Supplementary cementitious materials for mitigating degradation of kraft pulp fiber-cement composites

Kraft pulp fiber reinforced cement-based materials are being increasingly used where performance after exposure to environmental conditions must be ensured. However, significant losses in mechanical performance due to wet/dry cycling have been observed in these composites, when portland cement is the only cementitious material used in the matrix. In this research program, the effects of partial portland cement replacement with various supplementary cementitious materials were investigated. Binary, ternary, and quaternary blends of silica fume, slag, Class C fly ash, Class F fly ash, metakaolin, and diatomaceous earth/volcanic ash blends were examined for their effect on the degradation of kraft pulp fiber-cement composite mechanical properties (i.e., strength and toughness) during wet/dry cycling. After 25 wet/dry cycles, it was shown that binary composites containing 90% slag, 30% metakaolin, or greater than 30% silica fume did not exhibit any signs of degradation, as measured through mechanical testing and microscopy. Ternary blends containing 70% slag/10% metakaolin or 70% slag/10% silica fume were also effective in preventing degradation. A reduction in calcium hydroxide content and the stability of the alkali content due to supplementary cementitious material addition were shown to be primary mechanisms for improved durability.     

几种超细矿粉抑制混凝土碱骨料反应的试验研究

利用ASTM C441方法检验了矿物质超细粉对混凝土碱硅酸反应ASR的抑制作用，并利用小混凝土柱法检测了其抑制碱碳酸盐反应ACR的效果。试验表明，矿渣、粉煤灰、沸石等混合材掺入混凝土中均可以抑制ASR的发生，且偏高岭土和沸石粉的效果优于粉煤灰，粉煤灰又优于矿渣。矿物质混合材对ACR膨胀也有抑制作用，但效果不明显，掺30％的粉煤灰和30％A型偏高岭土超细粉试件的28d膨胀率为0．0953％和,0.108％，掺加其它混合材的小混凝土柱膨胀率则在0．12％-0．16％之间。     

The rheological properties of ternary binders containing Portland cement,limestone, and metakaolin or fly ash

The influence of limestone particle size and the type and extent of (partial) cement replacement on the yield stress and plastic viscosity of ternary pastes are studied. Interpretations based on Bingham model indicate: (i) for binary/ternary blends containing coarse limestone, the yield stress and plastic viscosity remain unchanged or decrease with increasing cement replacement, (ii) in ternary blends, plastic viscosity increases with the fine limestone content, and (iii) the yield stress in ternary blends containing fly ash is dependent on the limestone content and fineness whereas in blends containing metakaolin, the yield stress reduces with an increase in limestone content, irrespective of the limestone particle size. These are attributed to: particle packing, water demand, and the interparticle spacing and contacts which are quantified using microstructural simulations. The yield stress and plastic viscosity show strong direct correlations to the specific surface area and inverse correlations to the water film thickness.     

An extended chemical index model to predict the fly ash dosage necessary for mitigating alkali–silica reaction in concrete

Currently, the concrete prism test per ASTM C1293 or RILEM AAR-3 is considered the most reliable accelerated test to determine the dosage of pozzolans to suppress alkali–silica reaction (ASR) in concrete. However, the test takes 2 years, which makes it impractical as a mixture design tool for new concrete construction. In the present work, a multiple nonlinear regression model is developed for predicting the fly ash dosage necessary to mitigate ASR per CPT. The model uses the oxide compositions of Portland cement and fly ash as well as the reactivity of the aggregates. Seventy-six experimental data points on CPT expansion results for plain Portland cement and fly ash-blended concrete mixtures were used to develop and evaluate the model. The model successfully predicts the fly ash required to mitigate ASR for different aggregates, cement, and fly ash combinations. The prediction errors in most cases meet ASTM C1293 multi-laboratory precision criterion.     

