Analysis of C3A hydration using soft X-rays transmission microscopy: Effect of EVA copolymer

The hydration of pure C₃A (Ca₃Al₂O₆) in calcium hydroxide-gypsum saturated solution was analyzed using soft X-ray microscopy. The images show the presence of at least two different types of ettringite crystals during the first 4 h of hydration. They differ in morphology and growing rate. When poly(ethylene-co-vinyl acetate) (EVA) is present, there is a significant change in the hydration kinetics and morphology of the hydration products. EVA particles inhibited or even prevented the formation of ettringite crystals during the early stage of hydration. A cloud of small, bright particles are observed concentrated around the hydrating C₃A grains. The particles are most likely to be a product of reaction between EVA and inorganic species in solution.     

Microstructure of tricalcium silicate and Portland cement systems at middle periods of hydration-development of Hadley grains

The development of the microstructure of C₃S paste and a Portland cement paste was studied between 7 and 24 h by means of backscattered electrons in a field-emission SEM. The course of hydration was measured by isothermal calorimetry. While the abundant occurrence of Hadley grains (hollow-shells) in Portland cement systems is well documented from a number of SEM and other microscopy studies, some earlier reports have noted that Hadley grains do not form in C₃S or alite paste alone. This report shows evidence of Hadley grains in C₃S paste, and follows their development from middle to late hydration stages. At around 10 h the microstructure with respect to Hadley grains were seen to develop in a very similar manner in C₃S and cement. In both systems, a narrow gap often developed between the receding anhydrous cores and layer of reaction product enveloping the cores. By 1 day, Hadley grains had continued to develop only in the cement paste, where they became a prominent feature. Only small ‘hollowed-out’ hydration shells were observed in the C₃S paste by 1 day. These were presumably reminiscences of the small gapped Hadley grains seen at the earlier hydration stages.     

Hydration evolution of C3S-EVA composites analyzed by soft X-ray microscopy

The effect of poly(ethylene-co-vinyl acetate) or EVA on the hydration of a pure C₃S was investigated by transmission soft X-ray microscopy in highly diluted systems. EVA particles are readily recognizable by their spherical shape and semitransparency to soft X-rays. Polymeric particles adsorb on the surface of hydrating C₃S grains, and act as nucleation agents in the development of the composite microstructure. The formation of a polymeric film was observed after a few hours of hydration. Fourier-transform infrared spectroscopy supported the conclusions that a highly soluble phase is formed as a result of EVA-hydrating C₃S chemical interactions.     

A soft X-ray microscope investigation into the effects of calcium chloride on tricalcium silicate hydration

Calcium chloride (CaCl₂) is one of the most recognized and effective accelerators of hydration, setting, and early strength development in portland cement and tricalcium silicate (C₃S) pastes. The mechanisms responsible for this acceleration, as well as the microstructural consequences, are poorly understood. Soft X-ray transmission microscopy has recently been applied to the study of cementitious materials and allows the observation of hydration in situ over time. This technique was applied to the examination of tricalcium silicates hydrating in a solution containing CaCl₂. It appears that CaCl₂ accelerates the formation of “inner product” calcium silicate hydrate (C-S-H) with a low-density microstructure.     

The influence of an ion-exchange resin on the kinetics of hydration of tricalcium silicate

The addition of a finely-ground ion-exchange resin makes it possible to modify the hydration kinetics of C₃S pastes. Analyses of the liquid phase in pastes and more dilute suspensions show that the resin exchanges calcium ions for sodium ions very rapidly during the early stage of hydration and therefore the concentration of silica in solution increases. The resin impacts the hydration of C₃S by other mechanisms which depends on the resin quantity added. For a high resin quantity, the induction period is very short, but the longer-term hydration is enhanced compared to a reference sample without resin. We hypothesize that the surface of the resin can provide sites for the nucleation and growth of C-S-H hydrates and/or portlandite far away from the surface of the C₃S grains. This consequently increases the quantity of hydrates that can precipitate before a continuous hydrate layer forms over the surfaces of C₃S particles.     

