Dielectric spectra of fresh cement paste below freezing point using an insulated electrode

The spectra of complex dielectric constant were measured on a fresh cement paste with a water/cement ratio of 0.4 sandwiched between insulated electrodes in the frequency range 10 kHz–1 MHz and temperature range between 0 °C and — 30 °C. The bulk dielectric constant, 30–20, and conductivity, 6.14×10^–5–0.65×10^–5, in the temperature range –10 to –28 °C were much lower than those at room temperature, owing to the great decrease of ionic mobility caused by freezing the cement paste. The activation energy of 0.31 eV for the ionic conduction in fresh cement paste was obtained from an Arrhenius plot of conductivity at subzero temperature.     

Interpretation of the impedance spectroscopy of cement paste via computer modelling

The d.c. conductivity, , and low-frequency relative dielectric constant, k, of Portland cement paste were monitored, using impedance spectroscopy, during cooling from room temperature down to -50 °C. Dramatic decreases in the values of and k, as great as two orders of magnitude, occurred at the initial freezing point of the aqueous phase in the macropores and larger capillary pores. This result provides strong experimental support for the dielectric amplification mechanism, proposed in Part II of this series, to explain the high measured low-frequency relative dielectric constant of hydrating Portland cement paste. Only gradual changes in the electrical properties were observed below this sudden drop, as the temperature continued to decrease. The values of and k of frozen cement paste, at a constant temperature of -40 °C, were dominated by properties of calcium-silicate-hydrate (C-S-H) and so increased with the degree of hydration of the paste, indicating a C-S-H gel percolation threshold at a volume fraction of approximately 15%–20%, in good agreement with previous predictions. Good agreement was found between experimental results and digital-image-based model computations of at -40 °C. Freeze-thaw cycling caused a drop in the dielectric constant of paste in the unfrozen state, indicating that measurements of k could be useful for monitoring microstructural changes during freeze-thaw cycling and other processes that gradually damage parts of the cement paste microstructure.     

Drying/hydration in cement pastes during curing

As concrete cures in the field, there is a constant competition for the mixing water between evaporation and hydration processes. Understanding the mechanisms of water movement in the drying/hydrating cement paste is critical for designing curing systems and specialized rendering materials, as well as for selecting repair materials and methodologies. In this work, X-ray absorption measurements indicate that fresh cement paste dries uniformly throughout its thickness, as opposed to exhibiting the sharp drying front observed for most porous materials. Furthermore, in layered composite cement paste specimens, water always flows from the coarser-pore layer to the finer one, both when coarser pores are produced by using an increased water-to-cement ratio (w/c) and when they are present due to using a cement with a coarser particle size distribution at a constant w/c. Conversely, no clear differential water movement is observed between layers of cement paste and mortar of the same nominal w/c. Based on the results of these experiments, drying has been introduced into the NIST CEMHYD3D cement hydration and microstructure development model, by emptying the largest water-filled pores present at any depth in the model specimen at a user-specified (drying) rate. With this addition, the CEMHYD3D model produces results in good agreement with experimental observations of both the drying profiles and the hydration kinetics of thin cement paste specimens.     

Influence of curing at different relative humidities upon compound reactions and porosity in Portland cement paste

The reduction in relative humidity within drying concrete depends mainly on the depth from the exposed surface, exposure duration, temperature and environmental humidity; this limits hydration and coarsens pore structure, thus impairing durability. OPC paste, of 0.59 water/cement ratio, was cured for 2 days and then exposed to controlled relative humidity environments. After 14 and 90 days exposure, hydration of the individual compounds was measured using quantitative X-ray diffraction and thermogravimetry. Methanol adsorption was used to monitor porosity and gel formation. Even a small drop in relative humidity below 95% r.h. significantly limited cement hydration. Gel porosity increased with amount of hydration and, for a given level of hydration, decreased with drying. Curing below 80% r.h. produced a coarsened pore structure with a large-diameter porosity three times greater than that obtained with saturated curing.     

Numerical simulation of the hydration process and the development of microstructure of self-compacting cement paste containing limestone as filler

This paper presents a numerical model for the simulation of the hydration process and the development of the microstructure on Self-compacting cement paste (SCC) containing limestone powder as filler. Based on a series of experimental results, e.g. thermometric isothermal conduction calorimetry tests, environmental scanning electron microscopy (ESEM) image analysis, thermogravimetric analysis (TGA) and the derivative thermogravimetric analysis (DTG) measurements, the hydration process, the solid phase distribution, total porosity and pore size distribution have been determined at different hydration stages. Based on the hydration chemistry, the stoichiometry and the hydration kinetics of cement with limestone, an analytical hydration model and a microstructural model of self-compacting cement paste are proposed. Two SCC mixtures with w/c 0.41 and w/c 0.48, both with water/powder ratio (w/p) 0.27, were simulated and compared to a traditional cement paste (TC) with w/c 0.48. The simulation results were discussed and validated against experimental measurements.     

