Waste fuels: their effect on Portland cement clinker

Nowadays, different kinds of industrial wastes are increasingly used in the clinkering process by the cement industry, with the aim of taking advantage of their energy content or confining unsuitable substances. This work evaluates the physicochemical characteristics of the clinkers obtained after incorporating three different wastes in different proportions: two of them with energetic capacity—trade marked waste fuel and waste carbon of petroleum—and the third that would be confined—pyrolitic carbon.The fusion temperature of the mixtures, the differential thermal analysis and the thermogravimetric analysis (DTA/TG) during clinkering and after hydration, the specific surface area at the same milling times, X-ray diffraction (XRD) and mechanical strength of the pastes elaborated with a water/cement 0.4 relation were analyzed. The results obtained were compared to those of the clinker obtained without additions.     

Leaching kinetics of Cs and Co radionuclides fixed in cement and cement-based materials

Leach characteristics of ¹³⁷Cs and ⁶⁰Co radionuclides from both ordinary Portland cement and cement mixed with two different ratios of silica fume and ilmenite have been studied using International Atomic Energy's (IAEA) standard leach method. A mathematical model has been simulated to predict the release rate of each nuclide from cubic geometry waste matrix and the predicted values are discussed in relation to experimentally observed leach rates to confirm the validity of the proposed mechanism in the model. The effect of temperature on the radionuclides leaching rates was also studied and the effective diffusion coefficients were obtained at different temperatures. The net fractional release of the two radionuclides from different waste forms showed a decreasing pattern as ¹³⁷Cs>⁶⁰Co, indicating the largest diffusion coefficient for cesium in all waste matrices.     

Alkali binding in hydrated Portland cement paste

The alkali-binding capacity of C-S-H in hydrated Portland cement pastes is addressed in this study. The amount of bound alkalis in C-S-H is computed based on the alkali partition theories firstly proposed by Taylor (1987) and later further developed by Brouwers and Van Eijk (2003). Experimental data reported in literatures concerning thirteen different recipes are analyzed and used as references. A three-dimensional computer-based cement hydration model (CEMHYD3D) is used to simulate the hydration of Portland cement pastes. These model predictions are used as inputs for deriving the alkali-binding capacity of the hydration product C-S-H in hydrated Portland cement pastes. It is found that the relation of Na⁺ between the moles bound in C-S-H and its concentration in the pore solution is linear, while the binding of K⁺ in C-S-H complies with the Freundlich isotherm. New models are proposed for determining the alkali-binding capacities of C-S-H in hydrated Portland cement paste. An updated method for predicting the alkali concentrations in the pore solution of hydrated Portland cement pastes is developed. It is also used to investigate the effects of various factors (such as the water to cement ratio, clinker composition and alkali types) on the alkali concentrations.     

Effect of fly ash on the kinetics of Portland cement hydration at different curing temperatures

This paper describes the effect of fly ash on the hydration kinetics of cement in low water to binder (w/b) fly ash-cement at different curing temperatures. The modified shrinking-core model was used to quantify the kinetic coefficients of the various hydration processes. The results show that the effect of fly ash on the hydration kinetics of cement depends on fly ash replacement ratios and curing temperatures. It was found that, at 20 °C and 35 °C, the fly ash retards the hydration of cement in the early period and accelerates the hydration of cement in the later period. Higher the fly ash replacement ratios lead to stronger effects. However, at 50 °C, the fly ash retards the hydration of the cement at later ages when it is used at high replacement ratios. This is because the pozzolanic reaction of the large volumes of fly ash is strongly accelerated from early in the aging, impeding the hydration of the cement.     

