Mineral admixtures in mortars: Quantification of the physical effects of inert materials on short-term hydration

This work is the second part of an overall project, the aim of which is the development of general mix design rules for concrete containing different kinds of mineral admixtures. The first part presented the separation of the different physical effects responsible for changes in cement hydration when chemically inert quartz powders are used in mortars. This second part describes the development of an empirical model, based on semiadiabatic calorimetry measurements, which leads to the quantification of the enhancement of cement hydration due to the heterogeneous nucleation effect at short hydration times. Experimental results show that not all the admixture particles participate in the heterogeneous nucleation process. Consequently, the concept of efficient surface S_eff is introduced in the model. S_eff is the total admixture surface S (m² of mineral admixture/kg of cement) weighted by a function ξ(p). The efficiency function ξ(p) depends only on the replacement rate p and is independent of time, fineness and type of mineral admixture used. It decreases from 1 to 0: Low replacement rates give an efficiency value near 1, which means that all admixture particles enhance the hydration process. An efficiency value near 0 is obtained for high replacement rates, which indicates that, from the hydration point of view, an excess of inert powder does not lead to an increase in the amount of hydrates compared with the reference mortar without mineral admixture. The empirical model, which is mainly related to the specific surface area of the admixtures, quantifies the variation of the degree of hydration induced by the use of inert mineral admixtures. One application of the model, coupled with Powers' law, is the prediction of the short-term compressive strength of mortars.     

Mineral admixtures in mortars effect of type, amount and fineness of fine constituents on compressive strength

This work is the third part of an overall project the aim of which is the development of general mix design rules for concrete containing different kinds of mineral admixtures (also named mineral additions or mineral constituents). It deals with the compressive strength of mortars made with up to 75% of crushed quartz, limestone filler or fly ash of different fineness. The paper presents all the experimental results as a sort of database and emphasizes the effects on strength of the nature, amount and fineness of mineral admixtures. For short hydration times (1 to 2 days), the nature of mineral admixture is not a significant parameter, as mortars containing the same amount of different kinds of admixtures having equivalent fineness present similar strengths. For long hydration times (up to 6 months), the excess strength due to fly ash pozzolanic activity is quantified by the difference between the strengths of mortars containing the same proportions of inert and pozzolanic admixtures with the same fineness. In the case of inert mineral admixtures, the increase in strength with the fineness of mineral admixtures cannot be explained by the filler effect, but can be attributed to the physical effect of heterogeneous nucleation. In the next part of this work, these results will be used for the elaboration of an empirical model leading to the quantification of both physical and chemical effects. This model presents strong similarities with the previous model based on calorimetric results.     

Efficiency of mineral admixtures in mortars: Quantification of the physical and chemical effects of fine admixtures in relation with compressive strength

This work is the fourth part of an overall project the aim of which was the development of general mix design rules for concrete containing different kinds of mineral admixtures. The two first parts presented the separation and quantification, by means of an empirical model based on semi-adiabatic calorimetry measurements, of the different physical effects responsible for changes in cement hydration (short terms) when chemically inert quartz powders were used in mortars. Part three dealt with an intensive experimental program, presenting and commenting more than 2000 compressive strength measurements. This program concerned 1 day to 6 months old mortars containing up to 75% of inert and pozzolanic admixtures. All these compressive strength results are analyzed in this fourth part and the influence of three effects, namely dilution, heterogeneous nucleation and the pozzolanic effect, are discriminated and quantitatively evaluated. An efficiency concept is proposed in order to take into account the effect of mineral admixture in mortars from both the physical and chemical points of view. It uses an efficiency function ξ(p) that has notable properties: it is independent of time, independent of fineness and independent of the type of mineral admixture.     

