Ground iron blast furnace slag as a matrix for cellulose-cement materials

The use of ground iron blast furnace slag (BFS) as a low-cost alternative to ordinary Portland cement (OPC) binders in fibre-cement products was examined. Both high quality softwood fibres and residual sisal from agricultural waste were chemically pulped and used as reinforcement. Composites based on several different binder formulations consisting of slag chemically activated by mixtures of gypsum and hydrated lime displayed their optimum strength and fracture toughness properties at fibre contents between 8% and 12%, with values in the ranges of 14.7–24.5 MPa and 1.13–2.36 kJ/m², respectively. Corresponding flexural moduli lay in the range 4.3–7.8 GPa and, at 12% fibre content, the composites possessed water absorption values up to 34% by mass and densities in the region of 1.3 g/cm³. A formulation of BFS activated by 10% gypsum and 2% lime presented a good compromise between strength and energy absorption combined with a reasonable price.     

石膏对石灰石粉水泥基材料水化及硬化性能的影响

针对我国目前非荷载作用下混凝土严重开裂的问题,以"比表面积较低的水泥熟料-比表面积较高的掺合料-足够掺量的石膏"构成的胶凝材料体系为研究对象,通过水化热速率、X射线衍射(XRD)、扫描电子显微镜(SEM)、压汞法(MIP)及热重-差示扫描量热法(TG-DSC)等手段,研究石膏对石灰石粉水泥基材料水化及硬化体微结构的影响。结果表明,石灰石粉能够加速C3A与石膏作用生成钙矾石相,在足量石膏存在的条件下,能够阻碍钙矾石向低硫型硫铝酸钙转变;石灰石粉的掺入与石膏一起延缓了C3A的水化;在石灰石粉和足够石膏同时存在的情况下,C3A水化生成具有膨胀性的水化碳铝酸钙和高硫型硫铝酸钙,补偿了收缩,提高了水泥基材料的抗裂性能;熟料粗磨、掺合料细磨及较高石膏掺量的胶凝材料体系配制的C30和C50等级混凝土,强度能持续增大,从28d到180d,强度分别提高了36.7%和33.3%,混凝土结构紧密、孔隙率低、有害孔含量少。     

Potential application of coal-fuel oil ash for the manufacture of building materials

In this paper coal-fuel oil ash has been characterized in terms of leaching behaviour and reactivity against lime and gypsum in hydratory systems for the manufacture of building materials. Its behaviour was also compared to that of coal ash. Metal release was measured in a dynamic leaching test with duration up to 16 days. The results have shown that coal-fuel oil ash behaves very similarly to coal ash. The reactivity of coal-fuel oil ash against lime and gypsum was measured in mixtures containing only lime and in mixtures containing both lime and gypsum. These systems were hydrated at 25 and 40 degrees C under 100% R.H. The results have shown that the main hydration products are the same as those that are usually formed in similar coal ash-based systems. That is, calcium silicate hydrate in coal-fuel oil ash/lime systems and calcium silicate hydrate plus calcium trisulphoaluminate hydrate in coal-fuel oil ash/lime/gypsum systems. From the quantitative point of view, hydration runs showed that the amounts of both chemically combined water and reacted lime measured in the case under investigation are very similar to those found in similar coal ash-based systems. Finally, the measurement of unconfined compressive strength proved that the systems have potentiality for the manufacture of pre-formed building blocks.     

改性石膏对磷渣混凝土强度激发作用的研究

本文通过实验手段,研究了改性石膏对磷渣混凝土强度的影响,并结合XRD、SEM分析改性石膏-磷渣混凝土水化产物的结晶形态和矿物组成。结果表明：在磷渣粉掺量相同的情况下,加入天然石膏、120℃烧石膏、550℃烧石膏激发剂后,水化产物主要是水化硅酸钙、钙矾石,因此,磷渣混凝土抗压强度有了不同程度的提高,其中外掺6%的550℃烧石膏作激发剂的磷渣混凝土抗压强度最大。     

