Chemical characterisation of metakaolin and fly ash based geopolymers during exposure to solvents used in carbon capture

This paper presents an investigation into the chemical resistance of blended alkali activated aluminosilicate materials, specifically under exposure to two solvents used in post-combustion carbon capture, monoethanolamine (MEA) and potassium carbonate, as well as during immersion in distilled water. Geopolymers are formulated based on metakaolin and aon fly ash as aluminosilicate precursors, with the addition of ground granulated blast furnace slag (GGBFS) as a source of Ca. The samples are subjected to mineralogical and chemical characterisation in this paper, with data obtained through leaching analysis and X-ray diffraction, supported by compressive strength data. Exposure to solvents generally results in significant alteration of the geopolymer microstructure. The zeolitic phases formed in undamaged metakaolin-based binders are reduced to undetectable levels after 28 days of solvent exposure, although the hydrosodalite formed in the fly ash binders does persist. Leaching analysis indicates that resistance to structural damage in MEA is quite high, due to the low solubility of Na and hydroxides upon immersion. KCO solutions are aggressive towards geopolymers via alteration of the binder structure and dissolution of network-forming species (Si and Al), leading to the loss of binder strength. This is most marked in the fly ash/GGBFS formulations. Despite the low to intermediate level of Ca present in these geopolymer binders, significant formation of Ca-containing carbonate phases occurs upon exposure to KCO. The limited curing duration of the specimens tested here is certainly contributing to the degradation taking place under KCO exposure, whereas the low water activity in the MEA solutions used means that bond hydrolysis in the aluminosilicate geopolymer framework is restricted, and the materials perform much better than in a more water-rich environment. © 2014 Elsevier Ltd

Water content modifies the structural development of sodium metasilicate-activated slag binders

The effect of modifying the water content of an alkali - activated slag binder was assessed, in terms of the kinetics of reaction and the structural development of the material. There is not a s ystematic correlation between the water content of the mix and the rate of reaction, indicating that there is an optimal value that favours dissolution of the slag and precipitation of reaction products. A h igher water content reduce d the crystallinity and density of the reaction products, especially at advanced age. Small changes in the water content can have a significant impact on the compressive strength development of alkali - silicate activated slag mortars, suggesting that when producing materials base d on alkali - activated binders , it is essential to carefully control the water content

Role of carbonates in the chemical evolution of sodium carbonate-activated slag binders

Multi-technique characterisation of sodium carbonate-activated blast furnace slag binders was conducted in order to determine the influence of the carbonate groups on the structural and chemical evolution of these materials. At early age (<4 days) there is a preferential reaction of Ca2+ with the CO3 2− from the activator, forming calcium carbonates and gaylussite, while the aluminosilicate component of the slag reacts separately with the sodium from the activator to form zeolite NaA. These phases do not give the high degree of cohesion necessary for development of high early mechanical strength, and the reaction is relatively gradual due to the slow dissolution of the slag under the moderate pH conditions introduced by the Na2CO3 as activator. Once the CO3 2− is exhausted, the activation reaction proceeds in similar way to an NaOH-activated slag binder, forming the typical binder phases calcium aluminium silicate hydrate and hydrotalcite, along with Ca-heulandite as a further (Ca,Al)-rich product. This is consistent with the significant gain in compressive strength and reduced porosity observed after 3 days of curing. The high mechanical strength and reduced permeability developed in these materials beyond 4 days of curing elucidate that Na2CO3-activated slag can develop desirable properties for use as a building material, although the slow early strength development is likely to be an issue in some applications. These results suggest that the inclusion of additions which could control the preferential consumption of Ca2+ by the CO3 2− might accelerate the reaction kinetics of Na2CO3-activated slag at early times of curing, enhancing the use of these materials in engineering applications

Phase evolution of Na2O–Al2O3–SiO2–H2O gels in synthetic aluminosilicate binders

This study demonstrates the production of stoichiometrically controlled alkali-aluminosilicate gels (‘geopolymers’) via alkali-activation of high-purity synthetic amorphous aluminosilicate powders. This method provides for the first time a process by which the chemistry of aluminosilicate-based cementitious materials may be accurately simulated by pure synthetic systems, allowing elucidation of physicochemical phenomena controlling alkali-aluminosilicate gel formation which has until now been impeded by the inability to isolate and control key variables. Phase evolution and nanostructural development of these materials are examined using advanced characterisation techniques, including solid state MAS NMR spectroscopy probing 29Si, 27Al and 23Na nuclei. Gel stoichiometry and the reaction kinetics which control phase evolution are shown to be strongly dependent on the chemical composition of the reaction mix, while the main reaction product is a Na2O–Al2O3–SiO2–H2O type gel comprised of aluminium and silicon tetrahedra linked via oxygen bridges, with sodium taking on a charge balancing function. The alkali-aluminosilicate gels produced in this study constitute a chemically simplified model system which provides a novel research tool for the study of phase evolution and microstructural development in these systems. Novel insight of physicochemical phenomena governing geopolymer gel formation suggests that intricate control over time-dependent geopolymer physical properties can be attained through a careful precursor mix design. Chemical composition of the main N–A–S–H type gel reaction product as well as the reaction kinetics governing its formation are closely related to the Si/Al ratio of the precursor, with increased Al content leading to an increased rate of reaction and a decreased Si/Al ratio in the N–A–S–H type gel. This has significant implications for geopolymer mix design for industrial applications