矿物掺合料对水泥胶砂强度发展规律的影响

本文通过试验检测掺加矿物掺合料后水泥胶砂强度的变化,研究矿物掺合料对水泥胶砂强度发展规律的影响。     

The influence of mineral admixtures on resistance to corrosion of steel bars in green high-performance concrete

In this paper, the influences of the types, amount and adding approaches of mineral admixtures on pH values, electrical resistance of concrete, anodic polarization potential and mass loss ratio of steel bars in concrete subjected to 50 immersion-drying cycles were investigated. The testing results showed that the addition of mineral admixtures reduced the pH values of the binder pastes in green high-performance concrete (GHPC), especially when two or three types of mineral admixtures were added at the same time (double- or triple-adding approaches), whereas the final pH values were still above the critical breakage pH value of passivation film on the steel bar surface (11.5). Double- and triple-adding approaches also greatly increased the electrical resistance of concrete, which led to a delay in the initial time of corrosion and a decrease in the corrosion rate of steel bars. Additionally, double- and triple-adding mineral admixtures, instead of single-adding, fly ash can reduce the corrosion of steel bars when a large amount of fly-ash replacement was used. All the details of this paper provided a method to reduce or prevent the corrosion of steel bar in concrete, especially for the application in aggressive marine environments.     

Effect of the densification of C–S–H on hydration kinetics of tricalcium silicate

Effect of water to cement (w/c) ratio and temperature profiles on the densification of C–S–H (calcium silicate hydrate gel) and hydration kinetics of triclinic tricalcium silicate (C₃S) is studied beyond the first day of hydration. Calorimetry and quantitative X‐ray diffraction/Rietveld analysis show that degree of hydration is unaffected by w/c up to 7 days and marginally thereafter. Coupling the degree of hydration with the portlandite content measured from thermal analysis indicate that C/S ratio of C–S–H decreases with increasing w/c. There is a clear increase in the portlandite content with increasing w/c, even though the degree of hydration is unchanged, due to the variations in C/S ratio of C–S–H. On the other hand, when C₃S is initially cured at a lower temperature (20°C) and then at a higher temperature (40°C), there is a significant increase in the reactivity even until 28 days and vice versa. These experimental results were explained using the densified volumetric growth hypothesis, which assumes that hydration kinetics are dependent on the internal surface area of C–S–H.     

Suspended hydration and loss of freezable water in cement pastes exposed to 90% relative humidity

Degree of hydration (DOH) and differential scanning calorimetry (DSC) measurements are used to characterize the effect of early exposure to a 90% relative humidity (RH) environment on cement paste hydration. Early exposure to a 90% RH environment can lead to the consumption of freezable water and altered microstructural development. The minimum duration of 100% RH curing required to eliminate the effects of an unsaturated environment on microstructural development coincides with the appearance of a DSC peak near −30 °C that occurs in the range 1-14 days for the pastes studied. The Jennings colloidal microstructural model is used to argue that the −30 °C peak coincides with the cessation of capillary pore percolation. Alternatively, all samples cured under 100% RH conditions for 7 days prior to 90% RH exposure hydrated at the same rate as those continuously exposed to 100% RH. The application of these results to the formulation of separate curing practices for durability and strength is discussed.     

Effect of brief heat-curing on microstructure and mechanical properties in fresh cement based mortars

The effect of temperature on fresh mortar and cement paste was evaluated by simulating the curing conditions of external buildings plastering applied under extremely hot weather. The specimens were heated at controlled temperatures in the 40−80 °C range by exposure to IR radiation over short periods. The effect of soaking for a short time was also examined. The results of compressive strength tests, scanning electron microscopy, infrared spectroscopy and mercury porosimetry helped to characterize the mechanical and physico-chemical properties of the studied sample. Early age behaviour (28 days) in neat cement was barely affected by the temperature. By contrast, exposure to high temperatures caused significant microstructural changes in the mortar. However, successive soaking over short periods was found to reactivate the mechanism of curing and restore the expected mechanical properties. Based on the results, application of cement based mortar at high temperatures is effective when followed by a short, specific soaking process.     

Delayed ettringite formation symptoms on mortars induced by high temperature due to cement heat of hydration or late thermal cycle

Cases of delayed ettringite formation (DEF) have mainly been detected on mortars or precast concretes steam-cured according to a predefined temperature cycle during hydration. The present study shows that other situations in which the material is submitted to a temperature cycle can induce DEF expansions. Mortar bars were made with three different cements (types 10, 20M, and 30). As a first heat treatment, the mortar bars were steam-cured to reproduce the temperature cycle they would undergo if they were at the center of a large mortar member. The dimensional variations of these specimens were studied for 1 year. After 1 year, half of the specimens were steam-cured for 1 month at 85 °C. The expansions were followed for two more years. The early-age steam-cure-induced expansions for mortar types 10 and 30. Late steam-curing induced expansions for the three cements tested. In one case (cement type 20M), the early-age steam cure has suppressed or delayed the expansion induced by the late steam cure. A scanning electron microscopy (SEM) study showed that typical DEF symptoms are associated with the expansions.     

