Effect of calcium sulfate source on the hydration of calcium sulfoaluminate eco-cement

The availability of cements, including eco-cements, with tailored mechanical properties is very important for special applications in the building industry. Here we report a full study of the hydration of calcium sulfoaluminate eco-cements with different sulfate sources (gypsum, bassanite and anhydrite) and two water/cement ratios (0.50 and 0.65). These parameters have been chosen because they are known to strongly modify the mechanical properties of the resulting mortars and concretes. The applied multitechnique characterization includes: phase assemblage by Rietveld method, evolved heat, conductivity, rheology, compressive strength and expansion/retraction measurements. The dissolution rate of the sulfate sources is key to control the hydration reactions. Bassanite dissolves very fast and hence the initial setting time of the pastes and mortars is too short (20 min) to produce homogeneous samples. Anhydrite dissolves slowly so, at 1 hydration-day, the amount of ettringite formed (20 wt%) is lower than that in gypsum pastes (26 wt%) (w/c = 0.50), producing mortars with lower compressive strengths. After 3 hydration-days, anhydrite pastes showed slightly larger ettringite contents and hence, mortars with slightly higher compressive strengths. Ettringite content is the chief parameter to explain the strength development in these eco-cements.Universidad de Málaga. Campus de Excelencia Interncaional Andalucía Tech

Structure, Atomistic Simulations, and Phase Transition of Stoichiometric Yeelimite

ABSTRACT: Yeelimite, Ca4[Al6O12]SO4, is outstanding as an aluminate sodalite, being the framework of these type of materials flexible and dependent on ion sizes and anion ordering/disordering. On the other hand, yeelimite is also important from an applied perspective as it is the most important phase in calcium sulfoaluminate cements. However, its crystal structure is not well studied. Here, we characterize the room temperature crystal structure of stoichiometric yeelimite through joint Rietveld refinement using neutron and Xray powder diffraction data coupled with chemical soft-constraints. Our structural study shows that yeelimite has a lower symmetry than that of the previously reported tetragonal system, which we establish to likely be the acentric orthorhombic space group Pcc2, with a √2a × √2a × a superstructure based on the cubic sodalite structure. Final unit cell values were a = 13.0356(7) Å, b = 13.0350(7) Å, and c = 9.1677(2) Å. We determine several structures using density functional theory calculations, with the lowest energy structure being Pcc2 in agreement with our experimental result. Yeelimite undergoes a reversible phase transition to a higher-symmetry phase which has been characterized to occur at 470 °C by thermodiffractometry. The higher-symmetry phase is likely cubic or pseudocubic possessing an incommensurate superstructure, as suggested by our theoretical calculations which show a phase transition from an orthorhombic to a tetragonal structure. Our theoretical study also predicts a pressure-induced phase transition to a cubic structure of space group I43m. Finally, we show that our reported crystal structure of yeelimite enables better mineralogical phase analysis of commercial calcium sulfoaluminate cements, as shown by RF values for this phase, 6.9% and 4.8% for the previously published orthorhombic structure and for the one reported in this study, respectively.Universidad de Málaga. Campus de Excelencia Internacional. Andalucía Tech

Reactive belite stabilization mechanisms by boron-bearing dopants

Belite-rich cements hold promise for reduced energy consumption and CO2 emissions, but their use is hindered by the slow hydration rates of ordinary belites. This drawback may be overcome by activation of belite by doping. Here, the doping mechanism of B and Na/B in belites is reported. For B-doping, three solid solutions have been tested: Ca2-x/2□x/2(SiO4)1-x(BO3)x, Ca2(SiO4)1-x(BO3)xOx/2 and Ca2-xBx(SiO4)1-x(BO4)x. The experimental results support the substitution of silicate groups by tetrahedral borate groups with the concomitant substitution of calcium by boron for charge compensation, Ca2-xBx(SiO4)1-x(BO4)x. Otherwise, the coupled Na/B-doping of belite has also been investigated and Ca2-xNax(SiO4)1-x(BO3)x series is confirmed to exist for a large range of x values. Along this series, α'H-C2S is the main phase (for x≥0.10) and is single phase for x=0.25. Finally, a new structural description for borax doping in belite has been developed for α'H-Ca1.85Na0.15(SiO4)0.85(BO3)0.15, which fits better borax activated belite cements in Rietveld mineralogical analysisThis work has been supported by Spanish Ministry of Science and Innovation through MAT2010-16213 research grant which is cofunded by FEDER

