Fast physics-chemical and calorimetric characterization of natural pozzolans and other aspects

This research reports on the effects of including natural pozzolans in two Portland cements with different mineralogical compositions, with and without excess gypsum at amounts equivalent to 7.0% SO₃. The main analytical techniques used to study these effects were: the amount of water needed to make a paste of normal consistency, the 2-day Frattini pozzolanicity test and conduction calorimetry. The results obtained showed that these natural pozzolans caused contradictory (accelerating and retarding) effects on the rheology of the resulting cements, depending on the mineralogical composition of the respective Portland clinkers as well as the reactive chemical composition of the pozzolans, in particular their reactive alumina content (Al₂O₃ ^r−). The addition of gypsum also caused acceleration and delays in the calorimetric evolution of the resulting pastes, which proved to be heavily dependent upon the more or less aluminic chemical character of the natural pozzolans studied. This, in turn, was conditioned by the higher or lower Al₂O₃ ^r− content (for the SiO₂ ^r− content was of a very similar order of magnitude in all three pozzolans analyzed). The Al₂O₃ ^r− content was likewise responsible for paste behaviour in the afore-mentioned trials and analyses, and the pozzolanic activity exhibited by the compound was found to be more specific than generic, indirectly stimulating C₃A hydration more intensely and rapidly than C₃S hydration in PC1, one of the two Portland cements used. Indeed, when these natural pozzolans exhibited such prior pozzolanic activity in the second cement studied, PC2, the hydration of its 79.5% of C₃S was not indirectly stimulated to the same degree; rather, the contrary effect was observed, i.e., this cement was physically diluted by the three pozzolans. Pozzolan O stimulated hydration directly and non-directly more than indirectly, while pozzolan C acted conversely, and A exhibited varying combinations of the two patterns. The physical state of the reactive alumina, Al₂O₃ ^r−, in these three natural pozzolans, must be more amorphous than vitreous, i.e., resembling metakaolin more than fly ash in this regard. That notwithstanding, the reactive alumina content in each pozzolan must have conditioned the water/cementitious material ratio obtained for the respective blends with both types of Portland cement (a finding that could be used in future for speedy, simple, reliable and economical characterization), as well as their specific pozzolanicity developed and the rate and total heat of hydration generated by such blended cements.     

Calorimetry of Portland cement with metakaolins, quartz and gypsum additions

In this work two aluminic pozzolans (metakaolins) and a non-pozzolan were added to two Portland cements with very different mineral composition, to determine the effect on the rate of heat release and the mechanisms involved. The main analytical techniques deployed were: conduction calorimetry, pozzolanicity and XRD. The results showed that the two metakaolins induced stimulation of the hydration reactions due to the generation of pozzolanic activity at very early stage, because of their reactive alumina, Al₂O₃^r− contents, mainly. Such stimulation was found to be more specific than generic for more intense C₃A hydration than C₃S, at least at very early on into the reaction, and more so when 7.0% SO₃ was added, and for this reason, such stimulation is described as ‘indirect’ to differentiate it from the ‘direct’ variety. As a result of both stimulations, the heat of hydration released is easy to assimilate to a Synergistic Calorific Effect.     

Improvement of surface cementitious properties of coarse fly ash by dehydration and rehydration processes

Owing to poor bonding between coarse fly ash particles and hydration products, gap-graded blended cements with fly ash usually show lower compressive strengths than Portland cement. Surface cementitious properties of coarse fly ash were improved by dehydration and rehydration processes in the present study. The results show that during the calcination at 750?°C, C?CS?CH gel is mainly transformed into a new nesosilicate, which is similar to a less crystalline C₂S. The formation of melilite from hydration products is also noticed at 900?°C, however, this will not contribute to rehydration of calcined fly ash. Rehydration of new generated nesosilicate on the surface of coarse fly ash leads to a better bonding between coarse fly ash particles and hydration products. As a result, both early and late mechanical properties of gap-graded blended cements containing 25% cement clinker and 39% calcined coarse fly ash are higher than those of 100% Portland cements.     