The role of calcium ions and lignosulphonate plasticiser in the hydration of cement

Experiments involving equilibrium dialysis, conductivity, X-ray diffraction analysis (XRD), differential thermal analysis (DTA) and isothermal titration calorimetry (ITC) have been carried out to investigate the role of calcium ions and polymeric plasticisers in cement/admixture hydration. Results from a study of lignosulphonic acid, sodium salt, acetate as a plasticiser shows that a plasticiser has dual role; one mainly as a kinetic inhibitor (poison) in cement hydration mechanism and the other as a dispersant. Evidence of a weak Ca²⁺ binding to lignosulphonate sulphonic moieties was found at low ionic strengths of 0.1 M using ITC. No evidence of formal Ca²⁺ binding to lignosulphonate sulphonic acid moieties was found using equilibrium dialysis at higher ionic strength of 1 M (ionic strengths of 0.4 M are typically found in Portland cement pore solution), as is often suggested in cement/admixture literature.     

A new hydration kinetics model of composite cementitious materials,part 1: Hydration kinetic model of Portland cement

This work is the first part of an overall research project that aims to model the hydration kinetics of modern composite cementitious materials. The aim of this part is to build a hydration kinetic model to characterize the hydration behavior of cement at all ages. In this paper, the nucleation and growth of CSH and the diffusion of water are described by a modified BNG model and a modified Jander's model. The kinetic parameters are obtained by simulative fitting of the model to the experimental data. The linear functions between the nucleation and growth rates and the W/C ratios are given in this paper. The apparent activation energy of the nucleation rate constant, growth rate constant, and generalized diffusion constant are approximately 36.0, 37.5, and 42.0 kJ/mol, respectively. Finally, the phase compositions of hardened cement paste are calculated according to the kinetic model and the reaction formula of cement.     

Microstructural characterization of leaching effects in cement pastes due to neutralisation of their alkaline nature: Part I: Portland cement pastes

When concrete is exposed to the elements, its underlying microstructure can be attacked by a variety of aggressive agents; for example, rainwater and groundwater. The knowledge of concrete resistance to long term water aggression is necessary for predictions of their performance in different environments. This study aims to analyse the effects of leaching on the microstructure of Portland cement binders. Leaching of cement pastes was performed by an accelerated extraction leaching test that produces significant degradation and helps to achieve equilibrium or near-equilibrium conditions between the leachant medium and cement paste. FTIR spectroscopy, TG-DTA thermal analysis, low temperature nitrogen gas sorption, and geochemical modelling were used to characterize the microstructural changes produced in cement pastes at different equilibrium pHs reached during the leaching process.     

阿利特—硫铝酸盐水泥与硅酸盐水泥复合性能的研究

研究了阿利特－硫铝酸盐水泥与硅酸盐水泥复合所制备的水泥的性能。结果表明,复合后水泥的强度性能优于单一品种水泥的性能;凝结时间则由复合体中占比例较多的一种水泥所控制。     

International Summit on Cement Hydration Kinetics and Modeling Special Edition Québec City, July 27, 28 and 29, 2009

The performance of portland cement concrete relies upon a series of complex events that begin with raw minerals and end many years after the concrete is placed. Between these points, the life of this dynamic material is dominated by chemical reactions called hydration. While much is known about hydration, unfortunately, there is no unifying theory that describes the kinetics (rates) of these complex transformations from anhydrous cement to hydrous cement paste. Other industries including metalugy, petrochemicals, pharmaceuticals and semiconductors have asserted process control by developing a fundamental, mechanistic understanding of the kinetics of the chemical reactions and phase transformations that define their products. Might the concrete industry be moving along a similar trajectory?     

Early hydration and setting of Portland cement monitored by IR, SEM and Vicat techniques

Diffuse Reflectance Infrared DR-FTIR spectroscopy is employed to monitor chemical transformations in pastes of Portland limestone cement. To obtain a sufficient time resolution a freeze-dry procedure is used to instantaneously ceasing the hydration process. Rapid re-crystallization of sulphates is observed during the first 15 s, and appears to be complete after ~ 30 min. After ~ 60 min, spectroscopic signatures of polymerizing silica start to emerge. A hump at 970-1100 cm^− 1 in conjunction with increasing intensity in the water bending mode region at 1500-1700 cm^− 1 is indicative of the formation of Calcium Silicate Hydrate, C-S-H. Simultaneously with the development of the C-S-H signatures, a dip feature develops at 800-970 cm^− 1, reflecting the dissolution of Alite, C₃S. Setting times, 180 (initial) and 240 (final) minutes, are determined by the Vicat technique. Combining DR-FTIR, SEM and Vicat measurements it is concluded that the setting is caused by inter-particle coalescence of C-S-H.     

