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The effect of superplasticiser, borax and the water-to-cement ratio on BYF hydration and mechanical strengths has been studied. Two laboratory-scale BYF cements—st-BYF (with β-C2S and orthorhombic C4A3) and borax-activated B-BYF (with α’H-C2S and pseudo-cubic C4A3S)—have been used, and both show similar particle size distribution. The addition of superplasticiser and externally added borax to BYF pastes has been optimised through rheological measurements. Optimised superplasticiser contents (0.3, 0.4 and 0.1 wt % for st-BYF, B-BYF and st-BYF with externally added 0.25 wt % B2O3, respectively) result in low viscosities yielding homogeneous mortars. The calorimetric study revealed that st-BYF is more reactive than B-BYF, as the values of heat released are 300–370 J/g and 190–210 J/g, respectively, after 7 days of hydration, this fact is independent of the water-to-cement ratio. These findings agree with the higher degree of hydration at 28 days of β-C2S in st-BYF (from 45 to 60%) than α’H-C2S in B-BYF (~20 to 30%). The phase assemblage evolution has been determined by LXRPD coupled with the Rietveld method and MAS-NMR. The formation of stratlingite is favoured by increasing the w/c ratio in both systems. Finally, the optimisation of fresh BYF pastes jointly with the reduction of water-to-cement ratio to 0.40 have allowed the achieving of mortars with compressive strengths over 40 MPa at 7 days in all systems. Moreover, the st-BYF mortar, where borax was externally added, achieved more than 70 MPa after 28 days. The main conclusion of this work does not support Lafarge’s approach of adding boron/borax to the raw meal of BYF cements. This procedure stabilises the alpha belite polymorph, but its reactivity, in these systems, is lower and the associated mechanical strengths poorer.

This study, within the framework of eco-cement development, aims to manufacture reactive belite-sulfoaluminate cement (BYF) as alternative to Portland cement (PC). This ecological cement is obtained at low temperature from a mixture of industrial wastes using two synthetic methods, dry and hydrothermal treatment. The main minerals of this cement are β-C2S and calcium sulfoaluminate (C4A3Š), the latter being very reactive, which provide high performances cementitious materials. The hydrothermal treatment of raw mixture led to reduce the burning temperature of clinker up to 1200 °C. The mineral phases of the produced cements and theirs pastes were identified and quantified by XRPD coupled with Rietveld method. The hydraulic reactivity of cement was studied using XRPD and thermal analyses. The resulting mortars are very reactive and develop more than 42 MPa of compressive strengths after 28 days. UMA18-FEDERJA-095 y P18-RT-720 (ambos cofinanciados FEDER)

Presented within is a critical overview of the effect of sulfates on cement hydration, properties, and optimum sulfate content in Portland cement. Calcium sulfate is used in Portland cement to control the C3A reaction to induce the optimum hydration of C3S to occur. The amount of calcium sulfate in the Portland cement influences the hydration, rheology, setting, phase assemblage, porosity distribution, and strength in cementitious materials. If added in excess, it can also lead to durability problems, thus a better understanding is needed about the mechanisms of sulfate on C3A and C3S hydration. The optimum sulfate content is well known as a key pathway to produce workable, good strength, and durable concretes. Despite many years of research, questions regarding sulfate optimization remain. Further investigation on the influence of clinker and calcium sulfate characteristics, the use of different supplementary cementitious materials and chemical admixtures, and the curing conditions on the sulfate demand of Portland cement are needed. The main methods used to determine the optimum SO3 content are reported, and the advantages and disadvantages are examined. Finally, recommendation for future research is also discussed. JSAN thanked the financial support of CAPES [88882.439908/ 2019-01]. The participation APK was sponsored by CNPq (Brazilian National Council for Scientific and Technological Development) through the research fellowships PQ2017 305530/2017- 8. JSAN also thanked the Spanish Junta de Andalucía [UMA18-FEDERJA- 095] research project for the research stage at University of Málaga (Spain).

