水泥-粉煤灰-硅灰基超高性能混凝土水化过程微观结构的演变规律

超高性能混凝土(UHPC)具有卓越的力学性能和耐久性能,应用前景广阔。采用扫描电镜背散射电子图像、热重法和氮气吸附法系统研究了水泥-粉煤灰-硅灰基UHPC浆体水化过程中微观结构的演变过程。结果表明:UHPC浆体在早期水泥水化较快,但7d后水化变得较为缓慢,粉煤灰在UHPC浆体中反应较为缓慢,28d时反应程度仅为7%;UHPC浆体中Ca(OH)2含量早期上升快速,由于硅灰和粉煤灰的火山灰反应逐渐消耗,3d后含量开始下降,但28d时浆体中仍存在部分Ca(OH)2;此外,在水化过程中,UHPC浆体的比表面积不断降低,孔隙率逐渐下降,水化产物变得更为致密。     

Property investigation of individual phases in cementitious composites containing silica fume and fly ash

In this study, nanoindentation was used to investigate the microstructures of cementitious composites containing silica fume and fly ash. With the help of scanning electron microscope, the mechanical properties (elastic modulus and hardness) of individual phases (like outer product, inner product, calcium hydroxide, remained fly ash particles, residual cement grains) in cementitious composites containing silica fume and fly ash were investigated and analyzed. Additionally, this study examined the differences between the ‘C–S–H’ phases in the different cementitious composites and provided an insight into the influence of mineral admixtures (silica fume and fly ash) on the properties of the ‘C–S–H’ phase.     

微粉增强水泥基复合材料的早期界面显微结构研究

介绍了粉煤灰、硅灰、纳米SiO₂与水泥水化反应产物的早期界面显微结构,探讨了三种微粉与水泥水化反应的机理及对改善界面结构的作用,并提出了"二级界面"的概念。研究表明,三种微粉对界面的改善呈递增趋势,单一微粉中纳米SiO₂的水化产物结构最致密、均匀,微粉复合有效改善二级界面显微结构,有效提高水泥基材料性能。     

矿物掺合料对聚羧酸减水剂与水泥相容性的影响

高性能减水剂与水泥适应性差会导致混凝土流动性和坍落度损失过快,矿物掺合料将影响高性能减水剂与水泥的相容性。对比研究矿物掺合料种类和掺量对水泥净浆、砂浆和混凝土流动性的影响;采用TOC法测试了矿物掺合料对聚羧酸减水剂吸附量的影响;分析了矿物掺合料影响聚羧酸减水剂与水泥相容性的机理。结果表明,粉煤灰和矿渣对提高水泥净浆流动性具有一定的叠加效应,可用胶砂减水率的加权平均值进行量化;硅灰对水泥浆体流动性的不利影响远大于粉煤灰和矿渣的辅助减水分散作用,不利于改善聚羧酸减水剂与水泥的相容性;粉煤灰和矿渣增加聚羧酸减水剂在水泥体系中的吸附量;粉煤灰和矿渣对聚羧酸减水剂在混凝土中的减水分散效果有改善作用但不显著。     

The interfacial zone and bond strength between aggregates and cement pastes incorporating high volumes of fly ash

The weak transition zone between aggregate and cement paste controls many important properties of concrete. A number of studies dealing with interfacial zone are available in the literature for normal concrete and concrete containing silica fume. High-volume fly ash concrete for structural applications was developed at CANMET in the 1980s, but to date there has been no information available for interfacial zone in high-volume fly ash concrete.In this paper, the orientation index and mean size of Ca(OH)₂ crystals in the aggregate-paste interfacial zone were determined by the X-ray diffractometer. The bond strength between the aggregate and paste was also investigated. It was found that, at the age of 28 days, there was no obvious transition zone between the aggregate and cement paste incorporating high volumes of fly ash. The higher the paste strength, the higher is the bond strength.     

