利用磷石膏制备低热、微膨胀复合水泥的研究

为大量利用磷石膏,本文采用在复合水泥中掺加磷石膏的方法,开展了制备低热、微膨胀复合水泥的试验研究,并采用DSC、XRD、SEM及等温水化热仪表征了该复合水泥的水化特征.研究结果表明:磷石膏具有显著的缓凝效果,通过掺加Na2SO4和提高磷石膏掺量的方法,可大幅度缩短水泥的凝结时间、提高水泥的早期强度.当磷石膏掺量超过10％时,水泥水化产物中钙矾石量显著增加,并出现二水石膏,硬化水泥浆体呈现出微膨胀性.通过调整磷石膏的掺量,可控制复合水泥的膨胀率.     

Effect of material characteristics on the properties of blended cements containing high volumes of natural pozzolans

The effect of three different natural pozzolans from Turkish deposits on the properties of blended cements produced by intergrinding cement clinker with a high volume of natural pozzolan (55 wt.% of the cementitious material) was investigated. The particle size distribution of blended cements, setting time, heat of hydration, and compressive strength of blended cement mortars were determined. Experimental results showed that the hardness of the pozzolanic material strongly influenced the particle size distribution and the related properties of the blended cements by affecting the fineness of the components of the blended product. The early strength of the mortars was strongly affected by the particle size distribution of blended cements, whereas the strength development performance of the mortars was more related to the pozzolanic activity of the natural pozzolan present in the blended cement.     

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。     

A gap-graded particle size distribution for blended cements: Analytical approach and experimental validation

To increase the packing density of blended cement paste, a gap-graded particle size distribution (PSD) was theoretically deduced and modified according to the wet density of actual paste. Then experiments were conducted to validate the hypothesis of improvement of the properties of blended cements by the gap-graded PSDs proposed. The experimental results show that the gap-graded PSD resulted in a decreased water requirement and an increased packing density of blended cement paste, and modified gap-graded PSDs gave further effects. The heat of hydration of gap-graded blended cement pastes released slowly in the first 24 h and increased rapidly afterward. The microstructure of gap-graded blended cements was much more homogeneous and denser than that of reference blended cement, therefore both early and late mechanical properties of low clinker gap-graded blended cements were improved significantly and even higher than those of Portland cement.     

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 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.     

Cement hydration in the presence of high filler contents

To realise self-compacting concrete, high filler contents are often used, and in order to avoid problems with excessive heat development during hardening, inert filler materials can be used. In this research two different filler types, limestone and quartzite, are considered in combination with different Portland cements. Although the filler material has often been considered to be inert, experimental results show that it does influence the hydration processes. On the one hand the reaction rate is influenced due to a modified nucleation possibility, and on the other hand, in some cases, the reaction mechanisms are altered, with a new hydration peak occurring. Based on isothermal conduction calorimetry on different cement-filler systems, an existing hydration model for blended cement is modified for these systems. Within the degree of hydration based hydration model, the cement/powder ratio seems to be an important parameter for the cement-filler systems. The model accurately predicts the heat of hydration during the hardening process.     

Quantification and analysis of heat hydration of blended cement at different temperature

The study of the hydration kinetics appears as a prerequisite for understanding the physical and mechanical phenomena that control the behavior of cementitious materials. This research is based on monitoring the evolution of the degree of hydration for ordinary cement and those containing 10% of limestone powder, 20% of natural pozzolana or 30% of the blast furnace slag under high temperatures. The results provide a better understanding the effect of cure temperature on the hydration kinetics and understand the contribution of mineral additions on improving the cement properties. A new model proposed gives the satisfaction results for predicting in later age the heat of hydration of cements blended kept under constant temperatures. The latter has a wider appreciation of the results, where it gives correlation coefficients very close of unity. This justifies the reliability of this new model proposed.     

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.     

水泥熟料与辅助性胶凝材料优化匹配的基础研究进展(Ⅰ)——物理效应

本文分析了复合水泥性能较差的本质原因,并指出优化水泥浆的初始堆积状态和水化进程是改善复合水泥性能的根本途径。在分析经典颗粒堆积模型和水泥颗粒级配模型优缺点的基础上,提出了复合水泥的颗粒级配模型,显著提高了新拌水泥浆体的初始堆积密度(最大固含量提高10%),以改善复合水泥的性能。     

不同窑型水泥熟料共同粉磨对水泥性能的影响

实验室测试了共同粉磨不同窑型熟的水泥物理性能、颗粒级配和水化放热速率。结果表明,回转窑和立窑熟料混合,改善了水泥熟料的易磨性,水泥的标准稠度用水量随着立窑熟料掺入量和粉磨时间的延长而增大。泌水性得到明显改善,颗粒级配更加合理,水泥强度提高,特别是３ｄ的抗压、抗折强度,它并不是两种水泥强度的简单加权,而是表现出增强作用,混合水泥熟料放热量、放热速率界于两者之间。     

Early hydration of portland cement with crystalline mineral additions

This research presents the effects of finely divided crystalline mineral additions (quartz and limestone), commonly known as filler, on the early hydration of portland cements with very different mineralogical composition. The used techniques to study the early hydration of blended cements were conduction calorimeter, hydraulicity (Fratini's test), non-evaporable water and X-ray diffraction. Results showed that the stimulation and the dilution effects increase when the percentage of crystalline mineral additions used is increased. Depending on the replacement proportion, the mineralogical cement composition and the type of crystalline addition, at 2 days, the prevalence of the dilution effect or the stimulation effect shows that crystalline mineral additions could act as sites of heat dissipation or heat stimulation, respectively.     

