The influence of water removal techniques on the composition and microstructure of hardened cement pastes

The removal of water from hardened cement paste for analysis or to arrest ongoing hydration has been reported to affect the composition of hydrated phases and microstructure. The effect that arresting the hydration of hardened cement paste by replacing the pore water with acetone before drying, and by removing the water by freeze, vacuum and oven drying has on the hardened cement paste has been investigated. Two pastes were studied, a cemented iron hydroxide floc where a high proportion of ordinary Portland cement (OPC) had been replaced by pulverised fuel ash, and a pure hydrated OPC. The results showed that none of the water removal techniques caused any major deterioration in the composition and microstructure of the hardened cement pastes studied, but the pores appeared better preserved after arresting hydration using acetone quenching. Freeze drying appeared to cause more cracking of the microstructure than the other water removal techniques.     

Cement hydration and microstructure formation in the presence of water-soluble polymers

Hardening of cement mortars modified with small amounts of water-soluble polymers implies both cement hydration and polymer film formation. In this paper, the effect of the presence of water-soluble polymers on the cement hydration reactions is investigated by means of isothermal calorimetry, thermal analysis, FT-IR spectroscopy and SEM investigation. In spite of an initial retardation of the hydration reactions, a higher degree of hydration is found after 90 days for 1% PVAA, MC and HEC modified mortars, due to a better dispersion of the cement particles in the mixing water. MC also affects the morphology of the Ca(OH)₂ crystals. Polymer bridges are detected between the layered crystals, gluing the layers together and strengthening the microstructure. Additionally, the internal cohesion of all bulk polymer modified cement pastes is improved. In the presence of the polymers, a more cohesive microstructure with a smaller amount of microcracks is created.     

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.     

Influence of a fine glass powder on cement hydration: Comparison to fly ash and modeling the degree of hydration

This paper reports the results of an investigation carried out to understand the influence of a fine glass powder on cement hydration. The pozzolanicity of the glass powder and a Class F fly ash for comparison was evaluated using strength activity index over a period of time, and a rapid electrical conductivity based method. Flame emission spectroscopy and electrical conductivity tests were used to quantify the alkali release from glass powder, and gain information on the rate of alkali release. It was found that the glass powder releases only a very small fraction of sodium ions into the solution. It was observed that the glass powder modified pastes show higher non-evaporable water contents than the plain paste and fly ash modified pastes, indicating that glass powder facilitates enhancement in cement hydration. An expression has been developed for the change in non-evaporable water content as a result of enhancement in cement hydration and the hydration of the cement replacement material. The efficiency of any cement replacement material with age in the paste system can be quantified using this parameter. Based on this parameter, a 5% cement replacement with glass powder was found to be effective at the chosen water-to-cementing materials ratio (w/cm), whereas at higher replacement levels, the dilution effect dominates. A model to predict the combined degree of hydration of cement pastes incorporating more than one cementing material is outlined. The measured and predicted combined degrees of hydration agree well.     

Interactions between shrinkage reducing admixtures (SRA) and cement paste's pore solution

Shrinkage reducing admixtures (SRA) have been developed to combat shrinkage cracking in concrete elements. While SRA has been shown to have significant benefits in reducing the magnitude of drying and autogenous shrinkage, it has been reported that SRA may cause a negative side effect as it reduces the rate of cement hydration and strength development in concrete. To examine the influence of SRA on cement hydration, this study explores the interactions between SRA and cement paste's pore solution. It is described that SRA is mainly composed of amphiphilic (i.e., surfactant) molecules that when added to an aqueous solution, accumulate at the solution-air interface and can significantly reduce the interfacial tension. However, these surfactants can also self-aggregate in the bulk solution (i.e., micellation) and this may limit the surface tension reduction capacity of SRA. In synthetic pore solutions, SRA is observed to form an oil-water-surfactant emulsion that may or may not be stable. Specifically, at concentrations above a critical threshold, the mixture of SRA and pore fluid is unstable and can separate into two distinct phases (an SRA-rich phase and an SRA-dilute phase). Further, chemical analysis of extracted pore solutions shows that addition of SRA to the mixing water depresses the dissolution of alkalis in the pore fluid. This results in a pore fluid with lower alkalinity which causes a reduction in the rate of cement hydration. This may explain why concrete containing SRA shows a delayed setting and a slower strength development.     

