Prediction of diffusivity of concrete based on simple analytic equations

Proposed is a simple analytic model that can predict realistically the diffusivities of concrete and mortar. The basic concept of the model comes from the relation between the diffusivities and the microstructure of concrete. The microstructure that affects the diffusivity includes the interfacial transition zone (ITZ) between aggregates and cement pastes as well as the microstructure of cement paste itself. The general effective media (GEM) equation was introduced to derive the diffusivity of cement paste. The effective diffusivity of concrete is derived on the basis of the composite sphere assemblage model, which considers the diffusivities of both ITZ and cement paste. The main parameters in the proposed model are the microstructural properties of cement paste such as capillary porosity and pore structure parameter, solid phase diffusivity, aggregate volume fraction, and interfacial zone properties. To validate the proposed model, many series of concrete and mortar specimens have been tested to measure the diffusivities. The major test variables include the water-to-binder ratios, the types and amount of mineral admixtures on the diffusivities. The effects of compressive strength, water-to-binder ratio, and mineral admixtures have been investigated comprehensively. The comparison of the proposed theory with the test data exhibits reasonably good correlation. The proposed model allows more accurate prediction of diffusion process and, thus, more realistic durability design of concrete structures.     

Efficiency of mineral admixtures in concrete: Microstructure,compressive strength and stability of hydrate phases

The use of mineral additives in concrete such as fly ash, silica fume, natural pozzolan, metakaolin and calcined clay has become widespread due to their pozzolanic reaction and environmental friendliness. The microstructure characteristics of concrete including pore structure and interfacial transition zone (ITZ) with addition of metakaolin, silica fume and slag were investigated in this study. The experimental results show that the addition of mineral admixtures results in the denser ITZ, optimized pore structure and reasonable pore size distribution especially at later curing stages. Metakaolin presents the most distinct improvement effects on microstructure of concrete. The development of the compressive strength is quantificationally related to the total porosity and average microhardness of the ITZ. Importantly, the influence of metakaolin, silica fume and slag on concrete was analyzed from thermodynamic stability of hydrate phase aspects.     

Influence of aggregate size, water cement ratio and age on the microstructure of the interfacial transition zone

This paper presents the results of an investigation on the effect of water-cement ratio (w/c), aggregate size, and age on the microstructure of the interfacial transition zone (ITZ) between normal weight aggregate and the bulk cement paste. Backscattered electron images (BSE) obtained by scanning electron microscope were used to characterize the ITZ microstructure. The results suggest that the w/c plays an important role in controlling the microstructure of the ITZ and its thickness. Reducing w/c from 0.55 to 0.40 resulted in an ITZ with characteristics that are not distinguishable from those of the bulk paste as demonstrated by BSE images. Aggregate size appears to have an important influence on the ITZ characteristics. Reducing the aggregate size tends to reduce the ITZ porosity. The evolution of the ITZ microstructure relative to that of the bulk paste appears to depend on the initial content of the unhydrated cement grains (UH). The results suggest that the presence of a relatively low amount of UH in the ITZ at early age may cause the porosity of the ITZ, relative to that of the bulk paste, to increase with time. The presence of relatively large amount of UH in the ITZ at early ages may cause its porosity, relative to that of the bulk paste, to decrease with time.     

Effect of Condensed Silica Fume on the Microstructure of the Interfacial Zone in Portland Cement Mortars

The development of the microstructure at the cement paste-sand grain interfacial zone was studied, and the effect of condensed silica fume was evaluated. In portland cement mortars, the microstructure of the interfacial zone, extending to about 20 to 50 μm from the sand grain surface, was significantly different from that of the bulk paste, and it was characterized by a massive Ca(OH)₂ layer engulfing the sand grain and by some channel-type gaps. When 15% condensed silica fume was added, the interfacial zone had a homogeneous and dense microstructure, similar to that of the bulk paste, without the presence of a massive Ca(OH)₂ layer or gaps. On the basis of observations at early ages, it is suggested that these characteristics were the result of differences in the nature of the fresh paste, which was more prone to bleeding in the portland cement mortar.     

Assessing the influence of ITZ on the steady-state chloride diffusivity of concrete using a numerical model

In this study, the influence of the aggregate-cement paste interfacial transition zone (ITZ) on the steady-state chloride diffusivity of mortars and concretes was examined using a semi-empirical, three-phase composite sphere model. Mortars and concretes were modelled as three-phase composites consisting of the aggregate, bulk cement paste and an inhomogeneous ITZ. The latter was divided into a series of homogenous concentric shell elements of equal thickness. The initial porosity and cement gradients at the ITZ were first estimated from the overall water/cement ratio (w₀/c). The evolution of the porosity, solid hydration products and remnants of unreacted cement were then calculated from the hydration degree and local water/cement ratio (w/c) using Powers' empirical model. Based on the Laplacian equation, an element transfer matrix was derived analytically to predict the steady-state chloride diffusivity. The model was calibrated using the available experimental data and then applied to perform a sensitivity analysis to evaluate the effects of aggregate content, water/cement ratio, curing period, ITZ width, maximum aggregate size and aggregate gradation on diffusivity. Some of these variables are impractical to quantify by laboratory experimentation. Implications of the findings with regard to the role of ITZ on mass transport properties are discussed.     

