Hydration of Cement Slurry in The Presence of Spent Cracking Catalyst

The physicochemical properties of spent fluidized bed cracking catalyst and its influence on hydration process of cement slurry were studied. The samples were cement slurries prepared with water/solid=0.5 and additions of used catalyst amounted to 0, 5, 10, 15, 20 and 25%with resp. to the solid. After definite time they were subjected to thermogravimetric analysis (TG, DTG, DTA) and, in order to determine the progress of reaction with water, the heat of hydration was measured by means of isotherm calorimetry. The studies disclosed that the spent cracking catalyst is not merely an inactive filler in cement slurries, but it modifies the course of the hydration process. The spent catalyst is a pozzolana additive and its presence leads to a decrease of calcium hydroxide contents in the system. The spent catalyst affect on the heat of cement hydration. Small amounts additive accelerate the process of binding. This revised version was published online in August 2006 with corrections to the Cover Date.     

Studies on the influence of spent FCC catalyst on hydration of calcium aluminate cements at ambient temperature

The influence of spent catalyst from catalytic cracking in fluidized bed (FCC) on the hydration of two kinds of calcium aluminate cements (of about 40 and 70% content of alumina) was studied. Cement pastes were prepared with constant ratio of water/binder = 0.5 and with content of 0, 5 and 25% mass of addition as replacement of cement. The samples were stored at room temperature. Thermal analysis (TG, DTG), infrared absorption (FTIR) and X-ray diffraction methods were applied to investigate changes in various periods of hydration (up to 150 days). The compressive strength of cement mortars was also examined. On the basis of presented results it was affirmed that in studied conditions spent FCC catalyst is a reactive addition in calcium aluminate cement (CAC) pastes, which probably can create a new phase type C–A–S–H. It may be an interesting alternative for limitation of the negative phenomenon of conversion of aluminate hydrates, although the degree of the influence of the mineral additive depends on the composition of CAC and of the quantity of the used waste.     

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.     

Properties of Calcium Sulfoaluminate Cement Mortar Modified by Hydroxyethyl Methyl Celluloses with Different Degrees of Substitution

This paper studies the influence of hydroxyethyl methyl cellulose (HEMC) on the properties of calcium sulfoaluminate (CSA) cement mortar. In order to explore the applicability of different HEMCs in CSA cement mortars, HEMCs with higher and lower molar substitution (MS)/degree of substitution (DS) and polyacrylamide (PAAm) modification were used. At the same time, two kinds of CSA cements with different contents of ye’elimite were selected. Properties of cement mortar in fresh and hardened states were investigated, including the fluidity, consistency and water-retention rate of fresh mortar and the compressive strength, flexural strength, tensile bond strength and dry shrinkage rate of hardened mortar. The porosity and pore size distribution were also analyzed by mercury intrusion porosimetry (MIP). Results show that HEMCs improve the fresh state properties and tensile bond strength of both types of CSA cement mortars. However, the compressive strength of CSA cement mortars is greatly decreased by the addition of HEMCs, and the flexural strength is decreased slightly. The MIP measurement shows that HEMCs increase the amount of micron-level pores and the porosity. The HEMCs with different MS/DS have different effects on the improvement of tensile bond strength in different CSA cement mortars. PAAm modification can improve the tensile bond strength of HEMC-modified CSA cement mortar.     

An attempt to improve the pozzolanic activity of waste aluminosilicate catalyst

The so-called pozzolanic activity of waste catalysts from fluidised cracking was investigated. For this purpose a series of cement mixtures with this waste material were prepared and subsequently the pastes and mortars were produced. Waste aluminosilicate catalyst was used both in raw form and after grinding in a ball mill for 60 min. The hydrating mixtures were subjected to the calorimetric measurements in a non-isothermal/non-adiabatic calorimeter. After an appointed time of curing the hydrating materials were studied by thermal analysis methods (TG, DTG, DTA). The pozzolanic activity factors were determined, basing on the compressive strength data. The increased activity of cement — ground pozzolana systems has been thus proved. An accelerated Ca(OH)₂ consumption as well as higher strength were found for materials containing ground waste catalyst, as compared to those, mixed with the raw one. Thus grinding was also proved to result in mechanical activation in the case of the waste catalyst from fluidised cracking. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal analytical investigation of ancient mortars from gothic churches

