Fases termodinámicamente estables en el sistema cerrado CaO-SiO2-Al2O3-CaSO4-H2O a 25 ºC. Aplicación a sistemas cementantes

One of the chief causes of cement and concrete deterioration is the loss of durability prompted by sulphate attack. The existing standards call for long test periods (2- 12 months). Thermodynamic modelling is a particularly appropriate technique for studying systems that only reach equilibrium in the long term. Used in the present study to establish the fields of thermodynamic stability for the phases in the CaO-SiO2-Al2O3-CaSO4-H2O system at 25 ºC. According to the model, gypsum is stable at sulphate ion concentrations of 1.23e-2 mol/kg and over, while ettringite exhibits stability at concentrations ranging from 7.64e-6 to 1.54e-2 mol/kg. Ettringite is compatible with all system phases except SH and gypsum only with ettringite, the C-S-H gels, AH3 and SH. None of the calcium aluminates or silicoaluminates in the system is compatible with gypsum: in its presence, they all decompose to cement deteriorating ettringite. Finally, the model revealed that the maximum sulphate concentration at which C-S-H gel is stable is slightly higher in systems with than without Al2O3.Uno de los principales problemas asociados al deterioro de cementos y hormigones es la pérdida de durabilidad por ataque de sulfatos. La normativa existente requiere largos tiempos de ensayo (2-12 meses). La modelización termodinámica es una técnica particularmente adecuada para el estudio de sistemas que alcanzan el equilibrio en tiempos largos. Aplicando esta metodología se han establecido los campos de estabilidad termodinámica de las fases del sistema CaO-SiO2-Al2O3-CaSO4-H2O a 25 ºC. El yeso es estable a partir de la [SO42-] = 1,23e-2 mol/kg, y la ettringita es estable en un rango de [SO42-] = 7,64e-6 -1,54e-2 mol/kg. La ettringita es compatible con todas las fases del sistema excepto con SH y el yeso sólo con la ettringita, los geles C-S-H, el AH3 y el SH. Ninguno de los aluminatos o silicoaluminatos cálcicos son compatibles con el yeso, en su presencia se descomponen dando etringita. Finalmente, la máxima [SO42-] en la que es estable el gel C-S-H es ligeramente superior en sistemas que contienen Al2O3 con respecto a los que no lo poseen

C-S-H gels in blended cements: Study by infrared spectroscopy

ICCC 2015, Beijing, China, 13~16 October 2015; http://iccc2015.csp.escience.cn/dct/page/1C-S-H gel is the main product in the Portland cement (PC) hydration. Of their structure and composition depends the cement properties (strength, durability¿). The mixes of others materials with PC provides new cementitious materials with different properties. Understand the changes produces in the hydration products in these blends improves their use. This work studies the changes produced in the C-S-H gel by means Fourier Transform Infrared Spectroscopy (FTIR). Several samples were studied, PC (as reference system), a system formed by PC and calcium aluminate cement (CAC) with a 75/25 ratio, and two system formed by PC, CAC and calcium sulfate (C¿) with an 85/15 ratio of PC/CAC with 3 and 5% of C¿. All samples were cured in two environmental; at the air and under water, in order to observe the influence of curing. The samples were studied at the 6 hours, 7 days, 12 and 32 months of age. Results show in the PC, it changes to lower wavenumbers in the Q2 units positions over time. This fact indicates a little transformation of structure like-tobermorite to structure like-jennite providing a C-S-H less compact. Addition of CAC in PC hydration decreases the migration of Q2 units to lower wavenumbers indicating that C-S-H structure is more compact in this case. When C¿ is included in the system, this migration of Q2 units is lower and the bands are sharper indicating the structure like tobermorite presence. Other effect visible in the spectra is the decrease of bands due to Q1 units with the addition of CAC. The greater presence of aluminates in the system provides substitutions of Si4+ by Al3+ in the C-S-H structure. This fact produces longer chains reducing the units Q1. Different behaviors are observed in the cured conditions showing higher transformation towards structures like-jennite in the samples cured under water. Several conclusions can be drawn of this work. First, it use of infrared spectroscopy as powerful tool in the cement chemistry field. Not only as characterization technique but also it can be used for obtain structural information about cement phases, both hydrated as anhydrous. Regarding addition of other hydraulic materials at PC, the study shows formation of C-S-H more compact that will provide better mechanical properties. Also the cured conditions have influenced about hydrated products structure.Peer Reviewe

