Comparison between two ultrasonic methods in their ability to monitor the setting process of cement pastes

This paper presents the comparison between ultrasonic wave transmission (USWT) method and ultrasonic wave reflection (USWR) method in their ability to monitor the setting process of cement pastes. The velocity of ultrasonic longitudinal waves and shear wave reflection coefficient were measured simultaneously on cement pastes with different hydration kinetics. Even though both methods are able to reliably monitor the hydration process and formation of structure of an arbitrary cement paste, they monitor the setting process in different ways. The relationship between the velocity of longitudinal waves and shear wave reflection coefficient can be simplified into three characteristic phases and the end of the first phase can be used to define the beginning of the setting process of cement paste.     

Effects of air voids on ultrasonic wave propagation in early age cement pastes

The objective of this paper is to investigate effects of air voids on ultrasonic wave propagation in fresh cement pastes, and relate ultrasonic wave parameters to cement setting times. First, Biot's theory was used to analyze wave propagation in poroelastic media containing air bubbles. Then, in the experimental study, both the compressional (P) and shear (S) waves were monitored in cement pastes with different water/cement ratios (w/c = 0.4 and 0.5) and various air void content (0.1%–5.3% by cement paste volume). Experimental results indicated that existence of air bubbles in cement paste significantly decreases the P wave velocity, but has little effect on the shear wave propagation. Further analysis shows that the shear wave velocity corresponding to the Vicat initial setting times is a relatively constant value for the investigated air content range. This study shows the potential of using shear waves to monitor setting and hardening process of cement.     

Possibilities of using the ultrasonic wave transmission method to estimate initial setting time of cement paste

In this paper, the applicability of the ultrasonic wave transmission method to estimate the initial setting time of an arbitrary cement paste is discussed. Ultrasonic pulse velocity measurements were fully automated and measured continuously. The Vicat Needle Test was used in order to determine the initial setting time of cement pastes. Different cement pastes were prepared in order to check the influence of the water/cement ratio, type of cement, curing temperature, cement fineness, and some clinker compositions, on the relationship between the initial setting time and ultrasonic pulse velocity. It was found that the initial setting time of an arbitrary cement paste can be estimated very accurately by the time the first inflection point appears on the ultrasonic pulse velocity curve. Moreover, it can be estimated quite accurately by the time the ultrasonic pulse velocity reaches a fixed value, close to the value of the ultrasonic pulse velocity in water.     

An investigation of microstructure evolution in cement paste through setting using ultrasonic and rheological measurements

The response of hydrating cement paste through setting are monitored using rheological measurements and ultrasonic reflection measurements. Increases in the elastic modulus and yield stress of cement paste with time are obtained from the rheological measurements. Ultrasonic measurements are performed using horizontally polarized shear waves (SH) reflected off of the hydrating cement paste. Changes in the ultrasonic signal through setting are related with changes in the porosity and stiffness of an equivalent water-filled poroelastic material, which provides identical acoustic impedance. The measured changes in the shear modulus obtained from ultrasonic measurement are shown to correlate well with increase in elastic modulus obtained from rheological measurements. The increase in the shear modulus of the porous material obtained from the ultrasonic measurements is shown to correspond well with the observed increase in the yield stress of the cement paste. By combining the information from rheological and ultrasonic measurements, it is found that even in the fluid stage there is sufficient structural integrity in the arrangement of cement grains to support low-amplitude shear stress and the evolution of a continuously connected network of cement particles within the paste is coincident with a rapid increase in the shear modulus of the porous skeleton.     

Early age microstructure of Portland cement mortar investigated by ultrasonic shear waves and numerical simulation

This paper investigates the ability of a shear wave reflection (WR) method to monitor microstructural changes of Portland cement mortar during hydration. The wave reflection method measures the reflection loss of shear waves at an interface between a steel plate and mortar. Mortars with water/cement ratios of 0.35, 0.5 and 0.6 were tested at isothermal curing conditions of 25 °C. The numerical model HYMOSTRUC3D was used to simulate the evolution of microstructural properties of the cement paste phase of the tested mortars. The parameters obtained from the simulations were the volume fraction of the total and connected solid phase and the specific contact area of the hydrated cement particles. The investigations have shown that the wave reflection measurements are governed primarily by the degree of the inter-particle bonding of the cement particles as calculated from the specific contact area of a simulated microstructure.     

