A study on mitigating the effect of sulphates in lime stabilised Cochin marine clays

Soft clays known for their high compressibility, low stiffness and low shear strength are always associated with large settlement. In place soil treatment using calcium-based stabilizers like lime and cement is a feasible solution to readdress strength deficiencies and problematic shrink/swell behaviour of unstable subgrade soils. Out of these, lime has been proved unambiguously as the most effective and economical stabilising agent for marine clays. Lime stabilisation creates long-term chemical changes in unstable clay soils to create strong, but flexible, permanent structural layers in foundations and other pavement systems. Even though calcium-based stabilizers can improve engineering properties of soft clays, problems can arise when they are used in soils rich in sulphates. It is possible for marine clays to be enriched with sulphates, either by nature or due to the discharge of nearby industrial wastes containing sulphates. The presence of sulphates is reported to adversely affect the cation exchange and pozzolanic reactions of cement and lime treated soil systems. The anions of sulphates may combine with the available calcium and alumina, and form insoluble ettringite in the soil system. Literature on sulphate attack in lime treated marine clays reports that formation of ettringite in lime-sodium sulphate-clay system is capable of adversely affecting the engineering behavior of marine clays. Only very few studies have been conducted on soft marine clays found along the coastal belt of Kerala and that too, is limited to Cochin marine clays. The studies conducted also have the limitation that the strength behaviour of lime stabilised clay was investigated only for one year. Practically no data pertaining to long term adverse effects likely to be brought about by sulphates on the strength and compressibility characteristics of Cochin marine clays is available. The overriding goal of this investigation was thus to examine the effectiveness of lime stabilisation in Cochin marine clays under varying sulphate contents. The study aims to reveal the changes brought about by varying sulphate contents on both physical and engineering properties of these clays stabilised by lime and the results for various curing periods up to two years is presented in this thesis. Quite often the load causing an unacceptable settlement may be less than the load required to cause shear failure and therefore attempt has been made in this research to highlight sulphate induced changes in both the compressibility and strength characteristics of lime treated Cochin marine clays. The study also aimed at comparing the available IS methods for sulphate quantification and has attempted to determine the threshold level of sulphate likely make these clays vulnerable by lime stabilisation. Clays used in this study were obtained from two different sites in Kochi and contained sulphate in two different concentrations viz., 0.5% and 0.1%. Two different lime percentages were tried out, 3% and 6%. Sulphate content was varied from 1% to 4% by addition of reagent grade sodium sulphate. The long term influence of naturally present sulphate is also investigated. X-ray diffraction studies and SEM studies have been undertaken to understand how the soil-lime reactions are affected in the presence of sodium sulphate. Natural sulphate content of 0.1% did not seem to have influenced normal soil lime reactions but 0.5% sulphate could induce significant changes adversely in both compressibility and strength behaviour of lime treated clays after long duration. Compressibility is seen to increase drastically with increasing sulphate content suggesting formation of ettringite on curing for longer periods. Increase in compression index and decrease in bond strength with curing period underlined the adverse effects induced in lime treated marine clays by the presence of sulphates. Presence of sulphate in concentrations ranging from 0.5 % to 4% is capable of adversely affecting the strength of lime treated marine clays. Considerable decrease is observed with increasing concentrations of sulphate. Ettringite formation due to domination of sodium ions in the system was confirmed in mineralogical studies made. Barium chloride and barium hydroxide is capable of bringing about beneficial changes both in compressibility and strength characteristics of lime treated Cochin marine clays in the presence of varying concentrations of sulphate and is strongly influenced by curing time. Clay containing sodium sulphate has increased strength values when either of barium compounds was used with lime ascompared with specimens treated with lime only. Barium hydroxide is observed to remarkably increase the strength as compared to barium chloride,when used in conjunction with lime to counteract the effect of sulphate.