Influence of silica fume and flyash on chloride diffusion and pH values in cement paste

The diffusion rate for chloride in cement paste is a parameter of major significance for the resistance of concrete structures to seawater environments. The results of this investigation show that an addition of silica fume or flyash in ordinary Portland cement paste considerably reduces the diffusion rate for chloride. Other factors of major importance for the resistance of the concrete are the composition of the pore solution and the capacity of the cement paste to bind chloride chemically. Measurements of pH values in pore solution pressed out of cement paste show that mineral additions reduce the pH value and this has a negative effect on the capacity of the cement paste to resist reinforcement corrosion.A theoretical estimate, based on partly uncertain material parameters, nevertheless indicates that an addition of silica fume or flyash added in appropriate amounts extends the initiation time for diffusion-controlled chloride-initiated reinforcement corrosion.     

Effect of magnesium and sulfate ions on durability of silica fume blended mixes exposed to the seawater tidal zone

The effect of silica fume on deterioration resistance to sulfate attack in seawater within tidal zone and simulated wetting-drying condition has been studied in Portland cement concretes and pastes containing silica fume (SF) with/without ground granulated blast furnace slag (GGBS). Changes in the compressive strength and capillary water absorption of specimens as a function of SF content have been investigated combined with phases determination by means of scanning electron microscopy and X-ray energy dispersion analysis. The strength change factors (SCFs) of specimens with SF (the more SF content, the higher strength loss) were greater than that of the mixes without SF or cured under tap water. Mg²⁺ ion originated attack found to be the dominating deterioration mechanism as confirmed by X-ray and chemical analyses.Further, the incorporation of GGBS with SF mixes in different exposure conditions led to the worst performance in all of the test environments. Lower cement content and hydration rate accompanied with particular chemical composition of GGBS made concrete and paste specimens to be more susceptible to deleterious seawater environment.     

自养护路面混凝土抗盐冻性能及疲劳特性

为有效增强路面混凝土耐久性能,基于盐冻试验、盐冻前后的断裂性能试验及弯拉荷载疲劳试验,探索了高吸水性聚合物(SAP)自养护路面混凝土抗盐冻性能及疲劳特性随SAP掺量、粒径的变化规律,并结合自养护水泥浆体孔隙参数、微观形貌及骨料-水泥石界面过渡区(ITZ)特征,揭示了性能影响机理。结果表明:小粒径SAP形成的残留孔洞能有效释放拉应力,降低结冰点,细化孔结构,从而增强路面混凝土抗盐冻性能;当SAP粒径为100目(150 μm),掺量为0.145%(质量分数)时,路面混凝土在冻融30次时的断裂韧度损失率、断裂能损失率分别比基准组降低了25.25%、10.51%;小粒径SAP对疲劳寿命的提升程度随应力水平的提高而增大,当应力水平为0.80时,自养护组的疲劳寿命相比基准组提升了2.65倍;SAP能够有效提升水泥混凝土结构内部密实度,吸持ITZ区域部分水分,增强水泥石和骨料之间的粘结性,从而改善混凝土抗盐冻性能和疲劳特性。     

Influence of lightweight aggregate on the microstructure and durability of mortar

The results of an investigation on the effect of dry and prewetted lightweight aggregates on the microstructure and durability of mortar are presented in this paper. The results are compared with those obtained for normal aggregate mortar. There appears to be only a small difference in the microstructure of the interfacial transition zone (ITZ) between dry and prewetted lightweight aggregate mortars. The porous ITZ surrounding lightweight aggregate appears to extend for about 10 and 15 μm from the aggregate surface for dry and prewetted lightweight aggregates, respectively. The ITZ for dry and prewetted lightweight aggregates seems to be surrounded by dense paste that extends from 10 to about 50 μm from the aggregate surface. This dense paste has lower porosity than that observed in the bulk paste located 50 μm and farther from aggregate surface. The normal aggregate mortar prepared with the same water/cement ratio appears to have porous ITZ that extends beyond 35 μm from the aggregate surface. The dry and prewetted lightweight aggregate mortars seem to have a lower sorptivity and electrical conductivity than does the normal aggregate mortar. Lightweight aggregate mortars also appear to have excellent resistance to sulfate attack as compared with normal aggregate mortar.     