Estimating time and temperature dependent yield stress of cement paste using oscillatory rheology and genetic algorithms

A controlled shear stress–shear rate rheometer was used to determine the viscoelastic behavior of cement paste incorporating various superplasticizers and subjected to prolonged mixing at high temperature. At a low applied shear stress range, the oscillatory shear strain/stress curve of cement paste was characteristic of a linear elastic solid; while the higher stress range was characteristic of a viscous liquid exhibiting a linear strain increase with increasing applied shear stress. The transition from solid-like to liquid-like behavior occurred over a very narrow stress increment. This transition stress corresponded to the yield stress parameter estimated from conventional flow curves using the Bingham model. The yield stress from oscillatory shear stress tests was estimated using the intersection between the viscous part of the oscillatory shear strain/stress curve and the oscillatory shear stress axis. In this study, equations describing the variation of shear strain versus shear stress beyond the solid–fluid transition for cement pastes incorporating various superplasticizers at different ambient temperatures and mixing times were developed using genetic algorithms (GA). The yield stress of cement pastes was subsequently predicted using the developed equations by calculating the stress corresponding to zero strain. A sensitivity analysis was performed to evaluate the effects of the mixing time, ambient temperature, and superplasticizer dosage on the calculated yield stress. It is shown that the computed yield stress values compare well with corresponding experimental data measured using oscillatory rheology.     

减水剂的加入时间对新拌水泥浆体流变性能的影响

研究了三聚氰胺甲醛磺酸盐(MFS)减水剂的掺加时间对普通硅酸盐水泥浆体在初始120 min的水化时间内流变性能的影响,研究中MFS的后掺时间为0 min、5 min、10 min、15 min、20 min和25 min。检测了在不同减切速率(3～147 s-1)下水泥浆体水化30 min和120 min时的剪切应力和表观粘度。测定了水化120 min后的水泥浆体的Ca2+浓度和化学结合水。结果表明:推迟减水剂的后掺时间降低了水泥浆体在120 min内的屈服应力和表观粘度,减水剂MFS的最佳后掺时间为10～15 min。     

基于稳态流变测试的水泥浆体剪切模式研究

采用RHEORIAB QC型旋转黏度计测定不同剪切方式下水泥浆体稳态流变曲线,并用修正宾汉姆流变模型对其进行拟合,研究了剪切方式对水泥浆体稳态流变测试的影响.结果表明:预剪切对水泥浆体动态屈服应力和塑性黏度影响不大.恒定剪切变形速率小于、等于、大于、偏大于水泥浆体结构抗剪切破坏能力时,剪切应力随时间分别先线性增加接着保持同一值、直接保持恒定值、先减小接着保持同一值、轻微增加后达到平衡.随剪切速率增加,水泥浆体在0.1～100 s-1、100～400 s-1、400～600 s-1三个区段依次呈现出剪切变稀、宾汉姆流体、剪切增稠的流变行为.剪切速率变化范围向剪切变稀或剪切增稠段移动,水泥浆体动态屈服应力减小、塑性黏度增大;单个剪切速率的剪切时间越长,水泥浆体动态屈服应力、塑性黏度均越小.     

Influence of time addition of superplasticizers on the rheological properties of fresh cement pastes

It is well known that the fluidity and the fluidity loss of fresh cement pastes are affected by the kind and the time of addition of organic admixtures. The influence of the time addition of two chemical admixtures, namely, melamine formaldehyde sulfonate (MFS) and naphthalene formaldehyde sulfonate (NFS), on the rheological properties of ordinary Portland and sulfate-resisting cement pastes through the first 120 min of hydration was investigated. The admixture addition was delayed by 0, 5, 10, 15, 20, and 25 min. Shear stress and apparent viscosity of the cement pastes were determined at different shear rates (3-146 s⁻¹) and hydration times of 30, 60, 90, and 120 min. The concentration of Ca²⁺ and the combined water content of the cement pastes were determined after 120 min. Yield stress and plastic viscosity values were also determined by using the Bingham model. The results show that an increase in the addition time of the admixture reduces the shear stress, the yield stress, and the plastic viscosity of the cement pastes at the early ages (15 min) as well as at later early ages (120 min). The optimum delaying time of admixture addition is found to be 10-15 min. This time does not depend on the cement and superplasticizer type.     