Changes in microstructures and physical properties of polymer-modified mortars during wet storage

The decrease in strength of tile adhesive mortars during wet storage was investigated. In a first approach, the water resistance of the polymer phases was tested on structures isolated from the mortar and in situ. It was observed that cellulose ether and polyvinyl alcohol structures are water-soluble. Subsequent investigations on polymer mobility within the mortar showed that the migrating pore water transports cellulose ether and polyvinyl alcohol during periods of water intrusion and drying. This leads to enrichments at the mortar-substrate interface. In contrast, latices interacting with the cement are water-resistant, and therefore, immobile in the mortar. Further experiments revealed that the mortar underwent considerable volume changes depending on the storage condition. Cracking occurred mainly close to the mortar-tile interface, cement hydrates grew within these shrinkage or expansion cracks. Test results revealed that the strength decrease of wet stored tile adhesives is caused by different mechanisms related to cement hydration, volume changes of the mortar, and reversible swelling of latex films.     

The effect of drying on early-age morphology of C–S–H as observed in environmental SEM

The morphology of early-age C–S–H, often referred to as outer product or low-density C–S–H, is generally accepted to be fibrillar and forms mainly during the early stages of hydration. This paper reports the effect of drying on the microstructure in young tricalcium silicate paste, which provides insight into the mechanism that leads to the fibrillar morphology. During the first few days after C₃S is mixed with water, the morphology of C–S–H is more affected by drying rate than by relative humidity. This sensitivity is most apparent at partial pressures greater than 85%. During this time, the fibrillar C–S–H product can be suppressed by drying C₃S paste samples very slowly prior to imaging. This approach is interpreted as evidence that this fibrillar morphology, which naturally form over time, grow as tiny colloidal particles that rearrange during the early stages of hydration, leading to well-established larger scale morphologies.     

X-ray absorption study of drying cement paste and mortar

X-ray absorption was used to observe water evaporation with hydration time in paste and mortar specimens, with the aim of studying the influence of water/cement (w/c) ratio, presence of aggregates, curing conditions on drying during early hydration. For the samples subjected to surface drying immediately after mixing, there exists a moisture gradient within the internal part of the specimen. However, obvious top-down drying only occurs within a small zone near the surface for early age cement pastes and mortars. The evaporation rate of water is very high in the first day after casting and is drastically reduced afterwards due to the formation of a microstructure that greatly improves specimens resistance to moisture loss. Mortars reveal a slightly lower evaporation rate since the aggregate increases the length of the transport route because of a larger tortuosity. However, the effect of sealed curing is much more important than the tortuosity effect of the aggregates.     

A remastered external standard method applied to the quantification of early OPC hydration

A promising external standard method, first described by O'Connor [15], was used to determine the quantitative phase composition of a hydrating cement paste. On the basis of the data produced we can conclude that the method used is absolutely to be recommended for the examination of OPC pastes, since it displays many advantages in comparison to internal standard methods and other methods. No reaction of the phase alite could be detected during the initial and the induction periods of the cement hydration. Additionally it was found that the cement phases involved in the aluminate reaction (bassanite, gypsum, anhydrite and C₃A) react successively. The changes detected in the phase composition of the OPC paste could be assigned to the different periods of OPC hydration.     

Insights into early hydration of Portland limestone cement from infrared spectroscopy and isothermal calorimetry

Isothermal calorimetry and diffuse reflectance infrared DR-FTIR spectroscopy are combined to correlate evolutions of spectroscopic signatures with rates of chemical reactions as reflected in the rate of heat emitted during the first 38 h of cement hydration. Portland limestone cement mortar is employed and the analysis is repeated for two different mixing procedures. Intensive blender mixing with quartz sand is found to cause activation of the cement resulting in a faster hydration process. At early stages of hydration, two types of C-S-H are formed. The spectral intensity of the earlier C-S-H is found to saturate, while that of the later form continues to acquire intensity throughout the 38 h of the experiment. Evidences are presented which support the interpretation that the two forms differ mainly in morphology and water content. Simultaneously with the saturation of the early C-S-H, a transient species is observed with DR-FTIR. This species correlates with the observed thermogram fine-structure.     

