O, to a composition with at least 77 mol.% endmember hielscherite. In this series, the SO3:CO3 ratio is variable, whereas the SO4 content remains constant. Compositions with more than 50 mol.% endmember hielscherite have only been found at Graulay quarry near Hillesheim in the western Eifel Mountains, Rhineland-Palatinate, where they occur with phillipsite-K, chabazite-Ca and gypsum in cavities in alkaline basalt. Sulfite-rich thaumasite has been found in hydrothermal assemblages in young alkaline basalts in two volcanic regions of Germany: it is widespread at Graulay quarry and occurs at Rother Kopf, Schellkopf and Bellerberg quarries in Eifel district; it has also been found at Zeilberg quarry, Franconia, Bavaria. Hielscherite forms matted fibrous aggregates up to 1 cm across and groups of acicular to prismatic hexagonal crystals up to 0.3 × 0.3 × 1.5 mm. Individual crystals are colourless and transparent with a vitreous lustre and crystal aggregates are white with a silky lustre. The Mohs hardness is 2–2½. Measured and calculated densities are Dmeas = 1.82(3) and Dcalc = 1.79 g cm–3. Hielscherite is optically uniaxial (–), ω = 1.494(2), ε = 1.476(2). The mean chemical composition of holotype material (determined by electron microprobe for Ca, Al, Si, and S and gas chromatography for C, H and N, with the S4+:S6+ ratio from the crystal-structure data) is CaO 27.15, Al2O3 2.33, SiO2 7.04, CO2 2.71, SO2 6.40, SO3 12.91, N2O5 0.42, H2O 39.22, total 98.18 wt.%. The empirical formula on the basis of 3 Ca atoms per formula unit is Ca3(Si0.73Al0.28)Σ1.01(OH)5.71(SO4)1.00(SO3)0.62(CO3)0.38(NO3)0.05·10.63H2O. The presence of sulfite was confirmed by crystal-structure analysis and infrared and X-ray absorption near edge structure spectra. The crystal structure of sulfite-rich thaumasite from Zeilberg quarry was solved by direct methods based on single-crystal X-ray diffraction data (R1 = 0.064). The structure of hielscherite was refined using the Rietveld method (Rwp = 0.0317). Hielscherite is hexagonal, P63, a = 11.1178(2), c = 10.5381(2) Å, V = 1128.06(4) Å3 and Z = 2. The strongest reflections in the X-ray powder pattern [(d, Å (I)(hkl)] are: 9.62(100)(010,100); 5.551(50)(110); 4.616(37)(012,102); 3.823(64)(112); 3.436(25)(211), 2.742(38)(032,302), 2.528(37)(123,213), 2.180(35)(042,402;223). In both hielscherite and sulfite-rich thaumasite, pyramidal sulfite groups occupy the same site as trigonal carbonate groups, with analogous O sites, whereas tetrahedral sulfate groups occupy separate positions. Hielscherite is named in honour of the German mineral collector Klaus Hielscher (b. 1957).

The uptake of 137-Cs and 90-Sr on to synthetic zeolite A has been studied. The use of a combined barium exchange followed by a relatively mild heat treatment has been shown to fix the isotopes within a collapsed zeolite structure. Leaching experiments using deionized and simulated sea and pond waters were carried out on zeolite compacts and zeolite/cement composites. They demonstrated the effectiveness of the calcination and cement containment. Some comments on the interpretation of leach test data are made.

A series of long-term laboratory experiments was started in 1995 to investigate longer-term dissolution/ precipitation reactions that may occur in the alkaline disturbed zone surrounding a cementitious repository for radioactive waste. They consist of samples of UK basement rock reacting with either Na-K-Ca-OH water ('young' cement porewater) or Ca-OH water ('evolved' cement porewater) at 70°C. This paper summarizes results of reactions occurring over the first 15 months. Experiments of both fluid types showed many similar features, though primary mineral dissolution and secondary mineral precipitation were more extensive in the experiments involving Na-K-Ca (younger) cement porefluids compared to more evolved (Ca-rich) cement porefluids. Dissolution of dolomite, and to a lesser extent silicates (probably K-feldspar, but also possibly mica) occurred relatively rapidly at 70°C. Dolomite dissolution may have been a key factor in reducing pH values, and may be a key mineral in controlling the extent of alkaline disturbed zones. Dissolution was followed by precipitation of brucite close to dolomite grains, at least two generations of C-S-H phases (which may have contained variable amounts of K, Al and Mg); overgrowths of calcite; small crystals of hydroxyapophyllite; and elongate crystals of celestite. Though hydroxyapophyllite was observed (a phase commonly associated with zeolites), there was no evidence for the formation of zeolites in the experiments. Fluid chemical changes track the mineralogical changes, with C-S-H phases being a major control on fluid chemistry. In the 'young' porewater experiments there were decreases in pH, and K, Ca and Mg concentrations, together with transitory increases in SiO2 concentrations. In the 'evolved' porewater experiments there were decreases in pH, Mg, Ca and Sr concentrations, together with small increases in K and SiO2 concentrations. A number of experiments are still running, and will be sampled in coming years.

Concrete and bentonite are being considered as engineered barriers for the deep geological disposal of high-level radioactive waste in argillaceous rocks. Three hydrothermal laboratory experiments of different scalable complexity were performed to improve our knowledge of the formation of calcium aluminate silicate hydrates (C-A-S-H) at the interface between the two materials: concretebentonite transport columns, lime mortar-bentonite transport columns and a portlandite- (bentonite and montmorillonite) batch experiment. Precipitation of C-A-S-H was observed in all experiments. Acicular and fibrous morphologies with certain laminar characteristics were observed which had smaller Ca/Si and larger Al/Si ratios with increasing temperature and lack of accessory minerals. The compositional fields of these C-A-S-H phases formed in the experiments are consistent with Al/(Si+Al) ratios of 0.2– 0.3 described in the literature. The most representative calcium silicate hydrate (C-S-H) phase from the montmorillonite–cement interface is Al-tobermorite. Structural analyses revealed a potential intercalation or association of montmorillonite and C-A-S-H phases at the pore scale.

Cement pillars and graves play significant roles as land markers in disputes over land in postconflict northern Uganda. Contemporary land cases from Acholi and Ikland display different histories of land use and conflict. In Acholi, cemented graves constitute concrete indices of belonging in wrangles. In Ikland, national nature authorities have brought cement pillars into the landscape. We explore how cemented graves and cement pillars are used for land claims in societies affected by conflict and displacement and how articulations of belonging are created, with the specific materiality of cement signaling modernity, permanence, and inflexibility.

Irradiation is one of the characteristic conditions that nuclear wasteforms must withstand to assure integrity during their service life. This study investigates gamma irradiation resistance of an early age slag cement-based grout, which is of interest for the nuclear industry as it is internationally used for encapsulation of low and intermediate level radioactive wastes. The slag cement-based grout withstands a gamma irradiation dose of 4.77 MGy over 256 h without reduction in its compressive strength; however, some cracking of irradiated samples was identified. The high strength retention is associated with the fact that the main hydration product forming in this binder, a calcium aluminum silicate hydrate (C–A–S–H) type gel, remains unmodified upon irradiation. Comparison with a heat-treated sample was carried out to identify potential effects of the temperature rise during irradiation exposure. The results suggested that formation of cracks is a combined effect of radiolysis and heating upon irradiation exposure.