Mechanical properties and durability of mortar and concrete containing natural pozzolana and limestone blended cements

The benefits of limestone filler (LF) and natural pozzolana (NP) as partial replacement of Portland cement are well established. Economic and environmental advantages by reducing CO₂ emission are well known. However, both supplementary materials have certain shortfalls. LF addition to Portland cement causes an increase of hydration at early ages inducing a high early strength, but it can reduce the later strength due to the dilution effect. On the other hand, NP contributes to hydration after 28 days improving the strength at medium and later ages. Hence, ternary blended cement (OPC–LF–NP) with better performance could be produced. In this paper, mortar prisms in which Portland cement was replaced by up to 20%LF and 30%NP were tested in flexure and compressive strength at 2, 7, 28 and 90 days. Some samples were tested under sulfate and acid solutions and for chloride ions permeability. Results show that the use of ternary blended cement improves the early age and the long-term compressive and flexural strengths. Durability was also enhanced as better sulfate, acid and chloride ions penetration resistances were proved.     

Blended cements containing high volume of natural zeolites: Properties, hydration and paste microstructure

In this study, properties and hydration characteristics as well as paste microstructure of blended cements containing 55% by weight zeolitic tuff composed mainly of clinoptilolite mineral were investigated. Free Ca(OH)₂ content, crystalline hydration products and decomposition of zeolite crystal structure, pore size distribution and microstructural architecture of hydrated cement pastes were examined. Superplasticizer requirement and compressive strength development of blended cement mortars were also determined. The blended cements containing high volume of natural zeolites were characterized with the following properties; (i) no free Ca(OH)₂ in hardened pastes at the end of 28 days of hydration, (ii) less proportion of the pores larger than 50 nm when compared to portland cement paste, (iii) complete decomposition of crystal structure of zeolite at the end of 28 days of hydration, (iv) presence of tetra calcium aluminate hydrate as a crystalline product of pozzolanic reaction, (v) more compatibility with the melamine-based superplasticizer when compared to the naphthalene based product, and (vi) similar 28 days compressive strength of mortars to that of reference portland cement.     

Behaviour of ASTM Type V cement hydrated in the presence of sulfonated melamine formaldehyde

ASTM Types I and V Portland cements were hydrated up to 28 days in the presence of 0.3% and 0.6% sulfonated melamine formaldehyde (SMF), at a water/cement ratio of 0.35. Hydration was studied by conduction calorimetric and thermogravimetric analyses. The amount of Ca(OH)₂ produced, compressive strength and porosity were determined after 1, 3, 7 and 28 days of curing. The compressive strengths of all samples increased with the age of curing. In the period studied the values decreased in the order: Type I cement (reference)=Type I cement+SMF>Type V cement (reference)≥Type V cement+SMF. The superplasticizer addition retarded the development of heat in the cements, but more severely in Type V cements. Porosities were generally higher for samples with lower compressive strengths. In the presence of 0.6% SMF, the early low strengths in Type V cement mixtures could be attributed to lower degrees of hydration. At later ages, the microstructure rather than the degree of hydration determined the strength development. However, incorporation of 0.3% SMF in Type V cement did not affect its strength development.     

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.     

Micro-structural development of gap-graded blended cement pastes containing a high amount of supplementary cementitious materials

To clarify the strength improvement mechanism of gap-graded blended cements with a high amount of supplementary cementitious materials, phase composition of hardened gap-graded blended cement pastes was quantified, and compared with those of Portland cement paste and reference blended cement (prepared by co-grinding) paste. The results show that the gap-graded blended cement pastes containing only 25% cement clinker by mass have comparable amount of gel products and porosity with Portland cement paste at all tested ages. For gap-graded blended cement pastes, about 40% of the total gel products can be attributed to the hydration of fine blast furnace slag, and the main un-hydrated component is coarse fly ash, corresponding to un-hydrated cement clinker in Portland cement paste. Further, pore size refinement is much more pronounced in gap-graded blended cement pastes, attributing to high initial packing density of cement paste (grain size refinement) and significant hydration of BFS.     