Investigations of cement early hydration in the presence of chemically activated fly ash

The paper describes an attempt of chemical activation of fly ash and claims the usefulness of combination of such investigation methods as calorimetry and infrared absorption for investigations of early periods of cement hydration. The research samples were cement pastes made with an addition of fly ash and admixtures of chemical activators, CaCl₂, Na₂SO₄ and NaOH, whereas a cement paste without fly ash addition and a cement-fly ash paste (both without admixtures) were used as reference samples. In order to investigate early periods of cement pastes hydration, the amount and rate of heat release were registered, and IR spectrums were checked at appointed hydration moments. As a result, it was shown that the combination of calorimetric and IR absorption methods in the investigations of early periods of cement hydration was useful. It was confirmed that the use of chemical activators CaCl₂, Na₂SO₄ and NaOH accelerated the hydration of cement pastes containing fly ash additive in early hours after adding water. The action of activators on hydrating cement system is different for each of investigated compounds.     

Production and separation of no-carrier-added 48V from 16O irradiated chlorine target

The viability of ground coal bottom ash as a potential Portland cement constituent to be used in building materials is assessed. Currently, coal fly ash is used to produce Portland cements and concretes. However, coal bottom ash is mainly landfilled. Gamma spectrometry analysis, compressive strength, physical and chemical testing were performed. The ground coal bottom ash activity concentration index (I = 1.03) was compared to that of the coal fly ash (I = 1.11) provided from the same thermo-electrical power plant. Ground coal bottom ash could be used in building materials in the same way as coal fly ash as a Portland cement constituent.

     

Heat Evolution in Hydrated Cementitious Systems Admixtured with Fly Ash

In this study a calorimeter was applied to investigate the hydration of cements with fly ash (pulverised fuel ash – PFA) admixture. Four cements were used to produce the binders containing from 5 to 60% fly ash. The process of hydration in cementitious systems with fly ashes is slower than in reference pastes without admixtures. However, the calorimetric calculations and the shape of heat evolution curves seem to indicate a complex interaction between the components of cement and ash resulting in the increasing total heat evolved values per unit of cement. At higher fly ash content the accelerating effect of alkalis and alumina should be taken into account and discussed in terms of the composition of initial cement. The modifications of hydration kinetics and mechanism in this case is very well visualised by means of calorimetry. This revised version was published online in July 2006 with corrections to the Cover Date.     

Evaluation of Properties of Concrete Without Cement Produced Using Fly Ash-Based Geopolymer

The use of ordinary Portland cement (OPC) in the construction industry is inevitable. The huge production of OPC and its use in infrastructural development pose an environmental impact. Greenhouse gas emitted increases the global temperature and it is an alarming sign to everybody on the planet. Concrete is the most consuming material which is produced by using OPC and it is proven that OPC contributes a lot to CO₂ emission. Hence in this study attempt is made to produce concrete by using environment-friendly material like fly ash along with alkaline activators, which is termed Geo polymer concrete. The by-product fly ash is widely available worldwide. It is a by-product of thermal power plants. The use of fly ash in concrete produces less expensive and more cost-effective concrete than concrete made up using OPC. Due to its high silicate and alumina content, fly ash reacts with an alkaline solution to create an aluminosilicate gel that binds the aggregate and results in high-quality concrete. Fly ash is finer than cement, it occupies the pores of cement after hydration. This would result in denser concrete which gives higher strength. In comparison to ordinary concrete, fly ash-based geopolymer concrete offers better resistance to aggressive environments and high temperatures. In the present study, an alkaline activator of molarity 8 is used to prepare geopolymer concrete. The test specimens are cast and cured for 28 days. Test results indicate that an alkaline liquid fly-ash ratio (0.4) produces higher mechanical properties. Hence, geopolymer concrete produced in this study is found to be cost-effective and environment friendly.     

Hydration heat evolution of high-belite cement–phosphate slag binder

The influence of phosphate slag with different finenesses and activators on the hydration of high-belite cement has been studied by using the hydration heat of binders, the DTA curves, the SEM images, and the specific strength. Results indicated that doped phosphorus slag in the cement will reduce heat of hydration. The activity of phosphate slag was low at early stage, but pozzolanic activity of phosphorus slag is higher than that of fly ash. Increasing the specific surface area and curing time and using Ca(OH)₂ combined with gypsum can clearly promote the hydration degree of phosphorus slag. The findings in this paper show that since phosphorus slag can promote the hydration of high-belite cement, the strength contribution of cement is increased. Moreover, the greater the specific surface area is, the more significant the promotion effect at 90 d is.

