Investigation of blended cement hydration by isothermal calorimetry and thermal analysis

Hydration of portland cement pastes containing three types of mineral additive; fly ash, ground-granulated slag, and silica fume was investigated using differential thermal analysis, thermogravimetric analysis (DTA/TGA) and isothermal calorimetry. It was shown that the chemically bound water obtained using DTA/TGA was proportional to heat of hydration and could be used as a measure of hydration. The weight loss due to Ca(OH)₂ decomposition of hydration products by DTA/TGA could be used to quantify the pozzolan reaction. A new method based on the composition of a hydrating cement was proposed and used to determine the degree of hydration of blended cements and the degree of pozzolan reaction. The results obtained suggested that the reactions of blended cements were slower than portland cement, and that silica fume reacted earlier than fly ash and slag.     

Effect of size fraction and glass structure of siliceous fly ashes on fly ash cement hydration

Paper presents effect of size fraction and glass structure of fly ashes on cement hydration. Fly ashes below 16 μm and 16–32 μm, both from the 1st and 3rd section of electro-filter, were applied. Hydration heat, content of Ca(OH)₂ and unreacted C₃S were studied and compressive strength and microstructure were analysed. Results show that finer ashes have higher depolymerization degree of SiO₄ units in glass what increases pozzolanic reactivity. Incorporation of fly ashes below 16 μm from the 3rd section gives cement class 52.5 N. At 180 day, Ca(OH)₂ content decreases by 67% and C₃S hydration degree increases by 50% relative to control sample.     

Studies on blended cement with a large amount of fly ash

The influence of the contents of the clinker, activators and fly ash on the properties of blended cement with high fly ash content was studied. Experimental data from X-ray diffraction and pore size distribution indicated that the main hydration product of the fly ash blended cement was C-S-H gel, ettringite and a small amount of Ca(OH)₂. The volume porosity of the pores with diameter bigger than 0.1 μm was lower than that of the micro pores and gel pores with diameter lower than 0.05 μm. The amount of chemical combined water has increased with the curing age duration, while the content of Ca(OH)₂ has reduced after 7 days.     

An improved basis for characterizing the suitability of fly ash as a cement replacement agent

Fly ash is a critical material for partial replacement of ordinary portland cement (OPC) in the binder fraction of a concrete mixture. However, significant compositional variability currently limits fly ash use. For example, the performance of OPC‐fly ash blends cannot be estimated a priori using current characterization standards (eg, ASTM C618). In this study, fly ashes spanning a wide compositional range are characterized in terms of glassy and crystalline phases using a combination of X‐ray fluorescence (XRF), X‐ray diffraction (XRD), and scanning electron microscopy with X‐ray energy‐dispersive spectroscopy (SEM‐EDS) techniques. The compositional data are distilled to a unitless parameter, the network ratio (N_r), which represents the network behavior of atoms that form alkali/alkaline earth‐aluminosilicate glasses that make up fly ashes. N_r is correlated with known composition‐dependent features, including the glass transition temperature and amorphous XRD peak (“hump”) position. Analysis of heat release data and compressive strengths are used to evaluate the impact of fly ash compositions on reaction kinetics and on the engineering properties of cement‐fly ash blends. It is shown that fly ashes hosting glasses with a high network ratio (ie, having a less stable glass structure) are more reactive than others.     

Hydration of fly ash cement

It is necessary to establish the material design system for the utilization of large amounts of fly ash as blended cement instead of disposing of it as a waste. Cement blended with fly ash is also required as a countermeasure to reduce the amount of CO₂ generation. In this study, the influences of the glass content and the basicity of glass phase on the hydration of fly ash cement were clarified and hydration over a long curing time was characterized. Two kinds of fly ash with different glass content, one with 38.2% and another with 76.6%, were used. The hydration ratio of fly ash was increased by increasing the glass content in fly ash in the specimens cured for 270 days. When the glass content of fly ash is low, the basicity of glass phase tends to decrease. Reactivity of fly ash is controlled by the basicity of the glass phase in fly ash during a period from 28 to 270 days. However, at an age of 360 days, the reaction ratios of fly ash show almost identical values with different glass contents. Fly ash also affected the hydration of cement clinker minerals in fly ash cement. While the hydration of alite was accelerated, that of belite was retarded at a late stage.     

