Study of chloride binding and diffusion in GGBS concrete

Ordinary Portland cement (OPC) and OPC/ground granulated blastfurnace slag (GGBS) 70%, with or without 5% sulfates, were widely investigated in respect to their pore structures, chloride diffusion coefficients, internal and external chloride-binding capabilities by expression method and leaching method and the microstructure analysis on Friedel's salt such as differential thermal analysis (DTA), X-ray diffraction (XRD) and scanning electron microscopy (SEM). It can be concluded that GGBS can improve the pore structure of OPC and decrease the chloride diffusion coefficient greatly, and that sulfates do not do good for the pore structure and chloride diffusion for GGBS. GGBS increases the chloride-binding capability greatly without reference to the internal or external chloride and sulfates decrease the chloride-binding capability of GGBS greatly. It can be also found that the maximum intensity peak corresponding to Friedel's salt appears at about 8.0 Å, its endothermic effect appears at about 360 °C, its morphology is hexagonal slice whose size is about 2-3 μm; that the output of Friedel's salt formed by GGBS is much more than OPC; and that sulfates influence the output of Friedel's salt greatly. The corresponding mechanism was also analyzed.     

The influence of sulphates on chloride binding and pore solution chemistry

Ordinary Portland cement (OPC) and OPC/ground granulated blastfurnace slag (GGBS) 65% cements containing 2.0 to 9.0% sulphates derived from sodium sulphate and calcium sulphate were investigated in respect to their chloride binding properties and the concentrations of chloride and hydroxyl ions in the pore solutions. Chlorides derived from sodium and calcium chlorides were introduced at the time of mixing. The results indicate that calcium sulphate has a different effect on chloride binding and the pore solution chemistry than sodium sulphate. The slag cement has higher chloride binding capacities as a result of simple replacement for OPC, but at the same sulphate contents, the slag cement does not give the expected higher binding capacities, suggesting that the difference in sulphate content between the two cements may be the main reason for their different chloride binding behaviour.     

Tolerance limit of chloride for steel in blended cement mortar using the cyclic polarisation technique

The tolerance limit for chloride in ordinary Portland cement (OPC) and blended cements such as Portland pozzolana cement (PPC) and Portland slag cement (PSC) was assessed by cyclic polarisation. This study covers both cement extracts and mortar. The salient features of this investigation were: in extracts, the tolerance limit for chloride actually doubles for PSC when compared to PPC and OPC. The tolerance limit for chloride for various mortars follows the order: PSC > PPC > OPC. In OPC and PPC mortar, the repassivation potential (E _rep) shifted negatively with higher amounts of free chloride but in PSC mortar E _rep shifted positively (+590 mV) even in the presence of 5,000 ppm of free chloride. PSC takes longer time (50 days) to reach E _rep indicating perfect passivity maintained for the embedded steel.     

Effect of calcium chloride on the volume contraction,non-evaporable water content and bound chloride content of hydrated portland cement and blast-furnace slag

The change in volume during hydration, Δv, and the water retained at 105°C at ultimate hydration, w_n^o, have been measured for cement-calcium chloride-water systems in which the cements consisted of portland cement, blastfurnace slag and mixtures of portland cement and blastfurnace slag in equal parts by mass.The results showed that the quantity of chloride bound in the solid phases increased with the initial concentration of chloride in the aqueous phase but the parameters Δv and w_n^o for a particular system were independent of the initial chloride concentration in the aqueous phase.     

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。     

Nanostructure of Calcium Silicate Hydrate Gels in Cement Paste

High-resolution electron microscopy study of calcium silicate hydrate (C-S-H) gels in ordinary portland cement (OPC) and a slag/OPC blend has been performed. Nanocrystalline regions on the scale of ∼5 nm or less in C-S-H are found in both cement pastes, and they are formed after a curing time as brief as 7 d. A change in the d -spacing of the nanocrystalline regions with time is observed for the first time, which is believed to correspond to the development of C-S-H with time. The nanoheterogeneous nature of C-S-H is demonstrated and correlated to the strong Ca:Si ratio fluctuations that are observed.     

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.     

氯化钠对掺磨细矿渣粉硅酸盐水泥基材料活性激发能力和结合方式影响的试验研究

通过在掺磨细矿渣粉配制的硅酸盐混合水泥中掺加0.5%～4%的氯化钠进行的试验研究表明,加入的氯离子约37%～64%与硅酸盐水泥和矿渣形成化学结合状态,24%～50%为游离状态,2%～10%为物理吸附状态;氯化钠掺量在1%以下时水泥石早期强度显著提高,具有明显的活性激发和早强作用;Cl-和SO2-4互相取代产生复合化合物3CaO·Al2O3·(1-xCaCl2·xCaSO4)·yH2O,其x值随水泥石中Cl-浓度的变化而变化.并且与C-S-H混合生长.     