Publicado en: (Cement and Concrete Research 132 (2020) 106039) Microencapsulated phase change materials (MPCM) incorporated in buildings walls can reduce indoor temperature fluctuations, conserving energy and enhancing thermal comfort. MPCM were incorporated in calcium sulphoaluminate cement (CSA) at high concentrations to achieve a significant effect on the thermal properties. The cement hydration development was studied by isothermal calorimetry and laboratory X-ray powder diffraction (LXRPD). The hydration mechanism was not affected by the addition of MPCM. In order to obtain homogeneous mortars in the presence of MPCM, a superplasticizer (SP) was used. However, the SP causes a significant delay of the hydration. Although the mineralogical composition of the hydrated pastes did not change with the addition of MPCM, the mechanical strengths decrease dramatically. This decrease is well described by the Bolomey equation, assuming MPCMs act as air voids. This is a physical effect due to the high volume of MPCM, and not due to a change in the hydration chemistry. We gratefully acknowledge funding from the Research Council of Norway, project number 238198. The authors gratefully acknowledge PhD. Luis Miguel Ordoñez at Kheme Chemical S.L. and Eng. Rino Nilsen at Østfold University College for technical assistance.

Belite cements (BCs) could be a more sustainable binder than Portland cements (PCs) but adequate knowledge of the hydration features has still to be built. In particular, the mild curing hydration temperature effects have been extensively studied for PCs but not for BCs. This research was triggered by a previous work reporting improved mechanical strengths of BCs at higher curing temperatures. Here, we report the hydration characteristics of a BC at 20, 40 and 60 °C and compared to those of a typical PC. We have corroborated previous findings and used a multi-technique approach including Rietveld phase analysis, thermal analysis, calorimetry, silicon MAS-NMR, mercury intrusion porosimetry and chiefly synchrotron X-ray microtomography, to thoroughly understand the different behavior. In a nutshell, the improved mechanical performances at mild curing temperatures for BCs are mainly due to a much larger belite degree of reaction, with lower porosity coarsening of belite cements also playing a role.

Oil and gas well cements are multimineral materials that hydrate under high pressure and temperature. Their overall reactivity at early ages is studied by a number of techniques including through the use of the consistometer. However, for a proper understanding of the performance of these cements in the field, the reactivity of every component, in real-world conditions, must be analysed. To date, in situ high energy synchrotron powder diffraction studies of hydrating oil well cement pastes have been carried out, but the quality of the data was not appropriated for Rietveld quantitative phase analyses. Therefore, the phase reactivities were followed by the inspection of the evolution of non-overlapped diffraction peaks. Very recently, we have developed a new cell specially designed to rotate under high pressure and temperature. Here, this spinning capillary cell is used for in situ studies of the hydration of a commercial oil well cement paste at 150 bars and 150 &deg, C. The powder diffraction data were analysed by the Rietveld method to quantitatively determine the reactivities of each component phase. The reaction degree of alite was 90% after 7 hours, and that of belite was 42% at 14 hours. These analyses are accurate, as the in situ measured crystalline portlandite content at the end of the experiment, 12.9 wt%, compares relatively well with the value determined ex situ by thermal analysis, i.e., 14.0 wt%. The crystalline calcium silicates forming at 150 bars and 150 &deg, C are also discussed.

Microencapsulated phase change materials (MPCMs) were incorporated into cement pastes of Portland cement (PC). Minislump tests and rheological properties of cement pastes containing three MPCMs with different surfaces (hydrophilic, amphiphilic and hydrophobic) were measured, and the water demand of MPCM in the cement matrix was evaluated. The hydrophilic MPCM was chosen for a more thorough rheological study, since it was found to be more compatible with the cement matrix. The dispersion of a high amounts (45 wt% with respect to the cement content, which corresponds to about 62 vol% of the total solids) of the hydrophilic MPCM in the cement pastes was achieved by optimization of the amount of superplasticizer through rheological measurements. For the viscometer tests, a Power Law model was found to give the best fit to the experimental data. While pastes (with 45 wt% of hydrophilic MPCM) prepared with low superplasticizer contents (

