Analysis of calcium leaching behavior of plain and modified cement pastes in pure water

The calcium ion leaching behavior of cement pastes modified with a high-alkali fine glass powder, silica fume, and fly ash, exposed to deionized water, is reported in this paper. Porosity enhancement in pastes subjected to leaching is attributed both to the dissolution of calcium hydroxide (CH) as well as decalcification of C–S–H gel. A methodology that combines the measured porosity increase along with the CH and C–S–H contents remaining after leaching for a particular duration is developed to separate the porosities created due to CH and C–S–H leaching. In order to quantify the influence of leaching on the amounts of Ca ions remaining in the CH and C–S–H phases, solid–liquid equilibrium curves for calcium are developed for the unleached and leached pastes. Leaching depths are also calculated using the CH contents of the leached and unleached specimens. All the modified pastes show better leaching resistance than the plain paste. In addition to the microstructure densification, the lower Ca–Si molar ratio in modified pastes that reduces the equilibrium liquid Ca ion concentration contributes to this observation. For the glass powder modified paste, the presence of higher alkali content in the pore solution further reduces the dissolution of CH due to common ion effect, thus providing it with the highest leaching resistance. Fly ash and silica fume modified pastes demonstrate leaching resistance in between those of the plain and glass powder modified mixtures.     

Thixotropy and structural breakdown properties of self consolidating concrete containing various supplementary cementitious materials

In this study, thixotropy and structural breakdown of 57 self-consolidating concrete (SCC) mixtures containing various supplementary cementitious materials (SCM) were investigated by different approaches. The effects of SCM type and content on high range water reducer demand and plastic viscosity were also studied. For these purposes, various amounts of silica fume (SF), metakaolin (MK), Class F fly ash (FAF), Class C fly ash (FAC) and granulated blast-furnace slag (BFS) were utilized in binary, ternary, and quaternary cementitious blends in three water/binder (w/b) ratios. Results showed that except BFS, use of SCM in SCC mixtures increased thixotropy values in comparison with the mixtures containing only portland cement (PC). Good correlations were established between structural breakdown area and drop in apparent viscosity values for all w/b ratios. The different methods used to evaluate the thixotropy and structural breakdown got more consistent with each other as w/b decreased.     

Modification of phase evolution in alkali-activated blast furnace slag by the incorporation of fly ash

The microstructural evolution of alkali-activated binders based on blast furnace slag, fly ash and their blends during the first six months of sealed curing is assessed. The nature of the main binding gels in these blends shows distinct characteristics with respect to binder composition. It is evident that the incorporation of fly ash as an additional source of alumina and silica, but not calcium, in activated slag binders affects the mechanism and rate of formation of the main binding gels. The rate of formation of the main binding gel phases depends strongly on fly ash content. Pastes based solely on silicate-activated slag show a structure dominated by a C–A–S–H type gel, while silicate-activated fly ash are dominated by N–A–S–H ‘geopolymer’ gel. Blended slag-fly ash binders can demonstrate the formation of co-existing C–A–S–H and geopolymer gels, which are clearly distinguishable at earlier age when the binder contains no more than 75 wt.% fly ash. The separation in chemistry between different regions of the gel becomes less distinct at longer age. With a slower overall reaction rate, a 1:1 slag:fly ash system shares more microstructural features with a slag-based binder than a fly ash-based binder, indicating the strong influence of calcium on the gel chemistry, particularly with regard to the bound water environments within the gel. However, in systems with similar or lower slag content, a hybrid type gel described as N–(C)–A–S–H is also identified, as part of the Ca released by slag dissolution is incorporated into the N–A–S–H type gel resulting from fly ash activation. Fly ash-based binders exhibit a slower reaction compared to activated-slag pastes, but extended times of curing promote the formation of more cross-linked binding products and a denser microstructure. This mechanism is slower for samples with lower slag content, emphasizing the correct selection of binder proportions in promoting a well-densified, durable solid microstructure.     

