Efficiency of mineral admixtures in mortars: Quantification of the physical and chemical effects of fine admixtures in relation with compressive strength

This work is the fourth part of an overall project the aim of which was the development of general mix design rules for concrete containing different kinds of mineral admixtures. The two first parts presented the separation and quantification, by means of an empirical model based on semi-adiabatic calorimetry measurements, of the different physical effects responsible for changes in cement hydration (short terms) when chemically inert quartz powders were used in mortars. Part three dealt with an intensive experimental program, presenting and commenting more than 2000 compressive strength measurements. This program concerned 1 day to 6 months old mortars containing up to 75% of inert and pozzolanic admixtures. All these compressive strength results are analyzed in this fourth part and the influence of three effects, namely dilution, heterogeneous nucleation and the pozzolanic effect, are discriminated and quantitatively evaluated. An efficiency concept is proposed in order to take into account the effect of mineral admixture in mortars from both the physical and chemical points of view. It uses an efficiency function ξ(p) that has notable properties: it is independent of time, independent of fineness and independent of the type of mineral admixture.     

Mineral admixtures in mortars: Quantification of the physical effects of inert materials on short-term hydration

This work is the second part of an overall project, the aim of which is the development of general mix design rules for concrete containing different kinds of mineral admixtures. The first part presented the separation of the different physical effects responsible for changes in cement hydration when chemically inert quartz powders are used in mortars. This second part describes the development of an empirical model, based on semiadiabatic calorimetry measurements, which leads to the quantification of the enhancement of cement hydration due to the heterogeneous nucleation effect at short hydration times. Experimental results show that not all the admixture particles participate in the heterogeneous nucleation process. Consequently, the concept of efficient surface S_eff is introduced in the model. S_eff is the total admixture surface S (m² of mineral admixture/kg of cement) weighted by a function ξ(p). The efficiency function ξ(p) depends only on the replacement rate p and is independent of time, fineness and type of mineral admixture used. It decreases from 1 to 0: Low replacement rates give an efficiency value near 1, which means that all admixture particles enhance the hydration process. An efficiency value near 0 is obtained for high replacement rates, which indicates that, from the hydration point of view, an excess of inert powder does not lead to an increase in the amount of hydrates compared with the reference mortar without mineral admixture. The empirical model, which is mainly related to the specific surface area of the admixtures, quantifies the variation of the degree of hydration induced by the use of inert mineral admixtures. One application of the model, coupled with Powers' law, is the prediction of the short-term compressive strength of mortars.     

Mineral admixtures in mortars effect of type, amount and fineness of fine constituents on compressive strength

This work is the third part of an overall project the aim of which is the development of general mix design rules for concrete containing different kinds of mineral admixtures (also named mineral additions or mineral constituents). It deals with the compressive strength of mortars made with up to 75% of crushed quartz, limestone filler or fly ash of different fineness. The paper presents all the experimental results as a sort of database and emphasizes the effects on strength of the nature, amount and fineness of mineral admixtures. For short hydration times (1 to 2 days), the nature of mineral admixture is not a significant parameter, as mortars containing the same amount of different kinds of admixtures having equivalent fineness present similar strengths. For long hydration times (up to 6 months), the excess strength due to fly ash pozzolanic activity is quantified by the difference between the strengths of mortars containing the same proportions of inert and pozzolanic admixtures with the same fineness. In the case of inert mineral admixtures, the increase in strength with the fineness of mineral admixtures cannot be explained by the filler effect, but can be attributed to the physical effect of heterogeneous nucleation. In the next part of this work, these results will be used for the elaboration of an empirical model leading to the quantification of both physical and chemical effects. This model presents strong similarities with the previous model based on calorimetric results.     

含粉煤灰或石英粉复合胶凝材料的抗压强度发展规律

用细度基本相同的粉煤灰和石英粉作为活性和惰性矿物掺和料,研究了不同水胶比、不同养护温度条件下,矿物掺和料的种类和掺量对复合胶凝材料抗压强度发展特性的影响.在水化初期,颗粒形貌等物理因素比反应程度等化学因素更能影响含有矿物掺和料的复合胶凝材料的抗压强度发展特性,活性与惰性矿物掺和料的作用基本相同.热激发能明显促进粉煤灰的火山灰反应,有利于含粉煤灰的复合胶凝材料的抗压强度发展.含大掺量粉煤灰的复合胶凝材料特别适合用于内部能较长时间维持较高温度的大体积混凝土结构.     