循环流化床固硫灰渣低收缩水泥的制备及性能

通过分别使用循环流化床(CFBC)固硫灰、渣代替部分原材料制备低收缩水泥熟料,加入质量分数为10%的石膏即得到CFBC固硫灰、渣低收缩水泥,然后利用X射线衍射、扫描电镜等方法研究水与水泥的质量比(简称水灰比)对CFBC固硫灰渣低收缩水泥水化程度、抗压强度和线性膨胀率的影响。结果表明,随着水灰比的增加,CFBC固硫灰渣低收缩水泥的主要水化产物钙矾石数量增多,未水化的硅酸二钙含量减少,水化程度增大;而该水泥线性膨胀率与水灰比呈正比关系,抗压强度与其呈反比关系;利用固硫灰制备的水泥早期膨胀率随着水化时间而增大,但后期由于石膏量的不足,膨胀率则随着水化时间而减小。     

A hydration study of various calcium sulfoaluminate cements

The present work studies the hydration process and microstructural features of five calcium sulfoaluminate (CSA) cements and a ternary mixture including also ordinary Portland cement (OPC). The pastes were studied with simultaneous differential thermal-thermogravimetric (DTA-TG) analysis, mercury intrusion porosimetry (MIP), scanning electron microscopy (SEM), and expansion/shrinkage tests. The DTA-TG analysis confirmed the role of the hydration reactions involving the main CSA clinker constituent, tetracalcium trialuminate sulfate, which produced (i) ettringite when combined with lime and calcium sulfate, (ii) ettringite and aluminum hydroxide in the presence of calcium sulfate alone, and (iii) monosulfate and aluminum hydroxide in the absence of both lime and calcium sulfate. The MIP and SEM were able to discriminate between expansive (ternary mixture and CSA cement containing 50% gypsum) and non-expansive cements. Expansive cement pastes had (i) a nearly unimodal pore size distribution shifted toward higher radii and (ii) ettringite crystals smaller in size during the first day of curing. In a SEM image of a hardened paste of the CSA cement containing 50% gypsum, a stellate ettringite cluster was observed.     

Colemanite ore waste concrete with low shrinkage and high split tensile strength

A laboratory study was undertaken to assess the compressive and cylinder splitting tensile strength and drying shrinkage properties of concrete mixtures containing colemanite ore waste (CW). Possibility of using Kütahya–Emet CW in cement based materials as a shrinkage reducing ingredients was also discussed. Five concrete mixtures including Portland cement and CW concrete mixtures were prepared. The compressive strengths of concrete mixtures were measured at 7, 28, 56 and 90 days. The splitting tensile strength was measured at 28 days. The strength results showed that concrete mixtures containing 3 and 5% CW developed higher strength values than control concrete. The test results also showed that Kütahya–Emet CW reduced drying shrinkage of the mortar by 37% when compared to control concrete. Based on these results, it was concluded that Kütahya–Emet CW can be used as a cost-effective shrinkage-reducing agent.     

Effects of gypsum and phosphoric acid on the properties of sodium silicate-based alkali-activated slag pastes

In this paper, the effects of gypsum and phosphoric acid on the properties of sodium silicate-based alkali-activated slag paste were examined. Alkali-activated slag is recognized as a good performing binder. However, it suffers from fast setting and drying shrinkage. Phosphoric acid has been used as a retarder and gypsum has been used as a drying-shrinkage inhibitor in previous studies. However, it is not known what will happen if one adds both of them to alkali-activated slag. In this study, the effects of gypsum and/or phosphoric acid on the compressive strength development, setting time and drying shrinkage of alkali-activated slag were examined. Experimental results indicated that adding gypsum shortened the setting time, and at the same age, the compressive strength reached a higher value when the amount of used gypsum is higher. Drying-shrinkage decreased when the amount of used gypsum increased; however, when 0.82 M phosphoric acid was added in the activator with gypsum the results were somewhat different. With added phosphoric acid, adding more gypsum shortened the setting time as well. The compressive strength of specimens with added gypsum was lower than that of control specimens under 28 days. Drying-shrinkage increased with phosphoric acid as the amount of used gypsum increased.     