Mechanisms and parameters controlling the tricalcium aluminate reactivity in the presence of gypsum

To understand the mechanisms and the parameters controlling the reactivity of tricalcium aluminate in the presence of gypsum at an early age, a study of the hydration of the “C₃A-sulphate” system by isothermal microcalorimetry, conductimetry and a monitoring of the ionic concentrations of diluted system suspensions have been carried out with various gypsum quantities. The role of C₃A source and its fineness were also studied. This work shows the fast initial formation of AFm phase followed by ettringite formation during the period when the sulphate is consumed. It has been highlighted that the time necessary to consume all the gypsum varies with the type of C₃A and it has been attributed to the intrinsic reactivity of each one and mainly to the change of fineness from one C₃A to another. Results are discussed alongside hypothesis from the literature to explain the slowing down of C₃A hydration process in the presence of calcium sulphate.     

Early C3A hydration in the presence of different kinds of calcium sulfate

Hydration reactions of C₃A with various amounts of calcium sulfate hemihydrate, gypsum or a mixture of the two, were investigated by isothermal microcalorimetry, and a monitoring of the ionic concentrations of diluted suspensions. This study shows that sulfate type used modifies the early C₃A–CaSO₄ hydration products and the rate of this hydration. The fast initial AFm formation observed before ettringite precipitation in the C₃A–gypsum system is avoided as soon as hemihydrate is present in the suspension. This was attributed to higher super saturation degrees and then higher nucleation frequency with regard to the ettringite obtained in the presence of hemihydrate. Moreover, replacement of gypsum by hemihydrate also leads to an increase of the ettringite formation rate during at least the five first hours under experimental conditions.     

Structural and hydration properties of amorphous tricalcium silicate

Mechanical milling was carried out to synthesize amorphous tricalcium silicate (Ca₃SiO₅) sample, where Ca₃SiO₅ is the most principal component of Portland cement. The partial phase transformation from the crystalline to the amorphous state was observed by X-ray and neutron diffractions. Moreover, it was found that the structural distortion on the Ca-O correlation exists in the milled Ca₃SiO₅. The hydration of the milled Ca₃SiO₅ with D₂O proceeds as follows: the formation of hydration products such as Ca(OD)₂ rapidly occurs in the early hydration stage, and then proceeds slowly after about 15 h. The induction time for the hydration of the milled Ca₃SiO₅ is approximately one half shorter than that for the hydration of the unmilled one. This result means that the mechanical milling brings about the chemical activity of Ca₃SiO₅ for hydration, and may be particularly useful for increasing the reactivity in the early hydration stage.     

Early age hydration of rice hull ash cement examined by transmission soft X-ray microscopy

Early age hydration of barium-doped β-Ca₂SiO₄ cement, produced from rice hull ash (RHA), is examined by transmission soft X-ray microscopy. Use of low-energy cements produced from by-product materials, such as the cement considered here, may be economically and environmentally advantageous. However, the hydration kinetics and morphology and composition of the products of RHA-based β-Ca₂SiO₄ cements have not been investigated. Observation of the early age cement hydration shows evidence of cement dissolution and hydration product formation, including the formation of Hadley grains. The rates of the reaction and amount product formed appear to be related to the hydrothermal processing temperature and the chemical composition of the cement. That is, more rapid hydration is observed for barium-doped RHA cements produced at higher temperatures and for cements produced with higher barium contents, within the ranges examined.     

Effect of CuO on the formation of clinker minerals and the hydration properties

The purposes of this study are to explore the mechanisms of Cu element in clinker burning and hydration processes and to make effective use of waste containing copper in cement production. The effect of CuO on clinker mineral composition, C₃S polymorph and size, Cu element distribution and state, compressive strengths, hydration products, non-evaporable water quantity and hydration heat release rate was analyzed by XRD, SEM, DTA, isothermal heat-conduction calorimetry, etc. Results show that as the amount of CuO increases the formation and growth of C₃S grain are accelerated, R C₃S is gradually transformed into M₃ and the content of C₄AF increases; a small quantity of CuO increases the 3-day and 28-day strengths and the hydration degree of clinker, but excessive CuO has adverse effects. Those effects of CuO on clinker burning process are attributed to the formation of low-melting Cu₂O and the dissolution of CuO in C₄AF which decrease the formation temperature of liquid phase and increase its quantity. The effects on hydration process result from the combined action of the following factors: the induction period is prolonged; the hydration reactions in the initial and acceleration periods are accelerated.     