Estudio de la utilización de las cenizas de cenicero de centrales termoeléctricas de carbón como adición del cemento portland : análisis comparativo con las cenizas volantes

El empleo de nuevas adiciones en el cemento se plantea como una vía para que éste sea un material más sostenible. En este contexto, las cenizas de fondo o cenicero de las centrales termoeléctricas de carbón actualmente se están llevando a vertederos creando un problema medioambiental o se están empleando con usos minoritarios. Sin embargo, la presente Tesis doctoral demuestra cómo este material puede ser empleado como un componente principal de los cementos portland mezclado en una proporción optimizada con las cenizas volantes o solo. Por tanto, este estudio se puede considerar como un trabajo prenormativo que cubre las demandas de la sociedad tanto económicas como ambientales. Se han estudiado las propiedades químicas, físicas y mecánicas de las cenizas de fondo o cenicero de las centrales termoeléctricas de carbón como una adición potencial de los cementos portland (con adiciones) en comparación con los cementos portland con cenizas volantes. En consecuencia, el objeto de la presente Tesis Doctoral es el análisis de las prestaciones de morteros elaborados con clínkeres de cemento portland y cenizas de fondo o cenicero con cenizas volantes de las centrales termoeléctricas de carbón en unos porcentajes similares a los correspondientes a los CEM II/A-V, CEM II/B-V y CEM IV/A (V) de la UNE-EN 197-1:2011. La caracterización de las cenizas de fondo o cenicero y de las cenizas volantes de las centrales termoeléctricas de carbón se ha realizado mediante las técnicas analíticas de FRX, ICP, análisis químicos, DRX, densidad, granulometría láser, superficie específica Blaine, ATD, TG, puzolanicidad, MEB y EDX; mientras que la caracterización de las mezclas se ha realizado mediante análisis químico (análisis químico, FRX e ICP y), DRX, MIP, granulometría láser, puzolanicidad, MEB y EDX, agua de consistencia normal, inicio y final de fraguado, estabilidad de volumen, colorimetría, calor de hidratación, DTA y TG, asícomo ensayos de resistencia; resistencia a flexión y compresión y ensayos de durabilidad (carbonatación natural, resistencia al hielo-deshielo, resistencia a la acción de los sulfatos y resistencia a la reacción árido-álcali). Finalmente, se han comprobado las propiedades de las cenizas de cenicero y cenizas volantes en hormigones, realizando ensayos de resistencia a compresión y resistividad. Los resultados obtenidos indican que la sustitución parcial o completa de las cenizas volantes por las de cenicero no tiene un efecto tecnológicamente importante en las propiedades ni mecánicas ni durables, incluso los mejora en determinados aspectos. Por tanto, se recomienda la normalización de las cenizas de fondo o cenicero de las centrales termoeléctricas de carbón como componente principal de los cementos portland comunes de la UNE-EN 197-1:2011. Actualmente, la mayoría de las cenizas de fondo se consideran como un residuo que no tiene un posible uso. Sólo se han encontrado algunos datos relativos a la aplicación de este material combinado con cenizas volantes como un componente principal de los cementos portland. Por tanto, la realización de un estudio integrado considerando aspectos que van desde la caracterización de las cenizas hasta las mezclas de conglomerante y la hidratación de éstas, desarrollo de resistencias y demás prestaciones y durabilidad (carbonatación natural, resistencia al hielo-deshielo, resistencia a la acción de los sulfatos y resistencia a la reacción árido-álcali), así como los ensayos de resistencia en hormigón es totalmente novedoso. Como resultado final se propone incorporar estas nuevas adiciones en aplicaciones particulares y en la norma más apropiada para ello. Los resultados han demostrado que la sustitución completa o parcial de las cenizas volantes por cenizas de fondo o cenicero de las centrales termoeléctricas de carbón en cementos de los tipos CEM II/A-V, CEM II/B-V y CEM IV/A no afecta de forma significativa en la resistencia a compresión a 1, 3 ,7, 28 ni 90 días ni a la durabilidad. En parte esto se debe a que la composición química de ambas cenizas es muy similar en la mayoría de los elementos tales como Fe2O3, TiO2, P2O5, SrO2, aunque en algún caso, como en el ZnO, se encuentra alguna ligera diferencia. Por tanto, se pueden esperar unas ligeras diferencias en el mecanismo de hidratación de las diferentes mezclas estudiadas. La presencia de los óxidos mencionados afectará a la composición de la fase acuosa y, en consecuencia, podrían ser elementos lixiviables. Asimismo, influyen de distinta manera en propiedades tales como los tiempos de fraguado y en la durabilidad. New additions to the cement are needed to achieve a more sustainable construction material. Within this context, bottom ashes produced in coal-fired power stations are currently wastes which are dumped provoking an environmental problem. Only in few cases are being used in minor applications. However, the present PhD Thesis shows how this material can be used as a main constituent of Portland cement when it is mixed in an optimised proportion with fly ashes or added to the Portland clinker alone. Therefore, this study may also be considered as a pre-standardization work which covers both the environmental and economic demands of society. Chemical, physical and mechanical characteristics of pulverized coal combustion bottom ash used as a potential constituent of Portland cements (with additions) are studied in comparison to Portland cements with fly ashes. Therefore, the aim of this experimental PhD Thesis is the analysis of the performance of mortars made of clinker of Portland cement and bottom and/or fly ashes in similar proportions to those of CEM II/A-V, CEM II/B-V and CEM IV/A (V) according to EN 197-1:2011. Characterisation of bottom and fly ashes has been done by XRF, ICP, chemical analyses, XRD, density, laser granulometry, Blaine, ATD, TG, pozzolanity, SEM and EDS. Characterisation of bottom and fly ashes mixes has been perform by chemical analyses, XRF, ICP, XRD, MIP, laser granulometry, pozzolanity, SEM, EDS, setting time, soundness, colorimetric test, heat of hydration, ATD, TG, compressive strength, and durability tests (natural carbonation, frost-thaw resistance, sulphate resistance and silica-alkali resistance). In conclusion, it can be established that partial or complete replacement of fly ash by bottom ash has neither significant effect on mechanical nor durability properties. Even, they are improved in several aspects. Therefore, it is recommended to standardise the bottom ash as a main cement constituent of the European standard EN 197-1:2011. Nowadays, most bottom ashes are considered as waste without any potential re-use. Only a few papers deal with the study of this material and its use mixed with fly ashes to be employed as a main constituent of Portland cement. Therefore, the execution of an integrated study considering together aspects from the initial characterization of the ashes and blinder mixes to the hydration steps, strength achievement, leading behaviour and durability (natural carbonation, sulphate attack, aggregate-alcali reaction and freeze-thaw resistance) is totally new. As result, it is proposed to include this new addition for particular applications in the appropriate cement standard. The results have shown that with regard to the compressive strength at 1, 3, 7, 28 and 90 days, partial or complete replacement of fly ash by bottom ash in CEM II/A-V, CEM II/B-V and CEM IV/A has no more significant effects. Partially, this can be explained because the bottom ash contains a similar amount of most of the elements, Fe2O3, TiO2, P2O5, SrO2, and so on, instead of ZnO. Therefore, slight hydration differences are expected. The presence of such oxides might have a significant effect on pore solution concentration and so will be leachable constituents. They will also play an important role in the cement properties such as setting times and durability.