高掺量混合材复合水泥的水化性能

通过水化微量热、化学结合水测定和X射线衍射、热重-差热分析、扫描电镜等测试方法研究了3种高掺量矿渣、粉煤灰、石灰石复合水泥的水化性能,并与硅酸盐水泥的水化进行了对比。结果表明：高掺混合材复合水泥的水化放热特征与硅酸盐水泥有明显不同,早期水化反应速度低于硅酸盐水泥,但后期由于矿渣、粉煤灰的二次水化反应使其水化速度增长较快。主要的水化产物亦为水化硅酸钙凝胶、钙钒石和Ca(OH)2晶体,但Ca(OH)2含量明显低于硅酸盐水泥浆体中的Ca(OH)2含量。     

Microstructure of interface between fibre and matrix in 10-year aged GRC modified by calcium sulfoaluminate cement

Time-dependent property changes in glass fibre reinforced cement (GRC) mainly result from a combination of the alkalinity of the matrix and densification of the matrix (e.g. due to calcium hydroxide precipitation) within and around the glass fibre strands. The microstructure of the interface between matrix and fibres in GRC has a significant impact on its durability. This paper describes a study of two GRC formulations (with OPC, and OPC plus calcium sulfoaluminate based matrices) aged for 10 years at 25 °C. Thin-section petrography (TSP) and SEM are used to compare the microstructure of both polished surfaces and fractured surfaces. The aged OPC/GRC demonstrates significantly brittle behaviour with substantial densification of C–S–H/CH intermixture occurring around glass fibres. In contrary, the aged composite made with the OPC plus calcium sulfoaluminate shows greatly retained toughness, accompanied by considerably flexible interfacial and interfilamentary areas around the glass fibres.     

低品位粉煤灰的改性及其对水泥浆体强度和自收缩的影响

采用石灰石粉对低品位粉煤灰进行煅烧改性,利用X射线衍射、扫描电镜和能谱分析等方法对改性粉煤灰的矿物组成和化学组成进行表征.同时测定了掺改性粉煤灰的水泥浆体的抗压强度和自收缩,并采用背散射扫描电镜和压汞测孔仪研究了掺改性粉煤灰水泥浆体的微观结构.结果表明,粉煤灰经煅烧改性生成了水硬性矿物β-C2S,水化可生成CSH凝胶,改善了等外粉煤灰颗粒与水泥基体的界面粘接,降低了复合水泥浆体的孔隙率和自收缩,提高了复合水泥浆体的强度.     

Effect of large amounts of natural pozzolan addition on properties of blended cements

In this study, the effects of 35, 45, and 55 wt.% natural pozzolan addition on the properties of blended cement pastes and mortars were investigated. Blended cements with 450 m²/kg Blaine fineness were produced from a Turkish volcanic tuff in a laboratory mill by intergrinding portland cement clinker, natural pozzolan, and gypsum. The cements were tested for particle size distribution, setting time, heat of hydration, compressive strength, alkali-silica activity, and sulfate resistance. Cement pastes were tested by TGA for Ca(OH)₂ content and by XRD for the crystalline hydration products. The compressive strength of the mortars made with blended cements containing large amounts of natural pozzolan was lower than that of the portland cement at all tested ages up to 91 days. Blended cements containing large amounts of pozzolan exhibited much less expansion with respect to portland cement in accelerated alkali-silica test and in a 36-week sulfate immersion test.     

Solution‐Controlled Dissolution of Supplementary Cementitious Material Glasses at pH 13: The Effect of Solution Composition on Glass Dissolution Rates

Supplementary cementitious materials (SCMs) are widely used to partially replace portland clinker in blended cements. Reducing clinker contents further without compromising the development of early strength necessitates a better assessment and enhancement of the reactivity of the available SCMs. To this purpose, the reactivity of synthesized calcium aluminosilicate glasses covering a compositional range from blast‐furnace slags (BFS) over fly ashes to silica fume was analyzed by dissolution experiments. Initial glass dissolution rates were measured at 20°C and pH 13, and with varying initial concentrations of aqueous Al, Ca, and Si. At pH 13, glass dissolution rates were observed to scale linearly with the glass Ca/(Al + Si) molar ratio. Ca‐rich blast‐furnace type glass dissolution was shown to be up to one order of magnitude faster than tectosilicate fly ash and silica fume type glass dissolution, supporting different pathways to dissolution. In solutions that are strongly undersaturated with respect to hydrous glass and hydration products, glass dissolution rates are independent of changes in solution undersaturation and aqueous Si activity. In contrast, dissolution rates decrease with aqueous Ca concentration for all glasses and with aqueous Al concentration for tectosilicate‐type glasses. The insights gained are instrumental in finding ways to enhance SCM reactivity.     

