Pozzolanic properties of a residual FCC catalyst during the early stages of cement hydration

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 effect of polymer dispersions on the early hydration of calcium sulfoaluminate cement

The influence of three polymer dispersions [styrene–butadiene copolymer (SB), styrene–acrylic ester copolymer (SA) and polyacrylic ester (PA)] on the hydration of calcium sulfoaluminate (CSA) cement within 72 h was investigated by using isothermal conduction calorimetry, X-ray diffraction analysis and thermal gravimetric analysis. The results indicate that these three polymer dispersions perform different influences on the hydration heat flow of CSA cement during different periods, they all postpone the occurrence time of the maxima peaks, and its extent is mainly dependent on the addition amount. Polymer dispersions manifest great retardation on the initial hydration of CSA cement, and the effect is much more significant within 1 h. In this stage, the generation of ettringite is strongly delayed; however, the formation of ettringite is accelerated by these polymer dispersions at and after 2 h. Among these three polymer dispersions, PA demonstrates the highest acceleration effect on the hydration degree.

     

Effect of metakaolin pozzolanic activity in the early stages of cement type II paste and mortar hydration

The cement industry is one which most emits polluting gases to the environment, due to the calcium carbonate calcination, as well as to the burning of fossil fuels during the manufacturing process. Metakaolin (MK), in partial substitution to cement in its applications, is having a special worldwide growing role, for the technological increment due to its pozzolanic activity and mainly to the reduction of those emissions. In the present paper, the effect of pozzolanic activity of metakaolin was analyzed by thermal analysis in pastes and mortars of type II Portland cement in the first three days of the hydration, during which, relevant initial stages of the hydration process occur. By non-conventional differential thermal analysis (NCDTA), paste and mortar samples containing 0, 10, 20, 30 and 40% of metakaolin in cement mass substitution and using a 0.5 water/(total solids) mass ratio, were evaluated. The NCDTA curves, after normalization on cement mass basis and considering the heat capacity of each reactant, indicate that the pozzolanic activity behavior of metakaolin is different in pastes and mortars. Through the deconvolution of the normalized NCDTA curve peaks, it can be seen that ettringuite formation increases as cement substitution degree (CSD) increases, in both cases. Tobermorite formation is more enhanced in mortars than in pastes by MK, with a maximum formation at 30% of CSD. In the pastes, tobermorite formation increases as CSD increases but it is practically the same at 30 and 40% of CSD.     

Early stages hydration of high initial strength Portland cement

This work complements a quantitative thermogravimetric study of the first 24 h of hydration of a high initial strength and sulphate resistant Portland cement (HS SR PC) using non-conventional differential thermal analysis (NCDTA) and Vicat needle method. Different water/cement (W/C) ratios from 0.35 to 0.85 were used to evaluate the most indicated operating conditions to maximize calcium hydroxide production for further use in CO₂ capture. Thermogravimetric analysis data performed at 4 and 24 h of hydration were also compared to the NCDTA and Vicat data for each kind of paste, to analyze the influence of the W/C ratio on the simultaneous hydration and setting process. The increase of the W/C ratio increases the induction time retards the solidification and setting processes but increases the hydration degree as the W/C ratio is increased from 0.45. At 24 h, products prepared with 0.35 W/C ratio present a little higher hydration degree than those prepared with W/C = 0.45, because of the highest level of temperature in the reacting mixture in the former case, during the first 8 h. There is a practical limit of W/C = 0.66 to prepare the pastes, due to a limit of the miscibility between HS SR PC and water, above which, the excess of water forms a separated phase that does not interfere in the hydration process.     

Early stages hydration of high initial strength Portland cement

Thermogravimetry (TG) and derivative thermogravimetry (DTG) were used to analyze the early stages of hydration of a high-initial strength and sulphate resistant Portland cement (HS SR PC) within the first 24 h of setting. The water/cement (W/C) mass ratios used to prepare the pastes were 0.35, 0.45, and 0.55. The hydration behavior of the pastes was analyzed through TG and DTG curves obtained after different hydration times on calcined cement mass basis to have a same composition basis to compare the data. The influence of the W/C ratio on the kinetics of the hydration process was done through the quantitative analysis of the combined water of the main hydration products formed in each case. TG and DTG curves data calculated on calcined mass basis of all the results were converted to initial cement mass basis to have an easier way to analyze the influence of the W/C ratio on the free and combined water of the different main hydrated phases. The gypsum content of the pastes was totally consumed in 8 h for all cases. A significant part of the hydration process occurs within the first 14 h of setting and at 24 h the highest hydration degree, indicated by the respective content of formed calcium hydroxide, occurs in the case of the highest initial water content of the paste.     