C-S-H纳米晶核对矿物掺合料复合胶凝材料水化性能的影响研究

水泥中掺入大量矿物掺合料易造成其早期强度低、施工周期长等问题。本文研究了C-S-H晶核对含矿物掺合料的复合胶凝材料体系水化性能的影响规律;通过热力学计算阐述了C-S-H晶核降低水化产物成核势垒的机理,并通过离子溶出与沉积探讨大掺量矿物掺合料胶凝体系水化机理。结果表明：矿物掺合料复合胶凝材料体系水化能力较弱,这是由于Ca²⁺溶出受到制约,C₃S的水化反应缓慢;当加入晶核后,水泥中硅酸盐相溶解-结晶能力得到大幅提升,使得矿物掺合料水泥体系的水化反应活性接近纯水泥体系。研究表明,C-S-H晶核可解决大掺量矿物掺合料胶凝体系所带来的水化能力严重不足问题。     

含有活性或惰性掺合料的复合胶凝材料硬化浆体的微观结构特征

用压汞法测定了不同温度条件下养护的含有粉煤灰或石英粉的复合胶凝材料硬化浆体的孔隙率.用扫描电镜观察了硬化浆体的微观形貌,同时测定了各种组成的复合胶凝材料的净浆强度.常温水化初期,活性与惰性矿物掺合料都只具有物理填充的作用,硬化浆体的孔隙率和强度由矿物掺合料的掺量所决定.高温水化条件下粉煤灰的火山灰反应提前发生.随水化龄期延长,粉煤灰逐渐发生火山灰反应,使硬化浆体结构密实,其强度逐步提高.活性与惰性矿物掺合料对复合胶凝材料浆体结构与性能的影响的差异在水化后期逐渐显现.     

Effect of waste aluminosilicate material on cement hydration and properties of cement mortars

The effect of waste material (catalyst used previously in catalytic cracking of petroleum in fluidized bed—fluidized bed cracking catalyst denoted as FBCC) on cement hydration kinetics was investigated in terms of fineness of this admixture. The compressive strength and microstructure of cement mortars were also examined. Variable percentage of this aluminosilicate admixture, originating from batches of quite different grain size composition, was introduced to cement pastes. Further on, cement mortars were produced using the material of higher activity, as it has been found in admixtured cement investigations. The waste was added as cement replacement or, partially, as sand replacement. The activity of waste catalyst was strongly related to the fineness—finer grains indicate better activity. In the presence of a FBCC admixture, the Ca(OH)₂ content decrease in cement pastes due to the pozzolanic reaction is observed. The surface area of hydrated paste becomes higher and, simultaneously, the mean pore diameter decreases, as compared to reference sample, without admixture. The strength improvement is observed particularly when the aluminosilicate material is introduced as partial sand replacement.     

-3 ℃养护下考虑矿物掺合料影响的水泥水化程度计算模型

针对多年冻土地区工程施工时混凝土养护的问题,采用10%、20%、30%的矿粉和粉煤灰替代量等量替代水泥,测试了-3 ℃恒温养护条件下0.38水胶比水泥浆体在各个龄期的水泥水化热,计算了水泥水化程度;分析了龄期及矿物掺合料对水泥水化程度的影响规律,建立了综合考虑龄期和矿物掺合料替代量的水泥水化程度计算模型.结果表明:-3 ℃恒温养护下,矿物掺合料等量替代水泥,水泥浆体的水化程度会降低,粉煤灰降低水化程度的值要比矿粉高;在相同矿物掺合料替代量下,随着龄期的增长,矿物掺合料对水泥水化程度的影响逐渐减弱;同一龄期时,随着矿物掺合料的增加,矿物掺合料对水泥水化程度的影响逐渐增强;利用建立的模型计算了分别掺入15%矿粉和粉煤灰的水泥水化程度,与实测值相比,计算值偏离值较少,预测精度较高.     

矿物掺合料改性磷酸镁水泥研究进展

在总结磷酸镁水泥水化产物、水化速度、孔结构、流动性和物理力学性能等的基础上,综述了粉煤灰、矿渣、硅灰、赤泥和偏高岭土等矿物掺合料对磷酸镁水泥的改性效果和作用机理。矿物掺合料改性磷酸镁水泥具有优异的物理力学性能和经济性,耐水性、严苛条件下耐久性、负温下水化硬化特征和矿物掺合料改性机制等课题尚待深入研究,以期为促进磷酸镁水泥及其修补砂浆在重点工程中的应用提供参考。     

水泥与外加剂相容性差的原因分析及解决措施

水泥与外加剂相容性的影响因素众多,如熟料矿物组成、粉磨工艺、水泥细度、混合材种类等.本文结合本公司的实际问题,分析了水泥与外加剂相容性差的原因,提出了相应的解决措施.结果表明,从改善熟料矿物组成和提高熟料烧成质量入手,可改善水泥与外加剂的相容性,效果显著.     