Mechanism of stabilization of dicalcium silicate solid solution with aluminium

Stoichiometric dicalcium silicate, Ca2SiO4, displays a well-known polymorphism with temperature. When this phase is doped by a range of elements, belite, one of the main phases of cements, is generated. Here, we thoroughly study the aluminum doping of dicalcium silicate. This type of study is important for cement characterization and also from a basic point of view. Ca2Si1−2xAl2xO4−x□x (x = 0, 0.010, 0.014, 0.03) has been prepared and studied by X-ray powder diffraction and the Rietveld method. The limiting composition has been established as Ca2Si0.972Al0.028O3.986□0.014. The 27Al MAS NMR band located close to ∼−70 ppm is ascribed to tetrahedral environments, in agreement with the proposed aliovalent Si/Al atomic substitution mechanism. Thermal analysis measurements under a wet atmosphere indirectly confirm the increase of oxygen vacancies as the amount of incorporated protons increases with the aluminium content. A thorough electrical characterization has been carried out including overall conductivity measurements under wet and dry atmospheres and conductivity as a function of the oxygen partial pressure. The samples show oxide anion conductivity with a small p-type electronic contribution under oxidizing conditions. These compounds display a very important proton contribution to the overall conductivities under humidified atmospheres.This work has been supported by the Spanish Ministry of Science and Innovation through the research grant MAT2010- 15175 which is co-founded by FEDER and Junta de Andalucía (Spain) through the research grant P10-FQM-6680

Pseudo-cubic crystal structure and phase transition in doped ye'elimite

Sodalites are tridimensional alumino-silicate materials containing cages where loosely bonded anions are located. Ye'elimite, Ca4[Al6O12]SO4, is outstanding as an aluminate sodalite with a flexible framework accepting several type of dopants with important structural consequences. Moreover, ye'elimite is also important from an applied perspective as it is the most relevant phase in calcium sulfoaluminate cements. The crystal structure of stoichiometric ye'elimite has recently been unraveled but the structure of dopant-containing ye'elimite, which is presents in cements, is not well studied. Here, we report the pseudo-cubic crystal structure of doped ye’elimite, Ca3.8Na0.2Al5.6Fe0.2Si0.2O12SO4, from high-resolution synchrotron powder diffraction data. The powder pattern is indexed with a cubic cell and a structural model is reported based on the I4̅3m space group. However, this compound displays diffraction peak narrowing on heating. Furthermore, some high-angle split peaks become single peak on heating and a phase transition is measured at 525ºC. Therefore, it is concluded that the crystal structure at room temperature has lower symmetry although it can be described as cubic. The structural study at 800ºC suggests a truly cubic structure and we speculate that this phase transition, on heating, is likely related with the dynamical disordering of the sulfate anions. Finally it is concluded that the high temperature cubic state was not quenchable to ambient, even when the tested chemical substituents are introduced into the structure.Universidad de Málaga. Campus de Excelencia Internacional. Andalucía Tech

In-situ laboratory X-ray diffraction applied to assess cement hydration

In-situ X-ray diffraction (XRD) is a powerful tool to assess the hydration of cementitious materials, providing time-resolved quantitative analysis with reasonable accuracy without disturbing sample. However, the lack of guidelines and well-established procedures for data collection and analysis is the limiting factor for spreading this technique. This paper discussed using in-situ laboratory XRD to assess cement hydration. The first part was dedicated to a literature review on the topic. Then, experimental strategies were discussed, and recommendations related to the data analysis routine were drawn; the advantages and limitations of this technique were also discussed. We can conclude that the critical factors for a successful analysis are the choice of an adequate experimental setup with good statistics and low measurement time, the proper consideration of different amorphous contributions in the XRD pattern, and a good data analysis routine. Independent techniques are highly recommended to support the in-situ XRD data.PID2020-114650RB-I0