Impact of accelerated carbonation on OPC cement paste blended with fly ash

Cement is a huge carbon dioxide producer. Supplementary cementitious materials can help reduce this outcome. However, carbonation of these blended cements remains an active subject of research. Accelerated carbonation tests (10% CO₂, 25 °C and 62% RH) are performed on fly ash blended cement pastes. Experiments are performed at varying ages of carbonation (1 to 16 weeks) to measure the evolution of the carbonation depth over time and to quantify key parameters: thermogravimetric analysis (TGA), mercury intrusion porosimetry (MIP) and gamma ray attenuation method (GRAM). The total porosity decreases with a rearrangement of the microstructure due to carbonation and the creation of big capillary pores for the paste with the highest contents of fly ash (60 vol.%). The C-S-H molar volume evolution during fly ash-blended cement carbonation is calculated using a method combining MIP, TGA and GRAM formerly successfully applied to OPC paste in a paper published in the same journal.     

Effects of three Turkish fly ashes on the heat of hydration of PC-FA pastes

Effects of the type and amount of fly ash substitution on the heat of hydration of portland cement-fly ash pastes were investigated. Three Turkish fly ashes were used. One of them was a high-calcium and the other two were low-calcium fly ashes. The specimens contained 0, 10, 20, and 40% fly ash by weight of portland cement. The tests were carried out as described in ASTM C 186 however one separate set of specimens were first subjected to an early external temperature of 67±2°C for six hours followed by the standard temperature until time of test. The results revealed that the low-calcium fly ashes, regardless of their type, reduce the heat evolution when used for partial cement replacement. The high-calcium fly ash, on the other hand, does not produce significant changes in the heat of hydration.     

Estimation of the degree of hydration of blended cement pastes by a scanning electron microscope point-counting procedure

A scanning electron microscope (SEM) point-counting technique was employed to study the hydration of plain portland and blended cement pastes containing fly ash or slag. For plain portland cement pastes, the results for the degree of cement hydration obtained by the SEM point-counting technique were consistent with the results from the traditional loss-on-ignition (LOI) of nonevaporable water-content measurements; agreement was within ±10%. The standard deviation in the determination of the degree of cement hydration via point counting ranged from ±1.5% to ±1.8% (one operator, one sample). For the blended cement pastes, it is the first time that the degree of hydration of cement in blended systems has been studied directly. The standard deviation for the degree of hydration of cement in the blended cement pastes ranged from ±1.4% to ±2.2%. Additionally, the degrees of reaction of the mineral admixtures (MAs) were also measured. The standard deviation for the degree of fly ash reaction was ±4.6% to ±5.0% and ±3.6% to ±4.3% for slag. All of the analyses suggest that the SEM point-counting technique can be a reliable and effective analysis tool for use in studies of the hydration of blended cement pastes.     

Industrially interesting approaches to “low-CO2” cements

This article discusses the practicality of replacing portland cements with alternative hydraulic cements that could result in lower total CO₂ emissions per unit volume of concrete of equivalent performance. Currently, the cement industry is responding rapidly to the perceived societal need for reduced CO₂ emissions by increasing the production of blended portland cements using supplementary cementitious materials that are principally derived from industrial by-products, such as blast-furnace slags and coal combustion fly ashes. However, the supplies of such by-products of suitable quality are limited. An alternative solution is to use natural pozzolans, although they must still be activated either by portland cement or lime or by alkali silicates or hydroxides, the production of all of which still involves significant CO₂ emissions. Moreover, concretes based on activated pozzolans often require curing at elevated temperatures, which significantly limits their field of application.The most promising alternative cementing systems for general concrete applications at ambient temperatures currently appear to be those based at least in part on calcium sulfates, the availability of which is increasing due to the widespread implementation of sulfur dioxide emission controls. These include calcium sulfoaluminate-belite-ferrite cements of the type developed in China under the generic name “Third Cement Series” (TCS) and other similar systems that make good use of the potential synergies among calcium sulfate, calcium silicate and calcium aluminate hydrates. However, a great deal more research is required to solve significant unresolved processing and reactivity questions and to establish the durability of concretes made from such cements. If we are to use these potentially more CO₂-efficient technologies on a large enough scale to have a significant global impact, we will also have to develop the performance data needed to justify changes to construction codes and standards.     

DTA-TG study on the Ca(OH)2 - pozzolan reaction in cement pastes hydrated up to three years

In order to study the way in which Santorin earth (pozzolan) acts during its hydration with portland cements and specifically, the rates of its action and its optimum content, the amount of Ca(OH)₂ derived during the hydration has been quantitatively determined, by means of thermogravimetry. Thus, cement pastes have been prepared with mixtures of portland cement containing proportions of Santorin earth up to 40% of various finenesses. These pastes were cured in water up to three years.     