Hydration kinetics in hybrid binders: Early reaction stages

Activated blends of Portland cement and fly ash with a high ash content (>70%) are a new alternative to traditional OPCs. A number of papers have been published on C–S–H and N–A–S–H, the two gels that constitute the main cementitious products generated by the alkaline activation of these cements, and the elements that may be taken up into their structure. Very little is known about the kinetics of these systems, however, particularly during the early stages of the reaction. The present study used isothermal conduction calorimetry to explore hydration kinetics during the first 72 h in a cement containing 30% OPC and 70% fly ash. Two activating solutions were used: a mix of NaOH + Na₂SiO₃ and a Na₂CO₃ solution. The findings showed that hydration kinetics were substantially modified by the type of alkaline activator used, particularly with respect to the secondary phases generated. In both cases the main reaction product appeared to be a mix of C–A–S–H and (N,C)–A–S–H gels, whose proportions were clearly impacted by the type of activator used.     

Investigating the role of reactive silica in the hydration mechanisms of high-calcium fly ash/cement systems

High-calcium fly ashes (ASTM Class C) are being widely used as a replacement of cement in normal and high strength concrete. In Greece such fly ashes represent the majority of the industrial by-products that possess pozzolanic properties. Even thought the contribution of factors, such as fineness and water/binder ratio, on the performance of fly ash/cement (FC) systems has been a common research topic, little work has been done on examining whether and to what extent reactive silica of fly ashes affects the mechanisms occurring during their hydration.The work presented herein describes a laboratory scale study on the influence of active silica of two high-lime fly ashes on their behavior during hydration. Volumes up to 30% of Greek high-calcium fly ashes, diversified both on their reactive silica content and silicon/calcium oxides ratio, were used to prepare mixes with Portland cement. The new blends were examined in terms of compressive strength, remaining calcium hydroxide, generation of hydration products and microstructural development. It was found that soluble silica of fly ashes holds a predominant role especially after the first month of the hardening process. At this stage, silica is increasingly dissolved in the matrix forming additional cementitious compounds with binding properties, principally a second generation C–S–H. The rate however, that fly ashes react in FC systems seems to be independent of their active silica content, indicating that additional factors such as glass content and fineness should be taken into account for predicting the contribution of fly ashes in the final performance of pozzolanic cementitious systems.     

Compressive strength and drying shrinkage of fly ash-bottom ash-silica fume multi-blended cement mortars

This paper studies the physical properties, compressive strength and drying shrinkage of multi-blended cement under different curing methods. Fly ash, ground bottom ash and undensified silica fume were used to replace part of cement up to 50% by weight. Specimens were cured in air at ambient temperature, water at 25, 40 and 60 °C, sealed with plastic sheeting for 28 days. The results show that absorption and volume of permeable pore space (voids) of blended cement mortars at 28 day under all curing methods tend to increase with increasing silica fume replacement. The compressive strength of blended cement with fly ash and bottom ash was lower than that of Portland cement control at all curing condition while blended cement with silica fume shows higher compressive strength. In addition, the compressive strength of specimens cured with water increased with increasing curing temperature. The drying shrinkage of all blended cement mortar cured in air was lower than that of Portland cement control while the drying shrinkage of blended cement mortar containing silica fume, cured with plastic sealed and water at 25 °C was higher than Portland cement control due to pore refinement and high autogenous shrinkage. However, the drying shrinkage of blended cement mortar containing SF cured with water at 60 °C was lower than that of Portland cement control due to lower autogenous shrinkage and the reduced microporosity of C–S–H.     