The effect of temperature on the hydration of composite cements containing limestone powder and fly ash

The effect of the curing temperature (5, 20 and 40°C) on the degree of hydration, amount of bound water and calcium hydroxide, porosity and the development of mechanical properties was investigated on pastes and mortars prepared with fly ash (FA)?Climestone (L) Portland composite cements. Increasing the curing temperature for ordinary Portland cement (OPC) leads to a more inhomogeneous distribution of hydration products, resulting in an increased coarse porosity and therefore a lower compressive strength after 7?days and longer. In contrast, the FA containing mortars showed higher compressive strength with increasing curing temperature up to 90?days. The reaction of the FA is increased at 40°C and strongly retarded at 5°C. At 20 and 40°C, FA reduces the porosity at later ages. The replacement of 5% of the OPC or FA by L powder did not impair the strength at 5 and 20°C, but lowered strength slightly at 40°C for the FA blended cements. The porosity appears to be the dominating factor regarding the compressive strength, independent of whether part of the OPC is replaced by FA and L powder or not.     

A study on reinforcement corrosion and related properties of plain and blended cement concretes under different curing conditions

This paper presents the results of an experimental investigation on the steel reinforcement corrosion, electrical resistivity, and compressive strength of concretes. Concretes having two different water–cement ratios (0.65 and 0.45) and two different cement contents (300 and 400 kg/m³) were produced by using a plain and four different blended portland cements. Concrete specimens were subjected to three different curing procedures (uncontrolled, controlled, and wet curing). The effect of using plain or blended cements on the resistance of concrete against damage caused by corrosion of the embedded reinforcement has been investigated using an accelerated impressed voltage setup. The resistivity of the cover concrete has been measured non-destructively by placing electrodes on concrete surface. The compressive strength, electrical resistivity, and corrosion resistance of the concretes were determined at different ages up to 180 days. The results of the tests indicated that the wet curing was essential to achieve higher strength and durability characteristics for both plain and especially blended cement concretes. The concretes, which received inadequate (uncontrolled) curing, exhibited poor performance in terms of strength and corrosion resistance.     

Sulphate resistance of type V cements with limestone filler and natural pozzolana

Sulphate performance of concrete depends primarily on permeability. Under severe conditions of sulphate exposure, low-permeability concrete is prescribed and it must also be made with high sulphate resisting cement. For portland cement, the sulphate resistance depends on the C₃A content and the amount of CH produced at early stages of hydration. Some parameters that modify the quantity of early CH in the hardened cement paste are investigated in this paper. Two type V cements with quite different C₃S content and blended cements containing natural pozzolana or limestone filler were used. Expansion, flexural and compressive strength of mortar, immersed until 1 yr in sodium sulphate solution, with pH-controlled are presented. Results show that the sulphate performance of portland cement with high C₃S content is very poor compared with low C₃S portland cement. Addition of natural pozzolana provides the maximum sulphate resistance while the addition of 20% limestone filler declining sulphate performance of low C₃A cements. This behaviour can be attributed to the reaction between sulphate ions with CH into the paste that produces an alteration of the predominant mechanism of sulphate attack.     

High-volume natural volcanic pozzolan and limestone powder as partial replacements for portland cement in self-compacting and sustainable concrete

A laboratory study demonstrates that high volume, 45% by mass replacement of portland cement (OPC) with 30% finely-ground basaltic ash from Saudi Arabia (NP) and 15% limestone powder (LS) produces concrete with good workability, high 28-day compressive strength (39 MPa), excellent one year strength (57 MPa), and very high resistance to chloride penetration. Conventional OPC is produced by intergrinding 95% portland clinker and 5% gypsum, and its clinker factor (CF) thus equals 0.95. With 30% NP and 15% LS portland clinker replacement, the CF of the blended ternary PC equals 0.52 so that 48% CO₂ emissions could be avoided, while enhancing strength development and durability in the resulting self-compacting concrete (SCC). Petrographic and scanning electron microscopy (SEM) investigations of the crushed NP and finely-ground NP in the concretes provide new insights into the heterogeneous fine-scale cementitious hydration products associated with basaltic ash-portland cement reactions.     