Preprint publicado en: Materials Characterization Volume 155, September 2019, 109809 The present investigation deals with how minor elements (their oxides: MgO, Na2O and SO3) in industrial kiln feeds affect (i) chemical reactions upon clinkering, (ii) resulting phase composition and microstructure of clinker, (iii) hydration process during cement production. Our results show that all these points are remarkably sensitive to the combination and interference effects between the minor chemical species mentioned above. Upon clinkering, all the industrial raw meals here used exhibit the same formation temperature and amount of liquid phase. Minor elements are preferentially hosted by secondary phases, such as periclase. Conversely, the growth rate of the main clinker phases (alite and belite) is significantly affected by the nature and combination of minor oxides. MgO and Na2O give a very fast C3S formation rate at T > 1450 K, whereas Na2O and SO3 boost C2S After heating, if SO3 occurs in combination with MgO and/or Na2O, it does not inihibit the C3S crystallisation as expected. Rather, it promotes the stabilisation of M1-C3S, thus indirectly influencing the aluminate content, too. MgO increseases the C3S amount and promotes the stabilisation of M3-C3S, when it is in combination with Na2O. Na2O seems to be mainly hosted by calcium aluminate structure, but it does not induce the stabilisation of the orhtorhombic polymorph, as supposed to occur. Such features play a key role in predicting the physicalmechanical performance of a final cement (i.e. rate of hydration and hardening) when used as a bulding material. The present study has been partly funded by the project PRIN 2017 (2017L83S77), of the Italian Ministry for Education, University and Research (MIUR).

Portland cements are currently used as Oil‐Well‐Cements for the sheath between the metal casing and the borehole. At high pressures and temperatures, the resulting C–S–H gel(s) is partly unstable and it can react to give different crystalline phases and changing microstructure which increases porosity. It is known that the addition of silica-rich materials to Portland cements, used to decrease the overall Ca/Si molar ratio, avoids/minimises the early strength retrogression experienced by neat cement slurries. Alternatively, belite-rich cement could be used but belite reactivity in these conditions is largely unexplored. Here, belite-rich mixtures have been quantitatively studied at 180 bars and of 160 °C by in situ synchrotron powder diffraction using a tailored-designed spinning capillary cell. For model alite/belite mixtures, alite strongly accelerates belite hydration in these conditions. At 10 h of hydration, β-C2S shows a reaction degree of 30 and 80% for 20 wt%C3S-80 wt%C2S and 50 wt%C3S-50 wt%C2S mixtures, respectively. Furthermore, the 50 wt%C3S mixture hydrates yielding significant amounts of Jaffeite and α-C2SH and the 20 wt%C3S mixture gave no Jaffeite and much lower amount of α-C2SH. Finally, a belite cement has also been hydrated in these conditions and the reaction degree of belite was 50% at 10 h. The hydration of this cement did not yield Jaffeite neither α-C2SH in the studied experimental conditions.

This keynote lecture will be focused on the strategies for reducing CO2 emissions in the cement production. Concretely, the production of ecocements with optimised formulations that yield reductions in CO2 emissions of up to 25%, when compared to OPC production. Phase assemblage has to be carefully optimised to be competitive and these new ecocements should develop compressive strengths of at least 50 MPa at 28 days of hydration. Optimised compositions of several ecocements will be discussed, but all of them are ye'elimite or calcium sulphoaluminate containing ones: belite-ye'elimite-ferrite (BYF), belite-alite-ye'elimite (BAY) and ye'elimite rich ones (CSA). The clinkering temperature of BYF and BAY has to be established to obtain the targeted phase assemblages. Moreover, the stabilisation of alpha-forms of belite is needed to develop high mechanical strengths at early ages. The benefits of the use of waste materials (such as fly ash or slag) as additions to ecocements are three-fold: lower CO2 emissions due to clinker replacement; valorisation of “useless” products that need a lot of landscape and the consequent efficient consumption of raw materials; and to enhance mechanical properties of the corresponding mortars. The design of appropriate CSA, BYF and BAY mortars, with the final aim of knowing and controlling the hydration mechanisms, will be presented. Particularly, the role of i) type and amount of set regulator (gypsum, anhydrite, etc.), ii) water/cement ratio (w/c); iii) superplasticiser; and iv) pozzolanic additions will be discussed. The role of these parameters in the microstructure and hydraulic behaviour has been investigated through traditional techniques as well as advanced synchrotron characterisation. The formers include laboratory/synchrotron X-ray powder diffraction combined with Rietveld methodology (to obtain phase assemblage), electron microscopy techniques for paste microstructure determination, rheological studies (to control the effect of the different additives, w/c ratio and setting time retarders) and mechanical tests (setting times, compressive strengths and dimensional stability). The latters comprise a group of techniques available at synchrotrons such as: i) high temperature x-ray diffraction for clinkering studies and ii) total scattering data to be analysed by pair distribution function, PDF. Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech. PhD D. Londono-Zuluaga thanks Colciencias and Enlaza Mundos program PhD grant. Spanish MINECO (BIA2014-57658-C2-2-R, which is co-funded by FEDER, BIA2014-57658-C2-1-R and I3 (IEDI-2016-0079) grants) are acknowledged.