Potential use of natural perlite powder as a pozzolanic mineral admixture in Portland cement

This paper investigates the effect of incorporating natural perlite powder (NPP) as a cement replacement on cementitious materials properties. For this purpose, cement pastes and mortars were prepared by replacing 5, 10, 15, and 20% of NPP by mass of the Portland cement. Physicomechanical performances of pastes and mortars based NPP were inspected using normal consistency, setting times, heat of hydration, and compressive strength testing. Resistance against sodium sulfate attack and sulfuric acid attack were also assessed to investigate the durability characteristics of different mortar mixes. Experimental results show that cement pastes and mortars incorporating up to 20% of NPP demonstrate satisfactory physical and mechanical properties with very comparable results to cementitious materials without NPP. In addition, improved sulfate and acid attacks resistance with increased NPP content were demonstrated. The X-ray diffraction analyses confirm that NPP can be considered as a good pozzolanic material that can be used satisfactorily as a mineral admixture in cement production.     

A model to predict the amount of calcium hydroxide in concrete containing mineral admixtures

This study examines in detail the degree of reactivity of admixtures, such as fly ash and blast furnace slag, and their effect on the levels of calcium hydroxide in cement paste. Experimental results indicate that reactivity between calcium hydroxide and mineral admixture is dependent on the amount of calcium hydroxide and the degree of hydration of mineral admixtures.From these results, a model was formulated to predict the reaction between calcium hydroxide and mineral admixtures, and its validity verified by comparing calculated data with the data from the tests with cement mortar specimens. The calculated values of calcium hydroxide agree well with the test results. The parameters of the prediction model are dependent on the physical and chemical characteristics of mineral admixtures.     

矿物掺合料和减水剂对桥梁混凝土水泥石水化热的影响

采用等温量热法研究高效减水剂对普通、中热水泥掺入不同品种及不同掺量的掺合料后水化热的耦合作用规律,分析了减水剂、矿物掺合料及两者双掺对水泥水化热及放热速率的影响.结果表明:矿物掺合料可减缓水泥水化放热的速率,推迟放热峰值的出现,粉煤灰的缓凝效果和削峰效果较矿渣要显著.外加剂对掺粉煤灰水泥的早期水化热有显著的降低作用.     

Nanoparticles and Apparent Activation Energy of Portland Cement

Although chemically inert nanosize mineral fillers have been shown to modify early cement hydration kinetics, with the effects dependent upon usage rate, particle size, and dispersibility, the effects of such fillers on the “apparent activation energy” (E_a) of cement has not been previously examined. Here, cement E_a was calculated from isothermal calorimetry performed at different temperatures with two different types of fillers (i.e., titanium dioxide and limestone) using a linear method as well as a modified ASTM C1074 method. The use of both types of nanoparticles increased the rate of cement hydration as well as accelerated the reaction rate, due to heterogeneous nucleation effect, as previously demonstrated. E_a increased in the presence of nanosized fillers, demonstrating an increased temperature sensitivity of the filler‐cement composites relative to ordinary cement. These results show that chemically inert nanoparticles behave fundamentally differently compared with supplementary cementitious materials such as fly ash and silica fume which instead decrease temperature sensitivity. The increased temperature sensitivity could thus be used to modify and optimize the reaction mechanism and kinetics of cement hydration, especially to increase the rate of cement hydration, to decrease setting time, and to achieve faster strength gain accounting for higher or lower temperatures during curing.     

活性复合掺合料对水泥胶砂抗侵蚀性能影响

以防腐阻锈成分、粉煤灰、矿渣粉等量取代部分水泥,研究单掺防腐阻锈成分、双掺粉煤灰和矿渣粉以及复掺三者时对水泥胶砂抗蚀系数、电极电位的影响,并利用扫描电子显微镜(SEM)对不同复合掺合料水化产物和表面特征进行分析.试验结果表明:单掺FZJ的水泥胶砂,当掺量为6%时,其初始抗蚀系数比未掺的基准水泥胶砂高20%;双掺粉煤灰与矿渣粉的水泥胶砂,当两者掺量为65%时,100次循环后抗蚀系数远高于基准水泥胶砂,抗蚀效果显著;三者复掺最佳替代水泥量为71%时,56 d电极电位曲线趋向钝化,水泥胶砂的抗氯盐锈蚀效果最显著.电镜分析表明:防腐阻锈成分对粉煤灰、矿渣粉实现了碱改性,增加其二次水化活性,使三者复合掺合料的砂浆试块抗侵蚀性能随养护龄期的增长更加显著,为在氯盐、硫酸盐环境下矿物掺合料砂浆或混凝土耐久性研究提供应用技术.     