The application of expert systems techniques in the design of durable concrete

This thesis describes work done exploring the application of expert system techniques to the domain of designing durable concrete. The nature of concrete durability design is described and some problems from the domain are discussed. Some related work on expert systems in concrete durability are described. Various implementation languages are considered - PROLOG and OPS5, and rejected in favour of a shell - CRYSTAL3 (later CRYSTAL4). Criteria for useful expert system shells in the domain are discussed. CRYSTAL4 is evaluated in the light of these criteria. Modules in various sub-domains (mix-design, sulphate attack, steel-corrosion and alkali aggregate reaction) are developed and organised under a BLACKBOARD system (called DEX). Extensions to the CRYSTAL4 modules are considered for different knowledge representations. These include LOTUS123 spreadsheets implementing models incorporating some of the mathematical knowledge in the domain. Design databases are used to represent tabular design knowledge. Hypertext representations of the original building standards texts are proposed as a tool for providing a well structured and extensive justification/help facility. A standardised approach to module development is proposed using hypertext development as a structured basis for expert systems development. Some areas of deficient domain knowledge are highlighted particularly in the use of data from mathematical models and in gaps and inconsistencies in the original knowledge source Digests.

Sulfate Resistance of Alkali Activated Pozzolans

The consequence of sulfate attack on geopolymer concrete, made from an alkali activated natural pozzolan (AANP) has been studied in this paper. Changes in the compressive strength, expansion and capillary water absorption of specimens have been investigated combined with phases determination by means of X-ray diffraction. At the end of present investigation which was to evaluate the performance of natural alumina silica based geopolymer concrete in sodium and magnesium sulfate solution, the loss of compressive strength and percentage of expansion of AANP concrete was recorded up to 19.4% and 0.074, respectively.