Micro-Raman and Raman Imaging studies of glassy material produced by continuous wave (CW) CO2 laser irradiation of lime/pozzolan mortar

ICCC 2015, Beijing, China, 13~16 October 2015; http://iccc2015.csp.escience.cn/dct/page/1This work describes the distribution of the portlandite over the surface of the lime/pozzolan mortar and the mineral composition of the glassy material formed when the mortar was irradiated with continuous-wave-CO2 (CW-CO2) laser. Both Micro-Raman and Raman mapping have been used for structural studies. Lime/pozzolan/sand 1/1/2 mortars, 5 years at room temperature, were irradiated with CW-CO2 laser (Synrad Firestar t80, Mukilteo, WA) operating at a wavelength of 10.591 ¿m, 10P(20) CO2 laser line. Laser output: 8W, 18W and 38W (Synrad PW-250 (Mukilteo, WA)). The laser beam was focused by means of a NaCl lens of 10 cm focal length and the irradiation time was 5 seconds. Raman spectra were collected with a Raman Spectrometer (Renishaw Invia) equipped with a CCD camera, using 532 nm (Nd:YAG) excitation line. The laser on the sample was 5 mW and the integration time was 10 seconds. For mapping measurements, an area of 80 ¿m x 80 ¿m was chosen in the internal part of the glass. The step size was 5 ¿m with an individual grid size of 25 ¿m2. Glazing, vaporization and spalling process can produce over an irradiated surface with a high power laser beam. When the power density of the irradiating laser beam is high enough to raise the temperature beyond the glass transition, a glassy surface layer is formed. However, if surface temperatures are below that melting point, the vaporization of water can be produce over the material surface. Due to the small diffusivity of water vapour, its transport is hindered and an overpressure is attained. Hydraulic building materials have about 4-10% bounded water, after irradiation with the CW-CO2 laser, water vapour spread out in a vaporization front reacting with the CaO present in the sample and producing Ca(OH)2, besides a glassy surface.Peer Reviewe

Time- and space-resolved spectroscopic characterization of laser-induced swine muscle tissue plasma

10 págs.; 12 figs.; 1 tab.The spatial-temporal evolution of muscle tissue sample plasma induced by a high-power transversely excited atmospheric (TEA) CO2 pulsed laser at vacuum conditions (0.1–0.01 Pa) has been investigated using high-resolution optical emission spectroscopy (OES) and imaging methods. The induced plasma shows mainly electronically excited neutral Na, K, C, Mg, H, Ca, N and O atoms, ionized C+, C2 +, C3 +, Mg+, Mg2 +, N+, N2 +, Ca+, O+ and O2 + species and molecular band systems of CN(B2Σ+–X2Σ+), C2(d3Πg–a3Πu), CH(B2Σ−–X2Π; A2Δ–X2Π), NH(A3Π–X3Σ−), OH(A2Σ+–X2 Σ+), and CaOH(B2Σ+–X2Σ+; A2Π–X2Σ+). Time-resolved two-dimensional emission spectroscopy is used to study the expanded distribution of different species ejected during ablation. Spatial and temporal variations of different atoms and ionic excited species are reported. Plasma parameters such as electron density and temperature were measured from the spatio-temporal analysis of different species. Average velocities of some plasma species were estimated. © 2015 Elsevier B.V. All rights reserved.We gratefully acknowledge the support received in part by the DGICYT (Spain) Project MICINN: CTQ2013-43086-P for this research. The authors wish to thank the Geomaterials2 Program (S2013/MIT 2914) supported by the Comunidad de Madrid and EU structural and cohesion funds (FSE and FEDER).Peer reviewe