Physico-chemical interaction between mineral admixtures and OPC–calcium sulfoaluminate (CSA) cements and its influence on early-age expansion

The present study aims at examining the physico-chemical factors influencing the expansion characteristics of OPC–CSA blend in the presence of mineral admixtures. Three different admixtures: Class ‘F’ fly ash (‘F’FA), Class ‘C’ fly ash (‘C’FA) and silica fume (SF) were used as 15%, 15% and 5% replacement of total cementitious binder. Longitudinal expansion of cement pastes prepared at w/cm – 0.44 showed that the Class ‘F’FA increased the expansion whereas the Class ‘C’FA and SF reduced the expansion. The pore solution of the OPC–CSA cement pastes was extracted at different ages to monitor the concentration of various ionic species. The saturation level of ettringite was determined using a geochemical modeling program (GEMS). Furthermore, an upper bound of crystallization stress was estimated. The expansion behavior in the presence of Class ‘F’FA and SF was found to be influenced by the changes in the stiffness, whereas the expansion of the Class ‘C’FA-based mixture was governed by faster hydration of ye'elimite.     

Influence of fly ash and its mean particle size on certain engineering properties of cement composite mortars

An experimental investigation on the effects of incorporating large volumes of fly ash on the early engineering properties and long-term strength of masonry mortars is reported. The effect of fly ash and its mean particle size (PD) on the variation of workability and strength has been studied. It was found that fly ash and its mean particle size play a very significant role on the strength of masonry mortars. It has been observed that the early-term strength, except the mortars incorporating coarse fly ash (CFA), was slightly influenced by the replacement with fly ash. The long-term strength (both the bond strength and the compressive strength) will significantly increase, especially for the bond strength of mortars incorporating coarse fly ash. It was also found that the bond strength significantly increased as the mean particle size of fly ash decreases after 28 days curing. However, the 7-day strength was little influenced by fly ash particle size. The fluidity of composite mortar enhanced due to replace cement and lime with fly ash, and the mean PD of fly ash significantly influenced the workability.     

Slag-fly ash and slag-metakaolin binders: Part II—Properties of precursors and NMR study of poorly ordered phases

Sodium silicate-activated slag-fly ash binders (SFB) and slag-metakaolin binders (SMKB) are room-temperature hardening binders that have excellent mechanical properties and a significantly lower carbon footprint than ordinary Portland cement (OPC). The aim of this study was to use nuclear magnetic resonance (NMR) spectroscopy to study the nanostructure of poorly ordered phases in SFB by varying slag/fly ash ratio, curing time, and curing temperature. Fly ash was completely substituted with metakaolin and the effect of this substitution on the poorly ordered phases was studied. It was observed that the proportion of geopolymer was generally higher in SMKB when compared to SFB. Although C–N–A–S–H and geopolymer coexisted in SFB and SMKB, C–N–A–S–H was the major product phase formed. The mean chain length (MCL) and the structure of C–N–A–S–H gel were estimated as a function of time, temperature, and slag/fly ash ratio. The MCL was found to have a negative correlation with slag/fly ash ratio and Ca/(Si+Al) ratio, but positive correlation with curing temperature. The average Si/Al atom ratios for geopolymers were also estimated. Lastly, the increased proportion of five-coordinated aluminum (Al(V)) in metakaolin resulted in the decreased unreacted metakaolin in the hardened binder but did not increase the geopolymer content.     

High temperature behaviour of ambient cured alkali-activated materials based on ladle slag

This paper investigates the thermal properties of alkali activated materials (AAMs) made from ladle slag, a by-product from electric arc furnaces. AAMs have the potential to exhibit improved durability in high temperature environments over conventional materials such as ordinary Portland cement due to a reduced concentration of hydrated phases in their structure. A series of samples with varying compositional ratios was synthesised from a combination of ladle slag and metakaolin or ladle slag and fly ash. Ambient cured AAMs of moderate compressive strengths (between 11 and 46 MPa) were achieved. Samples were exposed to temperatures up to 1000 °C and analysed for residual strength, thermal expansion, phase and microstructural changes. The ladle slag and fly ash based AAMs exhibited superior strength gains and better thermal stability than the ladle slag and metakaolin based AAMs believed to be due to unstable C–A–S–H phases formed in the latter group of samples.     