Modified water-cement ratio law for silica fume concretes

The application of condensed silica fume as a mineral admixture in concrete is almost a routine one nowadays for the production of tailor-made high-performance concretes. Abrams' Law, which was originally formulated for conventional concrete containing cement as the only cementitious material, is not directly applicable to these new-generation concretes. In the present paper, modified relationships have been proposed to evaluate the strength of silica fume concrete. An extensive experimentation was carried out to determine the isolated effect of silica fume on concrete, and, analyzing the 28-day strength results of 32 concrete mixes performed over a wide range of water-binder ratios and silica fume replacement percentages, simplified relationships have been proposed. These simplified models might serve as useful guides for proportioning concrete mixes incorporating silica fume.     

The use of condensed silica fume to control alkali-silica reaction — a field case study

In 1980 a sidewalk was built at Bécancour, Québec, with condensed silica fume concretes containing highly reactive aggregates. Eleven concrete mixes were used with cement quantities from 140 to 405 kg of cement per m³ and condensed silica fume substitutions varying from 10 to 40%. In spite of the great reactivity of the aggregates, the alkali-aggregate reaction is still under control. Microstructural studies of four particular concretes have been made after the first and third winters. No silicate gel has been observed in the two leaner mixes but some has been found in a few locations encircling coarse aggregate particles in the two richer mixes. The severe scaling problem observed in one of the concrete is characterized at the microstructure level by frequent unbonding of coarse aggregates and presence of converging cracks around the aggregates.     

ITZ microstructure of concrete containing GGBS

The interfacial transition zone (ITZ) of aggregate-cement paste and the morphology of hydrates in concrete containing ground granulated blast-furnace slag (GGBS) have been investigated using XRD, SEM and microhardness measurements. The experimental results demonstrated that GGBS significantly decreases both the quantity and the orientating arrangement of CH crystals at the ITZ. The CH crystal size becomes smaller because of the addition of GGBS. The weak ITZ between aggregate and cement paste was strengthened as a result of the pozzolanic reaction of GGBS. The above improvements become much more significant with the decrease of particle sizes of GGBS.     

Using limestone aggregates and different cements for enhancing resistance of concrete to sulphuric acid attack

A research program was undertaken to improve concrete's resistance against sulphuric acid attack. Six concretes were investigated, four using calcareous limestone aggregates and two using silicious aggregates. Cements used in these concretes included a portland cement, a binary cement containing ground granulated blast furnace slag, and two ternary cements containing slag and silica fume or fly ash and silica fume. All the concretes had the same water/cement ratio of 0.4, with compressive strengths in the range of 45 MPa and 58 MPa at the age of 28 days. In the experiment, concrete cylinders were immersed in 1% sulphuric acid solution and they were periodically examined for appearance, measured for mass change and tested in compression up to 168 days. The concrete using limestone aggregates and the ternary cement containing silica fume and fly ash performed the best.     

On the mechanism of strength enhancement of cement paste and mortar with triisopropanolamine

Recent work on the strength-enhancing mechanism of triisopropanolamine (TIPA) suggested that TIPA enhances the mechanical properties of mortar and concrete by acting on the interfacial transition zone (ITZ) between paste and sand or aggregate rather than improving the properties of the hydrated binder. This paper presents compressive strength data for 10 Portland cements tested as cement paste as well as two different kinds of mortar after 28 days hydration, so that these two mechanisms could be compared directly. The average strength improvement with TIPA was 10% in the hydrated portland cement paste and 9% in the mortar, clearly showing that the strength enhancement is not dependent on an ITZ mechanism.     

Studies on chemical resistance of low water/cement ratio concretes

Solutions containing mineral acids, and certain organic acids and salts are highly corrosive to portland cement concrete. Since permeability is the key factor governing the rate of deterioration, it is customary to use a low water-cement ratio in making concretes or concrete overlays required to resist corrosive action of aggressive chemical solutions. Pozzolanic admixtures are often used to provide additional protection against acidic attack. Highly reactive pozzolanic admixtures, such as condensed silica fume, which rapidly react with calcium hydroxide and reduce both the alkalinity and permeability of concrete are now being used for improving durability. During the last two decades, latex admixtures have also found widespread application. The polymeric constituents of a latex seem to coat the alkaline hydration products of portland cement, thus protecting them from attack by aggressive solutions.

An experimental study was undertaken to evaluate the relative chemical resistance of low water-cement ratio concretes, containing either a styrene-butadiene latex or a silica fume admixture, to the following solutions; 1% HCl, 1% H₂SO₄, 1% lactic acid, 5% acetic acid, 5% ammonium sulfate, and 5% sodium sulfate. Time taken to register 25 percent weight loss by fully submerged concrete specimens was used as a criterion for failure. From the data it appears that, except for the ammonium sulfate solution, the concrete containing the silica fume generally showed better resistance to chemical attack than other concrete types.     