Pozzolanic cements

Natural and artificial pozzolanas have been used to obtain hydraulic binders for over a thousand years. Hardening of pozzolanic cement pastes can result from the reaction between pozzolana and the lime that is added to the mix as hydrated lime or is produced following hydration of portland cement silicates. The pozzolanic reaction does not alter cement clinker hydration; it complements and integrates the hydration process because it results in a lower portlandite content and an increase in calcium silicate hydrates.

Besides reviewing the most recent investigations on pozzolana-containing cements, this paper shows that the behaviour of different types of pozzolana can be quite similar when they are blended and become hydrated along with portland cement clinker. Portland cement properties may undergo several qualitative modifications the extent of which substantially depends on the pozzolana/clinker ratio. So, a maximum is reached in pozzolanic cements.

As in the case of pozzolanic cements, for which the current pozzolana content is about one third by weight of cement, the most outstanding variations induced in the behaviour of portland cement can be summarised as follows. Heat of hydration decreases whilst the rate of clinker hydration increases, paste porosity increases and permeability decreases, both portlandite content and Ca/Si ratio in C-S-H decrease and the C-S-H content increases.

Chemical and physical properties of pozzolanic cements eventually affect engineering ones. Early strength of both pastes and concretes decreases while ultimate strength is often found to exceed that of the reference portland cement.

If cements contain small amounts of very active pozzolana (silica fume, for example), both early and ultimate strengths may be higher than those of the substituted cement.

Creep is found to increase definitely with increasing pozzolana content whereas shrinkage remains practically unaffected.

Chemical and microstructural variations in the paste also influence resistance of concretes to environmental attacks.

The low basicity and permeability resulting from the presence of pozzolana increase the concrete's resistance to lime leaching, sulphate and sea water attacks, and chloride penetration. Carbonation depth is practically unaffected. Pozzolana containing cements can help avoid expansion induced by alkali-silica reaction. Concrete resistance to freezing is not affected by the use of pozzolanic cement since it basically depends on the entrained air content.

The results of a variety of studies introducing a comparison between pozzolana-containing cements and corresponding portland cements can be summarised as follows: cements with appreciable pozzolana contents perform better in the long term rather than at an early age.

In most cases, however, the differences between the two types of cements are not so marked and as a consequence both cements are interchangeable especially for the most common building types.     

The influence of mechanical activation by vibro-milling on the early-age hydration and strength development of cement

This paper presents results from an experimental investigation that evaluated the mechanical activation of portland cement using vibro-milling. In this investigation, the duration of the vibro-milling was systematically varied and its influence was evaluated using mortar samples. In addition, the amount of activated cement used in the mortar samples was varied and evaluated. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to evaluate differences in hydration products and the structure of activated cement and mortars. The activated cements were tested to determine the influence of activation on the rate of hydration and compressive strength development. The test results suggested that the use of mechanical activation can improve early-age structure formations and compressive strength. A 32% and 25% increase in 1-day strength were observed for the systems with Type I and Class H cements, respectively. This increase in 28-day strength was 16% and 58% for Type I and Class H cement, respectively. It was observed that longer milling times did not necessarily improve performance, and 15 min appeared to be sufficient vibro-milling time to provide valuable benefits.     

Optimization of ternary cementitious mortar blends using factorial experimental plans

Producing cements incorporating high-volume replacement of ordinary portland cement (OPC) by recycled industrial by-products is perceived as the most promising venture for the cement and concrete industry to meet its environmental obligations. However, the two-component (binary) cements thus produced are often associated with shortcomings such as the need for extended moist-curing, increased use of chemical admixtures, low early age strength, increased cracking tendency due to drying shrinkage, and de-icing salt scaling problems. There is need for research to investigate whether high-volume replacement multi-component (ternary and quaternary) cements could be optimized with synergistic effects allowing component ingredients to compensate for any mutual shortcomings. This study uses factorial experimental plans to investigate the performance of OPC-silica fume (SF)-class F fly ash (FA) and OPC-SF-ground granulated blast furnace slag (GBFS) ternary cementitious blends. Response surfaces for the superplasticizer requirement to achieve a constant flow, setting time, drying shrinkage up to 112 days, compressive strength at 1, 7, 28 and 56 days, and for the sulfate expansion up to 9-months were obtained for up to 20%, 60%, and 60% replacement levels of OPC by SF, FA and GBFS, respectively. A multiparametric optimization is used to establish response surfaces for a desirability function, which is used to rate ternary cementitious blends. Results indicate that when rheological, mechanical, durability and cost requirements are combined; the use of costly mineral admixtures such as silica fume is not economic in ternary OPC-SF-FA or OPC-SF-GBFS blends beyond levels of about 3 to 5% Moreover, it is shown that the major hurdle for high-volume replacement of OPC with class F fly ash is compromising the early age performance. Results also indicate that a good quality high-fineness GBFS can be used at replacement levels of OPC up to 60% without major disadvantages.     