Influence of fibre type on flexural behaviour of self-compacting fibre reinforced cementitious composites

This paper investigates the flexural properties of self-compacting fibre reinforced cementitious composites that contain high fly ash volume. Seven types of fibres were compared at the same volume fraction and in similar matrices containing high-volume fly ash and having a high compressive strength of around 85 MPa at 28 days. Third-point bending test was conducted on beam specimens to obtain their load–deflection curves, and investigate their fracture behaviour, flexural strength, deflection and toughness. The results showed that using straight steel and micro-polyvinyl alcohol fibres produced composites demonstrating stable deflection-hardening with multiple-cracking phenomenon. This behaviour resulted in high flexural strength, along with large maximum deflection and toughness values, which are important for applications in cementitious composites. This study indicates that fibres with both sufficiently high aspect ratio and high tensile strength are necessary for achieving deflection-hardening in self-compacting cementitious composites with high-strength matrices containing high-volume fly ash.     

Detection of nanostructural anomalies in hydrated cement systems

Monitoring the flow of helium gas into the structure of hydrated cement systems has proven to be a useful method for following nanostructural changes in the C–S–H phase of hydrated cement systems. The method is sensitive to changes that occur on removal of structural water from the layered silicates. The helium-inflow method was applied, in this study, to normally hydrated low-water–cement ratio (w/c) Portland cement pastes (w/c < 0.38) and to low w/c autoclaved cement systems containing fly ash and elemental sulfur. Unusually, high amounts and rates of inflow were observed for these pastes. It was postulated that inflow occurred into both interlayer and other spaces in the latter. The inflow into the other or ‘trapped’ space was unexpected and considered anomalous in absence of a widely accepted explanation. The structural differences which were observed at the nanoscale for the low w/c preparations were consistent with behavioral aspects for published structural models of layered C–S–H. These include the models of Richardson and Jennings and concepts involving the existence of two types of C–S–H. Arguments for the existence of ‘trapped’ space between aggregates of C–S–H layers are advanced. Evidence for the preservation of C–S–H structures (similar to those formed during normal hydration) for the autoclaved systems containing fly ash and sulfur is presented. The evidence is compatible with the existence of ‘trapped’ space within layered agglomerates and the collapse of C–S–H structure on removal of water from interlayer space, typical of normally hydrated pastes.     

Compressive strength and chloride resistance of self-compacting concrete containing high level fly ash and silica fume

The influence of high-calcium fly ash and silica fume as a binary and ternary blended cement on compressive strength and chloride resistance of self-compacting concrete (SCC) were investigated in this study. High-calcium fly ash (40–70%) and silica fume (0–10%) were used to replace part of cement at 50, 60 and 70 wt.%. Compressive strength, density, volume of permeable pore space (voids) and water absorption of SCC were investigated. The total charge passed in coulombs was assessed in order to determine chloride resistance of SCC. The results show that binary blended cement with high level fly ash generally reduced the compressive strength of SCC at all test ages (3, 7, 28 and 90 days). However, ternary blended cement with fly ash and silica fume gained higher compressive strength after 7 days when compared to binary blended fly ash cement at the same replacement level. The compressive strength more than 60 MPa (high strength concrete) can be obtained when using high-calcium fly ash and silica fume as ternary blended cement. Fly ash decreased the charge passed of SCC and tends to decrease with increasing fly ash content, although the volume of permeable pore space (voids) and water absorption of SCC were increased. In addition when compared to binary blended cement at the same replacement level, the charge passed of SCC that containing ternary blended cement was lower than binary blended cement with fly ash only. This indicated that fly ash and silica fume can improve chloride resistance of SCC at high volume content of Portland cement replacement.     