Shear-thickening behavior of high-performance cement grouts — Influencing mix-design parameters

Rheology of concrete is of great importance to its flow performance, placement and consolidation. A full understanding of fresh concrete flow behavior can be achieved through a good understanding of paste rheology. Cement pastes exhibit a complex rheological behavior affected by several physical and chemical factors, including water-to-cement ratio (w/c), high-range water-reducer (HRWR) type and dosage, and cement characteristics. An experimental investigation was carried out to evaluate the effect of w/c, HRWR–cement combinations, and supplementary cementitious materials (SCM) on the pseudoplastic behavior of high-performance cement grouts. Grout mixtures proportioned with w/c of 0.30, 0.33, 0.36, and 0.40, various cement–HRWR combinations, and cement substitutions by 8% silica fume were investigated. The incorporation of HRWR can lower the yield stress of mixtures, thus enhancing deformability, while silica fume improves mechanical and durability performances.High-performance structural grouts are shown to exhibit shear-thickening behavior at low w/c and shear-thinning behavior at relatively higher w/c. Mixtures made with polycarboxylate HRWR acting by steric effect exhibited greater shear-thickening behavior compared to those made with polynaphthalene sulfonate-based HRWR acting by electrostatic effect. The paper discusses the effect of mixture parameters on non–linear rheological behavior of various grout mixtures prepared with different w/c, HRWR–cement combinations, and silica fume.     

A new way to increase the long-term bond strength of new-to-old concrete by the use of fly ash

The short-term and long-term bond strengths of new-to-old concrete were experimentally investigated with an emphasis on the influence of new concretes and binders. These new concretes included ordinary Portland cement concrete, expansive concrete and high-volume fly ash concrete, while the binders included pure cement paste (C-binder), expansive binder (E-binder) and fly ash mortar (F-binder). The results showed that the short-term bond strength of all specimens with fly ash concrete was lower than that with ordinary Portland cement concrete, which in turn was lower than that with expansive concrete. The bond strength of the specimens with F-binder was the lowest at the age of 7 days. However, the long-term bond strength of all specimens with added fly ash was the highest and strength losses were observed in the specimens repaired with expansive concrete or E-binder at the age of 3 years. The microstructure of the transition zone with F-binder was also studied by using both scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) at the ages of 28 days and 1 year, respectively.     

在混凝土中掺用活性工业废渣改善界面效应和性能的研究

本文利用X射线衍射、压汞测孔等方法研究了在水泥浆体和混凝土中掺入硅灰、赤泥、矾泥、液态渣等活性工业废渣对混凝土界面效应区内Ca(OH)_2的取向指数、水泥浆体的孔径分布及水泥混凝土性能的影响。研究表明,由于这些工业废渣的掺入,大大减小了混凝土的界面效应区,提高了水泥浆体和混凝土的强度,对增强混凝土的抗冻性有很大益处。     

硅灰改性水泥/石灰砂浆微观结构的研究

以水泥和石灰为胶凝材料,中细砂为集料,再掺加有机聚合物流化剂制成水泥/石灰砂浆,水泥/石灰砂浆中添加外加剂的文献资料很少,通常是有关水泥砂浆的研究.本实验用硅灰取代10%(质量分数)的普通硅酸盐水泥,水泥、石灰和砂子的质量比为3:1:12,外加有机聚合物对砂浆改性,利用扫描电子显微镜、能谱仪和压汞仪对浆体进行微观分析.分析结果显示,由于硅灰的加入,浆体内部水化产物在早期先以Ⅲ型C-S-H凝胶的形式出现,随后,Ⅲ型和I型的C-S-H凝胶以并存的形式在水化后期出现;正如预期的那样,试样的总的孔隙率也比没加硅灰前有了大幅度的下降,而抗压强度的提高在水化后期才表现出来.     

A multiscale model for effective moduli of concrete incorporating ITZ water-cement ratio gradients, aggregate size distributions, and entrapped voids

This paper develops a model for the effective elastic properties of concrete, which is a function of the volume fractions, size distributions, and elastic properties of fine aggregate (FA) and coarse aggregate (FA) and entrapped voids. Furthermore, the model is a function of the overall water-cement ratio and specific gravity of cement. Explicitly modeled are the water-cement ratio gradients through the interfacial transition zone (ITZ), which, in turn, affect the variation of the cement paste elastic properties through the ITZ, while maintaining the total fractions of cement and water consistent with the overall water-cement ratio. The ITZ volume is also conserved.