     

Degree of hydration in cement paste and C<Subscript>3</Subscript>A-sodium carbonate-water systems

This research provides a fundamental understanding of the early stage hydration of Portland cement paste, tricalcium aluminate (C₃A) paste at water to cement ratio of 0.5 and C₃A suspension at water to cement ratio of 5.0 modified by 2 or 4 mass% of sodium carbonate. A high conversion of unreacted clinker minerals to gel-like hydration products in the cement-Na₂CO₃ pastes takes place rapidly between 1^st to 24^th h. Contrary the Ca(OH)₂ formation within the same time interval is retarded in the excess of CO₃²⁻ ions due to intensive rise and growth of CaCO₃ crystals in hydrated cement. Later, the conversion of clinker minerals to the hydrate phase is reduced and higher contents of calcite and vaterite relative to that of Ca(OH)₂ in comparison with those found in the Portland cement paste are observed. As a consequence a decrease in strength and an increase in porosity between hardened Portland cement paste without sodium carbonate and those modified by Na₂CO₃ are observed. C₃A hydrates very quickly with sodium carbonate between 1^st and 24^th h forming hydration products rich in bound water and characterized also by complex salts of (x)C₃A·(y)CO₂·(zH₂O type, whereas C₃A-H₂O system offers C₃AH₆ as the main hydration product. Higher content of the formed calcium aluminate hydrates in C₃A-Na₂CO₃-H₂O system also contributes to early strength increase of Portland cement paste.     

Calorimetry of portland cement with silica fume and gypsum additions

The use of active mineral additions is an important alternative in concrete design. Such use is not always appropriate, however, because the heat released during hydration reactions may on occasion affect the quality of the resulting concrete and, ultimately, structural durability. The effect of adding up to 20% silica fume on two ordinary Portland cements with very different mineralogical compositions is analyzed in the present paper. Excess gypsum was added in amounts such that its percentage by mass of SO₃ came to 7.0%. The chief techniques used in this study were heat conduction calorimetry and the Frattini test, supplemented with the determination of setting times and X-ray diffraction. The results obtained showed that replacing up to 20% of Portland cement with silica fume affected the rheology of the cement paste, measured in terms of water demand for normal consistency and setting times; the magnitude and direction of these effects depended on the mineralogical composition of the clinker. Hydration reactions were also observed be stimulated by silica fume, both directly and indirectly – the latter as a result of the early and very substantial pozzolanic activity of the addition and the former because of its morphology (tiny spheres) and large BET specific surface. This translated into such a significant rise in the amounts of total heat of hydration released per gram of Portland cement at early ages, that silica fume may be regarded in some cases to cause a synergistic calorific effect with the concomitant risk of hairline cracking. The addition of excess gypsum, in turn, while prompting and attenuation of the calorimetric pattern of the resulting pastes in all cases, caused the Portland cement to generate greater heat of hydration per gram, particularly in the case of Portland cement with a high C₃A content.     

Simultaneous determination of silicic acid, Ca, Mg and Al in mineral water and composite tablets by Ion chromatography

Summary A simple, selective and sensitive ion-chromatography method was investigated for simultaneously determining silicic acid, Ca²⁺, Mg²⁺, Al³⁺ and anions (Cl⁻ and NO ₃ ⁻ ) in real samples. It involved a single-column ion-chromatograph with sodium hydroxide-methanol-water eluent and conductometric detection. Cations were converted to complex anions by adding EDTA to the sample solution. A set of well-defined peaks of silicic acid, Ca²⁺, Mg²⁺, Al³⁺, Cl⁻ and NO ₃ ⁻ were obtained. Detection limits using 3.3σ (σ=standard deviation of blank solution) were 1.25×10⁻⁶ M for H₃SiO ₄ ⁻ , 1.32×10⁻⁶ M for Ca²⁺, 1.28×10⁻⁶ M for Mg²⁺, 1.33×10⁻⁶ M for Al³⁺, 1.31×10⁻⁶ M for Cl⁻ and 1.24×10⁻⁶ M for NO ₃ ⁻ . The method was successfully applied to analysis of mineral water and composite tablets.     