Pore structure in mortars applied on restoration: Effect on properties relevant to decay of granite buildings

Since mortars play a key role in buildings decay, their suitable choice is critical to the success of restoration projects. The focus of this paper is to characterise the pore structures of a set of mortars and correlate them with mechanical properties and vapour permeability, which are relevant to the decay of granite buildings. Water vapour transport was tested by means of a simple set-up developed in our laboratory. A good correlation was found between total porosity and the two parameters tested: strength and vapour diffusivity. Pore size distribution also showed a strong influence on diffusivity. A mix based on cement with a high sand proportion was considered as the most suitable for granite building restoration because it showed good mechanical properties and low free calcium content. A negative aspect was that this mix exhibited significantly lower vapour permeability than mortar containing lime; this could be explained by the smaller radius of its pores.     

Study on the hydration heat of binder paste in high-performance concrete

High-performance concrete (HPC) is a type of new concrete materials developed in the recent 10 years. Compared with normal strength concrete (NSC), HPC is made with lower water-binder ratio (W/B), larger dosage of superplasticizer and addition of different types of mineral admixtures. The objective of the article was to evaluate the effect of W/B, superplasticizer and mineral admixtures on the hydration heat of the binder paste in HPC. The testing results showed that the hydration heat reduced with the decrease of W/B of the binder paste. The total hydration heat did not decrease with the incorporation of superplasticizer containing retarding component, however, the hydration exothermic process was delayed. Mineral admixtures greatly reduced the hydration heat and the exothermic rate and prolonged the arrival time of the highest temperature, particularly when two or three types of mineral admixtures were added at the same time (double adding and triple adding). The influence of these three factors on hydration heat may counteract the deficiency of high hydration heat at early stage due to high cement content and high-strength cement usually used in HPC. This way, the influence of temperature stress is alleviated and the durability of concrete is enhanced.     

亚硫酸钙对水泥水化性能的影响

采用XRD、SEM等测试方法研究了亚硫酸钙(CaSO3.1/2H2O)对水泥水化性能的影响,并与石膏(CaSO4.2H2O)进行了对比.结果表明在水泥中CaSO3.1/2H2O不具有石膏那样的调节水泥凝结时间的作用.掺CaSO3.1/2H2O的水泥试样1d强度比掺CaSO4.2H2O试样显著降低,3d后两者强度相近.60d的抗折、抗压强度与28d相比,增幅很小,有的甚至倒缩.CaSO3.1/2H3O和铝酸盐矿物反应,主要生成片状的C3A.CaSO3.     

Microstructure and texture of hydrated cement-based materials: A proton field cycling relaxometry approach

We show how the measurement of proton nuclear magnetic spin-lattice relaxation as a function of magnetic field strength (and hence nuclear Larmor frequency) can provide reliable information on the microstructure (specific surface area and pore size distribution) throughout the progressive hydration of cement-based materials. We present in details the experimental and theoretical characteristic features of the relaxation dispersion to support an interpretation in terms of coupled solid-liquid relaxation at pore interfaces, surface diffusion, and nuclear paramagnetic relaxation. The measurement does not require any drying temperature modification and is sufficiently fast to be applied continuously during the progressive hydration of the material. Coupling this method with the standard proton nuclear spin relaxation and high resolution NMR allows us to follow the development of micro-scale texture within the material.     

Effect of pig slurry on two cement mortars: Changes in strength, porosity and crystalline phases

The present article addresses the variations observed in porosity and flexural and compressive strength in two types of cement mortar when submerged in pig slurry. The tests were conducted in a 100 m³ experimental lagoon. The mortars were exposed to three types of environments for 36 months: two submerged in the test lagoon, at two different depths, and one outside it. Bending and compression measurements were taken after 3, 12, 24, 36 and 48 months. In addition, 3, 24, 36 and 48 month specimens were tested for total porosity and pore-size distribution. Changes in the mineralogical characteristics of the mortars after 24, 36 and 48 months were also recorded. The strength studies showed that the load capacity attained by the two cements was similar after 48 months, the use of more expensive 42.5 sulphate-resistant cement is not justified. The XRD results showed no evidence in any of the cements of precipitation originating in the ions in the aggressive medium.     

