Microstructure and microanalysis of hardened cement pastes involving ground granulated blast-furnace slag

The microstructure and composition of hardened cement pastes of a wide range of blends of ground granulated blast-furnace slag with ordinary Portland cement have been studied, using techniques of transmission electron microscopy with microanalysis combined with electron microprobe analysis. Throughout the range, a calcium silicate hydrate gel (C-S-H) is the dominant cementing phase, present in the inner product within the space originally occupied by either slag grains or alite or belite grains originating from the Portland cement, or in the outer product in the originally water-filled spaces. The morphology and composition of the outer product C-S-H and the composition of inner product C-S-H change with blend composition. Inner product of slag grains contains C-S-H of the same composition as the outer product C-S-H, intimately mixed with a Mg, Al-rich hydroxide phase whose fineness shows considerable variation. Inner product C-S-H of alite or belite does not differ significantly in CaSi ratio from that of slag. The reduction of CaSi ratio of all forms of C-S-H with increasing slag loading may have implications for the pH-buffering capacity of blends of large slag loading.     

Micromachining of hardened Portland cement pastes using femtosecond laser pulses

Femtosecond laser pulses (30 fs in length) of various energies were utilised for production of single and multiple overlapping ablation sites on flat polished surfaces of hardened Portland cement pastes. In order to assess the sizes of the ablation sites and possible subsurface laser-induced damage, the ablation sites were investigated using environmental scanning electron microscopy (ESEM) – both from normal top–down view and in cross-sections. Furthermore, approximately 10-μm wide notches were produced using femtosecond pulses on cylindrical microspecimens (150 μm in diameter) of hardened Portland cement pastes. In addition to electron microscopy observations, several microspecimens were investigated using synchrotron-based X-ray computed microtomography (SRμCT). The results suggest that production of “damage-free” samples for micromechanical testing of hardened Portland cements pastes is possible.

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Résumé Des impulsions laser (de durée 30 fs) et d’énergie variable ont été utilisées pour produire une ablation ponctuelle ou linéique à la surface d’un ciment durci de type Portland et préalablement polie. Pour déterminer la taille des impacts et d’éventuels dommages causés par le laser sous la surface, les points d’impact ont été visualisés à l’aide de la technique de l’ESEM (microscope électronique à balayage environnemental). De plus, des piliers de 10 micromètres de diamètre environ ont été réalisés par ablation femtoseconde sur des échantillons cylindriques de 150 microns de diamètre. Pour compléter les observations faites au microscope électronique, certains échantillons ont été observés grace à la technique SRμCT (synchrotron-based X-ray computed microtomography). Les résultats montrent que la production d’échantillons non-endommagés de ciment de type Portland pour des tests micro-mécaniques ultérieurs est possible.

     

A conduction calorimetric study of early hydration of ordinary Portland cement/high alumina cement pastes

Conduction calorimetry was applied to an investigation of the early hydration of ordinary Portland cement (OPC)/high alumina cement (HAC) pastes. Three different rate of heat-evolution profiles were observed, depending on the HAC/OPC ratio. Relevant processes affecting heat development include ettringite formation, HAC and OPC hydration. Results from SEM examination and X-ray diffraction studies are also presented. An acceleration of OPC hydration was observed in pastes containing less than 12.5% HAC. A similar acceleration effect on HAC hydration was also obtained with the addition of OPC. A large amount of ettringite was formed and OPC hydration delayed in the pastes containing 15%–30% HAC. The latter could be one of the factors attributed to poor strength development in these HAC/OPC systems. Early hydration mechanisms of OPC/HAC systems are also discussed. This revised version was published online in November 2006 with corrections to the Cover Date.     

Silicate anion analysis in Portland cement pastes

Abstract

The analysis of silicate anions present in Portland cement using the trimethylsilylation technique, using modifications to the original methods described by Lentz and Tamas, have provided contrasting results. The Lentz method yields a large proportion of high molecular weight polyorganosiloxane derivatives of cyclic and straight silicate anion species. The Tamas method indicates the presence of initially straight chain and later cyclic anions that condense on prolonged hydration to form multicyclic species based on a cyclic octamer. The polyorganosiloxanes were separated and identified using conventional chromatography methods and anisotropic solvent induced shift ¹H nuclear magnetic resonance. The susceptibility of the Lentz method to side reactions and the superiority of the modified Tamas method in reducing these reactions were demonstrated.

