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Abstract
This paper presents a method to study cement hydration at ambient temperatures by using a micro processed non-conventional differential thermal analysis (DTA) system, which was used to evaluate the solidification/stabilization process of tannery wastes produced in the leather industry. The DTA curves of pastes composed by slag cement, Wyoming bentonite and waste are obtained in real time and used to analyze the heat effects of the reactions during the first 24 h of hydration. By applying a deconvolution method to separate the overlapped DTA peaks, the energy released in the several hydration stages may be estimated and consequently, the effects of each component on the solidification process. The highest separated DTA peak occurs during the several early stages of cement hydration and is due mainly to tricalcium silicate hydration. Very good correlation shows that the greater is the waste content in the paste composition, the higher is its effect on the rates of reactions occurring during the induction (dormant) period of cement hydration. The presence of bentonite used as a solidification additive in the stabilization process has a similar but less dramatic effect on the dormant period.
Abstract
The hydration of C3A, C3S and C3A+C3S mixtures was examined by thermogravimetry, differential thermogravimetry and calorimetry. The results showed the early hydration (15 min) of C3A+C3S is of two types: If the content of C3S<40%, then C3A hydrates as it does alone, but if the content of C3S≥40%, then the hydrate with the lowest temperature and the cubic one do not appear together up to 15 min.
A self-consistent mathematical model is proposed to describe the heat evolution during the hydration of inorganic binders. Such an approach reflects the sufficient role of the feedbacks in the systems under discussion. The principal physico-chemical reasons for the self-consistent description of the hydration kinetics are argued. To complete the phenomenology of the hydration of binders two more problems are solved: (i) quantitative determination of the characteristic periods of the hydration process, and (ii) the long-range forecast of integral heat evolution.
Investigations of cement early hydration in the presence of chemically activated fly ash
Use of calorimetry and infrared absorption methods
Abstract
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.
Abstract
Pozzolanic properties of a residual FCC catalyst during the early stages of cement hydration
Evaluation by thermal analysis
Abstract
The catalyst used in fluidized catalytic cracking (FCC) units of refineries after several recovery cycles in regeneration units, reduces its activity and it is partially substituted by new catalyst in the process. As it has a high silicon and aluminum oxides content, the pozzolanic properties of a Brazilian FCC spent residual catalyst, used in different substitution degrees to cement, were evaluated by three thermal analysis techniques during the early stages of hydration of a type II Portland cement. NCDTA curves show in real time that the residual catalyst, accelerates the stages of cement hydration. TG and DSC curves of respective pastes after 24 h of hydration evidence the pozzolanic activity of the waste, respectively, by the lower water mass loss during the dehydroxylation of the residual calcium hydroxide and by the lower dehydroxylation endothermal effect. Within the analyzed period, the higher is the cement substitution degree, the higher is the pozzolanic activity of the residual catalyst.
The hydration processes of mixtures containing calcined gypsum, blastfurnace slag or fly ash, portland cement and/or hydrated lime, able to generate calcium trisulphoaluminate and silicate hydrates, have been studied by means of differential thermal analysis. Samples were aged at 55°,70° and 85°C for 16, 24 and 48 hours, followed by a further curing at room temperature and humidity up to 28 days.
Abstract
DTA/TG thermoanalytical investigations and X-ray diffractometry were carried out which demonstrate the effect of MSW fly ash on the hydration reactions of pozzolanic cement. The MSW fly ash has high content of calcium sulphate, alkali chlorides and heavy metals. During the first curing period the calcium aluminate reacts with the sulphate to form ettringite. In that period also the presence of syngenite is noted in the pastes. With the growth of the fly ash content of the mixture there is a lengthening of the period in which the hydration reactions of the calcium silicates are inhibited. Subsequently with the progress of hydration in the pastes the CSH phase develops and the formation of calcium chloroaluminate phase is observed.
Abstract
Preparation and characterization of four new hydrated alkali metal molybdates Na2Mo4O136H2O, K2Mo4O133H2O, Rb2Mo4O132H2O and Cs2Mo4O132H2O are described. The compounds were prepared by crystallizing the solution obtained by dissolving MoO3 and corresponding alkali metal carbonates A2CO3 or molybdate A2MoO4 in stoichiometric amount in distilled water. The hydrated molybdates were characterized by thermal (TG/DTA) and X-ray diffraction (XRD) methods. The number of water molecules in the compounds were determined from their TG /DTA curves recorded in air and identification of their dehydration products was done by XRD. The cell parameters of the compounds were obtained by indexing their XRD patterns. Attempt to prepare the corresponding hydrated compound of lithium was not successful.
Heat capacities of structure I and II trimethylene oxide (TMO) clathrate hydrates doped with small amount of potassium hydroxide (x=1.8×10−4 to water) were measured by an adiabatic calorimeter in the temperature range 11–300 K. In the str. I hydrate (TMO·7.67H2O), a glass transition and a higher order phase transition were observed at 60 K and 107.9 K, respectively. The glass transition was considered to be due to the freezing of the reorientation of the host water molecules, which occurred around 85 K in the pure sample and was lowered owing to the acceleration effect of KOH. The relaxation time of the water reorientation and its distribution were estimated and compared with those of other clathrate hydrates. The phase transition was due to the orientational ordering of the guest TMO molecules accommodated in the cages formed by water molecules. The transition was of the higher order and the transition entropy was 1.88 J·K−1(TMO-mol)−1, which indicated that at least 75% of orientational disorder was remaining in the low temperature phase. In the str. II hydrates (TMO·17H2O), only one first-order phase transition appeared at 34.5 K. This transition was considered to be related to the orientational ordering of the water molecules as in the case of the KOH-doped acetone and tetrahydrofuran (THF) hydrates. The transition entropy was 2.36 JK−1(H2O-mol)−1, which is similar to those observed in the acetone and THF hydrates. The relations of the transition temperature and entropy to the guest properties (size and dipole moment) were discussed.