There are many commercially important multiphase materials which contain amorphous phases, such as cement pastes, porcelains, glass-ceramics or pharmaceutical compounds. However, the analysis of amorphous phase(s) within cement matrices that contain high amounts of crystalline phase(s) is a challenge. Here, we report measurements of total scattering data quantitatively analyzed by Pair Distribution Function (PDF) minimization and Rietveld methodology to determine phase compositions including both amorphous and nanocrystalline phase contents in cement-related samples. Furthermore, laboratory techniques were used to complement the sample characterization. In addition to five reference materials, the main phase of calcium aluminate cements, CaAl2O4 hydrated at 50 °C to yield crystalline hydrogarnet, Ca3Al2(OH)12, (43wt%) and nanocrystalline aluminum hydroxide gel, Al(OH)3·0.1H2O (50wt%) was also investigated. The PDF analyses revealed that the hydroxide gel has a gibbsite local structurewith an average particle size close to 5nm. PDF and Rietveld quantitative phase analysis results fully agree. This work has been supported by Spanish MINECO through BIA2014-57658-C2-1-R and BIA2014-57658-C2-2-R, which is cofunded by FEDER, research grants. R.U.I. acknowledges funding of CNPQ, grant no. 206983/2014-0/SWE. We also thank CELLS-ALBA (Barcelona, Spain) for providing synchrotron beamtime at BL04-MSPDand Dr. Oriol Vallcorba for his assistance during the synchrotron experiment. 2018-07-01

Building materials are very complex samples of worldwide importance; hence quantitative knowledge of their mineralogical composition is necessary to predict performances. Rietveld quantitative phase analysis (RQPA) allows a direct measurement of the crystalline phase contents of cements. We highlight in this paper the use of laboratory X-ray powder diffraction (LXRPD) employing high-energy radiation, molybdenum (Mo), for attaining the RQPA of cements. Firstly, we evaluate the accuracy of RQPA employing a commercial calcium sulfoaluminate clinker with gypsum. In addition to MoKα1 and MoKα1,2 radiations, Cu and synchrotron patterns are also analyzed for the sake of comparison. Secondly, the assessment of the accuracy of RQPA results obtained using different radiations (synchrotron, Mo, and Cu) and geometries (reflection and transmission) is performed by analyzing two well-known commercial samples. As expected, for LXRPD data, accuracy in the RQPA results improves as the irradiated volume increases. Finally, three very complex aged hydrated cements have been analyzed using MoKα1-LXRPD and Synchrotron-XRPD. The main overall outcome of this work is the benefit for RQPA of using strictly monochromatic MoKα1 radiation. Best laboratory results arise from MoKα1 data as the effective tested volume is much increased but peak overlapping is not swelled.

The effect of zinc oxide and calcium fluoride on the clinkering of alite-sulfoaluminate (ACSA) materials has been studied by laboratory X-ray powder diffraction (EDX) and scanning electron microscopy (SEM). ACSA clinkers without the addition of calcium fluoride did not contained C3S, and showed CaOfree (5·0(1) wt%). However, by adding 0·25 wt% of calcium fluoride, the obtained clinker did not contain free lime and showed C3S (20·0(2) wt%). The suitable clinkering temperature has been proved to be 1300°C, in order to avoid C4A3S decomposition. The optimum amount of zinc oxide was found to be 1·0 wt% as the maximum percentage of C3S was formed. An ACSA clinker prepared at 1300°C with 1·0 wt% of zinc oxide and 1·0 wt% of calcium fluoride contained 34·2(2) wt% of C3S coexisting with 15·2(2) wt% of C4A3S, determined by Rietveld methodology, including amorphous content. SEM-EDX results have been statistically analysed and particles have been univocally identified. It has been proved that zinc oxide is preferentially placed in C3S.

