A model to predict the amount of calcium hydroxide in concrete containing mineral admixtures

This study examines in detail the degree of reactivity of admixtures, such as fly ash and blast furnace slag, and their effect on the levels of calcium hydroxide in cement paste. Experimental results indicate that reactivity between calcium hydroxide and mineral admixture is dependent on the amount of calcium hydroxide and the degree of hydration of mineral admixtures.From these results, a model was formulated to predict the reaction between calcium hydroxide and mineral admixtures, and its validity verified by comparing calculated data with the data from the tests with cement mortar specimens. The calculated values of calcium hydroxide agree well with the test results. The parameters of the prediction model are dependent on the physical and chemical characteristics of mineral admixtures.     

A rate equation for Ca(OH)2 and CO2 reaction in a spouted bed reactor at low gas concentrations

In the present study, the carbonation reaction of hydrated lime in semi-dry condition is investigated experimentally in a laboratory-scale spouted bed reactor. Results show that for operating conditions where the concentration of CO₂ is low, the capture efficiency is raised by increasing the inlet CO₂ concentration. Additionally, because of the inconsistency between the experimental reaction rate and the calculated values based on the previous proposed equations, a new rate equation is introduced that considers the dependency of CO₂ concentration too. To validate the proposed equation, its predictions were compared with another set of experimental data.     

Polyethylene glycol as an efficient and reusable solvent medium for the synthesis of thiohydantoins using K2CO3 as catalyst

Polyethylene glycol was found to be an inexpensive, non-toxic, recyclable and an effective medium for the synthesis of thiohydantoin derivatives in the presence of K₂CO₃ as the catalyst. The procedure is operationally simple and environmentally benign.     

The experimental investigation of concrete carbonation depth

Phenolphthalein indicator has traditionally been used to determine the depth of carbonation in concrete. This investigation uses the thermalgravimetric analysis (TGA) method, which tests the concentration distribution of Ca(OH)₂ and CaCO₃, while the X-ray diffraction analysis (XRDA) tests the intensity distribution of Ca(OH)₂ and CaCO₃. The Fourier transformation infrared spectroscopy (FTIR) test method detects the presence of C-O in concrete samples as a basis for determining the presence of CaCO₃. Concrete specimens were prepared and subjected to accelerated carbonation under conditions of 23 °C temperature, 70% RH and 20% concentration of CO₂. The test results of TGA and XRDA indicate that there exist a sharp carbonation front. Three zones of carbonation were identified according to the degree of carbonation and pH in the pore solutions. The TGA, XRDA and FTIR results showed the depth of carbonation front is twice of that determined from phenolphthalein indicator.     

Development of new alumina-modified sorbents for CO2 sorption and regeneration at temperatures below 200 °C

A new regenerable alumina-modified sorbent was developed for CO₂ capture at temperatures below 200 °C. The CO₂ capture capacity of a potassium-based sorbent containing Al₂O₃ (KAlI) decreased during multiple CO₂ sorption (60 °C) and regeneration (200 °C) tests due to the formation of the KAl(CO₃)(OH)₂ phase, which could be converted into the original K₂CO₃ phase above 300 °C. However, the new regenerable potassium-based sorbent (Re-KAl(I)) maintained its CO₂ capture capacity during multiple tests even at a regeneration temperature of 130 °C. In particular, the CO₂ capture capacity of the Re-KAl(I)60 sorbent which was prepared by the impregnation of Al₂O₃ with 60 wt.% K₂CO₃ was about 128 mg CO₂/g sorbent. This excellent CO₂ capture capacity and regeneration property were due to the characteristics of the Re-KAl(I) sorbent producing only a KHCO₃ phase during CO₂ sorption, unlike the KAlI30 sorbent which formed the KHCO₃ and KAl(CO₃)(OH)₂ phases even at 60 °C. This result was explained through the structural effect of the support containing the KAl(CO₃)(OH)₂ phase which was prepared by impregnation of Al₂O₃ with K₂CO₃ in the presence of CO₂.     

Changes in portlandite morphology with solvent composition: Atomistic simulations and experiment

Experimental work has been done to determine changes in the particle shape of portlandite grown in the presence of different ions. To quantify the experimentally observed changes in morphology a new analysis tool was developed, allowing the calculation of the relative surface energies of the crystal facets. The observed morphology in the presence of chlorides and nitrates was facetted particles of a similar shape, the addition of sulfates leads to hexagonal platelet morphology and the addition of silicates leads to the formation of large irregular aggregates. In addition to the experimental work, the surfaces of portlandite were studied with atomistic simulation techniques. The empirical force field used has first been validated. The equilibrium morphology of portlandite in vacuum and in water was then calculated. The results indicate that the presence of water stabilizes the [20.3] surface and changes the morphology. This is consistent with the experimental observation of [20.3] surfaces.     