Influence of polyether polyol on the hydration and engineering properties of calcium sulfoaluminate cement

The aim of the present paper was to investigate the efficiency of polyether polyol as shrinkage-reducing admixture on pastes and mortars prepared with calcium sulfoaluminate cement (CSA). CSA was prepared by mixing CSA clinker and re-crystallized gypsum in different proportions. Three types of polyether polyol were added at a dosage of 1.5 wt% of CSA when hydrating pure pastes and standard mortars. The engineering properties of mortars (compressive strength, drying shrinkage) and the microstructure of pastes were investigated. The results show that polyol reduces drying shrinkage of CSA-based mortars without affecting the nature of hydrates formed. The effect of polyol mainly depends on its molecular weight.     

自燃煤矸石胶凝材料中钙矾石形成研究

采用XRD分析了自燃煤矸石胶凝材料中活性Al2O3在不同因素影响下水化形成钙矾石的情况.研究结果表明,在相同条件下芒硝存在,时自燃煤矸石中活性Al2O3水化生成钙矾石,而含等量硫的石膏存在时水化浆体中不但有水化产物钙矾石还有未反应的石膏;胶凝体系中不含熟石灰时,活性Al2O3水化首先生成石膏,随着水化的进行再转化成钙矾石,而在有熟石灰时水化则直接生成钙矾石;矿渣促进了自燃煤矸石中Al2O3水化形成钙矾石.     

On the interaction of Class C fly ash with Portland cement–calcium sulfoaluminate cement binder

Shrinkage cracking in concrete is a widespread problem, especially in concrete structures with high surface-to-volume ratio such as bridge decks. Expansive cements based on calcium sulfoaluminate phase were developed to mitigate the shrinkage cracking of concrete. The compressive stress induced due to restrained expansion of concrete has been shown to counteract the tensile stress generated during drying shrinkage. This research attempts to address the differential behavior of fly ash type (i.e., Class C vs. Class F) on early-age expansion and hydration characteristics of ordinary Portland cement (OPC)–calcium sulfoaluminate (CSA) cement blend. It was observed earlier that the presence of Class C fly ash (CFA), unlike Class F fly ash, shortened the expansion duration of OPC–CSA cement blend, which was hypothesized to be correlated to early depletion of gypsum. This paper presents a detailed verification of the hypothesis. Addition of external gypsum to OPC–CSA–CFA blend led to simultaneous increase in expansion and disappearance of a shoulder peak in the calorimetric curve. Thermodynamic calculations using a geochemical modeling program (GEMS-PSI) revealed higher saturation levels of ettringite in presence of external gypsum, which led to higher crystallization stress, and thereby increased expansion.     

活化煤矸石对水泥水化的影响

研究了活化煤矸石-氢氧化钙体系的水化热、水化产物成分以及活化煤矸石水泥体系的水化过程、水化产物的微结构,结果表明,在石膏的激发下,活化煤矸石能够发生二次水化,与Ca（OH）2反应形成钙矾石、水化硅酸钙、水化铝酸钙等有利于提高水泥石强度的水化产物;活化煤矸石水泥硬化浆体中Ca（OH）2的含量在水化3d时最多,而后随龄期逐渐减少;阐明了活化煤矸石能够降低水化产物中氢氧化钙的含量、抑制氢氧化钙晶体的生长和聚集,并改善水泥石结构．     

Analysis of cubic and orthorhombic C<Subscript>3</Subscript>A hydration in presence of gypsum and lime

Field emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD) have been used to study the microstructural changes and phase development that take place during the hydration of cubic (pure) and orthorhombic (Na-doped) tricalcium aluminate (C₃A) and gypsum in the absence and presence of lime. The results demonstrate that important differences occur in the hydration of each C₃A polymorph and gypsum when no lime is added; orthorhombic C₃A reacts faster with gypsum than the cubic phase, forming longer ettringite needles; however, the presence of lime slows down the formation of ettringite in the orthorhombic sample. Additional rheometric tests showed the possible effects on the setting time in these cementitious mixes.     