Simultaneous measurements of heat of hydration and chemical shrinkage on hardening cement pastes

Isothermal calorimetry and chemical shrinkage measurements are two independent techniques used to study the development of hydration in cementitious systems. In this study, calorimetry and chemical shrinkage measurements were combined and simultaneously performed on hydrating cement paste samples. Portland cement pastes with different water to cement ratios and a cement paste containing calcium sulfoaluminate clinker and anhydrite were studied. The combined calorimetry/chemical shrinkage test showed good reproducibility and revealed the different hydration behavior of sealed samples and open samples, i.e., samples exposed to external water during hydration. Large differences between sealed and open samples were observed in a Portland cement paste with low water to cement ratio and in the calcium sulfoaluminate paste; these effects are attributed to self-desiccation of the sealed pastes. Once the setup is fully automatized, it is expected that combined calorimetry/chemical shrinkage measurements can be routinely used for investigating cement hydration.     

Studies on the influence of different fly ashes and Portland cement on early hydration of calcium aluminate cement

The influence of three mineral additives, i.e. fly ashes from pulverized combustion and from fluidized combustion of hard coal as well as Portland cement, on early hydration (up to 28th day) of calcium aluminate cement was investigated. Cement pastes containing 0, 5 and 25 wt% of additives were studied by the use of calorimetry, thermal analysis and infrared spectroscopy methods. It was confirmed that hydration of calcium aluminate cement is closely dependent on the type of addition and its amount. The influence of additives of different properties on cement hydration was discussed basing on received results and other literature reports.     

The effect of dried paper-mill sludge on cement hydration

Journal of Thermal Analysis and Calorimetry - In the paper, the impact of paper-mill sludge dried at 75 °C (PS) on cement hydration is being analysed. The used specimens were made of...     

Calorimetric determination of the effect of additives on cement hydration process

Possibilities of a multicell isoperibolic-semiadiabatic calorimeter application for the measurement of hydration heat and maximum temperature reached in mixtures of various compositions during their setting and early stages of hardening are presented. Measurements were aimed to determine the impact of selected components?? content on the course of ordinary Portland cement (OPC) hydration. The following components were selected for the determination of the hydration behaviour in mixtures: very finely ground granulated blast furnace slag (GBFS), silica fume (microsilica, SF), finely ground quartz sand (FGQ), and calcined bauxite (CB). A commercial polycarboxylate type superplasticizer was also added to the selected mixtures. All maximum temperatures measured for selected mineral components were lower than that reached for cement. The maximum temperature increased with the decreasing amount of components in the mixture for all components except for silica fume. For all components, except for CB, the values of total released heat were higher than those for pure Portland cement samples.     

Effect of hydrothermal curing on early hydration of G-Oil well cement

G-Oil well cement has been cured under standard and hydrothermal conditions with different steam pressures and temperatures. Compressive strength, pore structure parameters, microstructure, and hydrated products were evaluated after 7 days curing by using SEM, MIP, and simultaneous TGA/DSC. Obtained results showed that 7 days aged sample cured under standard conditions has the highest compressive strength with compact pore structure and hydrated products similar to those found after hydration of Ordinary Portland cement. With increasing temperature and pressure from standard conditions (25 °C, 10125 Pa) to hydrothermal ones (150 °C and 0.3 MPa, 200 °C and 1.2 MPa), compressive strength has drastically decreased from 77.5 ± 2.0 to 20.5 ± 1.0 MPa due to the transformation of original hydrated products (C–S–H) to crystallized α-C₂SH and C₆S₂H₃. The crystallization has led, under hydrothermal curing, to the increase of permeability and pore structure depletion. The final compressive strength after curing for 7 days at 150 °C (51.8 ± 2.0 MPa) and 200 °C (20.5 ± 1.0 MPa), which significantly exceeds the recommended values of 3.45 MPa according to API to hold many casings of oil wells is questionable for application in geothermal ones.     