Portland cement-fly ash-silica fume systems in concrete

Laboratory flow, strength, and ultrasnic pulse velocity tests were performed on mortars made with 70% (by weight) of portland cement and 30% of pozzolanic materials where the pozzolanic materials consisted of various combinations of fly ash and silica fume. In addition to these ternary systems, binary blends, such as Portland cement and fly ash, and Portland cement and silica fume, along with 100% Portland cement mortars, were investigated for comparison. The purpose of the investigation, preliminary in nature, was to see under what circumstances, if any, would be a synergistic action when a ternary system of Portland cement-fly ash-silica fume is used in a mortar or concrete.Mortars were made with two cements of type I and two cements of type III along with class F and class C fly ashes. One silica fume was used. Standard flow tests were performed on the fresh mortars, and compressive strength as well as ultrasonic pulse velocity tests were performed with each hardened mortar at various ages up to 28 days. It is expected that the results and conclusions obtained here on mortars will be transferable to concretes.There are several novel, or at least lesser known, results of the investigation. For instance, a new explanation is offered for the plasticizing effect of fly ash which is based on the optimum particle-size distribution concept. Another such result is that ground fly ash produced greater flow increases with type I cement than with type III. A third finding is that the superplasticizer is more effective in increasing the flow as well as strength when the mortars contain fly ash and/or silica fume than in the case of mortars without mineral admixture. Also, it appears that when type I cement is used, the silica fume in the quantity of 5% of the weight of the cement produces relatively greater strength increase in the presence of fly ash than without fly ash.These promising results are preliminary in nature. Therefore, further research is justified with ternary systems in concrete. The presented work is a portion of a larger investigation.     

Compressive strength and chloride resistance of self-compacting concrete containing high level fly ash and silica fume

The influence of high-calcium fly ash and silica fume as a binary and ternary blended cement on compressive strength and chloride resistance of self-compacting concrete (SCC) were investigated in this study. High-calcium fly ash (40–70%) and silica fume (0–10%) were used to replace part of cement at 50, 60 and 70 wt.%. Compressive strength, density, volume of permeable pore space (voids) and water absorption of SCC were investigated. The total charge passed in coulombs was assessed in order to determine chloride resistance of SCC. The results show that binary blended cement with high level fly ash generally reduced the compressive strength of SCC at all test ages (3, 7, 28 and 90 days). However, ternary blended cement with fly ash and silica fume gained higher compressive strength after 7 days when compared to binary blended fly ash cement at the same replacement level. The compressive strength more than 60 MPa (high strength concrete) can be obtained when using high-calcium fly ash and silica fume as ternary blended cement. Fly ash decreased the charge passed of SCC and tends to decrease with increasing fly ash content, although the volume of permeable pore space (voids) and water absorption of SCC were increased. In addition when compared to binary blended cement at the same replacement level, the charge passed of SCC that containing ternary blended cement was lower than binary blended cement with fly ash only. This indicated that fly ash and silica fume can improve chloride resistance of SCC at high volume content of Portland cement replacement.     

Self-healing ability of fly ash–cement systems

Concrete is susceptible to cracking due to both autogenous and drying shrinkage. Nevertheless, most of these types of cracks occur before 28 days. Because fly ash continues to hydrate after 28 days, it is likely that hydrated products from fly ash may modify microstructure, seal these cracks, and prolong the service life. This research investigates the self-healing ability of fly ash–cement paste. Compressive strength, porosity, chloride diffusion coefficients, hydration reactions and hydrated products were studied. The research focuses on behavior after 28 days. According to the experimental results, the fly ash–cement system has the self-healing ability for cracks that occur from shrinkage. The self-healing ability increased when the fraction of fly ash increased.     

Prediction of compressive strength and optimization of mixture proportioning in ternary cementitious systems

This paper discussed the application of the method of the simplex-lattice design for predicting the properties of cement-based composites. On the basis of the compressive strength, its use was demonstrated on ternary paste systems composed of cement, silica fume and fly ash with constant water to binder ratio and a mass fraction of mineral admixtures not exceeding 30%. The regression model between compressive strength of paste and binder proportion was built up. The F-test method was utilized for validation of the regression model. The nonlinear programming system with upper and lower bound was solved. This allowed assessment of optimum mixture proportions and corresponding maximum compressive strength. It was shown that: (1) the 3rd-order regression model constructed by using the simplex-lattice design method could accurately predict the compressive strength in ternary paste system made of cement, silica fume and fly ash (the total mass fraction of all mineral admixtures was up to 30%); (2) to solve the nonlinear programming with the constraints of upper and lower bound played an important role in getting the optimum compressive strength and its corresponding mixture proportion at different ages; (3) the combination of the simplex-lattice design method and the optimization theory could be valuable tool for optimization of cement-based composites' properties.     

Effects of cold-bonded fly ash aggregate properties on the shrinkage cracking of lightweight concretes

This paper presents an experimental study on the restrained shrinkage cracking of the lightweight concretes made with cold-bonded fly ash lightweight aggregates. Two types of fly ash having different physical and chemical properties were utilized in the production of lightweight aggregates with different strengths. Afterwards, lower strength aggregates were also surface treated by water glass and cement–silica fume slurry to improve physical and mechanical properties of the particles. Therefore, a total of eight concrete mixtures were designed and cast at 0.35 and 0.55 water–cement ratios using four types of lightweight coarse aggregates differing in their surface texture, density, water absorption, and strength. Ring type specimens were used for restrained shrinkage cracking test. Free shrinkage, creep, weight loss, compressive and splitting tensile strengths, and modulus of elasticity of the concretes were also investigated. Results indicated that improvement in the lightweight aggregate properties extended the cracking time of the concretes resulting in finer cracks associated with the lower free shrinkage. Moreover, there was a marked increase in the compressive and splitting tensile strengths, and the modulus of elasticity.     