Belite calcium sulfoaluminate (BCSA) cements are low-CO2 building materials. However, their hydration behavior and its effect on mechanical properties have still to be clarified. Here, we report a full multitechnique study of the hydration behavior up to 120 days of nonactivated and activated BCSA laboratory-prepared clinkers, with β- or αH-belite as main phase, respectively. The effects of the amount of gypsum added were also studied. The hydration and crystallization processes are reported and discussed in detail. Finally, shrinkage/expansion data are also given. The optimum amount of gypsum was close to 10 wt %. Our study has demonstrated that β-belite reacts at a higher pace than α′H-belite, irrespective of the gypsum content. The hydration mechanism of belite determines the development of the mechanical strengths. These are much higher for activated BCSA cement, ∼65 MPa at 120 days, against ∼20 MPa for nonactivated BCSA cement, with the latter having larger amounts of stratlingite.

Calcium sulfoaluminate (CSA) cements are currently receiving a lot of attention because their manufacture produces less CO2 than ordinary Portland cement (OPC). However, it is essential to understand all parameters which may affect the hydration processes. This work deals with the study of the effect of several parameters, such as superplasticizer (SP), gypsum contents (10, 20 and 30 wt%) and w/c ratio (0.4 and 0.5), on the properties of CSA pastes during early hydration. This characterization has been performed through rheological studies, Rietveld quantitative phase analysis of measured x-ray diffraction patterns, thermal analysis and mercury porosimetry for pastes, and by compressive strength measurements for mortars. The effect of the used SP on the rheological properties has been established. Its addition makes little difference to the amount of ettringite formed but strongly decreases the large pore fraction in the pastes. Furthermore, the SP role on compressive strength is variable, as it increases the values for mortars containing 30 wt% gypsum but decreases the strengths for mortars containing 10 wt% gypsum. This work has been supported by Spanish Ministry of Science and Innovation through MAT2010- 16213 research grant, which is co-funded by FEDER, and Ramón y Cajal Fellowship (RYC-2008- 03523).

The Rietveld-internal standard method for Bragg-Brentano reflection geometry (q/2q) X-ray diffraction (XRD) patterns is implemented to determine the amorphous phase content. The effect of some minor phases on quantitative accuracy is assessed. The numerical simulation analysis of errors and the related corrections are discussed. The results reveal that high purity of crystalline phases in the standard must be strictly ensured. The minor amorphous or non-quantified crystalline phases exert significant effect on the quantitative accuracy, even with less than 2 wt% if ignored. The error levels are evaluated by numerical simulation analysis and the corresponding error-accepted zone is suggested. To eliminate such error, a corrected equation is proposed. When the adding standard happens to be present in sample, it should be also carefully dealt with even in low amounts. Based on that ignorance, the absolute and relative error equations (DAE, DRE) are derived, as proposed. The conditions for high quantitative accuracy of original equation is strictly satisfied with a lower amount of standard phase present in sample, less than 2 wt%, and a higher dosage of internal standard, larger than 20 wt%. The corrected equation to eliminate such quantitative error is suggested. MINECO BIA2014-57658-C2-2-R

High belite cements may be an alternative to reduce CO2 emissions. Although CO2 emissions may be depleted up to 10%, unfortunately, the hydration reactivity of belite phases is slow which leads to low mechanical strengths at early ages. In order to enhance their hydraulic reactivity, the activation of these cements by doping with alkaline oxides has been proposed. The authors synthesised a laboratory belite clinker without activation (47 wt.% of [beta]-C2S and 19 wt.% of [alpha]H'-C2S) and 2 alkaline oxide activated clinkers (one with 13 wt.% of [beta]-C2S, 24 wt.% of [alpha]H'-C2S and 19 wt.% of [alpha]-C2S; and the second with 12 wt.% of [beta]-C2S, 42 wt.% of [alpha]H'-C2S and 5 wt.% of [alpha]-C2S). A methodology to analyze quantitatively the phase evolution of cement pastes is developed and applied to these high belite cements. Rietveld quantitative phase analysis of synchrotron X-ray powder diffraction data, together with chemical constraints, is used to determine the phase development up to 1 year of hydration in the belite cement pastes. [beta]-C2S almost does not react during the first 3 months, meanwhile [alpha]H'-C2S reacts on average more than 50% in the same period. Moreover, the degree of reaction of [alpha]-C2S is slightly larger (on average about 70% after 3 months) than that of [alpha]H'-C2S. Full phase analyses are reported and discussed including the time evolution of amorphous phases and free water.