Application of rock wool waste in cement-based composites

This study investigates the properties of cement-based composites with addition of various rock wool wastes. The rock wool wastes are an insulating material. This study used rock wool waste with a cylindrical size distribution ranging from 17 to 250 μm, 30% of which is less than 150 μm. Rock wool waste can be used as a suitable substitute for coarse and fine aggregates, saving on the cost of natural aggregates and minimizing the environmental impact of solid waste disposal. In addition, because the composition of rock wool waste is similar to other pozzolan materials such as fly ash, ground granulated blast-furnace slag (GGBS), and silica fume, it can be considered as a supplementary cementitious material. Experimental results show that partially replacing natural aggregates with rock wool wastes improves the compressive strength, splitting tensile strength, abrasion resistance, absorption, resistance to potential alkali reactivity, resistivity, and chloride-ion penetration of cement-based composites. These improved properties are the result of the dense structure achieved by the filling effect of pozzolanic product. Pozzolanic strength activity index (PSAI) results and scanning electron microscope (SEM) observations confirm these findings. Therefore, rock wool wastes can act as either a cementitious material or inert filler in cement-based composites, depending on the particle size. The critical size appears to be 75 μm.     

High performance concrete—An overview

It is suggested that high performance concrete is not fundamentally different from the concrete used in the past, although it usually contains fly ash, ground granulated blastfurnace slag and silica fume, as well as superplasticizer. The cost aspects of the use of silica fume are considered. The content of cementitious material is high and the water/cement ratio is low; the maximum size of aggregate is small. Although ordinary Portland cement is used, it must be compatible with a given superplasticizer; the causes of incompatibility are discussed. The distinct shrinkage behaviour of high performance concrete is considered and the reasons for an absolute necessity of wet curing are given. Some uses of high performance concrete are mentioned. A ‘prediction’ of the future of high performance concrete and of concrete in general is offered.     

Evaluating the use of supplementary cementitious materials to mitigate damage in cementitious materials exposed to calcium chloride deicing salt

This paper discusses the role of supplementary cementitious materials (SCM) in reducing damage caused by calcium oxychloride formation. Calcium oxychloride is a destructive product of a reaction between calcium hydroxide (CH) that exists in a cementitious matrix and CaCl₂ that can enter the pores of the matrix when it is used as a deicing salt. Paste samples were prepared where a percentage of ordinary portland cement was replaced with various types of SCM (including fly ash, slag, and silica fume). This paper examined the amount of calcium oxychloride that formed using low-temperature differential scanning calorimetry, and damage development detected using acoustic emission. Thermogravimetric analysis was also performed to determine the relationship between the amount of CH in cementitious materials and the amount of calcium oxychloride formation. The results show that the use of SCM is effective in reducing the calcium oxychloride formation and resulting damage when cementitious materials are exposed to various compositions of solution containing CaCl₂. The explanation of the benefit of using SCM is that it can reduce the calcium oxychloride formation due to a reduction in the amount of CH in the cementitious materials through pozzolanic reaction and dilution of cement. As a result, cementitious materials with SCM exposed to CaCl₂ may experience less damage and have a longer service life.     

Optimization of the solidification/stabilization process of MSW fly ash in cementitious matrices

The solidification/stabilization (S/S) process of municipal solid waste (MSW) fly ash in cementitious matrices was investigated in order to ascertain the feasibility of a washing pretreatment of fly ash with water as a means of maximizing the ash content of cementitious mixtures. Four types of fly ash resulting from different Italian MSW incineration plants and ASTM Type III Portland cement were used in this study. Ash-cement mixtures with different fly ash/cement (FA/C) ratios were made using untreated and washed fly ash. Washing of fly ash with water was realized by a two-stage treatment (liquid/solid=25; mixing time=15 min for each stage). The cementitious mixtures were characterized for water demand, setting time, mechanical strength, and heavy metals leachability. Comparison between the above properties of mixtures incorporating untreated and washed fly ash (particularly, setting characteristics), coupled with economical evaluation of the S/S process when applied to untreated and washed fly ash, proved the feasibility of washing pretreatment as a means of maximizing the incorporation of MSW fly ash in cementitious matrices (ash content up to 75%-90% by weight of total solid).     