The use of thermal analysis in studying ancient mortars in English cathedrals is explained. Thermal analysis can be used to investigate both mortar and stone in dated structures. Analysis of ancient mortars show that though recarbonated, they remain soft, yielding to structural deformations. The use of hard (cement mortar) in modern renovation can result in micro-cracking in the stone and subsequent chemical attack from the atmosphere. Contrary to the literature, data developed in the present study suggests that most medieval mortars have reached a near total state of recarbonation.     

The microstructure of high-strength mortars and concretes

The influence of microsilica on the microstructure and compressive strength of mortars and concretes prepared with different contents of microsilica and plasticizer, several types of cement and water/cement ratios ranging from 0.28 to 0.55 has been studied. The use of an efficient system of cementmicrosilica-plasticizer-water for the production of mortars and concretes leads to a homogenization of the material structure which causes high strength values.     

Use of Aminosilane Coupling Agents in Cementitious Materials

The work presented in this paper has been focused on the evaluation of the influence of the addition of aminosilanes like γ-aminopropyl-triethoxysilane (3-AMPS) on physical and mechanical properties of fresh and hardened polymer modified cement mortars (PMCMs), which contained also mineral fillers like fumed silica and blast furnace slag. The role of the aminosilane in cementitious system was to produce surface modification and covalent bonding among different inorganic phases of inorganic matrix (cement, aggregate, fumed silica) and strong chemical interaction between inorganic matrix and organic (polymer) phase of the mortar. The strong chemical bonding of inorganic matrix and polymer phase transformed composite mortar into cementitious material with more like monolithic structure. Mortars with the addition of aminosilanes showed improved physical-mechanical properties like bending strength, adhesion to concrete, and lower dry-shrinkage.     

Study of a Brazilian spent catalyst as cement aggregate by thermal and mechanical analysis

Fluidized catalytic cracking units of refineries normally use zeolite catalysts to treat heavy oil fractions. This catalyst is regenerated continuously, but due to the reduction of its activity during the process, it is partially substituted by a new catalyst make-up. The spent residue has a high content of silicon and aluminum oxides and usually presents pozzolanic properties. This paper presents the study of a Brazilian spent catalyst, which is being tested as a pozzolanic aggregate in partial substitution to cement. Pastes were prepared with 15, 20 and 25% in substitution to cement mass and analyzed after 28 days of hydration. Hydrated paste samples were analyzed by simultaneous thermogravimetry and differential thermal analysis, to quantify the calcium hydroxide consumption, as well as the content of other main hydrated cement phases. Compressive strength analysis was also performed after 28 days of hydration. Although, as spent catalyst content is increased, the pozzolanic activity is confirmed by the increase of calcium hydroxide consumption on cement mass basis, unlikely to other studied spent FCC catalysts, tested for the same purpose, the compressive strength of respective paste specimens decreases, due to the increase of other hydrated phases formation.     

Pozzolanic reaction of a spent fluid catalytic cracking catalyst in FCC-cement mortars

This work presents the relation between the pozzolanic activity, the hydration heat and the compressive strength developed by blended mortars containing 10 and 35% of a spent fluid catalytic cracking catalyst (FCC). The results show that, in comparison with 100% Portland cement mortar, a mortar with 10% FCC increases the hydration heat all over the period of testing. This hydration heat increasing is due to the pozzolanic effect, therefore the resulting compressive strength is higher than the reference mortar. Whereas, in a mortar with 35% of FCC, the hydration heat is higher than 100% PC mortar, until 10 h of testing. After this age, the substitution degree predominates over the pozzolanic activity, showing in this case, lower hydration heat and developing lower compressive strength than 100% PC mortar.     