MST/691     

Kinetics of oxygen diffusion in hardened cement pastes

An electrochemical cell has been devised for measurement of the effective diffusivity of oxygen in water-saturated hardened cement pastes. The technique has been applied to investigate oxygen diffusion kinetics over the temperature range 15 to 35° C for Portland cement pastes of constant mineralogy but variable water-cement ratio. The values obtained for effective diffusivity and activation energy have been compared with previously published kinetic data for ionic diffusion in similar materials. Implications regarding the electrochemical behaviour of steel embedded in water-saturated cement matrices have also been examined with particular reference to prediction of limiting conditions of oxygen supply governing the transition from a state of passivity, characterized by a stable film of Fe₂O₃, to one of general dissolution, associated with a stable alkali-soluble species, Fe(OH)₃ ^–.     

Electrochemical behavior of Portland cement pastes containing phosphonates

An impedance measurement technique was used to investigate the effects of aminotri(methylenephosphonic acid) (ATMP), 1-hydroxyethylidene-1, 1-diphosphonic acid (HEDP), and diethylenetriaminepenta (methylenephosphonic acid) (DTPMP) on the hydration process and setting behavior of portland cement pastes. It was demonstrated that the impedance and capacitive responses can be used to characterize setting behavior and microstructural development of the hydrating pastes containing these chemical admixtures.The presence of a long induction period of up to 20 and more than 75 hours is revealed by the impedance curves of pastes containing ATMP, HEDP, and DTPMP at dosages of 0.05% and 0.2%, respectively. This confirms that phosphonates are efficient retarders. These compounds appear to have strong chelating or complexing capability, potentially poisoning CH and C-S-H nucleation. Stabilization of the C-S-H (metastable) film on the surface of cement grains appears to cause retarding effect.     

Influence of nano-SiO2 on the Portland cement pastes

The evolution of nanotechnology provides materials with new properties and over the last years a lot of effort has been put to introduce nano-particles into cement pastes in order to improve their properties and to produce materials of better performance. In the present research work, nano-SiO₂ produced by pyrolysis and with specific area of 200 m²/g has been added at different percentages (0%, 0.5%, 1%, 2% and 5%) to high-strength cement pastes. These pastes were tested for their mechanical and structural properties at different ages. Nanoparticles act as nuclei for crystallization and large, idiomorphic crystals of Ca–Si composition were formed assisting, up to a certain percentage, in producing materials with dense structure, reduced porosity and improved strength.     

Analytical and experimental study on thermal conductivity of hardened cement pastes

Thermal conductivity of hardened cement pastes (hcps) in a wide range of water–cement ratio (w/c) is quantitatively investigated using a transient plane source measurement technique. Alkyl alkoxysilane and rapeseed oil were also added to determine the effect of internal hydrophobation on thermal conductivity of solid structure of hcps. The measurements were performed after drying at 50 and 105 °C as well as water submersion. A nonlinear relation was observed between thermal conductivity and w/c which is in alignment with Powers’ model. Samples dried at 50 °C still contained some moisture which increased thermal conductivity up to 11 % compared to samples dried at 105 °C. Furthermore, hydrophobic agents reduced thermal conductivity of dried samples up to 9 % which indicates the reduction in thermal conductivity of solid structure and is in line with observations by scanning electron microscope. A three phase model which can predict thermal conductivity of plain and hydrophobed hcps at different moisture states is presented by exploiting composite models and Hashin–Shtrikman bounds.     

Early age and hardened performance of cement pastes combining mineral additions

To asses the influence of mineral additions (MA) at early age and on hardened performance of fluid cement based pastes, an experimental program was carried out. The design of the mixtures correspond to paste compositions used in self compacting concretes of moderated strength, as those employed for architectural applications. Two types of fillers (limestone and quartzite) have been used to substitute 50 % of cement in a reference paste, with and without a high range water reducing admixture. Then, three active MA (microsilica, nanosilica and metakaolin) were combined. A physical and mechanical characterization in the hardened state showed that the inclusion of MA to a cement-filler mixture can moderately improve the hardened performance of the pastes. Air and water cured samples were tested in order to evaluate the influence of curing conditions. At early ages (24 h), in situ temperature and ultrasonic pulse velocity were monitored on samples with limestone filler, combined with the three active MA, to study the reaction process and microstructure development, respectively. The reaction degree of the samples under study during the first 24 h was related to the microstructure development. Evaporation, drying shrinkage and cracking at early age were also monitored, considering an air flow of 3 m/s on the exposed sample surface. Some relations were described linking cracking risks at early ages with the chemical and physical phenomena involved at early age microstructure evolution.     