The effect of sodiumlignosulphonate on cement properties for conditioning the hazardous wastes

Sodiumlignosulphonate was added to sulphate resisting cement as chemical additive to modify its physical and chemical properties for conditioning hazardous and radioactive wastes for long term disposal. The effect of some organic and inorganic chemicals on sulphate resisting cement was investigated. The physical properties such as density, porosity percent and absorption percent for all the studied samples as well as the compressive strength values and the leaching properties were also determined. The thermal stability and the radiation stability were also investigated.     

Thermokinetic features of the early stages of hydration of slag alkaline binders

This paper presents results of thermokinetic studies on the early stages of hydration of some slag minerals, slag alkaline binders of traditional and new-generation compounds. A possibility of adjustment and control of hardening processes through thermokinetic indices of hydration (intensity and completeness of heat evolution) for various compounds, types and quantities of the alkaline components and temperatures is proved.     

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.     

Investigation of the cellulose ethers effect on the Portland cement hydration by thermal analysis

Cellulose ethers (CE) are introduced in almost all cement-based dry mortars in order to retain water in mortar mass avoiding losing it too quickly by substrate absorption or water evaporation. In this way the workability of the fresh material, the adherence to the substrate and internal-strength characteristics of mortar, render or tile adhesive are improved. One of the side effects of cellulose ethers is the Portland cement hydration delaying. The influence of six commercial cellulose ethers, hydroxyethylmethyl cellulose (HEMC) type, on the hydration of Portland cement CEM I 42.5 R, was followed by thermal analysis (TG and DTA curves). Three of these cellulose ethers are unmodified, and have different viscosities, while three of them have the same viscosity but differ in the degree of modification (unmodified, one with medium modification and one with high modification). The interest of dry mortars producers for the effects of these cellulose ethers, is generated by the wide offer available on the market and by the absence of systematic data on the effect of different viscosities and degrees of modification on dry mortars properties. In order to quantify the effect of the CE on the cement hydration, the surface area of the endothermic effect corresponding to the dehydration of portlandite (Ca(OH)₂), formed after 1, 3, and 7 days of hydration, was defined. It was noted that the proportion of Ca(OH)₂ in samples containing CE after 1 day was 30–40 % lower than in reference sample. After 3 and 7 days of hydration the proportion of Ca(OH)₂ in samples containing CE approaches that of reference sample (10–20 % less). For the same period of hydration, the different viscosity, and different degree of modification of cellulose ethers cause variations in narrow limits of the proportion of Ca(OH)₂, and the degree of cement hydration, respectively.     

Application of isothermal and isoperibolic calorimetry to assess the effect of zinc on cement hydration

The amount of zinc in the clinker or in the secondary raw materials has been increasing in recent years. Zinc can get to Portland cement from solid waste or tires which are widely used as a fuel for burning in a rotary kiln. The aim of this work was to determine the effect of zinc on Portland cement hydration. This effect was studied by isothermal and isoperibolic calorimetry. Both calorimetry methods are suitable for measurements during the first days of hydration. Isoperibolic calorimetry monitors hydration process in real-life conditions, while isothermal calorimetry does it at a defined chosen temperature. Zinc was added to the cement in the form of two soluble salts of Zn(NO₃)₂, ZnCl₂ and a poorly soluble compound ZnO. The concentration of zinc added was chosen as 0.05, 0.1, 0.5 and 1 mass%. The results show that increasing amounts of zinc ions in cement pastes lead to hydration retardation and reduce both the maximum temperature and the maximum heat flow due to the retarding effect of zinc. The newly formed compounds during hydration were identified by X-ray diffraction method.     

Early stages of solidification/stabilization of storm water runoff solid residuals in cement

Summary Results of the experimental investigation of the copper natural sulfide minerals (chalcocite and covellite) oxidation process in the air atmosphere are presented in this paper. Based on data obtained using thermal analysis methods and by construction of PSD diagrams for the Cu-S-O system at different temperatures, mechanisms of the investigated processes were determined. DTA-TG-DTG and RDA methods were used for the investigations given in this paper. Kinetic parameters as well as activation energies of investigated processes were determined using Sharp's method of reduced halftime of reaction.