Mössbauer and X-ray investigations of some portland cements

The Mössbauer spectroscopic and x-ray diffraction investigations have been carried out on a variety of ordinary portland, portland pozzolanic, portland slag and sulphate resisting portland cements, using dry as well as hydrated samples. The discussion of the Mössbauer parameters shows that Fe atoms occupying distorted octahedral and tetrahedral sites in the dry cements are hydrated to form ferrite monosulphate without producing Fe(OH)₃ and its gel; hydration of the slag cement proceeds much faster than other cements; and that the composition of the iron-bearing phase in the sulphate resisting portland cement, studied in detail, is close to C₄AF.     

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.     

Supersulphated cement from blastfurnace slag and chemical gypsum available in the Netherlands and neighbouring countries

The present report covers research into the mechanical strength development and the surface hardness of supersulphated cement from blastfurnace slag, chemical gypsum and portland clinker. The tests were carried out on sand/cement mortar as well as on concrete. A comparison was made with a type of supersulphated cement which was in the market until recently, and with portland and blastfurnace cement. A review has been made of the effects of the hardening temperature, the relative humidity, the degree of grinding of the cement, the use of a water-reducing additive, and treatment with a curing compound. The conclusion is drawn that one of the cements produced, consisting of 83% m/m Dutch blastfurnace slag, 15% m/m fluorogypsum (anhydrite) and 2% m/m portland clinker ground to the relatively high specific surface of 500 m²/kg, is not inferior to blastfurnace cement as regards the properties examined.     

Early stage hydration of slag-cement

The early hydration characteristics of slag cements (blends of separately ground granulated blast furnace slags with portland cement) have been examined. Isothermal calorimetry, chemical shrinkage and compressive strength measurements were made. The kinetics of hydration have been treated; apparent activation energies determined for a slag cement were ～49 KJ/mole compared with ～44 KJ/mole for the portland cement used in the blends.     

The alkali-silica reaction in alkali-activated granulated slag mortars with reactive aggregate

The expansion of alkali-activated granulated blast furnace slag (AAS) cement mortars with reactive aggregate due to alkali-silica reaction (ASR) was investigated. The alkaline activator used was NaOH solution with 4% Na₂O (by mass of slag). These results were compared to those of ordinary portland cement (OPC) mortars. The ASTM C1260-94 Standard Test Method based on the NBRI Accelerated Test Method was followed. The nature of the ASR products was also studied by SEM/EDX. The results obtained show that the AAS cement mortars experienced expansion due to the ASR, but expansion occurs at slower rate than with OPC mortars under similar conditions. The cause of the expansion in AAS cement mortars is the formation of sodium and calcium silicate hydrate reaction products with rosette-type morphology. Finally, in order to determine potential expansion due to ASR, the Accelerated Test Method is not suitable for AAS mortars because the reaction rate is initially slow and a longer period of testing is required.     

高强度碱矿渣水泥

本文研制了低水灰比高强度碱矿渣水泥。抗压强度高达350MPa以上。分析了工艺条件对水泥性能的影响以及强度与水化程度,孔隙率、孔分布的关系。比较了碱矿渣水泥和波特兰水泥的界面性能和耐蚀性。并对碱矿渣水泥的水化产物进行了x-射线衍射分析、红外光谱分析、差热分析、扫描电镜观察及能谱分析。     

Adsorption of superplasticizer admixtures on alkali-activated slag pastes

Alkali-activated slag (AAS) binders are obtained by a manufacturing process less energy-intensive than ordinary Portland cement (OPC) and involves lower greenhouse gasses emission. These alkaline cements allow the production of high mechanical strength and durable concretes. In the present work, the adsorption of different superplasticizer admixtures (naphthalene-based, melamine-based and a vinyl copolymer) on the slag particles in AAS pastes using alkaline solutions with different pH values have been studied in detail. The effect of the superplasticizers on the yield stress and plastic viscosity of the AAS and OPC pastes have been also evaluated.The results obtained allowed us to conclude that the adsorption of the superplasticizers on AAS pastes is independent of the pH of the alkaline solutions used and lower than on OPC pastes. However, the effect of the admixtures on the rheological parameters depends directly on the type and dosage of the superplasticizer as well as of the binder used and, in the case of the AAS, on the pH of the alkaline activator solution. In 11.7-pH NaOH-AAS pastes the dosages of the superplasticizers required to attain similar reduction in the yield stress are ten-fold lower than for Portland cement. In this case the superplasticizers studied show a fluidizing effect considerably higher in 11.7-pH NaOH-AAS pastes than in OPC pastes. In 13.6-pH NaOH-AAS pastes, the only admixture observed to affect the rheological parameters is the naphthalene-based admixture due to its higher chemical stability in such extremely alkaline media.     