Hydration kinetics modeling of the effect of curing temperature and pressure on the heat evolution of oil well cement

The heat evolution of Class G and Class H oil well cements cured under different temperatures (25 °C to 60 °C) and pressures (2 MPa to 45 MPa) was examined by isothermal calorimetry. Curing pressure was found to have a similar effect on cement hydration kinetics as curing temperature. Under isothermal and isobaric conditions, the dependency of cement hydration kinetics on curing temperature and pressure can be modeled by a scale factor which is related to the activation energy and the activation volume of the cement. The estimated apparent activation energy of the different cements at 2 MPa varies from 38.7 kJ/mol to 41.4 kJ/mol for the temperature range of 25 °C to 40 °C, which decreases slightly with increasing curing temperature and pressure. The estimated apparent activation volume of the cements at 25 °C varies from − 23.1 cm³/mol to − 25.9 cm³/mol for the pressure range studied here, which also decreases slightly in magnitude with increasing curing temperature.     

Early hydration of white Portland cement in the presence of bismuth oxide

Abstract

Abstract

Mineral trioxide aggregate (MTA) is a clinical product comprising a mixture of 80 wt-% Portland cement and 20 wt-% bismuth oxide, which is used as a root-filling material in dentistry. The influence of bismuth oxide on the hydration reactions of Portland cements is not well understood. In this study, the impact of 20 wt-% replacement of bismuth oxide on the hydration of white Portland cement was monitored by powder X-ray diffraction (XRD), ²⁹Si and ²⁷Al magic angle spinning nuclear magnetic resonance spectroscopy (MAS NMR) and transmission electron microscopy (TEM). The findings of this research have confirmed that bismuth oxide is an inert additive in white Portland cement, which does not participate in the hydration reactions.     

Thermodynamic modelling of the hydration of Portland cement

A thermodynamic model is developed and applied to calculate the composition of the pore solution and the hydrate assemblage during the hydration of an OPC. The calculated hydration rates of the individual clinker phases are used as time dependent input. The modelled data compare well with the measured composition of pore solutions gained from OPC as well as with TGA and semi-quantitative XRD data. The thermodynamic calculations indicate that in the presence of small amounts of calcite typically included in OPC cements, C-S-H, portlandite, ettringite and calcium monocarbonates are the main hydration products. The thermodynamic model presented in this paper helps to understand the interactions between the different components and the environment and to predict the influence of changes in cement composition on the hydrate assemblage.     

Effect of pressure on early hydration of class H and white cement

The change in viscosity of cement slurry with temperature and pressure can be predicted by assuming that hydration can be treated as an activated process and that a given viscosity corresponds to a fixed degree of reaction. For Class H and White cements, chemical shrinkage experiments indicate that the activation energy is 33.8 kJ/mole and rheological measurements yield an activation volume of −30 cm³/mole. With these parameters, it is possible to predict the limit of pumpability of the slurry (which corresponds to a viscosity of about 2.5 Pa s) for arbitrary temperature and pressure cycles. This method of prediction requires that the physics of the process remain the same, but simply change in rate; therefore, the range of applicability is expected to be limited to temperatures below about 100 °C, since new phases occur at higher temperatures.     