C-S-H纳米晶核对矿物掺合料复合胶凝材料水化性能的影响研究

水泥中掺入大量矿物掺合料易造成其早期强度低、施工周期长等问题。本文研究了C-S-H晶核对含矿物掺合料的复合胶凝材料体系水化性能的影响规律;通过热力学计算阐述了C-S-H晶核降低水化产物成核势垒的机理,并通过离子溶出与沉积探讨大掺量矿物掺合料胶凝体系水化机理。结果表明：矿物掺合料复合胶凝材料体系水化能力较弱,这是由于Ca²⁺溶出受到制约,C₃S的水化反应缓慢;当加入晶核后,水泥中硅酸盐相溶解-结晶能力得到大幅提升,使得矿物掺合料水泥体系的水化反应活性接近纯水泥体系。研究表明,C-S-H晶核可解决大掺量矿物掺合料胶凝体系所带来的水化能力严重不足问题。     

纳米SiO_2对硅酸盐水泥水化放热特性的影响

以硅灰为对比,利用微量热仪研究了纳米SiO2对硅酸盐水泥24 h内水化历程、水化放热特性的影响.研究结果表明:掺入纳米SiO2的水泥试样24 h内水化历程也可划分为类似于纯硅酸盐水泥水化的5个阶段;纳米SiO2的掺入,促使诱导期、加速期和减速期的出现提前,缩短了诱导期持续的时间;提高了水化开始时的放热速率,使第二放热峰的出现提前,增大了水化放热量.     

水浸泡养护对铝酸钙水泥水化行为影响的研究

为研究水浸泡养护对铝酸钙水泥水化行为的影响,以纯铝酸钙水泥Secar71为研究对象,试验温度为20℃,按水灰质量比0.3将水与铝酸钙水泥混合搅拌均匀,采用TG-DSC、XRD、SEM等方法对比研究了铝酸钙水泥在自然养护与水浸泡养护两种条件下分别养护1、7和15 d的水化行为。结果表明:铝酸钙水泥与水混合后,自然养护条件下,在最初的几分钟内有少量的放热,经过诱导期后有大量的放热,形成了一个"一次水化峰",之后进入稳定期;注水浸泡养护后试样内未水化水泥产生一个较"一次水化峰"低的"二次水化峰",之后水化缓慢;浸泡养护结束后试样内水化产物量与自然养护的相比明显增多,生长发育良好的片状CAH10相和絮状或粒状的三水铝石沿试样孔隙分布,填充气孔,试样结构更加致密。     

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.     

Effects of Al2O3 on the hydration activity of municipal solid waste incinerator fly ash slag

This study investigates the effects of slag composition on the hydration activity of slag-blended cement (SBC) pastes. Synthetic slag samples were prepared by melting Al₂O₃-modified, municipal solid-waste incinerator (MSWI) fly ash. In addition to the original slag (containing 25.0% CaO and 17% Al₂O₃), two other synthetic slag types, A1 and A2 slag, were prepared, having a 15% or 5% Al₂O₃ content, respectively. These synthetic slags were blended with ordinary Portland cement (OPC) at weight ratios ranging from 10% to 40%. The results indicate that the incorporation of 10% A1 slag tended to enhance the degree of hydration in SBC pastes during the early ages (3-28 days), but at later ages, significant difference in the degree of hydration between the OPC and SBC pastes with 10% A1 slag was not observed. The tendency of the 10% A2 slag case was similar, but with a limited enhancement during the early ages (3-28 days). However, samples that incorporated the Al₂O₃-modified slag (AMS) showed decreased degrees of hydration. The degree of hydration of the 40% blend ratio sample decreased significantly.     

Effect of silica fume and fly ash on heat of hydration of Portland cement

Results of calorimeter tests on Portland cement-silica fume-fly ash mixtures are presented. Data indicate that silica fume accelerates cement hydration at high water/cementitious ratios and retards hydration at low water/cementitious ratios. On the other hand, fly ash retards cement hydration more significantly at high water/cementitious ratios. When silica fume and fly ash are added together with cement, the reactivity of the silica fume is hampered and the hydration of the cementitious system is significantly retarded.