Altered Volcanic Tuffs from Los Frailes Caldera. A Study of Their Pozzolanic Properties

This work presents the results of the study of the physical, chemical, mineralogical and pozzolanic properties of the altered volcanic tuffs (AVT) that lie in the Los Frailes caldera, south of the Iberian Peninsula, and demonstrates their qualities as pozzolans for the manufacturing of mortars and pozzolanic cements of high mechanical strength. The main objective of this research is to show to what extent the AVTs can replace portland cement (PC) in mortars, with standardised proportions of 75:25% and 70:30% (PC-AVT). To achieve these objectives, three AVT samples were studied by a petrographic analysis of thin section (PATS), DRX, FRX and MEB. The pozzolanic properties were determined by three methods: electrical conductivity (ECT), chemical pozzolanicity tests (CPT) at 8 and 15 days and mechanical strength tests (MS) of the specimens at 2, 7, 28 and 90 days. Studies of a PATS, DRX, FRX and MEB showed that the AVT samples’ constitutions are complex where smectite (montmorillonite), mordenite, quartz, halloysite, illite, kaolinite, volcanic glass and lithic fragments coexist. The results of the ECT and CPT tests confirmed the pozzolanic properties of the samples analysed and proved an increase in mechanical strength from 2 to 90 days of testing.     

Calorimetric and thermal analysis studies on the influence of waste aluminosilicate catalyst on the hydration of fly ash–cement paste

Binders containing large amounts of cement substitutes have been a subject of interest for many years because of the possibility to reduce the amount of cement in concrete, and in consequence decrease negative influence of cement production on natural environment. In this work, studies related to hydration of binders where 80 % of cement was substituted by blended pozzolana were carried out. The aim of this work was to investigate activation of fly ash–cement system by addition of spent aluminosilicate catalyst, using calorimetry and thermal analysis as main methods of investigations. It was demonstrated that spent fine-grained fluidised catalytic cracking catalyst acts acceleratingly on early hydration of binder. It seems to be beneficial to use up to 10 mass% of this spent catalyst. Higher amounts may cause changes in the mechanism of early hydration. Because Ca(OH)₂ in such systems is quickly consumed due to pozzolanic reaction it seems beneficial to modify composition of binders by introducing additional amounts of Ca(OH)₂ or cement.     

Sulphate resistance and passivation ability of the mortar made from pozzolan cement with zeolite

Sulphate resistance and passivation ability of the mortars made from pozzolan cement of CEM IV/A (P) type according to European Standard EN 197-1 (zeolite blended cement with 60.82 mass% of PC clinker, 35.09 mass% of zeolite and 4.09 mass% of gypsum abbreviated as ZBC) and ordinary Portland cement (abbreviated as PC) are introduced. Resistance tests were performed in water and 5% sodium sulphate solution (both 20°C) for 720 days. The increased sulphate resistance of pozzolan cement relative to that of PC was found. The key quantitative insight into the hydrate phase behaviour is given by thermal analysis. This is due to pozzolanic reaction of zeolite with PC resulting in reduction of the formed Ca(OH)₂ opposite to the reference PC. Ability of pozzolan cements with 15 to 50 mass% of zeolite to protect steel against corrosion was verified in 20°C/85% RH-wet air within 180-day cure. Steel was not corroded in the mortars made with pozzolan cement containing up to 35 mass% of zeolite. Pozzolan cement of CEM IV/A (P) type containing 35 mass% of zeolite is a suitable cementitious material for concrete structures exposed to sulphate attack. Steel is protected against corrosion by this pozzolan cement in the same measure as the reference PC.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

Resistance of supersulfated cement to strong sulfate solutions

One of the principal uses of supersulfated cement has been for structures exposed to sea water and sulfate bearing ground waters. The resistance to such environments has been related to the absence of calcium hydroxide and the combination of much of the free alumina into ettringite during hydration. This paper reports the resistance of SSC to sulfate solutions in which ettringite has been decomposed. Prism samples were subjected to initial water storage at 25°C for both 28 days and 6 months. Samples were also cured for 6 months at 95°C and at both 11% and 100% R.H. The control samples of 28 days were compared with the 6 months samples of a more mature undecomposed SSC paste. After curing the prisms were measured and all the samples were immersed in three sulfate solutions (0.7M Na₂SO₄ , 0.7M MgSO₄ and saturated CaSO₄), and water at the same time. Measurements of linear expansion over 6 months were carried out. Core and surface material following immersion was examined by DTG and XRD. The study indicated that SSC is resistant to sodium and calcium sulfate solutions. Strong magnesium sulfate solutions decomposed the samples under all conditions. A possible mechanism for this attack is suggested. This revised version was published online in July 2006 with corrections to the Cover Date.     