Determination of the elastic constants of portlandite by Brillouin spectroscopy

The single crystal elastic constants C_ij and the shear and adiabatic bulk modulus of a natural portlandite (Ca(OH)₂) crystal were determined by Brillouin spectroscopy at ambient conditions. The elastic constants, expressed in GPa, are: C₁₁ = 102.0(± 2.0), C₁₂ = 32.1(± 1.0), C₁₃ = 8.4(± 0.4), C₁₄ = 4.5(± 0.2), C₃₃ = 33.6(± 0.7), C₄₄ = 12.0(± 0.3), C₆₆ = (C₁₁-C₁₂)/2 = 35.0(± 1.1), where the numbers in parentheses are 1σ standard deviations. The Reuss bounds of the adiabatic bulk and shear moduli are K_0S = 26.0(± 0.3) GPa and G₀ = 17.5(± 0.4) GPa, respectively, while the Voigt bounds of these moduli are K_0S = 37.3(± 0.4) GPa and G₀ = 24.4(± 0.3) GPa. The Reuss and Voigt bounds for the aggregate Young's modulus are 42.8(± 1.0) GPa and 60.0(± 0.8) GPa respectively, while the aggregate Poisson's ratio is equal to 0.23(± 0.01). Portlandite exhibits both large compressional elastic anisotropy with C₁₁/C₃₃ = 3.03(± 0.09) equivalent to that of the isostructural hydroxide brucite (Mg(OH)₂), and large shear anisotropy with C₆₆/C₄₄ = 2.92(± 0.12) which is 11% larger than brucite. The comparison between the bulk modulus of portlandite and that of lime (CaO) confirms a systematic linear relationship between the bulk moduli of brucite-type simple hydroxides and the corresponding NaCl-type oxides.     

Electrical conductivity and rheological properties of ordinary Portland cement-silica fume and calcium hydroxide-silica fume pastes

Two groups of solids mixtures were prepared: (i) the first group includes four mixes having different ordinary Portland cement/silica fume (OPC/SF) weight ratios and (ii) the second group consists of four blends having different Ca(OH)₂/SF molar ratios. Electrical conductivity measurements were carried out on the pastes of the first group mixes using two initial water-to-solid (W/S) ratios of 0.55 and 0.70 by weight; while the W/S ratios used for the second group mixes were 1.00 and 1.20 by weight. The measurements were done at 25 and 45 °C for each paste during setting and hardening processes after gauging with deionized water. Rheological properties were studied at room temperature for all mixes using various W/S ratios. The results obtained indicate clearly the effect of SF and W/S ratio on the rheological properties and electrical conductivity of all pastes under investigation. The relation between the electrical conductivity and rheological properties for different mixes were discussed based on the chemical nature and physical state of the hydration products formed at early ages of hydration.     

Characteristics of brick used as aggregate in historic brick-lime mortars and plasters

Mortars and plasters composed of a mixture of brick powder and lime have been used since ancient times due to their hydraulic properties. In this study, raw material compositions, basic physical, mineralogical, microstructural and hydraulic properties of some historic Ottoman Bath brick-lime mortars and plasters were determined by XRD, SEM-EDS, AFM, TGA and chemical analyses. The mineralogical and chemical compositions, microstructures, morphologies and pozzolanicities of the brick powders and fragments used as aggregates in the mortars and plasters were examined to find out the relationship between hydraulic properties of the mortars and the bricks. The characteristics of bricks used in the bath domes were also determined to investigate whether the brick aggregates used in mortar and plasters were prepared from these bricks. The results indicated that the mortars and plasters were hydraulic owing to the presence of crushed brick powders that have good pozzolanicity. The brick powders had high pozzolanicity because they contained high amounts of calcium-poor clay minerals in their raw materials that were fired at low temperatures. On the other hand, bricks used in the domes had poor pozzolanicity with different mineralogical and chemical compositions from bricks used in mortars and plasters. Based on the results of the analysis, it was thought that the bricks manufactured with high amounts of clays were consciously chosen in the preparation of hydraulic mortars and plasters.     