Studies on blended cements containing a high volume of natural pozzolans

This paper presents the results of an investigation on the characteristics of laboratory-produced blended portland cements containing 55% by weight volcanic tuffs from Turkey. Volcanic tuffs from two different resources were used. Using different grinding times, particle size distribution, setting time, compressive strength, and alkali-silica activity of the blended cements were investigated and compared with reference portland cements ground for the same time period. For the compressive strength test, a superplasticizer was used to obtain mortar mixtures of adequate workability at a constant water-to-cement (w/c) ratio of 0.45. Compared to portland cement, the blended cements containing 55% pozzolan showed somewhat lower strengths up to 91 days when the grinding time was 90 min. However, at 91 days, blended cements and portland cements ground for 120 min showed similar strength. Moreover, blended cements containing 55% natural pozzolans showed excellent ability to reduce the alkali-silica expansion.     

Strength optimization of “tailor-made cement” with limestone filler and blast furnace slag

The use of cements made with portland clinker and two or three additions has grown because they present several advantages over binary cements. Production of composite cements has produced a necessary shift in the manufacture process used in the cement industry. Now, it is known that the separate grinding and mixing technology is more convenient in order to produce these cements, called market-oriented or tailor-made cements. However, their optimum formulations require the help of methods of experimental design to obtain an appropriate performance for a given property with the least experimental effort.In this study, the interaction between limestone filler (LF) and blast-furnace slag (BFS) is analyzed in mortars in which portland cement (PC) was replaced by up to 22% LF and BFS. For this proposition, a two-level factorial design was used permitting to draw the isoresponse curves. Results show that compressive and flexural strength evaluated at 2, 7, 14, 28, 90 and 360 days are affected in different ways by the presence of mineral additions.     

Early activation and properties of slag cement

Early age activation of granulated blast-furnace slag (BFS) and blends of slag and portland cement (OPC) has been studied. Activators include sodium-hydroxide, sodium sulfate, alum (potassium aluminum sulfate), superplasticizer, and calcium aluminate cement. Heat of hydration, x-ray phase characterization, compressive strength, viscometry, pore size distribution and related characterization studies have been made. Activated BFS-cement mortars having equivalent strengths at 1 day to OPC have been prepared, which also have 28- and 90-day strengths exceeding those of the OPC. Mechanisms of activation are discussed.     

Alternative blended cement with ceramic residues: Corrosion resistance investigation on reinforced mortar

Blended cements are largely used for concrete: they are usually considered cements with a low environmental impact, as they require less clinker than ordinary Portland cement (OPC). Different constituents can be used as supplementary clinker component usually leading to cement with high resistance to outdoor environment. Polishing residue (PR), coming from porcelain stoneware tiles production, can be successfully used as new constituent for blended cement, however its action for enhancing the durability of cement matrix must be assessed. With this purpose, electrochemical tests (half cell potential, impressed voltage and linear polarization techniques) have been carried out on steel reinforced mortar samples, prepared using a 25% PR based cement and 100% OPC as binder and exposed to a 3.5% NaCl solution. The corrosion resistance results and microstructure analysis highlight better durability performances for PR based cement than those exhibited by OPC, mainly for curing time > 28 days.     

Multi-phase hydration model for prediction of hydration-heat release of blended cements

Recently, the heat release during cement hydration and the so-caused temperature rise was exploited for (i) identification of material properties of early-age cement-based materials (stiffness, strength), and (ii) determination of the diameter and the cement content of jet-grouted structures. In this paper, the underlying hydration model for determination of the heat release and its rate is refined for Ordinary Portland Cements (OPC) and extended towards blended cements. Hereby, the overall degree of hydration with one kinetic law is replaced by a multi-phase hydration model, taking the hydration kinetics of the main clinker phases into account. As regards blended cements, which are commonly used in engineering practice, the effect of slag hydration is incorporated into the presented multi-phase model. The developed hydration model for both plain and blended cement is validated by means of differential-calorimetry (DC) experiments.