Influence of a thermal cycle at early age on the hydration of calcium sulphoaluminate cements with variable gypsum contents

Hydration of a belite calcium sulphoaluminate cement was investigated over one year as a function of its initial gypsum content (variable from 0 to 35%). Particular attention was paid to the influence of the thermal history of the material at early age on its subsequent evolution. Pastes and mortars (w/c 0.55) were either cured at 20 °C or submitted for one week to a thermal treatment simulating the temperature rise (up to 85 °C) and fall occurring in drums of cemented radwastes. The thermal cycle accelerated the early stages of hydration and mainly decreased the proportion of AFt versus AFm hydrates, especially at low initial gypsum contents (≤ 20% by weight of cement). It also strongly reduced the compressive strength of gypsum-free specimens (by 35% after one year), and doubled their expansion under water. These results were explained by mineralogical evolutions towards a more stable phase assemblage which included retarded ettringite formation.     

Early-age deformation, drying shrinkage and thermal dilation in a new type of dental restorative material based on calcium aluminate cement

Dimensional changes during the first hour of hydration for small specimens of a dental material based on calcium aluminate cement (CAC) was examined. The study was conducted on specimens prepared in two different ways. First, intact tablets (three pieces per test) dipped in water were measured. Second, compacted specimens from four tablets were measured after 10 min of hydration. The dimensional changes were studied in both wet and dry conditions at 37 °C and in a dry condition at 25 °C. In the wet environment at 37 °C no dimensional change of the samples was observed. At normal room humidity (RH 55%) at both temperatures, shrinkage of 0.35-0.40% was observed. For comparison to the early-age drying shrinkage, a study of the drying shrinkage in mature material, hydrated for 50 and 100 days, respectively, was conducted. Furthermore the thermal expansion coefficient was determined and found to be close to that of tooth substance.     

Monitoring Early Hydration of Cement by Ex Situ and In Situ ATR‐FTIR – a Comparative Study

Diffuse Reflection Fourier Transform Infrared (DR‐FTIR) spectroscopy has previously proven to provide time‐resolved insights into early cement hydration spanning ~30 s to ~36 h after completing the mixing. Here, a previously validated ex situ freeze‐dry procedure to stop hydration at preset times is complemented by an in situ Attenuated Total Reflectance (ATR) infrared spectroscopy method. The qualitative overall agreement between ex situ freeze‐drying and in situ monitoring is demonstrated. Moreover, water conversion during hydration comes out clearly in the time‐resolved ATR‐FTIR spectra. This information is absent in DR‐FTIR where buildups of crystal water and hydroxides are observed, while quenching of the hydration process requires removal of free water prior to acquiring the spectra. The ability of the IR technique to monitor the initial rate of hydration as a function of time is validated by comparing to calorimetry. The two approaches are understood to be complementary in that the former monitors alite grain surface hydration, while the latter reflects bulk hydration. IR is complementary to the calorimetry in cases of surface processes in conjunction with low enthalpy changes, that is, initial C–S–H formation and additive related surface chemistry.     

缓凝剂对水泥浆中自由水状态演变的影响

用低场核磁共振技术考察了HN-1型缓凝剂对水泥浆体中可蒸发水的横向弛豫时间(T2)及状态演变过程的影响。结果表明:在初始水化阶段的150 min内,水泥浆GR(添加缓凝剂HN-1的水泥净浆)的弛豫峰峰形和峰顶位置均无明显变化,水泥浆G(纯水泥净浆)的弛豫峰峰形变窄且峰顶位置从2.15 ms迁移至0.95 ms,说明缓凝剂HN-1主要通过改变水泥浆体中不同状态水的存留时间来改变其水化进程。随养护时间的延长,硬化水泥石W0.44和WR0.5中可挥发水弛豫峰分布范围分别从0.11~4.75 ms变为0.08~0.58 ms、0.24~4.23 ms变为0.11~2.35 ms,总体趋向于短弛豫时间,表明水泥石中毛细水逐渐向凝胶水和物理结合水转化,水泥石养护龄期延长至25 d时,其内部凝胶结构水含量超过90%。利用XRD考察了缓凝剂对水泥浆水化产物的影响,结果表明:缓凝剂只改变水泥浆水化过程,对最终水化产物晶型及晶型结构不存在任何影响。     

Microwave and conventional treatment of low-cement high-alumina castables with different water to cement ratios; Part I. Drying