The structure of the calcium silicate hydrate phases present in hardened pastes of white Portland cement/blast-furnace slag blends

The C-S-H gels present in both water- and alkali-activated hardened pastes of white Portland cement/blast-furnace slag blends have been studied by solid-state ²⁹Si magic angle spinning nuclear magnetic resonance (NMR) spectroscopy and analytical transmission electron microscopy (TEM). Structural data are obtained by NMR for the semi-crystalline C-S-H gels in the alkali-activated systems and extended to the nearly amorphous gels in the water-activated systems by peak broadening; unambiguous chemical analyses are determined in the TEM. The following conclusions apply to both the semi-crystalline and nearly amorphous C-S-H gels: (1) aluminium substitutes for silicon at tetrahedral sites; (2) aluminium only substitutes for silicon in the central tetrahedron of pentameric silicate chains; (3) the results strengthen confidence in dreierkette-based models for the structure of C-S-H. Compositional similarities suggest that these conclusions will be true for OPC/slag blends, and possibly also for OPC/pulverized fuel ash blends indicating that the same structural model applies to C-S-H gels in a wide range of hardened cement pastes. This revised version was published online in November 2006 with corrections to the Cover Date.     

The nature of the hydration products in hardened cement pastes

An understanding of the performance of portland cement-based materials requires knowledge at the microstructural level. Developments in the instrumentation of several techniques have led to improved understanding of the composition, morphology, and spatial distribution of the various products of cement hydration. In particular, our understanding of the nature of the nearly amorphous calcium silicate hydrate (C–S–H) phases – which are the principal binding phases in all portland cement-based systems – has been advanced by developments in solid-state NMR spectroscopy and analytical TEM. This paper presents an overview of the nature of the hydration products formed in hardened portland cement-based systems. It starts with the most straightforward cementitious calcium silicate systems, C₃S and β-C₂S, and then considers ordinary portland cement and blends of portland cement with silica fume, ground granulated iron blast-furnace slag, and finally alkali hydroxide-activated slag cements.     

An assesment of porosity and pore sizes in hardened cement pastes

The porosity of hardened cement paste was analysed using fluid displacement methods, optical, scanning and transmission electron microscopy and mercury intrusion porosimetry. Attention has been drawn to the problems of mercury porosimetry and in particular to the extent of the pore volume which is missed by mercury. Previous workers have assigned the lost porosity to pore sizes too fine to be seen by mercury but this paper considers the contribution of closed pores. Nitrogen and water adsorption studies have been carried out on the pastes to determine qualitatively the magnitude of the pore volume beyond the range of mercury porosimetry. This volume was found to be very small. Emphasis has been placed upon the importance of large spherical pores, which may be missed by mercury porosimetry and adsorption studies, in determining the strength of cement pastes.     

Ultrasonic measurements during early-stage hydration of ordinary Portland cement

The variations of ultrasonic pulse velocity, peak amplitude of transmitted pulse and heat evolution rate were measured during the hydration process of ordinary Portland cement with water/cement ratio (W/C ratio) ranging from 0.4 to 0.6 at environmental temperatures between 20 and 40° C. The change of heat evolution rate reflected the kinetics of hydration and was sensitively affected by the W/C ratio and environmental temperature. The velocity and peak amplitude were compared with the heat evolution rate to investigate the correlation of elastic properties and structural development with the kinetics of hydration. The dependence of the velocity and the peak amplitude on W/C ratio and environmental temperature are discussed in terms of the concentration of solid phase in the cement paste varying with W/C ratio and the extent of hydration.     