Formulating a low-alkalinity, high-resistance and low-heat concrete for radioactive waste repositories

Investigations were carried out in order to formulate and characterize low-alkalinity and low-heat cements which would be compatible with an underground waste repository environment. Several systems comprising Ordinary Portland Cement (OPC), a fast-reacting pozzolan (silica fume (SF) or metakaolin (MK)) and, in some cases, a slow-reacting product (fly ash (FA) or blastfurnace slag (BFS)) were compared. Promising results were obtained with some binary mixtures of OPC and SF, and with some ternary blends of OPC, SF and FA or BFS: pH of water in equilibrium with the fully hydrated cements dropped below 11. Dependence of the properties of standard mortars on the high contents of FA and SF in the low-pH blends was examined. Combining SF and FA seemed attractive since SF compensated for the low reactivity of FA, while FA allowed to reduce the water demand, and dimensional variations of the mortars. Finally, low-heat (ΔT < 20 °C under semi-adiabatic conditions) and high strength (≈ 70–80 MPa) concretes were prepared from two low-pH cements: a binary blend made from 60% of OPC and 40% of SF, and a ternary blend including 37.5% OPC, 32.5% SF and 30% FA.     

High-percentage replacement of cement with fly ash for reinforced concrete pipe

Fly ash is commonly used as a substitute for cement within concrete in various applications. Manufacturers of reinforced concrete products commonly limit the quantity of fly ash used to 25% or less by weight. Test cylinders with varying percentages of Class C (25-65%) and Class F (25-75%) fly ash and a water-reducing admixture (WRA) were created under field manufacturing conditions and tested for 7-day compressive strength. Seven-day compressive strength for the concrete/fly ash/WRA was found to be highest when the concrete mix included approximately 35% Class C or 25% Class F fly ash. However, substitution ratios of up to 65% Class C or 40% Class F fly ash for cement met or exceeded American Society for Testing and Materials (ASTM) strength requirements for manufacture of Class I, II and III reinforced concrete pipe (RCP).     

Performance characteristics of high-volume Class F fly ash concrete

More than 88 million tonnes of fly ash is generated in India each year. Most of the fly ash is of Class F type. The percentage utilization is around 10 to 15%. To increase its percentage utilization, an extensive investigation was carried out to use it in concrete. This article presents the results of an experimental investigation dealing with concrete incorporating high volumes of Class F fly ash. Portland cement was replaced with three percentages (40%, 45%, and 50%) of Class F fly ash. Tests were performed for fresh concrete properties: slump, air content, unit weight, and temperature. Compressive, splitting tensile, and flexural strengths, modulus of elasticity, and abrasion resistance were determined up to 365 days of testing.Test results indicated that the use of high volumes of Class F fly ash as a partial replacement of cement in concrete decreased its 28-day compressive, splitting tensile, and flexural strengths, modulus of elasticity, and abrasion resistance of the concrete. However, all these strength properties and abrasion resistance showed continuous and significant improvement at the ages of 91 and 365 days, which was most probably due to the pozzolanic reaction of fly ash. Based on the test results, it was concluded that Class F fly ash can be suitably used up to 50% level of cement replacement in concrete for use in precast elements and reinforced cement concrete construction.     

硅灰、偏高岭土对矿渣-粉煤灰微珠胶凝材料性能的影响

首先通过改变粉煤灰微珠掺量,确定满足快速修补要求的矿渣-粉煤灰微珠胶凝材料基体的最佳配比,再调节偏高岭土、硅灰掺量,研究其对复合胶凝材料凝结时间、力学性能和水化机理的影响。研究发现,偏高岭土对凝结时间的改变较硅灰更敏感。通过化学结合水测试,分析了不同硅灰和偏高岭土掺量对矿渣-粉煤灰微珠胶凝材料水化反应程度影响的原因。力学实验结果表明：矿渣-粉煤灰微珠胶凝基体复合掺加5%硅灰（质量分数）+15%偏高岭土（质量分数）,试块2 h抗压强度为11.5 MPa、28 d抗压强度达到75.2 MPa,且呈现缓慢递增的趋势。     

Comparative performance of geopolymers made with metakaolin and fly ash after exposure to elevated temperatures

This paper presents the results of a study on the effect of elevated temperatures on geopolymers manufactured using metakaolin and fly ash of various mixture proportions. Both types of geopolymers (metakaolin and fly ash) were synthesized with sodium silicate and potassium hydroxide solutions.