An AFM-SEM investigation of the effect of silica fume and fly ash on cement paste microstructure

Atomic force microscopy (AFM) was used to observe particle shape and surface texture details of normal portland cement and supplementary cementing materials (silica fume, low-calcium fly ash, and high-calcium fly ash). The latter materials mixed with cement were examined after prolonged hydration. Significant innovative information on particle shape and hydrated paste microstructure was obtained. Conventional microscopy techniques, such as scanning electron microscopy (SEM), cannot provide such detailed images and surface texture characteristics of the fine materials (especially silica fume) and of the product microstructure. AFM showed, for the first time, that silica fume particles are primarily composed of two complimentary parts (hemispheres or semicylinders). Nano-size particles were found in all materials. A relatively smooth product surface was observed in the hydrated cement paste. The hydrated surface of the addition-cement pastes presented small spheroid bulges, giving an additional roughness as was measured by AFM. A sufficient correlation of this microscopical quantitative information with macroscopical engineering and durability properties of cement products is also presented.     

Service life and global warming potential of chloride exposed concrete with high volumes of fly ash

Today, it remains unclear how ‘green’ concrete with high volumes of fly ash really is, especially when subject to chloride-induced corrosion. This paper presents chloride diffusion test results for high-volume fly ash and fly ash + silica fume concrete. Apparent diffusion coefficients and surface concentrations were compared with those for traditional concrete. Instantaneous chloride diffusion coefficients and ageing exponents were estimated and critical chloride contents for submerged exposure conditions were experimentally verified. The estimated time to chloride-induced steel depassivation for the two concrete types with fly ash (60 to more than 100 years) was much longer than for traditional concrete (24–32 years). As a consequence, global warming potentials (GWPs) calculated for the required concrete volume per unit of strength and service life indicate that an important reduction in greenhouse gas emissions is possible for both concrete types with high volumes of fly ash (GWP –50 to −82%).     

Compressive strength and microstructure of fly ash based geopolymer blended with silica fume under thermal cycle

This work aims to reveal the effects of silica fume on properties of fly ash based geopolymer under thermal cycles. Geopolymer specimens were prepared by alkali activation of fly ash, which was partially replaced by silica fume at levels ranging from 0% to 30% with an interval of 10%, by mass. Microstructure, residual strength and mass loss of fly ash based geopolymer blended with silica fume before and after exposed to 7, 28 and 56 heat-cooling thermal cycles at different target temperatures of 200 °C, 400 °C and 800 °C were assessed and compared. The experimental results reveal that silica fume addition enhances strength development in geopolymer. Under thermal cycles, the compressive strength of geopolymer decreases, and the compressive strength loss, as well as the mass loss, increases with increasing target temperature. The strength loss is the same regardless of silica fume content after thermal cycles. Microstructure analysis uncovers that pore structure of geopolymer degrades after thermal cycles. The pores of geopolymer are refined by the addition of silica fume. The incorporation of silica fume optimizes the microstructure and improves the thermal resistance of geopolymer. Silica fume increases the strength of the geopolymer and even though the strength loss is the same, the strength after heat cycle exposure is still good.     

Use of natural zeolite as a supplementary cementitious material

Natural zeolite, a type of frame-structured hydrated aluminosilicate mineral, is used abundantly as a type of natural pozzolanic material in some regions of the world. In this work, the effectiveness of a locally quarried zeolite in enhancing mechanical and durability properties of concrete is evaluated and is also compared with other pozzolanic admixtures. The experimental tests included three parts: In the first part, the pozzolanic reactivity of natural zeolite and silica fume were examined by a thermogravimetric method. In this case, the results indicated that natural zeolite was not as reactive as silica fume but it showed a good pozzolanic reactivity. In the second part, zeolite and silica fume were substituted for cement in different proportions in concrete mixtures, and several physical and durability tests of concrete were performed. These experimental tests included slump, compressive strength, water absorption, oxygen permeability, chloride diffusion, and electrical resistivity of concrete. Based on these results, the performance of concretes containing different contents of zeolite improved and even were comparable to or better than that of concretes prepared with silica fume replacements in some cases. Finally, a comparative study on effect of zeolite and fly ash on limiting ASR expansion of mortar was performed according to ASTM C 1260 and ASTM C 1567. Expansion tests on mortar prisms showed that zeolite is as effective as fly ash to prevent deleterious expansion due to ASR.     