Nonevaporable water from neat OPC and replacement materials in composite cements hydrated at different temperatures

Pastes of two neat OPC and three blended cements using GGBFS (60%), PFA (30%) and a volcanic ash (23%), were cured for up to 1 year at five temperatures. The degree of hydration of the OPCs was estimated by quantitative X-ray diffraction analysis and by measurements of nonevaporable water by thermogravimetry. A correlation between the results from these techniques is presented for the neat OPCSs. The correlation was used to estimate the contribution to the nonevaporable water from the cement replacement material fraction for the blended cements. According to the estimated data, the slag displayed a hydraulic nature retaining significant amounts of water in its hydrates, the slag nonevaporable water values as function of time varied with temperature and the patterns were similar to those of degree of hydration of the neat cement. The data estimated for the two pozzolanic materials indicated that their hydrates retained small amounts of water in spite of the CH consumption.     

In situ synchrotron X-ray powder diffraction study of the early age hydration of cements blended with zeolitite and quartzite fines and water-reducing agent

A comparison was made between the early-age hydration of cements blended with micronized zeolitite and quartzite powders. The Portland cement replacement in the mixes was 30%, and the effect of introducing a superplasticiser to lower the required water to solid ratio was assessed. The cement pastes were hydrated at 40 °C and monitored in situ by time-resolved synchrotron X-ray powder diffraction combined with Rietveld quantitative phase analysis.The quantitative evolution of phase weight fractions showed that the addition of the zeolite tuff accelerated the hydration rate of the main C₃S cement component. Blending with the quartzite powder of similar fineness did not affect the C₃S hydration rate. Reduction of the water to solid ratio by introduction of the superplasticiser had a retarding effect on the hydration of the zeolitite-blended cement over the early hydration period up to 3 days.The AFt or ettringite reaction products, formed promptly after the addition of water to the mixtures, underwent a crystal structural modification over the induction period up to 4 to 6 hours of reaction. The continuous contraction of the c-cell parameter and expansion of the a-cell parameter towards the ideal values for AFt or ettringite reflects the structural adaptation of the AFt to the changing availability of sulphate over the course of the first hours of hydration. The observed structural changes were less pronounced in the zeolitite blended cement. This is related to the dilution of the overall sulphate content in the blended cement and highlights the need to control and optimise sulphate additions in blended cements.     

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.     

Effects of dosage and modulus of water glass on early hydration of alkali-slag cements

This paper examines the early hydration of alkali-slag cements activated with water glass with different n moduli and sodium metasilicate (Na₂SiO₃·5H₂O) in solution at 25 °C. The early hydration of alkali-activated blast furnace slag cements has been studied using isothermal conduction calorimetry. The cumulative heat of hydration increases by increasing the n modulus as well as the dosage of water glass, but is still lower than that of Portland cement. The compressive strength of normal-cured water glass slag cements is higher than Portland cement mortars. Drying shrinkage of alkali-slag cements is considerably higher than that of Portland cement. Consequently, industrial use of alkali-slag cement needs better understanding of the hardening mechanism and requires further research based on presented observations and results.     

Improvement of the durability of glass fiber reinforced cement using blended cement matrix

Blended cements prepared with two fly ashes were used as matrices in glass fiber reinforced cement (GRC) composites in an attempt to improve their durability. The hydrated matrices from the two blended cements investigated here had similar strength and composition. Both fly ashes reduced the Ca(OH)₂ content to the same extent but in both cases the pH level was only slightly reduced compared to the portland cement matrix. In spite of these similarities, the GRC prepared with one fly ash showed considerable improvement in durability while the other one had only a small positive effect. SEM observations indicated that the improved durability in one case was associated with modification in the microstructure of the hydration products deposited in between the glass filaments, resulting in a much more open structure compared to that of portland cement matrix or the other blended cement. It is therefore suggested that the potential of the blended cement matrix to improve the durability of GRC is associated with its ability to modify the microstructure of the paste at the glass interface. This characteristic is not necessarily related to the overall composition of the blended cement matrix and to the reactivity of fly ash with Ca(OH)₂.     

Use of X-ray diffraction to quantify amorphous supplementary cementitious materials in anhydrous and hydrated blended cements

The content of individual amorphous supplementary cementitious materials (SCMs) in anhydrous and hydrated blended cements was quantified by the PONKCS [1] X-ray diffraction (XRD) method. The analytical precision and accuracy of the method were assessed through comparison to a series of mixes of known phase composition and of increasing complexity. A 2σ precision smaller than 2–3 wt.% and an accuracy better than 2 wt.% were achieved for SCMs in mixes with quartz, anhydrous Portland cement, and hydrated Portland cement.The extent of reaction of SCMs in hydrating binders measured by XRD was 1) internally consistent as confirmed through the standard addition method and 2) showed a linear correlation to the cumulative heat release as measured independently by isothermal conduction calorimetry.The advantages, limitations and applicability of the method are discussed with reference to existing methods that measure the degree of reaction of SCMs in blended cements.     

水泥熟料与辅助性胶凝材料优化匹配的基础研究进展(Ⅱ)——化学效应

在分析水泥熟料与辅助性胶凝材料水化程度、填充能力和强度贡献率的基础上,提出了水泥熟料与辅助性胶凝材料优化匹配原则。利用该原则,可在降低水泥熟料用量、提高辅助性胶凝材料(特别是低活性辅助性胶凝材料)掺量的同时,显著改善复合水泥的强度、体积稳定性等性能,实现水泥熟料、矿渣等胶凝材料的高效利用。