The aim of this study was to determine the effect of the microwave and conventional drying method on the strength, porosity and composition of low-cement alumina castables with various water to cement ratios (wcr). High-alumina low-cement castable samples were prepared with different w/c ratios: 0.64, 0.75, 0.82 and 1.13. Changes in wcr were effected through volumetric replacement of cement with 0–0,045-mm tabular alumina having a comparable particle size. Water content in all the composition was constant (4,5%). After curing, the samples were dried conventionally in a laboratory electric drier or in a laboratory microwave drier. After drying open porosity and modulus of rupture were determined. The pore size distribution, pore median and tortuosity of the samples were measured by the mercury porosimetry method. Phase composition was determined using X-ray diffraction. The Rietveld method was used for quantitative analysis. It was found that at low wcr (0.62) the main hydrate formed in the castable was C₃AH₆, which caused a release of a smaller amount of water during the drying process, mainly pore water, resulting in lower open porosity and lower pore size than in the castables with a high wcr (1.13). At a low wcr, the strenght of castable was higher due to a higher amount of hydrates, low porosity and small pore size. On the other hand, at a high wcr, the strength of castable was lower owing to a higher amount of water released in the drying process, which led to loosening the structure of castable. With an increased water-to-cement ratio the degree of CA₂ hydration decreased. The temperature rise due to cement hydration probably influenced the kinetics of this process.     

Determining the water–cement ratio, cement content, water content and degree of hydration of hardened cement paste: Method development and validation on paste samples

We propose a new method to estimate the initial cement content, water content and free water/cement ratio (w/c) of hardened cement-based materials made with Portland cements that have unknown mixture proportions and degree of hydration. This method first quantifies the composition of the hardened cement paste, i.e. the volumetric fractions of capillary pores, hydration products and unreacted cement, using high-resolution field emission scanning electron microscopy (FE-SEM) in the backscattered electron (BSE) mode and image analysis. From the obtained data and the volumetric increase of solids during cement hydration, we compute the initial free water content and cement content, hence the free w/c ratio. The same method can also be used to calculate the degree of hydration. The proposed method has the advantage that it is quantitative and does not require comparison with calibration graphs or reference samples made with the same materials and cured to the same degree of hydration as the tested sample. This paper reports the development, assumptions and limitations of the proposed method, and preliminary results from Portland cement pastes with a range of w/c ratios (0.25–0.50) and curing ages (3–90 days). We also discuss the extension of the technique to mortars and concretes, and samples made with blended cements.     

Influence of nucleation seeding on the hydration kinetics and compressive strength of alkali activated slag paste

Addition of pure calcium silicate hydrate (C–S–H) to alkali-activated slag (AAS) paste resulted in an earlier and larger hydration rate peak measured with isothermal calorimetry and a much higher compressive strength after 1 d of curing. This is attributed to a nucleation seeding effect, as was previously established for Portland cement and tricalcium silicate pastes. The acceleration of AAS hydration by seeding indicates that the early hydration rate is controlled by nucleation and growth. For the experiments reported here, the effect of C–S–H seed on the strength development of AAS paste between 1 d and 14 d of curing depended strongly on the curing method. With sealed curing the strength continued to increase, but with underwater curing the strength decreased due to cracking. This cracking is attributed to differential stresses arising from chemical and autogenous shrinkage. Similar experiments were also performed on Portland cement paste.     

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?     

Mechanistic investigation of drying regimes during solvent removal from poly(vinyl alcohol) films

The mechanism of removal of solvents such as water and methanol from semicrystalline poly(vinyl alcohol) films was investigated using various thermal analysis techniques to obtain a mechanistic understanding of the drying process. Various drying regimes were identified, which correspond to different rate‐controlling steps, and characterized by differences in drying rates and mechanisms. The kinetics of solvent removal was measured gravimetrically using thermogravimetric analysis (TGA). The drying kinetics studies yielded four distinct drying regimes hypothesized to be due to (1) removal of free solvent, (2) elimination of bound solvent, (3) solvent removal during the rubbery‐glassy transition, and (4) drying when the polymer is in the glassy state. The amounts of free and bound water present in the polymer were measured using differential scanning calorimetry and compared with the TGA results, and they were found to verify the proposed hypothesis. The rubbery‐glassy transition observed in TGA results was confirmed using dynamic mechanical analysis. The thickness of the films was also measured as a function of drying time using thermomechanical analysis. The drying rate plots were found to be qualitatively similar to the plots of changes in film thicknesses as functions of drying time. The results of these various techniques were analyzed to propose a comprehensive mechanism of solvent removal from poly(vinyl alcohol) films. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1913–1920, 1999