Thermodynamic modelling of the effect of temperature on the hydration and porosity of Portland cement

The composition of the phase assemblage and the pore solution of Portland cements hydrated between 0 and 60 °C were modelled as a function of time and temperature. The results of thermodynamic modelling showed a good agreement with the experimental data gained at 5, 20, and 50 °C. At 5 and at 20 °C, a similar phase assemblage was calculated to be present, while at approximately 50 °C, thermodynamic calculations predicted the conversion of ettringite and monocarbonate to monosulphate.Modelling showed that in Portland cements which have an Al₂O₃/SO₃ ratio of > 1.3 (bulk weight), above 50 °C monosulphate and monocarbonate are present. In Portland cements which contain less Al (Al₂O₃/SO₃ < 1.3), above 50 °C monosulphate and small amounts of ettringite are expected to persist. A good correlation between calculated porosity and measured compressive strength was observed.     

铝酸盐水泥熟料对粉煤灰硅酸盐水泥性能的影响

以铝酸盐水泥熟料、硅酸盐水泥熟料和粉煤灰为原料,探讨了掺加少量铝酸盐水泥熟料对硅酸盐水泥及粉煤灰硅酸盐水泥复合体系水化、凝结和硬化性能的影响。结果表明,在硅酸盐水泥及粉煤灰硅酸盐水泥中掺加铝酸盐水泥熟料,可以明显缩短水泥的初、终凝时间,但复合体系的需水量增加;掺加少量铝酸盐水泥熟料(≤3%)可明显提高硅酸盐水泥的早期强度,但后期强度(28d)有所降低;当铝酸盐水泥熟料的掺量达5%时,水泥的各龄期强度均明显降低。少量铝酸盐水泥熟料掺加到粉煤灰硅酸盐水泥中,复合体系的各龄期强度都明显提高,且早期强度的提高幅度较大。     

Modeling the linear elastic properties of Portland cement paste

The linear elastic moduli of cement paste are key parameters, along with the cement paste compressive and tensile strengths, for characterizing the mechanical response of mortar and concrete. Predicting these moduli is difficult, as these materials are random, complex, multi-scale composites. This paper describes how finite element procedures combined with knowledge of individual phase moduli are used, in combination with a cement paste microstructure development model, to quantitatively predict elastic moduli as a function of degree of hydration, as measured by loss on ignition. Comparison between model predictions and experimental results are good for degrees of hydration of 50% or greater, for a range of water : cement ratios. At early ages, the resolution of the typical 100³ digital microstructure is inadequate to give accurate results for the tenuous cement paste microstructure that exists at low degrees of hydration. Elastic computations were made on higher resolution microstructures, up to 400³, and compared to early age elastic moduli data. Increasing agreement with experiment was seen as the resolution increased, even when ignoring possible viscoelastic effects.     

The hydration products of Portland cement in the presence of tin(II) chloride

The hydration products of Portland cement pastes cured using water containing tin(II) chloride have been compared with those using distilled water. In the latter case, the expected products—portlandite, ettringite and calcite—were observed. The X-ray diffraction patterns of the cement pastes cured in the presence of tin(II) chloride showed several additional peaks that have been attributed to the formation of calcium hydroxo-stannate, CaSn(OH)₆, and Friedel's salt (tetracalcium aluminate dichloride-10-hydrate), Ca₃Al₂O₆·CaCl₂·10H₂O. The amount of portlandite formed was reduced in the presence of tin(II) chloride. Calcium hydroxo-stannate contains tin in the +IV oxidation state and equations are presented to account for the oxidation of Sn(II) to Sn(IV) preceding the formation of CaSn(OH)₆ and Friedel's salt.     

Natural cement as the precursor of Portland cement: Methodology for its identification

When cements appeared in the 19th century, they took the place of traditional binding materials (lime, gypsum, and hydraulic lime) which had been used until that time. Early cements can be divided into two groups, natural and artificial (Portland) cements. Natural cements were introduced first, but their widespread usage was short-lived as they were quickly replaced by artificial cements (Portland), still the most important and predominant today. The main differences between natural and artificial cements arise during the manufacturing process. The final properties of the cements are greatly influenced by differences in the raw materials and burning temperatures employed.The aim of this paper is to assess the efficiency of traditional analytical techniques (petrographic microscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR)) used to differentiate natural and artificial cements.