混凝土矿物掺合料的强度效应研究

矿物掺合料对混凝土具有重要的强度效应。本文认为掺有矿物掺合料的混凝土复合材料的强度由水泥混凝土基体（水泥浆体和砂石集料）产生的强度和帮物掺合料的物理和化学两方面效应对强度的贡献两部分构成，据此提出了全面估算混凝土矿物掺合料强度效应的新方法。并从理论和试验两方面分析了水胶化、掺合料掺量以有龄期对矿物掺合料强度效应的影响规律。     

Modeling the hydration of concrete incorporating fly ash or slag

Granulated slag from metal industries and fly ash from the combustion of coal are industrial by-products that have been widely used as mineral admixtures in normal and high strength concrete. Due to the reaction between calcium hydroxide and fly ash or slag, the hydration of concrete containing fly ash or slag is much more complex compared with that of Portland cement. In this paper, the production of calcium hydroxide in cement hydration and its consumption in the reaction of mineral admixtures is considered in order to develop a numerical model that simulates the hydration of concrete containing fly ash or slag. The heat evolution rates of fly ash- or slag-blended concrete is determined by the contribution of both cement hydration and the reaction of the mineral admixtures. The proposed model is verified through experimental data on concrete with different water-to-cement ratios and mineral admixture substitution ratios.     

Single-drop agglomeration of fine mineral admixtures for concrete and water requirement of pastes

This paper deals with water requirement determination of fine mineral admixtures for concrete by a simple and rapid test based on “single-drop” agglomeration. Eighteen fine and very fine mineral admixtures for concrete, different in origin and characteristics are tested. The influence of cement and high-range water-reducing admixtures are also studied. The “single-drop” test results are compared with standard tests proposed in concrete technology. The water–fine mineral admixture ratio of the formed agglomerate is proportional to the water requirement of the mineral admixture determined by the standard tests for concrete mixtures. However, the frictional forces between particles are not taken into account by the “single-drop” test and consequently the dispersing effect of high-range water-reducing admixtures. Round- and angular-shaped particles present a linear function between the water–fine mineral ratio and fineness, which is determined by the BET specific surface area or the average particle size of the minerals. Irregular-shaped particles present two to three times higher water–fine mineral ratio than that of round-shaped particles with equivalent fineness. In this case, the very low granular packing of mixtures exclude any use in concrete. When there is low cement content, the water–fine mineral-plus-cement ratio and consequently the porosity of binary blended mixtures increase significantly because of interaction phenomena between cement particles and water.     

矿物掺合料细度对水泥胶砂力学性能的火山灰效应

通过分析单掺矿粉、单掺不同磨细程度的粉煤灰及复掺粉煤灰和矿粉的胶砂早期强度的变化规律,得出粉煤灰的磨细程度及粉煤灰与矿粉的复掺比例会影响胶砂的早期强度。粉煤灰越细,越有利于提高胶砂早期强度,复合掺合料之间各成分的最佳配合比可以充分发挥各自的活性,从而提高胶砂早期力学性能。     

Combined effect of expansive and shrinkage reducing admixtures to obtain stable and durable mortars

In order to improve the dimensional stability of cement based mortars, the effects produced on cement hydration of a shrinkage reducer (propyleneglycol ether based—SRA) and an expansive admixture (calcium oxide based—EXP) were investigated. Mortar samples (prepared without admixtures or with SRA or EXP or SRA and EXP) were compared through compressive strength measurements, water evaporation, restrained shrinkage and restrained expansion measurements. Setting time and free expansion were also detected on cement paste specimens.

A synergistic effect on the shrinkage reduction was observed when the shrinkage reducing admixture and the expansive agent were used together. In order to clarify this phenomenon, the hydration of cement pastes containing these kinds of admixtures was followed by ESEM-FEG (environmental scanning electron microscopy–field emission gun), TG (thermogravimetry), specific surface area measurements (by BET—Brunauer–Emmet–Teller-method) and XRDS (X-ray diffraction spectroscopy).