Calorimetric and thermogravimetric study on the influence of calcium sulfate on the hydration of ye’elimite

Calcium sulfoaluminate (CSA) cements, which represent a CO₂-friendly alternative to conventional Portland cements, are produced by blending CSA clinker with gypsum and/or anhydrite. The hydration kinetics and the hydrated phase assemblages of the main hydraulic phase ye’elimite (calcium sulfoaluminate) with calcium sulfate were studied by isothermal conduction calorimetry, thermogravimetric analysis, X-ray diffraction analysis and thermodynamic modelling. Two calcium sulfates with different reactivities (gypsum and anhydrite) were applied. It was found that the pure phase without any calcium sulfate addition exhibits very slow hydration kinetics during the first 10 h. The hydration can be accelerated by the addition of calcium sulfate or (less effective) by increasing the pH of the aqueous phase. The amount of the calcium sulfate determines the ratio between the hydration products ettringite, monosulfate and amorphous aluminium hydroxide. The reactivity of the added calcium sulfate determines the early hydration kinetics. It was found that the more reactive gypsum was better suited to control the hydration behaviour of ye’elimite.     

Identification of Composite Cement Hydration Products by Means of X-Ray Diffraction

 In this paper the effect of limestone, fly ash, slag and natural pozzolana on the cement hydration products is studied. Four composite cements containing limestone, natural pozzolana from the Milos Island, slag and fly ash have been produced by intergrinding clinker (85%), the above main constituent (15%) and gypsum. The grinding process was designed in order to produce cements of the same 28d compressive strength. The hydrated products, formed after 1–28 days, were studied by means of X-ray diffraction. Unhydrated calcium silicate compounds of clinker and hydration products such as C*H, C*S*H and ettringite are clearly observed. Although there is not significant differentiation among samples hydrated for the same period of time, modifications of calcium aluminate hydrates as well as sulfoaluminate hydrates, are indicated by the XRD patterns. In samples of limestone cement, monocarboaluminate is formed in the first 24 hours and is still present after 28 days.     

Microstructural,physical, and thermal analyses of Portland cement–fly ash–calcium hydroxide blended pastes

The effect of calcium hydroxide (CH) on the properties of Portland–fly ash cement pastes, at up to high-volume fly ash mixes has been investigated using normal consistency, setting time, compressive strength, thermal analysis and scanning electron microscope. CH as an additive material (5 and 10 wt%), lignite fly ash (FA) up to 50 wt% was used to produce Portland cement (PC)–FA–CH pastes at w/PC + FA ratio of 0.5. Water requirement for normal consistency was found to increase with increasing CH content while a decrease in initial setting time was found. Furthermore, the compressive strengths of all FA mixes with CH were found to be higher than the mixes without CH. Thermal analysis and scanning electron microscope were used to study the hydration of PC–FA–CH system. The results showed that the first phase transition detected by thermal analyses was attributed to ettringite, calcium silicate hydrate, gehlenite hydrate and was found to be higher in PC–FA–CH mixes than in pure Portland–FA cement paste resulting in an increase in compressive strength. Moreover, the hydration phases were also found to increase with increasing curing time. Overall, the results show that the additional of 5 wt% CH in Portland–FA mixes especially at high-volume FA mixes was found to accelerate FA pozzolanic reaction at early ages (7 and 28 days), resulting to an increase in compressive strength.     

Structures and aromaticity of the planar Al<Subscript>2</Subscript>P<Subscript>2</Subscript><Superscript><Emphasis Type="Italic">n</Emphasis>−</Superscript> (<Emphasis Type="Italic">n</Emphasis>=1–4) clusters

Clusters Al₂P₂ ⁿ⁻ (n = 1–4) were theoretically investigated using density functional theory (DFT) methods at the B3LYP/6-311+G* and B3PW91/6-311+G* levels of theory. The calculated results showed that the planar structure (D _2h symmetry) of Al₂P₂ ⁿ⁻ (n = 1–4) species was the global minimum. And the negative nucleus-independent chemical shift (NICS) value of Al₂P₂ ⁿ⁻ (n = 1–4) species indicated the existence of a ring current in the planar structure (D _2h symmetry). A detailed molecular orbital (MO) analysis revealed that the planar structures (D _2h symmetry) had π aromaticity, which further exhibited the strongly aromatic character for Al₂P₂ ⁿ⁻ (n = 1–4) species.     