Validity of water industry wastes in cement industry

This paper examines the validity of several water industry wastes to be reused in different stages of cement production. The wastes considered are: a drinking water treatment plant sludge (DWTP), a sewage sludge (SS) and a spent activated carbon. Different procedures of drying of wastes using a novel dry spray system or subjected to thermal drying or stabilization and dried with lime are analysed. The spray drying process was successfully used with the DWTP sludge (but not with SS). The material was not found to be suitable as a supplementary material in blended cements. Despite this, the spray dried sludge did show good potential as partial or full substitute for clay as a raw material in cement clinker manufacture. A novel thermally drying process (Turbo-drying RINA-JET) was applied to produce dried sewage sludge. The dry sludge consisted of 56 % organic matter and has a high calorific value (8291 J / g), making it valid as an alternative fuel. The ash (35% of dry SS) contains Ca, Fe, P, Si and Al as main inorganic elements which are incorporated into the clinker phases. The burnability of the raw mixture containing this SS sludge was better than in the control raw mix. Furthermore, the paper describes an industrial process for stabilising sewage sludge (SS) with lime and evaluates the viability of the stabilised product, referred to as “Neutral”, as a raw material in the production of Portland cement clinker for the cement industry. The proposed process for sewage sludge treatment has a number of advantages over traditional treatments. In the Basic plant design, the chemical energy in the reagents generates sufficient thermal energy for the moisture to evaporate. This makes the process more energy-efficient than others. The validity of the “Neutral” product as a starting material in raw mixes for the production of cement clinker by substitution of limestone is demonstrated. Regarding the validity of spent activated carbon as an alternative to pet coke as fuel in Portland cement kilns, the carbon differed substantially from the coke, having lower calorific value (18 % less). However, the qualities of the spent coke were still sufficient for the intended use. The ash fraction of the spent activated carbon was mainly composed of anhydrite and quartz (SO3 = 14.1 %) and it is included into the clinker phases during the burning. The SO3 from the ashes promotes a very large growth in alite crystals in the clinker

Diet and Lifestyle in Nonalcoholic Fatty Liver Disease

The liver is an essential metabolic organ which governs body energy metabolism connected with adipose tissue and skeletal muscle among other tissues. The prevalence of obesity has reached epidemic proportions in many countries around the world and continues to grow every year which is caused by multiple factors, with diet and lifestyle being the most researched and therefore most important. Nonalcoholic fatty liver disease (NAFLD) is one of the several metabolic complications associated with obesity. The pathology of NAFLD is difficult to recognize or diagnose especially in early stages without a biopsy and therefore can remain undetected for significant time allowing the disease to progress. The diagnosis of NAFLD is crucial to be able to start adequate treatment including changes in diet and lifestyle in the first stage of the disease when the pathology is reversible and prevent the development of severe forms of the disease such as nonalcoholic steatohepatitis (NASH) or the irreversible cirrhosis stage. When the liver becomes damaged, this can lead to some metabolic alterations that have a severe and multifaceted impact in type 2 diabetes mellitus (T2DM), visceral obesity, and cardiovascular disease related to elevated plasmatic cholesterol, triglycerides, transaminases, and others that indicate hepatic disorders and oxidative stress. ..

Thermodynamic modeling of sulfate-resistant cements with addition of barium compounds

Comunicación presentada en el International Congress Science and Technology for the Conservation of Cultural Heritage (TechnoHeritage), celebrado en Santiago de compostela del 2 al 5 de octubre de 2012.Sulfate attack by ground waters, soils, etc. is one of the threats to the built heritage in concrete. This study validated through thermodynamic modeling with GEMS geochemical code a new sulfate-resistant formulation based on the addition of BaCO3 and BaO to ordinary Portland cement (OPC), which could be used to replace weathered concrete. The thermodynamic calculations pointed out that Ba ions were able to form an insoluble salt, barite (BaSO4) with the dissolved sulfate which inhibited the formation of ettringite, the latter oc- curred when the concentrations of BaCO3 and BaO were ≥ 6 and ≥ 4 wt.%, respectively. The results of a simulated sulfate a ttack revealed that ettringite precipitated upon ingression of ≥46 ml of a Na2SO4 solution (44 wt.%) in OPC blends with 20 wt.% of BaCO3; whereas with 20 wt.% of BaO, the sulfate that precipitated besides ba rite was monosulfoaluminate when sulfate solution was ≥40 ml (tested up to 52 ml).Funding from the Spanish Ministry of Education and Science (Project CONSOLIDER CSD2007-00058) and the Regional Government of Madrid (Geomaterials Programme) is gratefully acknowledged.Peer Reviewe