Microwave compressive strength estimation of cement paste using monopole probes

In-situ evaluation of the compressive strength of existing concrete structures using a direct approach is the objective of this investigation. The principle factor affecting the compressive strength of a concrete structure is its water/cement (w/c) ratio. The reflection properties of four cement paste samples with w/c ratios of 0.35, 0.40, 0.50, and 0.55 were measured using several monopole probes at microwave frequencies of 5, 9, and 12 GHz. The effect of several parameters, such as the operating frequency, the probe length (h), and the properties of the cement paste (w/c ratio) on the measurement sensitivity, were studied theoretically as well. For a given monopole probe (fixed diameter),h and the operating frequency can be optimized such that any slight change in the w/c ratio causes a large change in the reflection coefficient. Lower microwave frequencies are shown to be more sensitive in detecting variation in the reflection coefficient of these samples as a function of the w/c ratio. After the reflection coefficient measurements for these samples were conducted, they were tested to measure their compressive strength. Subsequently, a correlation between the compressive strength and the reflection coefficient of these samples was shown. The effect of an air gap around the monopole was investigated as well.     

Interpretation of the impedance spectroscopy of cement paste via computer modelling

Dielectric properties of cement pastes are measured using impedance spectroscopy, and the effective dielectric constants of the low frequency bulk arcs are reported. The unusually high values thereby obtained, and their dependence on reaction time and water:cement ratio, are explained by the presence of microstructural features that serve to amplify the dielectric constants of the individual material phases. The dielectric properties of three-dimensional cement paste models and of simple two-dimensional models of the hypothesized microstructural features are analysed. The model results provide insight into the proposed dielectric amplification mechanism in real cement paste.     

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.     

Pore structure of hardened cement paste and mortar

The paper describes an experimental investigation into the pore structure of hardened cement paste and mortar. The pore structure was studied using mercury porosimeter. Ordinary portland cement and natural river sand were used. Pore structure determination was carried out for both the cement paste and mortar mixes over four hydration periods and five water-cement ratios. The threshold radius which was found to be prominent in the hardened cement paste, flattens out as the fine aggregate content increased.     

Modeling the elastic properties of concrete composites: Experiment,differential effective medium theory,and numerical simulation

Concrete is a mixture of cement, water and aggregates. In terms of microstructure, besides the cement paste matrix and aggregate inclusions, there is a third phase, which is called the interfacial transition zone (ITZ), which forms due to the wall effect and can be thought of as a thin shell that randomly forms around each aggregate. Thus, concrete can be viewed as a bulk paste matrix containing composite inclusions. To compute the elastic properties of a concrete composite, a differential effective medium theory (D-EMT) is used in this study by assigning elastic moduli to corresponding bulk paste matrix, ITZ and aggregate. In this special D-EMT, each aggregate particle, surrounded by a shell of ITZ of uniform thickness and properties, is mapped onto an effective particle with uniform elastic moduli. The resulting simpler composite, with a bulk paste matrix, is then treated by the usual D-EMT. This study shows that to assure the accuracy of the D-EMT calculation, it is important to consider the increase in the water:cement mass ratio (w/c) of the ITZ and the corresponding decrease in w/c ratio of the bulk matrix. Because of this difference in w/c ratio, the contrast of elastic moduli between the ITZ and the bulk paste matrix needs to be considered as a function of hydration age. The Virtual Cement and Concrete Testing Laboratory (VCCTL) cement hydration module is used to simulate the microstructure of cement paste both inside and outside the ITZ. The redistribution of calcium hydroxide between ITZ and bulk paste regions can further affect the elastic contrast between ITZ and bulk paste. The elastic properties of these two regions are computed with a finite element technique and used as input into the D-EMT calculation. The D-EMT predictions of the elastic properties of concrete composites are compared with the results measured directly with a resonant frequency method on corresponding composites. This comparison shows that the D-EMT predictions agree well with experimental measurements of the elastic properties of a variety of concrete mixtures.     