Effect of some water‐soluble melamine formaldehyde‐free polycondensates on the rheological properties of cement pastes

Water‐soluble melamine formaldehyde‐free polycondensate products were prepared. The chemical structure of these polymers was confirmed with different spectroscopic techniques. The effects of these polymers on the rheological properties of the cement pastes were investigated. The rheological parameters (shear stress, yield stress, and plastic viscosity) were calculated with the Bingham model. The minislump of superplasticized cement pastes at different interval times (5, 30, 60, 90, and 120 min) was determined. The results showed that the new superplasticizers increased the fluidity and minislump of the cement pastes and reduced the minislump loss of the cement pastes not only at early ages (30 min) but also at later early ages (120 min). © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2212–2218, 2005     

The pozzolanic reactivity of monodispersed nanosilica hydrosols and their influence on the hydration characteristics of Portland cement

This study reveals that the nanosilica hydrosols with higher specific surface areas had faster pozzolanic reactivity, especially at early ages; moreover, the results are indicative of the accelerating influence of nanosilicas and silica fume on the hydration of cement. Faster initial and final setting times observed for cement pastes containing nanosilicas are consequence of these mechanisms. However, less hydration degree of cement compared to the plain paste was observed at age of 7 days and after. This can be attributed to the entrapment of some of mix water in the aggregates of nanosilicas formed in cement paste environment, making less water available for the progress of cement hydration. The same mechanism is believed to be responsible for the reduction of flowability of cement pastes.     

Measuring Permeability of Rigid Materials by a Beam-Bending Method: III, Cement Paste

The evolution of permeability and elastic modulus for Type III portland cement pastes with water/cement ratios varying from 0.4 to 0.6 were measured using a beam-bending method. Young's modulus was independently verified by measuring the ultrasonic pulse velocity. The permeability ranged over 2 orders of magnitude, depending on the water/cement ratio and the age of the samples. The advantage of the beam-bending method is that the permeability results are obtained in a few minutes to a few hours, whereas conventional techniques take hours or days to measure permeability of this order of magnitude. More importantly, there is no need to maintain high pressure during the measurement period, so leaks are not a problem.     

Experimental study and numerical simulation on the formation of microstructure in cementitious materials at early age

The formation of microstructure in early age cement paste and concrete was examined with an ultrasonic experimental set-up. Research parameters included the influence of curing temperature (isothermal curing at 20, 30 and 40 °C), water/cement ratio (0.40, 0.45 and 0.55) and amount of aggregate. In parallel with the experiments, the cement hydration model HYMOSTRUC was utilized to simulate the formation of the microstructure. In this study, the cement paste was considered as a four-phase system consisting of water, unhydrated cement, hydration products and that part of the hydration product that causes the contact between the hydrating cement grains (so called “bridge volume”). A correlation has been found between the growth of bridge volume calculated with the model and the changes in the pulse velocity. It is believed that ultrasonic pulse velocity (UPV) measurements can represent a valuable tool to investigate the development of the microstructure at early age.     

硅微粉对水泥浆体流变性能的影响

运用水化热测定仪、流变仪、以及Dinger-Funk紧密堆积等方法,研究了硅微粉掺入水泥中对复合浆体的流变性能的影响,比较了不同硅微粉掺量对复合浆体的早期水化放热、紧密堆积程度、屈服应力和塑性粘度的作用.结果显示:硅微粉取代水泥后,降低浆体水化热放热量,提高了体系紧密堆积程度;Bingham流体仍适用于硅微粉-水泥复合浆体,取代5%、10%、15%水泥的复合浆体,屈服应力和塑性粘度在0、60 min时都小于纯水泥浆体,并且取代10%水泥的复合浆体,其屈服应力和塑性粘度在0、60 min时都最小,流变性能最好.     

Time-dependent flow of cement pastes

The time-dependent behavior of viscosity of clinker pastes was studied with a coaxial cylinder type viscometer. In order to characterize the flow behavior of cement pastes, the flow curve obtained by the minimum values of shear stresses at different shear rates was proposed. Two types of time dependence were found; the increase in viscosity caused by shearing and the increase in minimum viscosity caused by hydration. The effect of sodium lignosulfonate on the flow behavior was also considered.     