Structural evolution of synthetic alkali-activated CaO-MgO-Na2O-Al2O3-SiO2 materials is influenced by Mg content

Stoichiometrically controlled alkali-activated materials within the system CaO-MgO-Na2O-Al2O3-SiO2 are produced by alkali-activation of high-purity synthetic powders chemically comparable to the glass in ground granulated blast furnace slag, but without additional minor constituents. Mg content controls the formation of hydrotalcite-group and AFm-type phases, which in turn strongly affects C-(N)-A-S-H gel chemistry and nanostructure. Bulk Mg content and the Mg/Al ratio of hydrotalcite-group phases are strongly correlated. With sufficient Ca, increased bulk Mg promotes formation of low-Al C-(A)-S-H and portlandite, due to formation of hydrotalcite-group phases and a reduction in available Al. Hydrotalcite-group phase formation is linked to increased C-(N)-A-S-H gel polymerisation, decreased gel Al uptake and increased formation of the ‘third aluminate hydrate’. These findings highlight the importance of considering available chemical constituents rather than simply bulk composition, so that the desired binder structure for a particular application can be achieved

New Structural Model of Hydrous Sodium Aluminosilicate Gels and the Role of Charge-Balancing Extra-Framework Al

A new structural model of hydrous alkali aluminosilicate gel (N-A-S-H) frameworks is proposed, in which charge-balancing extra-framework Al species are observed in N-A-S-H gels for the first time. This model describes the key nanostructural features of these gels, which are identified through the application of 17O, 23Na, and 27Al triple quantum magic angle spinning solid-state nuclear magnetic resonance spectroscopy to synthetic 17O-enriched gels of differing Si/Al ratios. The alkali aluminosilicate gel predominantly comprises Q4(4Al), Q4(3Al), Q4(2Al), and Q4(1Al) Si units charge-balanced by Na+ ions that are coordinated by either 3 or 4 framework oxygen atoms. A significant proportion of Al3+ in tetrahedral coordination exist in sites of lower symmetry, where some of the charge-balancing capacity is provided by extra-framework Al species which have not previously been observed in these materials. The mean SiIV–O–AlIV bond angles for each type of AlIV environments are highly consistent, with compositional changes dictating the relative proportions of individual AlIV species but not altering the local structure of each individual AlIV site. This model provides a more advanced description of the chemistry and structure of alkali aluminosilicate gels and is crucial in understanding and controlling the molecular interactions governing gel formation, mechanical properties, and durability

Structural evolution of synthetic alkali-activated CaO-MgO-Na₂O-Al₂O₃-SiO₂ materials is influenced by Mg content

Stoichiometrically controlled alkali-activated materials within the system CaO-MgO-Na₂O-Al₂O₃-SiO₂ are produced by alkali-activation of high-purity synthetic powders chemically comparable to the glass in ground granulated blast furnace slag, but without additional minor constituents. Mg content controls the formation of hydrotalcite-group and AFm-type phases, which in turn strongly affects C-(N)-A-S-H gel chemistry and nanostructure. Bulk Mg content and the Mg/Al ratio of hydrotalcite-group phases are strongly correlated. With sufficient Ca, increased bulk Mg promotes formation of low-Al C-(A)-S-H and portlandite, due to formation of hydrotalcite-group phases and a reduction in available Al. Hydrotalcite-group phase formation is linked to increased C-(N)-A-S-H gel polymerisation, decreased gel Al uptake and increased formation of the ‘third aluminate hydrate’. These findings highlight the importance of considering available chemical constituents rather than simply bulk composition, so that the desired binder structure for a particular application can be achieved