硬化水泥净浆基于纳米压痕的相态识别与水化程度计算

采用纳米原位压痕手段测量硬化水泥净浆中单一相态的代表性微观力学性能,并采用纳米点阵压痕研究各相态的含量。研究对象囊括水灰比为0.3、0.4、0.5的纯水泥净浆和水灰比为0.3情况下含50%、70%矿渣掺量复合体系,共5种配比,以表征它们的相态分布和微观力学性质的异同点。掺矿渣的试件中含有明显多的复合相,因此提出三相模型测算复合相中未水化物的体积分数。此外,提出基于纳米压痕技术计算纯水泥和掺矿渣水泥试件水化程度的方法,结果吻合于热重分析的结果,其中纯水泥净浆中复合相较少,计算得到的水化程度优于对掺矿渣水泥试件的计算。     

Depercolation threshold of porosity in model cement: approach by morphological evolution during hydration

The depercolation threshold of porosity is an important parameter to assess the permeability of cement-based materials. The depercolation threshold is usually defined as the porosity whereby the volume fraction of connected pores in the cement paste decreases to zero. In this paper, the depercolation threshold is defined and determined with respect to the morphological development of pore space during hydration. The morphology of solid phase and pore structure is studied on model cement simulated by the SPACE system, using stereological theory. The influences of particle size distribution and water to cement ratio (w/c) on the depercolation threshold of porosity are discussed. It is found that particle size distribution of cement has significant influence on the depercolation threshold of porosity. The depercolation threshold is higher for finer cement system. However, the influence of w/c on the depercolation threshold of porosity is negligible. For a model cement of moderate fineness, depercolation is not possible at a relatively high w/c (say, 0.6), because the porosity of cement paste remains above the depercolation threshold even at complete hydration.     

Rheological and hydration characterization of calcium sulfoaluminate cement pastes

Calcium sulfoaluminate (CSA) cements are currently receiving a lot of attention because their manufacture produces less CO₂ than ordinary Portland cement (OPC). However, it is essential to understand all parameters which may affect the hydration processes. This work deals with the study of the effect of several parameters, such as superplasticizer (SP), gypsum contents (10, 20 and 30 wt.%) and w/c ratio (0.4 and 0.5), on the properties of CSA pastes during early hydration. This characterization has been performed through rheological studies, Rietveld quantitative phase analysis of measured X-ray diffraction patterns, thermal analysis and mercury porosimetry for pastes, and by compressive strength measurements for mortars. The effect of the used SP on the rheological properties has been established. Its addition makes little difference to the amount of ettringite formed but strongly decreases the large pore fraction in the pastes. Furthermore, the SP role on compressive strength is variable, as it increases the values for mortars containing 30 wt.% gypsum but decreases the strengths for mortars containing 10 wt.% gypsum.     

Electrical conductivity based characterization of plain and coarse glass powder modified cement pastes

This paper describes the use of electrical conductivity to characterize plain and coarse glass powder modified cement pastes. It is observed that the glass powder addition facilitates improved hydration of the cement grains. For the proportions investigated in this study, and the particle size of glass powder, this advantage is negated by the reduced amount of hydration products, i.e., the dilution effect. The variation of electrical conductivity and its derivative with time can be related to the various phases in the microstructural development of the paste. It is observed from the time derivative of conductivity plots that the addition of glass powder results only in minor changes in the setting time of the pastes. Higher the glass powder content, higher the normalized conductivity (ratio of conductivity at a certain glass powder content to that of plain paste) at very early times, and then it falls to a value closer to or less than 1.0 at later times. A parallel model is used to represent effective conductivity as a function of the pore solution conductivity, porosity, and pore connectivity factor. The pore solution conductivity increases with increase in glass powder content. The porosity of the pastes reduces with increase in glass powder content at early ages and increases at later ages. A reduced pore connectivity factor is observed for pastes with higher glass powder content at later times. However, this does not imply increased volume of hydration products as is commonly interpreted for normal pastes, but the electrical conduction pathways are made more tortuous by the relatively large volume of un-reacted filler material in the pore structure.     

Study of dielectric and electrical properties of mortar in the early hydration period at microwave frequencies

The dielectric constant, , and electrical conductivity, , of mortars with various sand-cement ratios,s/c, were measured for the first 30 h hydration using microwave techniques in the frequency range 8.2–12.4 GHz. The and of the mortars were found to increase linearly with increasing water-solid ratiow/(s + c), but decrease with increasings/c. It was found that as long as thes/c values were the same, the rate of changes in and of the mortars were the same. It appears that thes/c is the key factor controlling the rates of changes in dielectric and electrical parameters of cement hydration in mortar. The relationship between compressive strength and dielectric and electrical properties of mortars was also discussed.     