The strength of the fly ash-based geopolymer increased after exposure to elevated temperatures (800 °C). However, the strength of the corresponding metakaolin-based geopolymer decreased after similar exposure. Both types of geopolymers were subjected to thermogravimetric, scanning electron microscopy and mercury intrusion porosimetry tests. The paper concludes that the fly ash-based geopolymers have large numbers of small pores which facilitate the escape of moisture when heated, thus causing minimal damage to the geopolymer matrix. On the other hand, metakaolin geopolymers do not possess such pore distribution structures. The strength increase in fly ash geopolymers is also partly attributed to the sintering reactions of un-reacted fly ash particles.     

不同炉型潞安煤灰理化及酸/碱溶解特性

对潞安煤经循环流化床、煤粉炉和气化炉处理后得到的煤灰进行了化学组成、矿物组成、特征基团、粒径分布、比表面积及微观形貌等理化性质的对比研究,并考察了其在酸浸和碱浸过程中Al^3+,Si^4+,Fe^3+,Ca^2+,K^+和Ti^4+等离子的溶解特性。结果表明:不同炉型潞安煤灰中铝、钙、硫等元素的含量有明显的差异;矿物组成包括晶相的鳞石英、方石英、莫来石、硬石膏及非晶相的偏高岭石、假莫来石、无定型二氧化硅等;相比较而言,气化炉灰中铝硅酸盐矿物结构更加不稳定。循环流化床灰颗粒呈具有一定孔洞结构的不规则状,而煤粉炉灰和气化炉灰均为光滑球形颗粒,循环流化床灰的粒径>煤粉炉灰的粒径>气化炉灰的粒径,循环流化床灰的比表面积>气化炉灰的比表面积>煤粉炉灰的比表面积。在HCl溶液中,Al^3+,Fe^3+,Ca^2+,K^+,Ti^4+的溶出率均较高;在NaOH溶液中,仅Si^4+和K^+的溶出率较高。不同炉型潞安煤灰中各元素的溶出率具有较大差异,主要与其矿物组成、结构稳定性、粒径和比表面积等相关。     

New technique for improvement on reactivity of cement industry wastes

Abstract

A new technique, in which fly ash was first ground before grinding together with cement kiln dust (CKD), was developed in order to activate reactivity of CKD–fly ash systems. Test results of particle size distribution, rate of heat evolution and compressive strength of mixtures made with the new technique are discussed and compared with those of mixtures made with previous technique, in which CKD and fly ash were ground together without prior grinding of fly ash. The test results showed that CKD–fly ash mixtures made with the new technique exhibited significantly improved performance in comparison with that of mixtures made with the previous process.     

Method for Direct Determination of Glassy Phase Dissolution in Hydrating Fly Ash‐Cement System Using X‐ray Diffraction

A method for quantitative X‐ray diffraction analysis is developed for direct determination of the glassy phase content of fly ash in a hydrating binary blend of cement and low‐calcium, siliceous fly ash. The intensity contributions of the unhydrated glassy phase of fly ash and the amorphous reaction products to the intensity pattern of the total amorphous phase in the hydrating binary blend are obtained by decomposition of the total intensity signature as a sum of component pseudo Voigt (PV) peaks. An experimental program involving binary blends with three different low calcium siliceous fly ashes and two different curing temperatures is reported. The centers of the component PV peaks of the fly ash glassy phase fitted to the overall intensity pattern are found to be invariant. The glassy phase content of hydrating binary blends determined from the XRD method were found to agree well with the values obtained from a selective dissolution method.     