A Survey of Rheological Properties of One-Component Epoxy Adhesives

Flow characteristics of seven commercially available one-component epoxy adhesive pastes were measured using a controlled shear stress rheometer and a controlled shear rate rheometer over a temperature range from 5°C to 60°C. Combining data obtained from both controlled rate and controlled stress experiments over a wide range of shear rates, we observed Newtonian flow (shear stress proportional to shear rate) at very low shear rates, a plateau “shear thinning” region at intermediate shear rates, and a second region of linear dependence of shear stress on shear rate at high shear rates. The adhesive pastes exhibited a very broad range of rheological behavior. Two flow parameters important to adhesive application technology, the plastic viscosity and the apparent yield stress, were measured for each adhesive. The plastic viscosity ranged from 11.6 to 329.5 Pa. s; the apparent yield stress ranged from 56.2 to 413 Pa. The temperature dependence of the rheological parameters of the epoxy adhesive pastes was also determined. The results are reported as the activation energies, E_η and E_σ, of plastic viscosity and apparent yield stress, respectively. The apparent yield stress of each adhesive paste was much less sensitive to changes in temperature than was the plastic viscosity. This suggests that the processing characteristics are likely to show qualitative as well as quantitative changes with temperature.     

Effect of delaying addition of some concrete admixtures on the rheological properties of cement pastes

The effect of delayed addition of two concrete admixtures, namely melamine formaldehyde sulfonate (MFS) and naphthalene formaldehyde sulfonate (NFS), on the rheological and adsorption properties of ordinary Portland cement (OPC), sulfate-resisting cement (SRC) and silica fume-ordinary Portland cement (SF-OPC) pastes was investigated. The admixture addition was delayed by 1, 3, 6, 10 and 13 min after the addition of mixing water. The shear stress, as well as the apparent viscosity of these cement pastes, was determined at different shear rates. Total organic carbon (TOC), Ca²⁺ concentration and conductivity of the filtrate and the combined water content of the precipitated cement pastes were determined. The results show that delaying the admixtures addition increases the cement pastes workability than that of simultaneous addition.     

Use of creep recovery protocol to measure static yield stress and structural rebuilding of fresh cement pastes

In this study, a creep recovery shear rheological protocol was applied to fresh cement pastes. A viscosity bifurcation behavior was observed through applying a range of creep stresses. When applied stress is sufficiently low viscosity increases and the material yields, exhibiting viscoelastic solid-like behavior. Beyond a critical stress viscosity decreases and the material flows, exhibiting viscoelastic liquid-like behavior. Through examining this bifurcation behavior we found that the transition of viscosity occurs at very low strains. The strains at which this transition occurred were compared with critical strains measured through low amplitude oscillatory shear. Results provided support that the solid-liquid transition occurs beyond the critical stress measured through creep, thereby tying it to static yield stress. The protocol was implemented to probe pastes modified with attapulgite clays, a highly thixotropic system, and was found to be effective in characterizing static yield stress and thixotropic rebuilding.     

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.     

A Survey of Rheological Properties of One-Component Epoxy Adhesives

Flow characteristics of seven commercially available one-component epoxy adhesive pastes were measured using a controlled shear stress rheometer and a controlled shear rate rheometer over a temperature range from 5°C to 60°C. Combining data obtained from both controlled rate and controlled stress experiments over a wide range of shear rates, we observed Newtonian flow (shear stress proportional to shear rate) at very low shear rates, a plateau “shear thinning” region at intermediate shear rates, and a second region of linear dependence of shear stress on shear rate at high shear rates. The adhesive pastes exhibited a very broad range of rheological behavior. Two flow parameters important to adhesive application technology, the plastic viscosity and the apparent yield stress, were measured for each adhesive. The plastic viscosity ranged from 11.6 to 329.5 Pa. s; the apparent yield stress ranged from 56.2 to 413 Pa. The temperature dependence of the rheological parameters of the epoxy adhesive pastes was also determined. The results are reported as the activation energies, E_η and E_σ , of plastic viscosity and apparent yield stress, respectively. The apparent yield stress of each adhesive paste was much less sensitive to changes in temperature than was the plastic viscosity. This suggests that the processing characteristics are likely to show qualitative as well as quantitative changes with temperature.