Properties of some cement stabilised compressed earth blocks and mortars

Findings from an on-going investigation into the effects of soil properties and cement content on physical characteristics of compressed earth blocks and soil mortars are presented. A series of test blocks were fabricated using a range of composite soils, stabilised with 5% and 10% cement, and compacted with a manual press. Results for saturated compressive strength, drying shrinkage, wetting/drying durability, and water absorption testing are presented in the paper. In conjunction with the block tests, workability and compressive strength characteristics of suitable soil: cement and cement: lime: sand mortars were also studied. Mortar consistency was assessed using cone penetrometer and slump tests. Water retention properties of the mortars were also measured. For a given compactive effort, the strength, drying shrinkage, and durability characteristics of the compressed earth blocks improved with increasing cement and reducing clay content. Slump testing proved the most reliable means of assessing soil: cement mortar consistency. Both the flow table and cone penetrometer tests were found to be unsuitable. Water retention properties of soil: cement mortars appear well-suited to typical unit water absorption characteristics. Mortar strengths were closely related to cement and clay contents, but as expected were less than the average unit strengths.     

How do recycled concrete aggregates modify the shrinkage and self-healing properties?

This paper presents the main results of a research carried out to analyze the mechanical properties, intrinsic permeability, drying shrinkage, carbonation, and the self-healing potential of concrete incorporating recycled concrete aggregates. The recycled concrete mixtures were designed by replacing natural aggregates with 0%, 30%, and 100% of recycled concrete gravel (RG) and 30% of recycled concrete sand (RS). The water to equivalent binder ratio was kept constant and recycled concrete aggregates were initially at saturated surface dried (SSD) state. The contribution of the porosity of natural and recycled aggregates to the porosity of concrete was estimated to understand the evolution of the intrinsic permeability and the open porosity. At long term, the maximum variation of drying shrinkage magnitude due to recycled concrete gravels did not exceed 15%. The correlation between drying shrinkage and mass-loss through “drying depth” concept showed that recycled concrete aggregates are affected by drying as soon as concrete is exposed to desiccation. A good correlation between 1-day compressive strength and 18-month carbonation depth was observed. The recycled concrete aggregates presented a good potential for self-healing as the relative recovery of cracks reached up to 60%.     

Carbonate binders: Reaction kinetics,strength and microstructure

This study focussed on the synthesis of calcium carbonate binders, in situ, from the reaction between hydrated lime and carbon dioxide (CO₂). The aim was to establish the characteristics of the calcium carbonate binders that are associated with its strength, which was considered as an indicator of binder performance. The role of the parameters that are known to play an important part in the kinetics of hydrated lime carbonation processes, in changing the strength of a binder was examined in detail.The parameters identified were CO₂ gas pressure, exposure time and the initial degree of compaction of raw material. All hydrated lime mixtures were prepared at a constant water/solid ratio of 0.25. The hydrated lime compacts made at a range of compaction water/solid ratio (W/S) of 0.25. The hydrated lime compacts made at a range of compaction pressures (0.65–6.0 MPa) were exposed to different CO₂ gas pressures (ambient to 2 MPa) for different periods of time. The resulting products were tested for the amount of Ca(OH)₂ that had converted to carbonate, and for compressive strength. A microstructural analysis of the products was carried out using scanning electron microscopy.The rate of Ca(OH)₂ conversion to carbonate seemed to be enhanced with increasing gas pressure, but it decreased with increasing compaction of the initial mixture. It was revealed that the crystalline state and the morphology of the carbonate formed, rather than the degree of conversion of calcium hydroxide into carbonate, is highly critical to the strength of the binder. The study concluded that in the development of calcium carbonate binder, it is important to meet the experimental conditions that favour the crystallisation of calcium carbonate.     