Chemical resistance of lime-based grouts for masonry strengthening

The stone masonry walls are present in many buildings and historical monuments, with undeniable asset value, but also in old buildings housing both in Portugal and in Europe. Most of these buildings in masonry are in certain cases in a high state of degradation needing urgent intervention. This requires the identification of deficiencies and the application of appropriate intervention techniques. One of the possible techniques for structural consolidation works of stone masonry walls is the injection of fluid mortars currently called grouts. The choice of grouts is very important with regard in particular to their chemical and physical properties. In this study, carried out under the Master of Chemical Engineering, two types of lime-based grouts were used, in order to evaluate and compare their chemical resistance due to the crystallization of soluble salts. One of the grouts is a pre-dosed blend commercially available, Mape-Antique I from company Mapei (CA), and the second grout is a mixture prepared in the laboratory (LB), comprising metakaolin, cement, hydrated lime, water and superplasticizer. With the purpose of evaluating the action of sulphates on these grouts, a series of samples underwent several wetting-drying cycles using two different temperatures, 20 °C and 50 °C. During the experiment it was determined the change of weight and compressive strength in the analyzed grouts, as well as the sulphate ion concentration and pH of the solution in which the samples were dipped. The commercial grout (CA) apparently has a greater chemical resistance to sulphates. However grout LB showed to have positive results in some parameters.

Electrochemical behaviour of heat-treated Al-Zn-Mg alloys in chloride solutions containing sulphate

The electrochemical corrosion and passivation of Al-5Zn-1.7Mg-0.23Cu-0.053Nb alloys, submitted to different heat treatments (cold-rolled, annealed, quenched and aged, and quenched in two steps and aged), in sulphate-containing chloride solutions, has been studied by means of cyclic polarization, electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), and X-ray photoelectron spectroscopy (XPS). The cyclic polarization curves showed that sulphate addition to the chloride solution produced a poor reproducible shift of the breakdown potential to more positive potentials. The repassivation potentials, much more reproducible, and practically separating the passive from the pitting potential region, were slightly displaced in the negative direction with that addition. When the alloys were potentiodynamically polarized in the passive potential region, sulphate was incorporated in the oxide film, thus precluding chloride ingress. In addition, Zn depletion was favoured, whereas Mg losses were avoided. Different equivalent circuits corresponding to different alloys and potentials in the passive and pitting regions were employed to account for the electrochemical processes taking place in each condition. This work shows that sulphate makes these alloys more sensitive to corrosion, increasing the fracture properties of the surface layer and favouring the pitting attack over greater areas than chloride alone. (C) 2002 Elsevier B.V. Ltd. All rights reserved.

An improved procedure for flow-based turbidimetric sulphate determination based on a liquid core waveguide and pulsed flows

An improved flow-based procedure is proposed for turbidimetric sulphate determination in waters. The flow system was designed with solenoid micro-pumps in order to improve mixing conditions and minimize reagent consumption as well as waste generation. Stable baselines were observed in view of the pulsed flow characteristic of the systems designed with solenoid micro-pumps, thus making the use of washing solutions unnecessary. The nucleation process was improved by stopping the flow prior to the measurement, thus avoiding the need of sulphate addition. When a 1-cm optical path flow cell was employed, linear response was achieved within 20-200 mg L(-1), described by the equation S = -0.0767 + 0.00438C (mg L(-1)), r = 0.999. The detection limit was estimated as 3 mg L(-1) at the 99.7% confidence level and the coefficient of variation was 2.4% (n = 20). The sampling rate was estimated as 33 determinations per hour. A long pathlength (100-cm) flow cell based on a liquid core waveguide was exploited to increase sensitivity in turbidimetry. Baseline drifts were avoided by a periodical washing step with EDTA in alkaline medium. Linear response was observed within 7-16 mg L(-1), described by the equation S = -0.865 + 0.132C (mg L(-1)), r = 0.999. The detection limit was estimated as 150 mu g L(-1) at the 99.7% confidence level and the coefficient of variation was 3.0% (n = 20). The sampling rate was estimated as 25 determinations per hour. The results obtained for freshwater and rain water samples were in agreement with those achieved by batch turbidimetry at the 95% confidence level. (C) 2008 Elsevier B.V All rights reserved.

