Adsorption kinetic, thermodynamic and desorption studies of phosphate onto hydrous niobium oxide prepared by reverse microemulsion method

A type of Nb(2)O(5)center dot 3H(2)O was synthesized and its phosphate removal potential was investigated in this study. The kinetic study, adsorption isotherm, pH effect, thermodynamic study and desorption were examined in batch experiments. The kinetic process was described by a pseudo-second-order rate model very well. The phosphate adsorption tended to increase with a decrease of pH. The adsorption data fitted well to the Langmuir model with which the maximum P adsorption capacity was estimated to be 18.36 mg-Pg(-1). The peak appearing at 1050 cm(-1) in IR spectra after adsorption was attributed to the bending vibration of adsorbed phosphate. The positive values of both Delta H degrees and Delta S degrees suggest an endothermic reaction and increase in randomness at the solid-liquid interface during the adsorption. Delta G degrees values obtained were negative indicating a spontaneous adsorption process. A phosphate desorbability of approximately 68% was observed with water at pH 12, which indicated a relatively strong bonding between the adsorbed phosphate and the sorptive sites on the surface of the adsorbent. The immobilization of phosphate probably occurs by the mechanisms of ion exchange and physicochemical attraction. Due to its high adsorption capacity, this type of hydrous niobium oxide has the potential for application to control phosphorus pollution.

Eucalyptus pulp fibres as alternative reinforcement to engineered cement-based composites

This paper evaluates the advantages of using hardwood short fibre pulp (eucalyptus) as alternative to softwood long fibre pulp (pinus) and polymer fibres, traditionally used in reinforcement of cement-based materials. The effects of cellulose fibre length on microstructure and on mechanical performance of fibre-cement composites were evaluated before and after accelerated ageing cycles. Hardwood pulp fibres were better dispersed in the cement matrix and provided higher number of fibres per unitary weight or volume, in relation to softwood long fibre pulp. The short reinforcing elements lead to an effective crack bridging of the fragile matrix, which contributes to the improvement of the mechanical performance of the composite after ageing. These promising results show the potential of eucalyptus short fibres for reducing costs by both the partial replacement of expensive synthetic fibres in air curing process and the energy savings during pulp refining. (C) 2009 Elsevier B.V. All rights reserved.

Cellulose modified fibres in cement based composites

The objective of the present work is to evaluate the effect of surface modification of cellulose pulp fibres on the mechanical and microstructure of fibre-cement composites. Surface modification of the cellulose pulps was performed with Methacryloxypropyltri-methoxysilane (MPTS) and Aminopropyltri-ethoxysilane (APTS) in an attempt to improve their durability into fibre-cement composites. The surface modification showed significant influence on the microstructure of the composites on the fibre-matrix interface and in the mineralization of the fibre lumen as seen by scanning electron microscopy (SEM) with back-scattered electron (BSE) detector. Accelerated ageing cycles decreased modulus of rupture (MOR) and toughness (TE) of the composites. Composites reinforced with MPTS-modified fibres presented fibres free from cement hydration products, while APTS-modified fibres presented accelerated mineralization. Higher mineralization of the fibres led to higher embrittlement of the composite after accelerated ageing cycles. These observations are therefore very useful for understanding the mechanisms of degradation of fibre-cement composites. (C) 2009 Elsevier Ltd. All rights reserved.

Effect of fibre morphology on flocculation of fibre-cement suspensions

The objective of the present research was to evaluate the effect of fibre morphology (e.g., length, width, fibrillation, broken ends, content of fines and number of fibres per gram) on flocculation and drainage properties of fibre-cement suspensions and on physical properties of the fibre-cement composites. Mechanical refining was used to change the morphological properties of Eucalyptus and Pinus pulps. Results show that the mechanical refining increased the size of the formed flocs and decreased the concentration of free small particles (with dimensions between 1 and 20 pm) as a consequence of the increased fibrillation and content of fines, which increased the capacity of the fibres to capture the mineral particles. High levels of refining were necessary for Pinus pulp to obtain cement retention values similar to those obtained by unrefined Eucalyptus pulp. This is due to the higher number of fibres per gram in Eucalyptus pulp than in Pinus pulp. Pulp refining improved the packing of the particles and, although decreased the drainage rate. it contributed to a less porous structure, which improved the microstructure of the composite. (C) 2009 Elsevier Ltd. All rights reserved.

Influence of aggregates grading and water/cement ratio in workability and hardened properties of mortars

Mortar is the material responsible for the distribution of stresses in masonry structures. The knowledge about the fresh and hardened properties of mortar is fundamental to ensure a good performance of masonry walls. Water/cement ratio and aggregates grading are among several variables that influence physical and mechanical behaviour of mortars. An experimental program is presented in order to evaluate the influence of aggregates grading and water/cement ratio in workability and hardened properties of mortars. Eighteen compositions of mortar are prepared using three relations cement:lime:sand, two types of sand and three water/cement ratios. Specimens are analyzed through flow table test, compressive and flexural strength tests. Results indicate that the increase of water/cement ratio reduces the values of hardened properties and increases the workability. Besides, sands grading has no influence in compressive strength. On the other hand, significant differences in deformation capacity of mortars were verified with the variation of the type of sand. Finally, some correlations are presented among hardened properties and the compressive strength. (C) 2010 Elsevier Ltd. All rights reserved.