Deterioro de morteros de cemento producido por la "deposición" seca y húmeda de contaminantes atmosféricos

The reaction of portland cement mortars with SO2 gaseous pollutant and artificial 'acid rain' solution has been examined using laboratory exposure chambers, with realistic presentation rates of pollutants. The mortar were previously carbonated to produce superficial carbonation. Two mortars with different w/c ratio and hence specific surface were prepared and exposed into the chambers. For dry deposition of SO2 pollutant gas, the important roles of water and water plus oxidant in increasing chemical reaction are readily revealed. Further, accessible porosity also increases reaction through increased times of reaction of pollutant with the mortars. Interestingly, in the absence of deliberate surface wetting, the presence of oxidant, ozone, leads to a reduction in the already limited extent of reaction. Wet deposition studies using artificial 'acid rain' solution result in gypsum formation, which is more extensive for mortars of increased w/c ratios.Se han realizado ensayos de laboratorio de simulación de los procesos ambientales de "deposición" seca y húmeda sobre morteros de cemento portland, estudiándose las reacciones que se producen con el contaminante SO2 ("deposición" seca) y la disolución de 'lluvia acida' ("deposición" húmeda). Los morteros de cemento se carbonataron para favorecer la carbonatación superficial de los mismos. Se prepararon morteros con dos relaciones a/c con el fin de estudiar la influencia que la variable superficie específica tenía en el proceso de deterioro de dichos materiales. En los estudios de deposición seca con SO2 como gas agresivo se ha visto la importancia que el agua y el agua junto a un oxidante tienen en la reacción del contaminante con los componentes del mortero. La superficie específica Juega un papel importante, ya que al aumentar, aumenta la reacción con el contaminante. La reacción en presencia de oxidante, (SO2+O3) es inferior en medio con aporte sólo de S2. Los estudios de deposición húmeda usando una disolución de 'lluvia acida ', producen la formación de yeso, fundamentalmente para los morteros de mayor relación a/c

Influence of relative humidity on the carbonation of calcium hydroxide nanoparticles and the formation of calcium carbonate polymorphs

A consolidating product based on nanoparticles of slaked lime (Ca(OH)2) dispersed in isopropyl alcohol was exposed under different relative humidities (RH), 33%, 54%, 75% and 90% during 7, 14, 21 and 28days. The characterization of the calcium hydroxide nanoparticles and the formed calcium carbonate polymorphs have been performed by Micro Raman spectroscopy, Transmission Electron Microscopy (TEM), Environmental Scanning Electron Microscopy (ESEM) with Energy Dispersive X-ray Spectroscopy (EDS) and X-ray Diffraction (XRD). Precipitation and transformation of calcium carbonate polymorphs strongly depend on the relative humidity (RH). Higher RH (75%-90% RH) gives rise to amorphous calcium carbonate and monohydrocalcite, calcite, aragonite and vaterite, faster carbonation and larger particles sizes with higher crystallinity compared to lower RH (33%-54% RH) that gives rise mainly to portlandite and vaterite, slower carbonation and smaller particle sizes with lower crystallinity. © 2010 Elsevier B.V.This study was funded by the Government of the Community of Madrid by GEOMATERIALES (S2009/MAT-1629) and CONSOLIDERTCP (CSD2007-0058) and to the JAE-Doc CSIC contracts for supporting P. López-Arce and L.S. Gómez-Villalba to develop this work.Peer Reviewe

In-situ Micro-Raman spectroscopic analysis of Handprints in Maltravieso Cave (Cáceres), Spain

TECHNART 2015 − Catania, April 27 - 30, 2015; http://technart2015.lns.infn.it/Peer Reviewe