Comparative investigation of reactivity of different kinds of fly ash in alkaline media

Comparison of the influence of temperature and different alkali activators on the reactivity of two types of fly ash (conventional, fluidized) was presented. The main emphasis was put on fluidized fly ash as potential component of binding mixtures containing low amount of cement. Conventional fly ash was used as a reference. It was found that for these materials the key differences affecting products of activation are: availability of calcium and sulfate ions as well as structure of fly ash grains influencing dissolution of aluminate and silicate species. Fluidized fly ash, contrary to conventional fly ash, undergoes reaction in 0.1 M solutions of hydroxides forming mainly ettringite. In the case of 4 M hydroxides, both fly ashes undergo hydration processes. Conventional fly ash formed mainly amorphous aluminosilicate gel, while fluidized fly ash may create zeolitic products especially in the case of elevated temperature of early hydration. Sulfate and alkali ions can be incorporated into aluminosilicate structure of new formed products; however, this process depends strictly on the type of used hydroxide and its concentration. The presence of Ca(OH)₂, carbonates and alkali sulfates was also registered in the case of hydrated fluidized fly ash.

     

Thermal analysis and microstructure of Portland cement-fly ash-silica fume pastes

Thermal analysis (thermogravimetry and differential thermal analysis) was used with scanning electron microscopy technique to investigate the hydration mechanisms and the microstructure of Portland cement-Fly ash-silica fume mixes. Calcium silicate hydrate (C–S–H), ettringite, gehlenite hydrate (C₂ASH₈), calcium hydroxide (Ca(OH)₂) and calcium carbonate (CaCO₃) phases were detected in all mixes. In the mixes with the use of silica fume addition, there is a decrease in Ca(OH)₂ with increasing silica fume content at 5 and 10% compared to that of the reference Portland-fly ash cement paste and a corresponding increase in calcium silicate hydrate (C–S–H).     

Reactivity of fly ash in cement paste studied by means of thermogravimetry and isothermal calorimetry

Four paste mixtures with varying replacement level of the cement content by fly ash have been studied. Due to fly ash, the acceleration period decreased and a third hydration peak was noticed with isothermal calorimetry. The total heat after 7 days increased with increasing fly ash content. From 1 to 7 days, thermogravimetry showed a higher chemically bound water and Ca(OH)₂-content for the pastes with fly ash. Between 7 and 14 days the calcium hydroxide started to be depleted due to the pozzolanic reaction. A unique relation was found between calcium hydroxide and total heat development.     

Formulation of a holistic model for the kinetics of steady state growth of porous anodic alumina films

A holistic model for the kinetics of steady state growth of porous anodic alumina films in oxalic acid, H₂C₂O₄, solution was developed not necessarily requiring the adoption of any ‘a priori’ mechanism of porous film growth. By this model the effect of anodising conditions on the transport numbers of Al³⁺ cations and O²⁻ anions across the barrier layer was revealed. The cation (anion) transport number decreased (increased) with current density, increased (decreased) with temperature and was unaffected by the concentration of electrolyte or pH. A complementary atomistic-ionic kinetic model was developed that fully justified these results and showed that the activation distances of Al³⁺ and O²⁻ transport are comparable, but the activation energy of Al³⁺ transport is lower mainly due to the much smaller size of Al³⁺. The validity of the model was tested on the basis of SEM observations, while structural features and the rate of pore wall dissolution were determined.     

Influence of mechanical grinding on pozzolanic characteristics of circulating fluidized bed fly ash (CFA) and resulting consequences on hydration and hardening properties of blended cement

This paper investigates the influence of mechanical grinding on pozzolanic characteristics of circulating fluidized bed fly ash (CFA) from the dissolution characteristics, paste strength, hydration heat and reaction degree. Further, the hydration and hardening properties of blended cement containing different ground CFA are also compared and analyzed from hydration heat, non-evaporable water content, hydration products, pore structure, setting time and mortar strength. The results show that the ground CFA has a relatively higher dissolution rate of Al₂O₃ and SiO₂ under the alkaline environment compared with that of raw CFA, and the pozzolanic reaction activity of ground CFA is gradually improved with the increase of grinding time. At the grinding time of 60 min, the pozzolanic reaction degree of CFA paste is improved from 6.32% (raw CFA) to 13.71% at 7 days and from 13.65 to 28.44% at 28 days, respectively. The relationships of pozzolanic reaction degree and grinding time of CFA also conform to a quadratic function. For ground CFA after a long-time grinding such as 60 min, the hydration heat and non-evaporable water content of blended cement containing CFA are significantly improved. Owing to relatively smaller particle size and higher activity of ground CFA, the blended cement paste has more hydration products, narrower pore size distribution and lower porosity. For macroscopic properties, with increase in grinding time of CFA, the setting time and strength of blended cement are gradually shortened and improved, respectively.