Strength and resistance to sulfate and sulfuric acid of ground fluidized bed combustion fly ash–silica fume alkali-activated composite

Fluidized bed combustion (FBC) is an environmentally friendly process for burning of coal and is used in many small factories located in urban area. The FBC fly ash is an environmental problem and needs good disposal or utilization. This research studied the strength and resistance to sulfate and acid of alkali-activated FBC fly ash–silica fume composite. The FBC fly ash was interground with silica fume (at the dosage levels of 1.5%, 3.75% and 5.0%) to make the source material homogenous with increased reactivity. Addition of silica fume enabled the adjustment of SiO₂/Al₂O₃ ratios (6.55-7.54) of composite and improved the strength and resistance to sulfate and acid of composite. The composite with 3.75% silica fume showed the optimum strength with 28-day compressive strength of 17.0 MPa. The compressive strengths of composite with 3.75% silica fume immersed in 5% magnesium sulfate solution and 3% sulfuric acid solutions were substantially higher than the control. The strength loss was from the high calcium content of FBC fly ash and incorporation of silica fume thus increased the durability of the composite.     

水泥-粉煤灰-硅灰基超高性能混凝土水化过程微观结构的演变规律

超高性能混凝土(UHPC)具有卓越的力学性能和耐久性能,应用前景广阔。采用扫描电镜背散射电子图像、热重法和氮气吸附法系统研究了水泥-粉煤灰-硅灰基UHPC浆体水化过程中微观结构的演变过程。结果表明:UHPC浆体在早期水泥水化较快,但7d后水化变得较为缓慢,粉煤灰在UHPC浆体中反应较为缓慢,28d时反应程度仅为7%;UHPC浆体中Ca(OH)2含量早期上升快速,由于硅灰和粉煤灰的火山灰反应逐渐消耗,3d后含量开始下降,但28d时浆体中仍存在部分Ca(OH)2;此外,在水化过程中,UHPC浆体的比表面积不断降低,孔隙率逐渐下降,水化产物变得更为致密。     

复合盐浸下多元外掺剂-混凝土抗干湿-冻融循环性能

通过对粉煤灰、硅灰、矿渣、膨胀剂、引气减水剂（Air-Entrained Water Reduce Agent,AEWRA）和水泥基自愈合防水材料（Cementitious Capillary Crystalline Waterproofing Material,CCCWM）等多元外掺剂进行组合搭配掺入混凝土中,设计了5组混凝土配比。分析了复合盐（氯盐、硫酸盐和碳酸盐）浸-干湿-冻融循环等多种因素共同作用下多元外掺剂-混凝土的腐蚀破坏现象、质量损失率、相对动弹性模量衰减规律和抗侵蚀系数变化规律。采用SEM、EDS和XRD,研究了多元外掺剂-混凝土腐蚀的微观结构变化规律。研究结果表明,双掺粉煤灰和硅灰混凝土提高混凝土的抗侵蚀性能作用有限;在双掺粉煤灰和硅灰基础上加入适量的膨胀剂能够较大幅度提高混凝土的抗侵蚀性能,经11次复合盐浸-干湿-冻融循环后,其相对动弹性模量仍然在80%以上,抗侵蚀系数在0.9以上;CCCWM作为一种外掺剂加入混凝土会降低混凝土的耐侵蚀性,经4次复合盐浸-干湿-冻融循环后,相对动弹性模量就降到了60%以下,抗侵蚀系数从1.0降到了0.3。微观机制研究也表明,在复合盐浸-干湿-冻融循环作用下,腐蚀产物钙矾石和方解石共同作用会加速混凝土的腐蚀破坏。