Metakaolin as a main cement constituent. Exploitation of poor Greek kaolins

In this work, the properties and the hydration procedure of cements containing metakaolin were monitored for periods up to 180 days. Four metakaolins, derived from poor Greek kaolins, as well as a commercial metakaolin of high purity were used. Cement mortars and pastes, with 0%, 10% and 20% replacement of cement with the above metakaolins, were examined. Strength development, water demand and setting time were determined in all samples. In addition, XRD and TGA were applied in order to study the hydration products and the hydration rate in the cement–metakaolin pastes. It is concluded that metakaolin has a very positive effect on the cement strength after 2 days and specifically at 28 and 180 days. The blended cements demand significantly more water than the relatively pure cement and the water demand increase is higher, the higher the metakaolin content. The produced metakaolins as well as the commercial one give similar hydration products after 28 days and the pozzolanic reaction is accelerated between 7 and 28 days, accompanied by a steep decrease of Ca(OH)₂ content. Finally, it is concluded that a 10% metakaolin content seems to be, generally, more favorable than 20%. The produced metakaolins, derived from poor Greek kaolins, as well as the commercial one impart similar properties with respect to the cement strength development, the setting and the hydration.     

Influence of 15 and 80 nano-SiO2 particles addition on mechanical and physical properties of ternary blended concrete incorporating rice husk ash

This study demonstrates the effects of SiO₂ nanoparticles as additives with two different sizes of 15 and 80?nm on compressive strength and porosity of rice husk ash (RHA) blended concrete. Up to 20% of ordinary Portland cement (OPC) was replaced by RHA with average particle size of 5 micron. Also, SiO₂ nanoparticles were added to the above mixture at four different weight percentages of 0.5, 1.0, 1.5 and 2.0 and cured in lime solution. The results indicated that compressive strength of Portland cement–nano SiO₂–rice husk ash (PC–NS–RHA) ternary blended concrete was considerably increased. Moreover, the total amount of porosity decreased to a minimum with respect to the control concrete. This improvement was observed at all the curing ages and replacement levels, but there was a gain in the optimal point with 20% of RHA plus 2% of 80?nm SiO₂ particles at 90 days of curing.     

Hydration of quaternary Portland cement blends containing blast-furnace slag,siliceous fly ash and limestone powder

In this study the hydration of quaternary Portland cements containing blast-furnace slag, type V fly ash and limestone and the relationship between the types and contents of supplementary cementitious materials and the hydrate assemblage were investigated at ages of up to 182 days using X-ray diffraction and thermogravimetric analysis. In addition thermodynamic modeling was used to calculate the total volume of hydrates. Two blast-furnace slag contents of 20 and 30 wt.% were studied in blends containing fly ash and/or limestone at a cement replacement of 50 wt.%. In all cases the experiments showed the presence of C–S–H, portlandite and ettringite. In samples without limestone, monosulfate was formed; in the presence of limestone monocarbonate was present instead. The addition of 5 wt.% of limestone resulted in a higher compressive strength after 28 days than observed for cements with lower or higher limestone content. Overall the presence of fly ash exerts little influence on the hydrate assemblage. The strength development reveals that amounts of up to 30 wt.% fly ash can be used in quaternary cements without significant loss in compressive 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.     