Preparation and Characterization of Nano structured Materials from Fly Ash: A Waste from Thermal Power Stations, by High Energy Ball Milling

The Class F fly ash has been subjected to high energy ball milling and has been converted into nanostructured material. The nano structured fly ash has been characterized for its particle size by using particle size analyzer, specific surface area with the help of BET surface area apparatus, structure by X-ray diffraction studies and FTIR, SEM and TEM have been used to study particle aggregation and shape of the particles. On ball milling, the particle size got reduced from 60 μm to 148 nm by 405 times and the surface area increased from 0.249 m²/gm to 25.53 m²/gm i.e. by more than 100%. Measurement of surface free energy as well as work of adhesion found that it increased with increased duration of ball milling. The crystallite was reduced from 36.22 nm to 23.01 nm for quartz and from 33.72 nm to 16.38 nm for mullite during ball milling to 60 h. % crystallinity reduced from 35% to 16% during 60 h of ball milling because of destruction of quartz and hematite crystals and the nano structured fly ash is found to be more amorphous. Surface of the nano structured fly ash has become more active as is evident from the FTIR studies. Morphological studies revealed that the surface of the nano structured fly ash is more uneven and rough and shape is irregular, as compared to fresh fly ash which are mostly spherical in shape.     

Early longitudinal dimensional changes of fresh fly ash mortar exposed to drying conditions

The present work examines the effect of fly ash (ASTM Class F) on early longitudinal dimensional changes in fresh cement-fly ash (10, 25 and 40 percent cement replacement) mortar mixes exposed to drying conditions immediately after casting at elevated temperature (30 C, 86 F).

It was found that the fly ash affects expansion in the fresh mortar mix: the larger the cement replacement percentage (i.e. increased amount of fly ash in the mix), the higher the expansion values and the longer its duration. However, the effect of the fly ash on plastic shrinkage during drying has no clear trend, as it is governed both by the preceding expansion and by the duration of the shrinkage phase (both influenced in turn by the specific chemical composition and physical properties of the fly ash and the cement).     

Characteristics and pozzolanic reactivity of glass powders

This paper deals with the morphology, fineness and pozzolanic activity of four glass powders: one (GP-fine) from the screening of crushed waste glasses, one (GP-dust) from a dust collector for the glass crushing process and two (GP-4000 and GP-6000) from further grinding of the powder from the dust collector in a ball mill. GP-fine and GP-dust consist mainly of large flaky particles, while GP-4000 and GP-6000 consist mainly of small angular particles. The finenesses of these glass powders are measured by particle size distribution and Blaine fineness method. For a similar particle size distribution, ground glass powder has a higher Blaine specific surface area than Portland cement due to the angular morphology of glass particles. Finely ground glass powders exhibited very high pozzolanic activity. The finer the glass powder is, the higher its pozzolanic reactivity is. An increase in curing temperature accelerates the activation of pozzolanic reactivity of both glass powder and coal fly ash in terms of strength development rate. Mortar cube strength results (ASTM C109) indicated that curing temperature has a greater influence on the glass powder than on fly ash. The rapid mortar bar expansion test (ASTM C1260) results indicate that the replacement of Portland cement with ground glass powder also reduces the expansion due to alkali-aggregate reactions, although it is not as effective as coal fly ash.     

The effect of pozzolans and slag on the expansion of mortars cured at elevated temperature: Part II: Microstructural and microchemical investigations

The microstructural and microchemical development of heat-cured Portland cement mortars containing silica fume, metakaolin, blast-furnace slag, and fly ash were analysed using pore solution analysis, X-ray diffraction (XRD) and scanning electron microscopy (SEM) with energy-dispersive X-ray analysis (EDX). Incorporation of these materials into the mixture modifies the composition of the C-S-H gel, the quantities of the hydration products, and the microstructure. Ettringite was formed during moist storage in all specimens, but was not accompanied by expansion where a sufficient amount of metakaolin, blast-furnace slag, or a suitable fly ash replaced a proportion of the Portland cement; replacement with silica fume was not as effective at eliminating expansion. The different behaviour of silica fume from the other supplementary cementing materials is believed to reflect a difference in the way ettringite is formed in the presence of Al₂O₃-bearing mineral admixtures.