Tailored setting times with high compressive strengths in bassanite calcium sulfoaluminate eco-cements

This work deals with the hydration of a calcium sulfoaluminate (CSA) eco-cement prepared with bassanite and different additives (type and content) at a fixed water/CSA ratio of 0.5. Pastes prepared with bassanite show high water demands, high viscosity values and short initial setting times which are related to the fast dissolution rate of bassanite and the subsequent precipitation of gypsum. These facts have a dramatic effect onto the mechanical strength values, and make necessary the addition of additives. Here, the addition of different amounts of specific retarders (polycarboxylate, tartaric acid and phosphonic acid) not only improved the workability of pastes and mortars, but also delayed the setting time, by modifying the dissolution rates of the phase(s), and improved mechanical strengths. Finally, mortars with high compressive strengths (46 and 84 MPa at 1 and 7 days of hydration, respectively) and, chiefly, tailored setting times with high strengths have been prepared.Funding from Junta de Andalucía (P11-FQM-7517 and P12-FQM-1656), FEDER/University of Málaga (FC14-MAT-23), MINECO (BIA2014-57658-C2-1-R and BIA2014-57658-C2-2-R, the latter co-funded by FEDER) are acknowledged

Rietveld quantitative phase analysis of Yeelimite-containing cements

Yeelimite-containing cements are attracting attention for their tailored properties. Calcium sulfoaluminate, CSA, cements have high contents of Yeelimite and they are used for special applications. Belite calcium sulfoaluminate, BCSA or sulfobelite, cements have high contents of belite and intermediate contents of Yeelimite, and they may become an alternative to OPC. Here, we report Rietveld quantitative phase analyses for three commercially available CSA clinkers, one CSA cement, and two laboratory-prepared iron-rich BCSA clinkers. The crystalline phases are reported and quantified. Selective dissolutions are employed for BCSA clinkers to firmly establish their phases. Finally, the overall unaccounted contents (amorphous plus crystalline not quantified) have been determined by two approaches: i) external standard procedure (G-method) with reflection data; ii) internal standard procedure (spiking method with ZnO) with transmission data. The overall unaccounted contents for CSA clinkers were ~10 wt.%. Conversely, the unaccounted contents for BCSA clinkers were higher, ~25 wt.%

Intensive care unit discharge to the ward with a tracheostomy cannula as a risk factor for mortality: A prospective, multicenter propensity analysis

To analyze the impact of decannulation before intensive care unit discharge on ward survival in nonexperimental conditions. DESIGN: Prospective, observational survey. SETTING: Thirty-one intensive care units throughout Spain. PATIENTS: All patients admitted from March 1, 2008 to May 31, 2008. INTERVENTIONS: None. MEASUREMENTS AND MAIN RESULTS: At intensive care unit discharge, we recorded demographic variables, severity score, and intensive care unit treatments, with special attention to tracheostomy. After intensive care unit discharge, we recorded intensive care unit readmission and hospital survival. STATISTICS: Multivariate analyses for ward mortality, with Cox proportional hazard ratio adjusted for propensity score for intensive care unit decannulation. We included 4,132 patients, 1,996 of whom needed mechanical ventilation. Of these, 260 (13%) were tracheostomized and 59 (23%) died in the intensive care unit. Of the 201 intensive care unit tracheostomized survivors, 60 were decannulated in the intensive care unit and 141 were discharged to the ward with cannulae in place. Variables associated with intensive care unit decannulation (non-neurologic disease [85% vs. 64%], vasoactive drugs [90% vs. 76%], parenteral nutrition [55% vs. 33%], acute renal failure [37% vs. 23%], and good prognosis at intensive care unit discharge [40% vs. 18%]) were included in a propensity score model for decannulation. Crude ward mortality was similar in decannulated and nondecannulated patients (22% vs. 23%); however, after adjustment for the propensity score and Sabadell Score, the presence of a tracheostomy cannula was not associated with any survival disadvantage with an odds ratio of 0.6 [0.3-1.2] (p=.1). CONCLUSION: In our multicenter setting, intensive care unit discharge before decannulation is not a risk factor