Efficient utilization of cementitious materials to produce sustainable blended cement

To achieve sustainable development of cement industry, cementitious efficiency of different cement clinker and supplementary cementitious materials (SCMs) fractions, in terms of hydration process and strength contribution ratio, was characterized. The results show that blast furnace slag and steel slag should preferably be arranged in fine fractions due to their desirable hydration processes and high strength contribution ratios. Cement clinker should be positioned in intermediate fraction (8–24 μm) due to its proper hydration process. Replacement of cement clinker by SCMs with low activity or inert fillers in coarse fractions was also suggested, because coarse cement clinker fractions gave very low hydration degrees and little strength contribution. Both early and late properties of gap-graded blended cements prepared can be comparable with or higher than those of Portland cement, indicating both cement clinker and SCMs were used more efficiently. These blended cements also give additional cost savings and reduced environmental impact.     

Properties of self-compacting portland pozzolana and limestone blended cement concretes containing different replacement levels of slag

In order to reduce energy consumption and CO₂ emission, and increase production, cement manufacturers are blending or inter-grinding mineral additives such as slag, natural pozzolana, and limestone. This paper reports on the results of an experimental study on the production of self-compacting concrete (SCC) produced with portland cement (PC), portland pozzolana (PPC) and portland limestone (PLC) blended cements. Moreover, the effect of different replacement levels (0–45%) of ground granulated blast furnace slag (GGBFS) with the PPC, PLC, and PC cements on fresh properties (such as slump flow diameter, T ₅₀₀ slump flow time, V-funnel flow time, L-box height ratio, setting time, and viscosity) and hardened properties (such as compressive strength and ultrasonic pulse velocity) of self-compacting concretes are investigated. From the test results, it was found that it was possible to manufacture self-compacting concretes with PPC or PLC cements with comparable or superior performance to that of PC cement. Furthermore, the use of GGBFS in plain and especially blended cement self-compacting concrete production considerably enhanced the fresh characteristics of SCCs.     

Improvement of the early-age reactivity of fly ash and blast furnace slag cementitious systems using limestone filler

This article analyzes the effects of the addition of limestone filler on the hydration rate, setting times and early-age mechanical properties of binary and ternary-binder mortars containing Portland cement, blast furnace slag (BFS) and fly ash (FA), with various substitution rates of cement with mineral additions going up to 50%. Vicat needle penetration tests and measurements of heat flow of reaction, compressive strength and dynamic Young’s modulus were carried out on 14 mortars prepared with binary and ternary binders, at 20°C. The results obtained on the mortars containing binary binders, show that their loss of mechanical strength at early age is not caused by a deceleration of the reactions of cement in the presence of mineral additions, but is mainly explained by the dilution effect related to the reduction in cement content. A moderate addition of limestone filler (8–17%) makes it possible to obtain ternary binders with early-age reactivity equal or even higher than that of Portland cement, and with 28-days mechanical resistance close to those of the binary-binder mortars. This accelerating effect of limestone filler is particularly sensitive in the case of mortars containing FA.     

Development of engineered cementitious composites with limestone powder and blast furnace slag

Nowadays limestone powder and blast furnace slag (BFS) are widely used in concrete as blended materials in cement. The replacement of Portland cement by limestone powder and BFS can lower the cost and enhance the greenness of concrete, since the production of these two materials needs less energy and causes less CO₂ emission than Portland cement. Moreover, the use of limestone powder and BFS improves the properties of fresh and hardened concrete, such as workability and durability. Engineered cementitious composites (ECC) is a class of ultra ductile fiber reinforced cementitious composites, characterized by high ductility, tight crack width control and relatively low fiber content. The limestone powder and BFS are used to produce ECC in this research. The mix proportion is designed experimentally by adjusting the amount of limestone powder and BFS, accompanied by four-point bending test and uniaxial tensile test. This study results in an ECC mix proportion with the Portland cement content as low as 15% of powder by weight. This mixture, at 28 days, exhibits a high tensile strain capacity of 3.3%, a tight crack width of 57 μm and a moderate compressive strength of 38 MPa. In order to promote a wide use of ECC, it was tried to simplify the mixing of ECC with only two matrix materials, i.e. BFS cement and limestone powder, instead of three matrix materials. By replacing Portland cement and BFS in the aforementioned ECC mixture with BFS cement, the ECC with BFS cement and limestone powder exhibits a tensile strain capacity of 3.1%, a crack width of 76 μm and a compressive strength of 40 MPa after 28 days of curing.