Durability of reactive powder composites: influence of silica fume on the leaching properties of very low water/binder pastes

Reactive Powder Composites are new cement-based materials which could be used for the storage of nuclear wastes thanks to their excellent microstructural properties. This paper studies their durability when submitted in the laboratory to a water leaching attack. In order to understand the behaviour of the hydrates (CSH), the study was carried out on a pure cement paste and on a cement + silica fume paste. The beneficial effect of silica fume is demonstrated from considerations on the calcium leaching, from XRD analysis, from SEM observations and from the tritium diffusion and pore distribution analysis. It was found that the leaching greatly affects the microstructure, especially that of the anhydrous cement grains remaining in the paste.     

辅助胶凝材料对硬化水泥浆体结合氯离子的影响综述

辅助胶凝材料富含SiO2和Al2O3,参与二次水化反应生成更多的C-S-H凝胶,降低硬化水泥浆体的碱度,对硬化水泥浆体结合氯离子具有显著的影响。本文重点综述了矿渣、粉煤灰、硅灰、偏高岭土和煤矸石对硬化水泥浆体结合氯离子的影响,并对物理吸附和化学结合氯离子机理进行了深入分析。掺辅助胶凝材料氯离子结合等温线均适合Freundlich非线性吸附关系,最后对辅助胶凝材料结合氯离子研究的不足进行探讨,为后续的研究工作提供理论依据。     

A transmission electron microscopy study of interfaces and matrix homogeneity in ultra-high-performance cement-based materials

Ultra-high-performance cement-based materials produced under different conditions have been characterized by transmission electron microscopy (TEM), scanning transmission electron Microscopy (STEM), high resolution transmission microscopy (HRTM) and chemical analysis. In addition to cement, these materials contain large amounts of crushed quartz and amorphous submicrometre silica. A post-set heat treatment was also applied in some cases. An abrasive thinning method combined with grazing angle ion etching allowed the preparation of 100 nm thick specimens with wide observation surface areas while avoiding any water or CO₂ contact which may cause changes. Clinker, silica fume and crushed quartz reactivity as a function of the curing processes have been studied, as well as the interfacial zones with the hydrated matrices. The Ca/Si ratio spatial distribution in hydrated products has been analyzed and shown to undergo strong local fluctuations. Nevertheless, the composition fluctuations were less pronounced and the average Ca/Si ratio was lower than in silica-free cement paste. HRTM lattice imaging shows the coexistence of nanocrystalline phases and mesoscale ordered regions within an amorphous matrix. A d-spacings analysis of the nanocrystalline phase suggests a tobermorite-like structure for the calcium silicate hydrates, whereas the mesoscale order might reflect modulations in the water content.     

Effect of aggregates on the diffusion properties and microstructure of cement with slurried silica fume based materials

Diffusivity of cement-based materials is an important factor regarding durability and the service life prediction of concrete structures. The present research focuses on investigating the influence of aggregates on tritiated water diffusivity of cement-based materials containing slurried silica fume. Effective diffusion coefficients of mortars with several sand volume fractions varying from 0 to 65% were determined by through-out diffusion tests. Microstructure was examined by scanning electron microscopy associated to energy dispersive spectrometry analysis, thermogravimetric analysis, water and mercury porosimetry, and BET adsorption analysis. It was found that large agglomerated particles of silica fume observed in cement paste and mortar with a low sand content (here 10%), reduce pozzolanic reactivity and thus affect the effectiveness of silica fume on the materials sustainability parameters. The clusters present in these formulations are mainly due to the interaction of silica fume with calcium hydroxide of the mixing solution and not to the initial state of the slurry, which was well stirred and whose particles size were checked before use. However, the presence of high content of aggregates (more than 30% of sand volume fraction) during mortar's mixing improves the dispersion of slurried silica fume particles and helps to ‘shear’ and break up agglomerates of silica fume providing a better homogenization of the material and improving the microstructural and diffusivity parameters. The addition of superplastizer in mortars with more than 50% sand content may also participate in dispersing silica fume.     