The early-age short-term creep of hardening cement paste: AC impedance modeling

Impedance spectra were monitored at early ages on hydrating Portland cement pastes subjected to a sustained load. The pastes were prepared with two different water-cement ratios (0.35 and 0.50). The experiments were conducted in a controlled chamber maintained at (96±2)% relative humidity. The three ages at loading investigated were 18, 24 and 30 hrs. Real-time changes in paste microstructure due to sustained load were followed through the coupling of an AC impedance frequency analyzer with a miniature loading system. Cement paste specimens were in the form of T-shaped columns with a minimum thickness value (for the web and flanges) less than 1.25 mm. The impedance analysis included an assessment of the relevance of the high frequency arc depression angle to an understanding of the creep and shrinkage behavior of cement paste. Electrical models were developed in order to predict the creep coefficient of normal (w/c = 0.50) and high strength (w/c = 0.35) cement pastes from early age data.     

Influence of limestone powder used as filler in SCC on hydration and microstructure of cement pastes

In recent years, self-compacting concrete (SCC) has gained wide application in the construction industry. As for high performance concrete (HPC) and traditional concrete (TC), the microstructural properties of SCC are the main factors, which determine the material properties, i.e. the mechanical properties, transport properties and the durability behaviour.In order to investigate the development of the microstructure of SCC, the microstructural parameters of the paste including porosity, pore size distribution and phase distribution are determined by means of mercury intrusion porosimetry (MIP) and scanning electron microscopy (SEM). The thermogravimetric analysis (TGA) and the derivative thermogravimetric analysis (DTG) are used to identify the phase constituents. These parameters as studied for self-compacting concrete are compared with high performance concrete and traditional concrete. The specimens of self-compacting cement paste (SCCP) are made with water/binder ratio 0.41 and 0.48, the high performance cement paste (HPCP) with w/c 0.33 and traditional cement paste (TCP) with w/c 0.48. The measurements are performed at different hydration stages, i.e. at 1, 3, 7, 14, 28 and 56 days.The result of this research shows that the pore structure, including the total pore volume, pore size distribution and critical pore diameter, in the SCCP is very similar to that of HPCP. The fact that limestone powder does not participate in the chemical reaction was confirmed both from thermal analysis and BSE image analysis.     

Interpretation of impedance spectroscopy of cement paste via computer modelling

Computer simulation of impedance spectroscopy (IS) of hydrating cement paste, using a three-dimensional, four-phase model, is described. Two puzzling features of experimental IS results, the possible offset resistance in the Nyquist plot and the sharp decrease in normalized conductivity within the first 50 h of reaction, have been studied using the computer simulation model. Insight is provided into these features using the ability of the model to compare quantitatively microstructure and properties. It is concluded that the offset resistance is an experimental artefact, and does not directly relate to microstructure. The drop in conductivity during the first 50 h is shown to be a consequence of a gradual shift from parallel-dominated to series-dominated behaviour of the electrical conductivity, as microstructural modifications take place during hydration, causing the capillary pore structure to become more tortuous. This tortuousity can also explain the high-frequency impedance behaviour in terms of a two-arc response.Part II of this has been previously published in volume 29 issue 19, pages 4984–4992 of this journal.     

Lateral creep of maturing cement paste

This investigation was conducted to study systematically the lateral creep of maturing cement paste under constant stress-strength ratio. The age at loading ranged from 0.75 to 28.75 days. It has been found from these tests that lateral creep is much more for maturing cement paste than for mature cement paste. When hydration is stopped by cooling to ?11°C, the creep values are the same. The creep Poisson's ratio values tend to be higher for earlier age of loading.     

1-3型水泥基压电复合材料的制备及性能

采用切割-浇注法, 以硫铝酸盐水泥为基体, 制备了1-3型水泥基压电复合材料。详细阐述了1-3型水泥基压电复合材料的制备过程; 研究了0.375Pb(Mg_1/3Nb_2/3)O₃-0.375PbTiO₃-0.25PbZrO₃压电陶瓷柱的宽厚比w/t对1-3型水泥基压电复合材料的压电性能、 介电性能和声阻抗的影响。结果表明: 压电陶瓷柱的宽厚比w/t对1-3型水泥基压电复合材料性能有很大影响, 随着w/t的增加, 其压电应变常数d₃₃、 机电耦合系数K_p与K_t、 机械品质因数Q_m、 介电常数ε_r和介电损耗tanδ均随着w/t的增加而减小, 而压电电压常数g₃₃值几乎不受w/t的影响。在压电陶瓷体积分数仅为22.72%的条件下, 调节压电陶瓷柱的宽厚比w/t至0.130, 可使复合材料的声阻抗与混凝土的声阻抗十分接近, 从而有效地解决了智能材料在土木工程中的声阻抗相容性问题。