Activated white cement clinkers with a theoretical 60% (wt) belite (dicalcium silicate) content were prepared at a temperature 100 ºC lower than used to manufacture conventional white Portland cement clinkers. Activation was achieved by adding variable amounts of K2CO 3 or Na2CO 3 to the raw mixes. Rietveld quantitative analysis of X-ray diffraction findings showed that adding the alkalis stabilized the high temperature belite polymorphs. When 2.0% (wt) of Na2O was added, the composition (by wt) found was 16.4(4)% alpha-C2S, 16.7(8)% alpha’-H-C2S, 23.2(6)% beta-C2S, 32.7(7)% total C3S, 9.5(2)% orthorhombic C3A and 1.50(5)% free lime. Due to the high volatilization rate of K2O under the experimental conditions, it stabilized the alpha-type C2S less effectively than Na2O. A calorimetric study was likewise performed to correlate the phase composition with early age hydration (behaviour)., Se han preparado clínkeres blancos activados con un porcentaje en peso teórico de belita (silicato dicálcico) del 60%, a una temperatura 100 ºC menor que los clínkeres Portland blancos convencionales. El proceso de activación se ha llevado a cabo añadiendo a las mezclas crudas cantidades variables de K2CO3 o Na2CO 3. Utilizando la difracción de rayos-X y la metodología de Rietveld se ha comprobado la estabilización a temperatura ambiente de porcentajes variables de los polimorfos de alta temperatura de la belita por la adición de alcalinos. De hecho, al añadir 2,0% en peso de Na2O se ha obtenido 16,4(4)% de alfa-C2S, 16,7(8)% de alfa’-H-C2S, 23,2(6)% de beta-C2S, 32,7(7)% de C3S total, 9,5(2)% de C3A ortorrómbico y 1,50(5)% de cal libre, porcentajes en peso. Se ha comprobado que el grado de volatilización de los alcalinos, en estas condiciones de preparación, ha sido muy acusado para el K2O, lo que ha provocado una menor estabilización de los polimorfos tipo-alfa-C2S. Además, se ha realizado un estudio calorimétrico para correlacionar el ensamblaje de fases con el comportamiento de hidratación a edades tempranas.

The activation of laboratory belite clinkers has been carried out by adding variable amounts of alkaline salts (K2CO3, Na2CO3), and/or SO3 as gypsum in the raw materials but keeping almost constant the main elements ratios, Ca/Si/Al/Fe. Quantitative phase analyses by the Rietveld method using high resolution synchrotron and strictly monochromatic CuKα1 laboratory X-ray powder diffraction data has been performed. Quantitative phase analysis results have been compared to validate the protocol using laboratory X-ray data. The agreement in the results is noteworthy, which indicates that good quantitative phase analyses can be obtained from laboratory X-ray powder data. Qualitative studies have confirmed that the addition of alkaline salts to raw mixtures promotes the stabilization, at room temperature, of the highest temperature polymorphs: α′H-C2S and α-C2S. Quantitative studies gave the phase assemblage for ten different laboratory belite clinkers. As an example, an active belite clinker with 1.0 wt.% of K2O and 1.0 wt.% of Na2O (amounts added to the raw mixtures) contains 8.5(3) wt.% of β-C2S, 21.2(3) wt.% of α'H-C2S, 24.1(2) wt.% of α-C2S, 18.9(3) wt.% of total C3S, 17.3(2) wt.% of C3A and 10.0(2) wt.% of C4AF. A belite clinker with 0.8 wt.% SO3 (nominal loading) contains 60.7(1) wt.% of β-C2S, 6.7(2) wt.% of α′H-C2S, 12.3(7) wt.% of C3S, 9.1(2) wt.% of C3A and 11.2(2) wt.% of C4AF. Overall, quantitative phase analyses have shown that alkaline oxides stabilize α′H-C2S and α-C2S, sulfur stabilizes β-C2S, with a large unit cell volume, and the joint presence of alkaline oxides and sulfur promotes mainly the stabilization of the α′H-C2S polymorph.