纳米SiO2粉在水泥基复合材料中的试验研究

研究了硅粉、纳米SiO2粉的活性,二者及复合粉体与C3S的二次水化反应产物成分,并研究了水泥基材料的力学性能和显微结构,探讨了纳米SiO2粉改善显微结构的机理,获得纳米SiO2粉应用于水泥基材料适合的方法.研究表明,纳米SiO2粉为非晶态,活性高于硅粉.粉体二次水化速率大小及水化程度高低依次为复合粉体、纳米SiO2粉、硅粉.复合粉体应用于水泥基材料中可增加致密性、提高均匀性,并提高强度.纳米SiO2粉与粉煤灰、硅粉复合应用于水泥基材料能够体现优异的使用性和经济性.     

Comparing the pozzolanic behavior of sugar cane bagasse ash to amorphous and crystalline SiO2

The present paper aims to clarify the pozzolanic behavior of sugar cane bagasse ash-SCBA by comparing it to amorphous and crystalline silica. It is shown that calcium silicate hydrate is formed in lime solution with SCBA but the reaction is slow and does not consume all the material. Comparing its results with the obtained in tests with silica fume and with crushed quartz show a better agreement with the latter. Characterization of cement pastes shows 20% of cement replacement by sugar cane bagasse ash leads to only a minor reduction in the amount of calcium hydroxide formed. This behavior is also closer to the observed in quartz than in silica fume. The results suggest SCBA should be used as a replacement for inert constituents in cement composites rather than pozzolanic addition. Analysis of the microstructure of the cement pastes revealed the presence of calcium hydroxide in samples prepared with partial replacement by silica fume, quartz and sugar cane bagasse ash. The presence of this phase in the sample prepared with silica fume was attributed to agglomeration of the particles that affected the reactivity of this material.     

环境湿度对玻璃纤维增强水泥力学性能的影响

通过开展在不同龄期、不同环境湿度下玻璃纤维增强水泥(GRC)试件的抗折强度、抗压强度试验和基体pH值测定,研究了环境湿度对掺加粉煤灰和硅灰等活性矿物掺合料的GRC试件力学性能的影响。结果表明:环境湿度对GRC试件的抗折强度有重要影响,相对湿度越大,随着龄期增加, GRC试件抗折强度降低越严重;在温度60℃、相对湿度95%条件下,经过56 d龄期后,掺有40%粉煤灰和10%硅灰的GRC试件抗折强度比未掺加粉煤灰和硅灰的GRC试件的抗折强度提高48.5%、抗压强度提高23.6%, GRC基体pH值降低6%。在相同的湿度条件下,掺有粉煤灰和硅灰试件的pH值在各个龄期都低于普通硅酸盐水泥试件,说明粉煤灰和硅灰的掺入能降低水泥水化液相的碱度,进而延缓了纤维受侵蚀的速度,显著改善了GRC试件的力学及耐久性能。通过对试验结果进行分析,利用MATLAB软件建立了GRC试件抗折强度和抗压强度与水泥砂浆基体pH值及时间的关系式。      

Effect of fly ash fineness on compressive strength and pore size of blended cement paste

This paper presents an experimental investigation on the effect of fly ash fineness on compressive strength, porosity, and pore size distribution of hardened cement pastes. Class F fly ash with two fineness, an original fly ash and a classified fly ash, with median particle size of 19.1 and 6.4 μm respectively were used to partially replace portland cement at 0%, 20%, and 40% by weight. The water to binder ratio (w/b) of 0.35 was used for all the blended cement paste mixes.Test results indicated that the blended cement paste with classified fly ash produced paste with higher compressive strength than that with original fly ash. The porosity and pore size of blended cement paste was significantly affected by the replacement of fly ash and its fineness. The replacement of portland cement by original fly ash increased the porosity but decreased the average pore size of the paste. The measured gel porosity (5.7–10 nm) increased with an increase in the fly ash content. The incorporation of classified fly ash decreased the porosity and average pore size of the paste as compared to that with ordinary fly ash. The total porosity and capillary pores decreased while the gel pore increased as a result of the addition of finer fly ash at all replacement levels.     

Recommendation of RILEM TC 238-SCM: determination of the degree of reaction of siliceous fly ash and slag in hydrated cement paste by the selective dissolution method

The performance of slag and fly ash in hydrated cementitious materials depends on the degree of reaction developed at the evaluated age. Several methods for the determination of the reaction degree of supplementary cementitious materials are available, among which the selective dissolution method is one of methods developed the earliest. This is a direct method that aims to quantify the amount of unreacted slag or fly ash in the sample by applying a selective acid attack. The degree of reaction is obtained from the comparison between the remaining unreacted SCM, which should not dissolve, and the total amount initially included in the mix. This recommendation indicates suitable procedures for computing the degree of reaction by selective dissolution of cement pastes containing slag and fly ash. Specific considerations are indicated for necessary corrections due to the imperfect selective dissolution when the procedure is applied to hydrated cement paste.