Role of delayed release of sulphates from clinker in DEF

Two clinkers rich in sulphate burned in the pilot plant rotary kiln and cements prepared from them were investigated. Clinker richer in sulphate (SO₃=3.6%) contained independent anhydrite grains as well as inclusions of anhydrite in belite. The mortar from it expanded after heat treatment at 90 °C and the addition of Na₂SO₄ or NaOH accelerated and increased this expansion. The expansion occurred irrespective of the fact that the clinker contained only 3% of C₃A, although the C₄AF content was 13%. The second clinker with 2.6% SO₃ contained mainly calcium langbeinite and expanded only when 2% of Na₂SO₄ was added. The SEM examination of the mortars revealed the presence of numerous bands of massive ettringite around sand grains. Agglomerates of cracked ettringite in cement gel were also present. In addition, microcracks were seen inside the darker C-S-H gel. The conclusion is that anhydrite forming inclusions in belite gives an expanding mortar after heat treatment at 90 °C independently of the tricalcium aluminate content. Such clinkers are not typical of industrial conditions. The expansion is caused by the bands of massive ettringite as well as its agglomerates present in the cement gel and nanometric ettringite in the C-S-H phase.     

Anomalous fluorescence in near-infrared Raman spectroscopy of cementitious materials

The results of near-infrared Fourier transform Raman spectral examination of cement minerals, several commercial Portland cements, and hydrating Portland cements are critically examined. It is shown that structured fluorescent effects dominate the observed spectra for C₃S, C₂S, and cement, and none of the bands generated by this mode of examination is a true Raman band. The apparent bands for the Portland cements are in different positions to those for the individual cement minerals. The fluorescence-derived spectra for different cements are similar to each other but vary enormously in intensity for different cements. Hydration progressively reduces the intensity of the bands, but does not generate bands at new locations. It is tentatively suggested that the fluorescence effect may be somehow associated with the status of the cement components as orthosilicates (i.e., composed of isolated silica tetrahedra. Samples of high-purity C₂S exhibit the fluorescence effect, but samples of CS (wollastonite) of similar purity do not. The latter are metasilicates (i.e., composed of linked chains of silica tetrahedra). They exhibit normal Raman Stokes and anti-Stokes bands.     

Effect of polymer latexes with cleaned serum on the phase development of hydrating cement pastes

The effects of polymer latexes on cement hydration were investigated by the combination of isothermal calorimetry, in-situ XRD and Cryo-SEM. Two model latexes with varied amounts of anionic charges were used for measurements after cleaned by dialysis to remove the serum components. This study confirms that in-situ XRD technique can be successfully adapted to hydrating cementitious systems in the presences of polymer latexes to quantitatively follow evolution of mineral phases involved in cement hydration. Results show that both polymers retard aluminate reaction and depress silicate reaction, by delaying the dissolution of C₃A, anhydrite and gypsum and consequently the formation of ettringite, and reducing the dissolution of C₃S and the formation of C-S-H. The anionic colloidal polymers exhibit more pronounced retardation effect on aluminate reaction than on silicate reaction due to stronger electrostatic interaction between the polymer particles and the positively charged aluminate phases. The more charged latex shows stronger retardation.     

Crystal structure refinement and hydration behaviour of doped tricalcium aluminate

In this paper analytical evidence on crystal structure and hydration behaviour of C₃A solid solutions with MgO, SiO₂, Fe₂O₃, Na₂O and K₂O is given. Samples were prepared using an innovative sol-gel process as precursor, examined by X-ray powder diffraction, infra-red spectroscopy and the crystal structure was refined by the Rietveld method. A significant shift of lattice parameters was found for C₃A solid solutions with SiO₂, Fe₂O₃ or Na₂O but only minor changes were detected for K₂O. The hydration of C₃A solid solutions in the absence of CaSO₄ was accelerated for samples doped with SiO₂ or K₂O and it was retarded in the case of MgO, Fe₂O₃ or Na₂O. The hydration in the presence of CaSO₄ was accelerated when C₃A was doped with K₂O or Na₂O, whereas Fe₂O₃ strongly retarded the hydration. The doping with SiO₂ nearly had no influence on the hydration, the effect of MgO was not straight forward.     

Tricalcium silicate (C3S) hydration under high pressure at ambient and high temperature (200 °C)

The hydration of a tricalcium silicate paste at ambient temperature and at 200 °C under high pressure (up to 1000 bar) has been studied. Two high pressure cells have been used, one allows in-situ electrical conductivity measurements during hydration under high pressure. The hydration products were characterized by thermal analysis, X-ray diffraction and ²⁹Si NMR measurements. The pressure has a large kinetic effect on the hydration of a C₃S paste at room temperature. The pressure was seen to affect drastically the hydration of a C₃S paste at 200 °C and this study evidences the competition between the different high temperature phases during the hydration.     