Diversity and identification of methanogenic archaea and sulphate-reducing bacteria in sediments from a pristine tropical mangrove

Mangrove sediments are anaerobic ecosystems rich in organic matter. This environment is optimal for anaerobic microorganisms, such as sulphate-reducing bacteria and methanogenic archaea, which are responsible for nutrient cycling. In this study, the diversity of these two functional guilds was evaluated in a pristine mangrove forest using denaturing gradient gel electrophoresis (DGGE) and clone library sequencing in a 50 cm vertical profile sampled every 5.0 cm. DGGE profiles indicated that both groups presented higher richness in shallow samples (0-30 cm) with a steep decrease in richness beyond that depth. According to redundancy analysis, this alteration significantly correlated with a decrease in the amount of organic matter. Clone library sequencing indicated that depth had a strong effect on the selection of dissimilatory sulphate reductase (dsrB) operational taxonomic units (OTUs), as indicated by the small number of shared OTUs found in shallow (0.0 cm) and deep (40.0 cm) libraries. On the other hand, methyl coenzyme-M reductase (mcrA) libraries indicated that most of the OTUs found in the shallow library were present in the deep library. These results show that these two guilds co-exist in these mangrove sediments and indicate important roles for these organisms in nutrient cycling within this ecosystem.

An expert flow system involving in-line prior assay for turbidimetric determination of chloride and sulphate in natural waters

A multi-pumping flow system exploiting prior assay is proposed for sequential turbidimetric determination of sulphate and chloride in natural waters. Both methods are implemented in the same manifold that provides facilities for: in-line sample clean-up with a Bio-Rex 70 mini-column with fluidized beads: addition of low amounts of sulphate or chloride ions to the reaction medium for improving supersaturation; analyte precipitation with Ba(2+) or Ag(+); real-time decision on the need for next assay. The sample is initially run for chloride determination, and the analytical signal is compared with a preset value. If higher, the sample is run again, now for sulphate determination. The strategy may lead to all increased sample throughput. The proposed system is computer-controlled and presents enhanced figures of merit. About 10 samples are run per hour (about 60 measurements) and results are reproducible and Unaffected by the presence of potential interfering ions at concentration levels usually found in natural waters. Accuracy was assessed against ion chromatography. (C) 2008 Elsevier B.V. All rights reserved.

Relationship between attack and skipping in taekwondo contests

Santos, VGF, Franchini, E, and Lima-Silva, AE. Relationship between attack and skipping in Taekwondo contests. J Strength Cond Res 25(6): 1743-1751, 2011-The purpose of this study was to determine the relationship between attack time (AT) and skipping time (ST) during the 2007 Taekwondo World Championship and 2008 Beijing Olympic Games. A total of 22 matches (65 rounds, 13 semifinals, and 8 finals) from the World Championship and 23 matches (63 rounds, 22 rounds with 16 athletes each and 1 quarterfinal round) from the Olympic Games, both in the male category, were assessed using time-motion analysis. The AT was considered as the total time during which the athlete attacked or tried to attack, whereas ST was the total time without attempting to attack. The ratio of AT to ST was similar to 1:7 based on the data pooled from the 2 competitions. The AT/ST ratio was significantly lower for the World Championship than for the Olympic Games (p <= 0.05). In the Olympic Games, no consistent differences across weight divisions were found. However, during the World Championship, the heavier weight divisions (>78 kg) exhibited a lower average AT, lower summed AT, lower attack numbers (ANs) and higher average ST than lighter weight divisions (<58 kg, p <= 0.05). For both competitions, the ST was lower, and the ANs and AT/ST ratio were higher in round 3 than in round 1 or 2. In conclusion, the results of this study suggest that matches in the Olympic Games were less cadenced than in the World Championship, but that in both competitions, the intensity of the match increased in round 3. Practically, these data suggest that coaches need to structure Taekwondo training sessions in a manner that allows the work/pause ratio to mirror the physical demand imposed during competitions.