Hydration of fly ash-portland cements

Hydration products of fly ash-portland cements were studied with x-ray diffraction (XRD), differential thermal analysis (DTA) and scanning electron microscopy (SEM) as part of a continuing research effort to understand the pozzolanic activity of fly ashes. It was found that the amount of calcium hydroxide crystals in the cement pastes is diminished due to the addition of fly ash to the cement. Ettringite was produced in the early age, and the consumption of sulfate by the formation of ettringite was accelerated by the addition of fly ash. A partial conversion of ettringite to monosulfate within the first 7 days of hydration in the fly ash-portland cement pastes, but the formation of ettringite continued to form up to at least 28 days of hydration in the pastes without fly ash. Examination of the fly ash bearing pastes showed, in all cases, varying amounts of calcium hydroxide and unreacted portland cement, with minor quartz and gehlenite hydrate. It appears that hydration reactions actually occur in the fly ash cement pastes more or less on a particle-by-particle basis.     

Study on high-strength composite portland cement with a larger amount of industrial wastes

It is one of important measures for the sustainable development of cement industry to utilize industrial wastes. High-strength composite portland cement with a large amount of granulated blast furnace slag (GBFS), fly ash and limestone was prepared by separate grinding method, optimizing gypsum and using activators. The total amounts of blending materials are between 45% and 65% and the strength grades of cements reach 525 or even 625 according to Chinese national standard for composite portland cement. Besides setting time and strength, the hydration heat, drying shrinkage and sulfate resistance were also determined.     

Application of Powers’ model to modern portland and portland limestone cement pastes

Powers’ model is a simple approach for estimating the relative volumes of hydration products, porosity, and chemical shrinkage present in portland cement paste as a function of its starting water‐to‐cement ratio (w/c) and current degree of hydration. It forms an important link between cement composition, microstructure, and performance, necessary for modeling cement‐based systems. Previous researchers have adapted Powers’ model for inert fillers to illustrate their effects on the hydration, porosity, and chemical shrinkage of blended cements; however, it is well‐documented that limestone is not, in fact, an inert filler, but rather participates in cement hydration through both chemical and physical processes. This research experimentally investigates the applicability of Powers’ model to modern portland cements containing up to 15% by mass finely divided limestone. The results demonstrate that the modified Powers’ model is insufficient for predicting the influence of finely divided limestone additions on the chemical shrinkage of both ordinary portland cement pastes and portland limestone cement pastes. Possible explanations for the discrepancy are discussed and a plausible source is proposed.     

Biomass fly ash in concrete: Mixture proportioning and mechanical properties

ASTM C 618 prohibits use of biomass fly ashes in concrete. This document compares the properties of biomass fly ashes from cofired (herbaceous with coal), pure wood combustion and blended (pure wood fly ash blended with coal fly ash) to those of coal fly ash in concrete. The results illustrate that with 25% replacement (wt%) of cement by fly ash, the compressive strength (one day to one year) and the flexure strength (at 56th day curing) of cofired and blended biomass fly ash concrete is statistically equal to that of two coal fly ash concrete in this investigation (at 95% confidence interval). This implies that biomass fly ash with co-firing concentration within the concentration interest to commercial coal-biomass co-firing operations at power plants and blended biomass fly ash within a certain blending ratio should be considered in concrete.     

Mechanical and durable behaviour of alkaline cement mortars reinforced with polypropylene fibres

The development of new binders, alternative to traditional cements and concretes obtained by the alkaline activation of different industrial by-products (blast furnace slags and/or fly ashes), is an ongoing study and research topic of the scientific community.

The mechanical and durable behaviour of alkaline cement mortars reinforced with polypropylene fibres has been the object of the present investigation. Three different alkaline matrices were used: (a) granulated blast furnace slag activated with waterglass (Na₂SiO₃+NaOH) with a concentration of 4% Na₂O by mass of slag and cured at room temperature, (b) aluminosilicate fly ash activated with 8M NaOH and cured at 85 °C during the first 24 h and (c) 50% fly ash+50% slag activated with 8M NaOH solution at room temperature. In the mechanical tests (flexural and compressive strengths), two different dosages of fibres were used: 0.5% and 1% by mortar volume. Shrinkage tests according to ASTM C 806-87 standard with (1%) and without fibres were also carried out. The durability tests carried out were freeze/thaw and wet/dry cycles. In these tests, the dosage of fibre was 0.5% by mortar volume. The results obtained show that the nature of the matrix is the most important factor to strength development, more than fibre presence and content amount.