Time to failure for concrete exposed to severe sulfate attack

In the 1940s, the U.S. Bureau of Reclamation (USBR) began a long-term, nonaccelerated laboratory test program to determine the influence of a variety of concrete-mix parameters on resistance to severe sulfate exposure conditions. This paper reports the time of failure of these samples as influenced by their water-to-cement (w/c) ratio, cement composition, and percent replacement of cement with fly ash. The analysis indicates that there is a “safe zone” for concrete made with w/c ratio lower than 0.45 and cement with unhydrated tricalcium aluminate (C₃A) content lower than 8% where failure did not occur within the 40-year exposure period. As expected, concrete samples cast with high amount of C₃A failed after a relatively short time of sulfate exposure. Expansion tests indicated that cements containing high amounts of C₃S may lead to premature failure of concrete, even when moderate w/c ratios are used. Samples prepared with 25% and 45% replacement of cement with fly ash showed significantly less expansion than comparable mixtures containing no pozzolans.     

Alkaline Hydration Of C2S and C3S

This study analyzed the behavior of two laboratory‐synthesized calcium silicates, C₃S and C₂S, after hydration in 8‐M NaOH and in water as a control. Two‐ and 28‐d mechanical strength values were determined and the products were characterized with XRD, TEM, and ²⁹Si and ²³Na MAS NMR. The results showed that hydrating C₃S in a highly alkaline medium had no significant effect on the mechanical development of the material, whereas in C₂S hydration, that medium hastened hydration substantially, impacting setting and hardening times. This finding has technological implications, given the low early‐age reactivity of dicalcium silicate under normal hydration conditions.     

The superstructure of C3S from synchrotron and neutron powder diffraction and its role in quantitative phase analyses

We have synthesised the room temperature MIII form of alite stabilised by doping with Mg and Al. The complex disordered superstructure of this tricalcium silicate [Ca₃SiO₅ (C₃S)] sample has been studied by a joint Rietveld refinement of ultra-high-resolution synchrotron X-ray powder diffraction data, medium-resolution neutron powder diffraction data and soft constraints of interatomic distances. Alite crystallises in a monoclinic cell with dimensions a=33.1078(6) Å, b=7.0355(1) Å, c=18.5211(4) Å, β=94.137(1)° and V=4302.9(2) ų. The final R factors were R_WP=8.76% and R_F(C₃S)=3.45% for the synchrotron data and R_WP=6.09% and R_F(C₃S)=5.10% for the neutron data. The reported superstructure is simpler than those previously reported, and it fits properly to a variety of Portland clinker and cement patterns. The Rietveld analyses of four clinkers with variable Mg contents have shown that the refinements are good. The Bogue approach gave quite poor results when compared to these state-of-the-art powder diffraction analyses. Bogue method slightly underestimates the C₃S+C₂S content, overestimates the C₃A fraction and underestimates the C₄AF content. Similar analyses of Portland cements with nine crystalline phases are shown to be feasible.     

Phase separation induced by hydration of the mixed Ca/Sr aluminates Ca3−xSrxAl2O6: A crystallographic study

The compounds formed by the hydration of single-phase samples of the mixed, solid solution, Ca/Sr aluminates, Ca_3−xSr_xAl₂O₆, 3≤x≤0 have been studied using high-resolution synchrotron powder diffraction. Hydration of these mixed metal aluminates generally resulted in the formation of at least two hydrogarnet phases, one Ca-rich and the other Sr-rich. The structures of these hydrogarnets have been refined from neutron or synchrotron powder X-ray diffraction (XRD) data. A simple solubility model to explain the phase separation is presented.     

Morphology and microstructure of hydrating portland cement and its constituents III. Changes in the hydration of a mixture of C3S,C3A and gypsum with and without triethanolamine and calcium lignosulphonate present

Systematic sequential observations with the electron microscope were made of the morphological changes which occurred during the hydration of a paste mixture of C₃S, C₃A and gypsum. It was found that this system produced hydration products similar in nature to those produced by the monomineral systems with gypsum present. The two organic admixtures studied had some effect on changes in morphology and microstructure of the hydrating mixture, but they showed a pronounced influence on the rate of the hydration processes.