The influence of relative humidity on structural and chemical changes during carbonation of hydraulic lime

Studies monitoring the carbonation of NHL3.5 hydraulic lime are described. Weight-gain measurements, focused ion beam imaging, X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectroscopy were used to monitor changes in structure and composition occurring in lime pastes after exposure to 100% carbon dioxide at relative humidities of 65 and 97%. Lime paste exposed to a relative humidity (R.H.) of 97% indicated a higher carbonation rate compared to paste exposed to 65% R.H. Surface analysis showed that the sample exposed to a relative humidity of 97% was completely carbonated. No calcium hydroxide was detected. A small amount of calcium hydroxide was, however, present at the surface of the sample exposed to 65% R.H. These observations suggest that high humidity results in the formation of a thin layer of crystalline calcium carbonate covering silicate and hydroxide phases. The actual mass increase of the sample also indicated that uncarbonated calcium hydroxide remained beneath the surface.     

Carbonation reaction of lime, kinetics at ambient temperature

The uptake of carbon dioxide due to the carbonation reaction of Ca(OH)₂ in ambient temperature of approximately 20 °C has been studied. Different types of lime have been used and the CO₂ concentration has been varied to identify the influence of different variables on the kinetics of the reaction. A closed loop system has been developed and validated that allows measurement of the carbonation progress directly from monitoring CO₂ uptake. Thermal analysis (TA) was used to verify the degree of carbonation that reached up to 83%. Factor analysis on the data set has demonstrated that reaction speed is not dependent upon the CO₂ concentration within the limits tested. Carbonation speed depends on the specific surface of the lime. The results of this study contribute to research carried out on lime mortar carbonation models and on the carbonation process in general.     

Lime-pozzolana mortars in Roman catacombs: composition, structures and restoration

Analyses of microsamples collected from Roman catacombs and samples of lime-pozzolana mortars hardened in the laboratory display higher contents in carbonated binder than other subaerial Roman monuments. The measured environmental data inside the Saint Callistus and Domitilla catacombs show a constant temperature of 15-17 °C, a high CO₂ content (1700 to 3500 ppm) and a relative humidity close to 100%. These conditions and particularly the high CO₂ concentration speed-up the lime calcitization roughly by 500% and reduce the cationic diffusion to form hydrous calcium aluminosilicates. The structure of Roman catacomb mortars shows (i) coarser aggregates and thicker beds on the inside, (ii) thin, smoothed, light and fine-grained external surfaces with low content of aggregates and (iii) paintings and frescoes on the outside. The observed high porosity of the mortars can be attributed to cracking after drying linked with the high binder content. Hardened lime lumps inside the binder denote low water/mortar ratios for slaking. The aggregate tephra pyroclasts rich in aluminosilicate phases with accessorial amounts of Ba, Sr, Rb, Cu and Pb were analysed through X-ray diffraction (XRD), electron microprobe analysis (EMPA) and also by environmental scanning electron microscopy (ESEM) to identify the size and distribution of porosity. Results support procedures using local materials, special mortars and classic techniques for restoration purposes in hypogeal backgrounds.     

Study of the water-retention capacity of a lime-sand mortar: Influence of the physicochemical characteristics of the lime

The purpose of this study is to evaluate the influence of limes' characteristics on the water-retention capacity of a lime-cement-sand mortar. Toward this aim, various categories of lime were partially substituted for the cement Portland CEM I 52.5 in mortars. The total binder/sand ratio has been maintained constant.Experimental results have highlighted the combined influence of both lime characteristics and lime content.As the proportion of lime in the mix increases the results demonstrate that the action of lime in a cement-lime mortar must not be analysed in terms of morphology and chemical nature alone. However, the electrical phenomena capable of being generated must be taken into account.     

Non-ideal solid solution aqueous solution modeling of synthetic calcium silicate hydrate

New data relevant to calcium silicate hydrate (C-S-H) gels prepared at room temperature have been obtained over a time period of up to 112 weeks. X-ray diffraction (XRD) indicates equilibrium was attained after 64 weeks. Coupled with fourier transform infrared (FT-IR) spectroscopy, a phase change in C-S-H gel at Ca/Si ≈ 1.0 was identified and the occurrence of portlandite as a distinct phase for Ca/Si > 1.64. The incongruent dissolution of C-S-H gel was modeled as a non-ideal solid solution aqueous solution (SSAS) between the end-member components CaH₂SiO₄ (CSH) and Ca(OH)₂ (CH) using equations defining the solidus and solutus curves on a Lippmann phase diagram. Despite being semi-empirical, the model provides a reasonable and consistent fit to the solubility data and can therefore be used to describe the incongruent dissolution of C-S-H gels with compositions Ca/Si ≥ 1.0.     