Stratlingite, Ca4Al2(OH)12[AlSi(OH)8]2·2H2O, is an AFm phase which appears as a hydration product of aluminium-rich cements. These binders may be calcium aluminate cements, calcium sulfoaluminate cements and also belite calcium sulfo-aluminate (BCSA) cements. The structure of stratlingite is known from single-crystal studies of tiny minerals but their bulk formation, crystal structure and microstructure of powders is poorly understood. This paper reports on the synthesis of stratlingite and a complete structural and microstructural characterisation by synchrotron X-ray powder diffraction, nuclear magnetic resonance, scanning electron microscopy and thermal analyses. The structural and microstructural models have important implications for a correct quantitative phase analysis of stratlingite in cement pastes (for instance, in pastes of BCSA cements). The microstructure of stratlingite formed in cement pastes is highly dependent on the hydration conditions. In BCSA pastes, the (003) line position of stratlingite appears slightly shifted towards higher diffracting angles (lower inter-layered distance) after stopping hydration compared to that of a similar phase present in a paste analysed without stopping hydration. This is related to dehydration and disorder. This shift and peak broadening is even larger when the paste has suffered partial dehydration during curing (apart from stopping hydration). A microstructural study is presented., This work has been supported by Junta de Andalucía through P11-FQM-07517 research project. I. Santacruz offers thanks for a Ramón y Cajal fellowship, RYC-2008–03523. Synchrotron experiments were performed in the MSPD (Materials Science and Powder Diffraction) beamline at Alba Synchrotron Light Facility with the collaboration of François Fauth.

The study undertaken in this work indicates that it is possible to exploit the industrial by products such as fly ash and bottom ash from the combustion of coal in Jorf lasfar thermal power and valorize them as additive in the construction materials. Because in addition to their poozolanic activity, these ashes have technical, economical and ecological compelling interests.In this work we have studied the effects of substitution of limestone in the CPJ45 cement by fly ash or bottom ash on the mechanical properties of prepared mortars, on the grinding time and on the hydration of the new cements.Different analysis techniques were undertaken to determine the physico-chemical characteristics of the starting materials.X-ray fluorescence (XRF) had permitted the classification of fly ash and bottom ash in the class F from their levels on major oxides. Rietveld quantitative phase analysis (RQPA) allowed us to compare the percentages of clinker phases with that calculated with bogue formulas. The result showed that the values found by RQPA of C 3 S and C 3 A were much higher than those calculated, while for the C 2 S the values given by RQPA were much lower.The isothermal conduction micro calorimeter was used to measure the heat evolution during the hydration of the cements prepared. We noticed that the additions of fly ash or bottom ash have accelerated the hydration of C 3 A and have delayed that of C 3 S.The tests performed by substituting limestone in CPJ 45 by different proportions of fly ash or bottom ash have shown that the effect of these ashes on the mechanical properties of cement CPJ 45 . We have observed that the 28days mechanical strengths of the mortar went for a maximum with the substitution of lime stone by 6% of fly ash and 7% of bottom ash;We have also observed that increasing the amount of substitution of lime stone by fly ash had decreased the grinding time and had eliminated the clogging of the cement on the mill balls.

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.

Belite sulfoaluminate (BSA) cements have been proposed as environmentally friendly building materials, as their production may release up to 35% less CO{sub 2} into the atmosphere when compared to ordinary Portland cements. Here, we discuss the laboratory production of three aluminum-rich BSA clinkers with nominal mineralogical compositions in the range C{sub 2}S (50-60%), C{sub 4}A{sub 3}$$ (20-30%), CA (10%) and C{sub 12}A{sub 7} (10%). Using thermogravimetry, differential thermal analysis, high temperature microscopy, and X-ray powder diffraction with Rietveld quantitative phase analysis, we found that burning for 15 min at 1350 deg. C was the optimal procedure, in these experimental conditions, for obtaining the highest amount of C{sub 4}A{sub 3}$$, i.e. a value as close as possible to the nominal composition. Under these experimental conditions, three different BSA clinkers, nominally with 20, 30 and 30 wt.% of C{sub 4}A{sub 3}$$, had 19.6, 27.1 and 27.7 wt.%, C{sub 4}A{sub 3}$$ respectively, as determined by Rietveld analysis. We also studied the complex hydration process of BSA cements prepared by mixing BSA clinkers and gypsum. We present a methodology to establish the phase assemblage evolution of BSA cement pastes with time, including amorphous phases and free water. The methodology is based on Rietveld quantitative phase analysis of synchrotron and laboratory X-ray powder diffraction data coupled with chemical constraints. A parallel calorimetric study is also reported. It is shown that the beta-C{sub 2}S phase is more reactive in aluminum-rich BSA cements than in standard belite cements. On the other hand, C{sub 4}A{sub 3}$ reacts faster than the belite phases. The gypsum ratio in the cement is also shown to be an important factor in the phase evolution.