Structure of white cement mortars with high content of marble powder

In this study, three types of cementitious composites based on (i) white Portland cement and sand (cement-to-aggregate 1:3, and water-to-cement 0.50), (ii) white Portland cement and marble powder (cement-to-aggregate 1:2, and water-to-cement 0.60), and (iii) white Portland cement and marble powder with polycarboxylate-based admixture (HRWR) (cement-to-aggregate 1:2, and water-to-cement 0.40?+?HRWR) were studied. Their states after 28 and 120?days of water curing were evaluated by measurement of physical?Cmechanical properties, such as density, compressive strength and porosity. Thermal analysis, X-ray diffraction analysis and scanning electron microscopy were used to identify the crystal phases and their morphology. The experimental data show that the white cement mortars with higher water content exhibit larder variety of newly formed phases, like hydration products of the C?CS?CH type. The structure of mortars with polycarboxylate-based admixture is so dense that there is no possibility of crystal hydrates development at late curing ages. The use of marble as filler leads to a partial inclusion of carbonate ions in the newly formed hydrated phases (carbo-aluminates).     

Characterization of hydraulic mortars by means of simultaneous thermal analysis

The properties of hydraulic mortars were studied by means of simultaneous thermal analysis (STA), according to a procedure proposed in the literature. Hydraulic limes, cement and/or slaked lime were mixed using different proportions of both inert and reactive aggregates, in order to test the effectiveness of such procedure in distinguishing the different degree of hydraulicity of such samples. The use of the normalized coordinates suggested in the literature results in overlapping of the clusters of different kinds of mortars. Modified coordinates are proposed, which give promising results in view of outlining a ‘master curve’ of hydraulicity.     

Characterization of mortars from ancient and traditional water supply systems in Sicily

Long aged mortars from ancient hydraulic constructions of Sicily, i.e. the Roman aqueduct of Thermae and the Punic cisterns and traditional water supply systems in Pantelleria, have been characterised by means of XRD analysis, optical microscopy and simultaneous thermal analysis to correlate the hydraulic properties to the texture and to their different role in the construction, i.e. lining, covering, roofing and joint mortars. According to a procedure proposed in the literature all of the samples, but two air hardening ones, show high hydraulicity, which somehow can be related to the characteristics of aggregates.     

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.     

Theory of Microbial Carbonate Precipitation and Its Application in Restoration of Cement-based Materials Defects

Bacterial induced carbonate mineralization has been demonstrated as a new potential method for restoration of limestones in historic buildings and monuments. We claim here the formation of calcium carbonate was controlled by extracellular polymeric substances (EPS) isolated from Bacillus pasteurii. The process of crystallization nucleation was accelerated in the presence of cells and inhibited in the presence of EPS. The CaCO₃ film deposited on cement paste surface was about 100 µm after 7 d treatment. The results of various restoring methods showed that higher decrease of water absorption of cement paste was gained in brushing application in the presence of agar, which could maintain urease with high activity in long term compared to spraying method. The coefficient of capillary suction of cement paste treated with brushing method was reduced by 90%. Mixed media consisted of sands, urea, Ca²⁺ and concentrated biomass, was injected into artificial cracks of cement paste followed by continual nutrient supplement, and CaCO₃ particles were precipitated gradually between sands particles which were combined with cement matrix. The results showed that the compressive strength of recovered specimens was restored to 84%, which demonstrated that this kind of bio‐restoration method is effective in repairing surface defects of cement‐based materials.