The solid state chemistry of metakaolin-blended ordinary Portland cement

The hydration of ordinary Portland cement (OPC) pastes containing 0 and 20% metakaolin was monitored by differential thermal analysis (DTA) and solid state magic angle spinning nuclear magnetic resonance spectroscopy (MAS NMR). The presence of hydrated gehlenite and a relative reduction in calcium hydroxide content of the metakaolin-blended OPC pastes observed by DTA are indicative of the pozzolanic reaction of metakaolin. An increase in the capacity of metakaolin-blended OPC pastes to exclude chloride ions from the pore electrolyte phase, via solid phase binding, has been reported. It is proposed that this increase in chloride binding capacity could be attributed to the participation of calcium aluminate species in the formation of Friedel's salt which would otherwise be engaged in the formation of hydrated gehlenite and other AFm phases. The accelerating effect of replacement additions of metakaolin has been shown by ²⁹Si NMR and was denoted by a comparative increase in the intensity of resonances arising from Q¹ and Q² species compared with that of Q⁰ species for metakaolin-blended specimens. The primary reactive centres of the pozzolan have been shown to be the 5-coordinate aluminium and amorphous silica. The spreading of the Q⁴ resonance of the amorphous silica of metakaolin through the Q³ and into the Q² and Q¹ regions of the NMR spectrum during pozzolanic reaction has been observed.     

Properties and interaction of cement with polymer in the hardened cement pastes added absorbent polymer

Ordinary Portland cement mixed with various amounts of absorbent polymer in the form of sodium acrylate ((–CH–)_nCOONa) have been studied. As the content of absorbent polymer increased, heat evolution of samples decreased up to 1.15 wt % of absorbent polymer addition and conversely increased over 1.75 wt %. Flexural strength of cement paste with absorbent polymer was improved more than 20%. As the content of absorbent polymer increased, the porosity values decreased and mean pore diameter shifted to small pore diameter region. Flexural strength of ordinary Portland cement paste had a linear correlation with non-evaporable water content but, that of cement paste with absorbent polymer deviated from a linear correlation with non-evaporable water content. The chemical difference between cement pastes with and without absorbent polymer was found by the inductively coupled plasma-atomic emission spectroscopy and the infrared spectroscopy. For the infrared spectra of absorbent polymer, bands at 1416 and 1560 cm^{– 1} were assigned to C–O single bond and C=O double bond respectively, namely, unidentate complex. As the curing time increased, the absorption bands near 1416 cm^{– 1} shifted to longer wave number and the absorption bands near 1560 cm^{– 1} to shorter wave number and finally bidentate complex was formed. Absorbent polymer released sodium ions to pore solution under the basic condition of pH 12.5–13.5 and became polyacrylic acid. Then some of these polyacrylic acid were crosslinked with others by calcium ions leached from cement grains. Calcium ion was regarded as a central charge connecting the negative parts in carbon-oxygen polarization of absorbent polymer' functional groups.     

硬化水泥浆体弹性模量细观力学模型

应用复合材料力学理论和有孔介质力学(Poromechanics)理论建立了一个描述硬化硅酸盐水泥浆体弹性模量的细观力学模型, 将硬化水泥浆体从不同尺度上划分为4个层次, 即C-S-H凝胶、 水泥水化产物、 水泥浆体骨架和水泥浆体, 分别应用不同的细观力学模型予以描述: 将C-S-H视为饱和的有孔介质; 应用Mori-Tanaka模型描述水泥水化产物的弹性性质; 应用三相模型(Three-phase model)模拟水泥浆体骨架的有效弹性模量; 最后, 再次应用Mori-Tanaka模型和有孔介质理论, 计算水泥浆体的排水和不排水弹性模量(Drained and undrained elastic moduli)。该模型所需要的参数为水泥浆体各个组成部分的自身弹性性质, 使用方便。通过预测文献中的实测结果, 证明了该模型的有效性。      

Electrical effects generated by mechanical loading of hardened Portland cement paste

This work presents results on the effect of applied load on the electrical properties (resistivity and capacitance) of hardened cement paste. Impedance spectroscopy measurements in the high frequency region (100 kHz–15 MHz) show two time constants, one associated to the solid phase, and the other to the liquid filling the pores. The time constant associated with the liquid phase is sensitive to external loads acting on the specimen. The observed variations are explained in terms of electrolyte drag from interlaminar spaces and structure pores and vice versa. The importance of those electrolyte movements concerning structure fatigue and rebars corrosion is also discussed.