Strength,drying shrinkage,and water permeability of concrete incorporating ground palm oil fuel ash

In this study, palm oil fuel ash (POFA) was used as a pozzolanic material in concrete. The POFA was ground to obtain two different finenesses: coarse (CP) and fine (FP). A portion of ordinary type I Portland cement (OPC) was replaced by CP and FP at 10%, 20%, and 30% by weight of binder to cast concrete. Compressive strength, modulus of elasticity, drying shrinkage, and water permeability of concretes containing ground POFA were measured. The results showed that the compressive strength of the concrete increased with the fineness of the POFA. With 10% and 30% replacement of OPC by CP and FP, respectively, the compressive strength of the resulting concrete was as high as that of OPC concrete at 90 days. Moreover, the use of 10–30% of FP as a cement replacement in concrete reduced its drying shrinkage and water permeability. Finally, there was also a strong correlation between the compressive strength and the water permeability of ground POFA concrete.     

Strength of lime–fly ash compacts using different curing techniques and gypsum additive

Lime–fly ash mixtures are exploited for the manufacture of fly ash bricks finding applications in load bearing masonry. Lime–pozzolana reactions take place at a slow pace under ambient temperature conditions and hence very long curing durations are required to achieve meaningful strength values. The present investigation examines the improvements in strength development in lime–fly ash compacts through low temperature steam curing and use of additives like gypsum. Results of density–strength–moulding water content relationships, influence of lime–fly ash ratio, steam curing and role of gypsum on strength development, and characteristics of compacted lime–fly ash–gypsum bricks have been discussed. The test results reveal that (a) strength increases with increase in density irrespective of lime content, type of curing and moulding water content, (b) optimum lime–fly ash ratio yielding maximum strength is about 0.75 in the normal curing conditions, (c) 24 h of steam curing (at 80°C) is sufficient to achieve nearly possible maximum strength, (d) optimum gypsum content yielding maximum compressive strength is at 2%, (e) with gypsum additive it is possible to obtain lime–fly ash bricks or blocks having sufficient strength (>10 MPa) at 28 days of normal wet burlap curing.     

Rheological and hydration characterization of calcium sulfoaluminate cement pastes

Calcium sulfoaluminate (CSA) cements are currently receiving a lot of attention because their manufacture produces less CO₂ than ordinary Portland cement (OPC). However, it is essential to understand all parameters which may affect the hydration processes. This work deals with the study of the effect of several parameters, such as superplasticizer (SP), gypsum contents (10, 20 and 30 wt.%) and w/c ratio (0.4 and 0.5), on the properties of CSA pastes during early hydration. This characterization has been performed through rheological studies, Rietveld quantitative phase analysis of measured X-ray diffraction patterns, thermal analysis and mercury porosimetry for pastes, and by compressive strength measurements for mortars. The effect of the used SP on the rheological properties has been established. Its addition makes little difference to the amount of ettringite formed but strongly decreases the large pore fraction in the pastes. Furthermore, the SP role on compressive strength is variable, as it increases the values for mortars containing 30 wt.% gypsum but decreases the strengths for mortars containing 10 wt.% gypsum.     

Utilization of jarosite/alunite residue for mortars restoration production

The present study was carried out to produce artificial hydraulic lime mortars for repair and conservation of historic masonry using a jarosite/alunite precipitate, a waste product of a novel Greek hydrometallurgical process developed to treat economically low grade nickel oxides ores. Alternative mortars were prepared by mixing lime powder, quartz sand and the above residue, substituting lime up to 50%. The mortars were prepared and tested according to European Norm EN 1015. They were cured for periods of 28 and 90 days and the compressive and flexural strengths were determined. The best mechanical behavior was observed for the mortar with 50% lime replacement, which also presented a low ratio of compressive to flexural strength (f _c/f _f). X-Ray diffraction, TG-DTA and mercury porosimetry were used to characterize the hydration products at 28 and 90 days. The results showed that the jarosite/alunite residue was dissolved in the high alkaline environment of the mortar, producing CaSO₄ · 2H₂O and AlOOH. During hydration, gypsum and some of the Ca(OH)₂ were consumed, together with aluminum hydroxide in order to produce ettringite, a fact that improved the mechanical behavior of the produced mortars.