Oval Domes: History, Geometry and Mechanics

An oval dome may be defined as a dome whose plan or profile (or both) has an oval form. The word Aoval@ comes from the latin Aovum@, egg. Then, an oval dome has an egg-shaped geometry. The first buildings with oval plans were built without a predetermined form, just trying to close an space in the most economical form. Eventually, the geometry was defined by using arcs of circle with common tangents in the points of change of curvature. Later the oval acquired a more regular form with two axis of symmetry. Therefore, an “oval” may be defined as an egg-shaped form, doubly symmetric, constructed with arcs of circle; an oval needs a minimum of four centres, but it is possible also to build polycentric ovals. The above definition corresponds with the origin and the use of oval forms in building and may be applied without problem until, say, the XVIIIth century. Since then, the teaching of conics in the elementary courses of geometry made the cultivated people to define the oval as an approximation to the ellipse, an “imperfect ellipse”: an oval was, then, a curve formed with arcs of circles which tries to approximate to the ellipse of the same axes. As we shall see, the ellipse has very rarely been used in building. Finally, in modern geometrical textbooks an oval is defined as a smooth closed convex curve, a more general definition which embraces the two previous, but which is of no particular use in the study of the employment of oval forms in building. The present paper contains the following parts: 1) an outline the origin and application of the oval in historical architecture; 2) a discussion of the spatial geometry of oval domes, i. e., the different methods employed to trace them; 3) a brief exposition of the mechanics of oval arches and domes; and 4) a final discussion of the role of Geometry in oval arch and dome design

Daily Physical Activities and Sports in Adult Survivors of Childhood Cancer and Healthy Controls: A Population-Based Questionnaire Survey

BACKGROUND: Healthy lifestyle including sufficient physical activity may mitigate or prevent adverse long-term effects of childhood cancer. We described daily physical activities and sports in childhood cancer survivors and controls, and assessed determinants of both activity patterns. METHODOLOGY/PRINCIPAL FINDINGS: The Swiss Childhood Cancer Survivor Study is a questionnaire survey including all children diagnosed with cancer 1976-2003 at age 0-15 years, registered in the Swiss Childhood Cancer Registry, who survived ≥5 years and reached adulthood (≥20 years). Controls came from the population-based Swiss Health Survey. We compared the two populations and determined risk factors for both outcomes in separate multivariable logistic regression models. The sample included 1058 survivors and 5593 controls (response rates 78% and 66%). Sufficient daily physical activities were reported by 52% (n = 521) of survivors and 37% (n = 2069) of controls (p<0.001). In contrast, 62% (n = 640) of survivors and 65% (n = 3635) of controls reported engaging in sports (p = 0.067). Risk factors for insufficient daily activities in both populations were: older age (OR for ≥35 years: 1.5, 95CI 1.2-2.0), female gender (OR 1.6, 95CI 1.3-1.9), French/Italian Speaking (OR 1.4, 95CI 1.1-1.7), and higher education (OR for university education: 2.0, 95CI 1.5-2.6). Risk factors for no sports were: being a survivor (OR 1.3, 95CI 1.1-1.6), older age (OR for ≥35 years: 1.4, 95CI 1.1-1.8), migration background (OR 1.5, 95CI 1.3-1.8), French/Italian speaking (OR 1.4, 95CI 1.2-1.7), lower education (OR for compulsory schooling only: 1.6, 95CI 1.2-2.2), being married (OR 1.7, 95CI 1.5-2.0), having children (OR 1.3, 95CI 1.4-1.9), obesity (OR 2.4, 95CI 1.7-3.3), and smoking (OR 1.7, 95CI 1.5-2.1). Type of diagnosis was only associated with sports. CONCLUSIONS/SIGNIFICANCE: Physical activity levels in survivors were lower than recommended, but comparable to controls and mainly determined by socio-demographic and cultural factors. Strategies to improve physical activity levels could be similar as for the general population

Correlation of Serotype-Specific Dengue Virus Infection with Clinical Manifestations

Dengue virus (DENV) causes disease in millions of people annually and disproportionately affects those in the developing world. DENVs may be divided into four serotypes (DENV-1, DENV-2, DENV-3, and DENV-4) and a geographical region may be affected by one or more DENV serotypes simultaneously. Infection with DENV may cause life-threatening disease such as dengue hemorrhagic fever (DHF) or dengue shock syndrome (DSS), but more often causes less severe manifestations affecting a wide range of organs. Although many previous reports have explored the role of the different DENV serotypes in the development of severe manifestations, little attention has focused on the relative role of each DENV serotype in the development of cutaneous, respiratory, gastrointestinal, musculoskeletal, and neurological manifestations. We recruited a large group of participants from four countries in South America to compare the prevalence of more than 30 manifestations among the four different DENV serotypes. We found that certain DENV serotypes were often associated with a higher prevalence of a certain manifestation (e.g., DENV-3 and diarrhea) or manifestation group (e.g., DENV-4 and cutaneous manifestations)