Autogenous deformations of cement pastes: Part II. W/C effects, micro-macro correlations, and threshold values

A broad experimental study has been performed, from the end of mixing up to 2 years, on a set of plain cement pastes prepared with the same type I ordinary portland cement (OPC) and various water-to-cement ratios (W/C), and cured at various constant temperatures. Several parameters have been measured on the hydrating materials, such as chemical shrinkage, volumetric and one-dimensional autogenous deformations, degree of hydration of the cement, Ca(OH)₂ content and Vicat setting times. Drying shrinkage has also been measured on the mature materials. In this part II of the paper, the effects of W/C within the range 0.25-0.60 have in particular been analysed in relation to the microstructural characteristics of the materials. This micro-macro analysis has highlighted a W/C threshold value (located around 0.40) both at the macro-level (on autogenous, but also on drying deformations and durability-related properties) and at the micro-level (characteristics of the hydration products, MIP porosity and pore size distribution, etc.).In addition, volumetric and one-dimensional autogenous shrinkage deformations have been compared in the case of W/C=0.25 and T=20 °C. Finally, a critical twofold (chemical and structural) effect of calcium hydroxide has been found. When significant structural effects, generated by the formation and the growth of large-size Ca(OH)₂ crystals, take place, swelling can become prominent, as observed for one-dimensional autogenous deformations in the case of medium and high W/C, and deviations are recorded on linear relationships.     

Pozzolanic reactions of common natural zeolites with lime and parameters affecting their reactivity

The pozzolanic reaction between portlandite and different types of nearly pure natural zeolites was studied. Analcime, phillipsite, chabazite, erionite, mordenite and clinoptilolite-rich tuffs were mixed with portlandite and water (1:1:2 by weight), and the progress of the pozzolanic reaction was quantitatively determined by thermogravimetrical analyses from 3 to 180 days.A thorough characterization of the raw materials was performed by quantitative XRD, XRF, SEM-EDX, BET specific surface area measurements, grain-size analyses, FTIR and Cation Exchange Capacity measurements. The difference in reactivity of the samples containing zeolites with varying Si/Al ratios, as well as between clinoptilolite-rich samples exchanged with different cations or ground to different grain sizes was assessed.The results indicate that the external surface area only influences the short-term reactivity, whereas the cation content has an effect on both the long- and short-term reactivity. The early reactivity of the unexchanged samples can be explained by these two parameters, but their long-term reactivity is mainly related to the Si/Al ratio of the zeolites. Samples with zeolites rich in Si react faster then their Al-rich counterparts.     

Facile synthesis and flame retardant performance of NaAl(OH)2CO3 whiskers

The regular and well-dispersed NaAl(OH)₂CO₃ whiskers were successfully synthesized via facile hydrothermal route using aluminium isopropoxide and NaHCO₃. The effects of reactants and reaction temperature on the structure and morphology of NaAl(OH)₂CO₃ whiskers have been investigated. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and thermo-gravimetric analysis (TGA) were employed to characterize the synthesized samples. Most NaAl(OH)₂CO₃ whiskers possess an average diameter of about 500 nm and lengths ranging from 10 to 30 μm. NaAl(OH)₂CO₃ whiskers exhibit excellent flame retardant performance and mechanical strength in poly(ethylene-co-vinyl acetate) matrix (EVA).     

Synthesis of carbon nanotubes by pyrolysis of solid Ni(dmg)2

We describe the high yield synthesis of multi-walled carbon nanotubes (MWCNTs) and the determination of the optimum production conditions. The method involves the catalytic pyrolysis of solid Ni(dmg)₂ under an Ar atmosphere. The obtained materials were characterized by scanning electron microscopy (SEM), energy dispersive X-ray (EDX) analysis, high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), Raman spectroscopy and thermogravimetry analysis (TGA). The data revealed the formation of MWCNTs surrounded by a varying quantity of byproducts such as amorphous carbon and metallic particles, depending mainly on the reaction temperature. Pyrolysis of Ni(dmg)₂ at 900 °C results in the production of nanotube material with the highest degree of crystallinity.     

Rheological characterization of C-S-H phases-water suspensions

The aim of this experimental work was to investigate the performance of microsilica-calcium hydroxide-water suspensions. Interactions between the raw material particles and between water and the raw material particles lead to the formation of gelatinous structures in this suspension. It is essential to use oscillation methods to examine the structure without destruction. The characterization of the tests is made by the storage modulus G′ in dependence of the frequency. The tests show an unexpectedly strong elastic behaviour.