Investigation of Normal Force and Moment Coefficients for an AUV at Nonlinear Angle of Attack and Sideslip Range

This paper presents a comparative study of computational fluid dynamics (CFD) and analytical and semiempirical (ASE) methods applied to the prediction of the normal force and moment coefficients of an autonomous underwater vehicle (AUV). Both methods are applied to the. bare hull of the vehicle and to the body-hydroplane combination. The results are validated through experiments in a towing tank. It is shown that the CFD approach allows for a good prediction of the coefficients over the range of angles of attack considered. In contrast with the traditional ASE formulations used in naval and aircraft fields, an improved methodology is introduced that takes advantage of the qualitative information obtained from CFD flow visualizations.

Influence of ammonium sulphate feeding time on fed-batch Arthrospira (Spirulina) platensis cultivation and biomass composition with and without pH control

Previous work demonstrated that a mixture of NH(4)Cl and KNO(3) as nitrogen source was beneficial to fed-batch Arthrospira (Spirulina) platensis cultivation, in terms of either lower costs or higher cell concentration. On the basis of those results, this study focused on the use of a cheaper nitrogen source mixture, namely (NH(4))(2)SO(4) plus NaNO(3), varying the ammonium feeding time (T = 7-15 days), either controlling the pH by CO(2) addition or not. A. platensis was cultivated in mini-tanks at 30 degrees C, 156 mu mol photons m(-2) s(-1), and starting cell concentration of 400 mg L(-1), on a modified Schlosser medium. T = 13 days under pH control were selected as optimum conditions, ensuring the best results in terms of biomass production (maximum cell concentration of 2911 mg L(-1), cell productivity of 179 mg L(-1) d(-1) and specific growth rate of 0.77 d(-1)) and satisfactory protein and lipid contents (around 30% each). (C) 2011 Elsevier Ltd. All rights reserved.

A New Approach to Ammonium Sulphate Feeding for Fed-Batch Arthrospira (Spirulina) platensis Cultivation in Tubular Photobioreactor

Arthrospira platensis was cultivated in tubular photobioreactor using different photosynthetic photon flux densities (PPFD) and protocols of (NH(4))(2)SO(4) fed-hatch supply. Results were evaluated by variance analysis selecting maximum cell concentration (X(m)), cell productivity (P(x)), nitrogen-to-cell conversion factor (Y(X/N)) and biomass, protein and lipid contents as responses. At PPFD of 120 and 240 mu mol-photons/m(2) s, a parabolic profile of (NH(4))(2)SO(4) addition aiming at producing biomass with 7% nitrogen content ensured X(m) values (14.1 and 12.2 g/L, respectively) comparable to those obtained with NaNO(3). At PPFD of 240 mu mol-photons/m(2) s, P(x) (1.69 g/Ld) was 36% higher, although the photosynthetic efficiency (3.0%) was less than one-half that at PPFD of 120 mu mol-photons/m(2) s. Biomass was shown to be constituted by about 35% proteins and 10% lipids, without any dependence on PPFD or kind of nitrogen source. These results highlight the possible use of (NH(4))(2)SO(4) as alternative, cheap nitrogen source for A. platensis cultivation in tubular photobioreactors. (C) 2010 American Institute of Chemical Engineers Biotechnol. Prog., 26: 1271-1277, 2010

Chitosan microparticles for sustaining the topical delivery of minoxidil sulphate

Given the hypothesis that microparticles can penetrate the skin barrier along the transfollicular route, this work aimed to obtain and characterise chitosan microparticles loaded with minoxidil sulphate (MXS) and to study their ability to sustain the release of the drug, attempting a further application utilising them in a targeted delivery system for the topical treatment of alopecia. Chitosan microparticles, containing different proportions of MXS/polymer, were prepared by spray drying and were characterised by yield, encapsulation efficiency, size and morphology. Microparticles selected for further studies showed high encapsulation efficiency (similar to 82%), a mean diameter of 3.0 mu m and a spherical morphology without porosities. When suspended in an ethanol/water solution, chitosan microparticles underwent instantaneous swelling, increasing their mean diameter by 90%. Release studies revealed that the chitosan microparticles were able to sustain about three times the release rate of MXS. This feature, combined with suitable size, confers to these microparticles the potential to target and improve topical therapy of alopecia with minoxidil.