Effect of HMEC on the consolidation of cement pastes: Isothermal calorimetry versus oscillatory rheometry

Chemical admixtures increase the theological complexity of cement pastes owing to their chemical and physical interactions with particles, which affects cement hydration and agglomeration kinetics. Using oscillatory rheometry and isothermal calorimetry, this article shows that the cellulose ether HMEC (hydroxymethyl ethylcellulose), widely used as a viscosity modifying agent in self-compacting concretes and dry-set mortars, displayed a steric dispersant barrier effect during the first 2 h of hydration associated to a cement retarding nature, consequently reducing the setting speed. However, despite this stabilization effect, the polymer increased the cohesion strength when comparing cement particles with the same hydration degree. (C) 2009 Elsevier Ltd. All rights reserved.

Bond strength and transversal deformation aging on cement-polymer adhesive mortar

Polymer-modified mortar is widely used to set ceramic tiles used as external finishing for high rise buildings in countries such as Brazil, Israel, Singapore and Portugal, mainly because it shows better bond strength and flexibility as compared to the traditional ones. Despite this, the results in the literature already published concerning the long-term performance of those composite mortars are is not conclusive. This paper, based on a laboratory program, compared the performance over time of four commercial polymer-modified adhesive mortars exposed to a typical Brazilian outdoor aging environment and to an indoor environment in terms of mortar flexibility and the bond strength to porcelain tiles. The results show that under laboratory condition, the mortars are more flexible and have higher bond strength than under external condition, and that there is an important correlation between the transversal deformability and the bond strength. (C) 2008 Elsevier Ltd. All rights reserved.

The influence of moisture on the deformability of cement-polymer adhesive mortar

Adhesive mortars are widely used to set porcelain stoneware tiles on buildings because their bond strength and flexibility properties increase the cladding serviceability. However, their long-term performance is not well understood, mainly the degradation of the polymeric matrix. The influence of moisture content on the flexibility of six adhesive mortars is investigated, based on standard EN 12002. Four of them have defined formulations and the other two are commercial and are widely used to set porcelain stoneware tiles on building facades in Brazil. The results show that moisture content above 6% is sufficient to reduce 50% of the mortar deformability, but that the drying process allows it to recover to a value similar to that prior to saturation; a logarithmic function best fits the correlation between moisture content and flexibility; water immersion increases matrix rigidity. It is suggested that standards should consider flexibility tests on both dried and wet samples as a requirement for polymer-modified mortars. (C) 2010 Elsevier Ltd. All rights reserved.

Hybrid Reinforcement of Sisal and Polypropylene Fibers in Cement-Based Composites

Several studies using vegetable fibers as the exclusive reinforcement in fiber-cement composites have shown acceptable mechanical performance at the first ages. However, after the exposure to accelerated aging tests, these composites have shown significant reduction in the toughness or increase in embrittlement. This was mainly attributed to the improved fiber-matrix adhesion and fiber mineralization after aging process. The objective of the present research was to evaluate composites produced by the slurry dewatering technique followed by pressing and air curing, reinforced with combinations of polypropylene fibers and sisal kraft pulp at different pulp freeness. The physical properties, mechanical performance, and microstructural characteristics of the composites were evaluated before and after accelerated and natural aging. Results showed the great contribution of pulp refinement on the improvement of the mechanical strength in the composites. Higher intensities of refinement resulted in higher modulus of rupture for the composites with hybrid reinforcement after accelerated and natural aging. The more compact microstructure was due to the improved packing of the mineral particles with refined sisal pulp. The toughness of the composites after aging was maintained in relation to the composites at 28 days of cure.

Discoloration and fungal growth on three fiber cement formulations exposed in urban, rural and coastal zones

Three formulations of fiber cement were evaluated for fungal colonization and color change after five years of exposure in aging stations located in urban (Sao Paulo), rural (Pirassununga) and coastal (Rio Grande) zones in Brazil. The lowest color change and fungal colonization were registered in Rio Grande, which has a temperate climate, as opposed to Sao Paulo and Pirassununga, which are tropical. The highest fungal colonization was recorded in Sao Paulo, one of the most air polluted cities in Brazil. Pirassununga samples had an intermediate fungal colonization, in spite of showing the highest color change with visible dark spots on the surfaces. These spots were identified as cyanobacteria, which significantly contributed to the darkening of the specimens. The fiber cement formulation, varying in proportion of organic fibers such as poly (vinyl alcohol) and cellulose, was less significant for fungal bioreceptivity than the characteristics of the exposure site. The most frequent fungal genus found in the tropical climate, in both urban and rural zones, and the main one responsible for the higher records in Sao Paulo, was Scytalidiurn sp. which was registered for the first time on this building material in Brazil. (C) 2010 Elsevier Ltd. All rights reserved.

Exploring the potential of functionally graded materials concept for the development of fiber cement

In this study we establish the concept of functionally graded fiber cement. We discuss the use of statistical mixture designs to choose formulations and present ideas for the production of functionally graded fiber cement components for Hatschek machines. The feasibility of producing functionally graded fiber cement by grading PVA fiber content has been experimentally evaluated. Thermogravimetric analysis (TG) was employed to assess fiber distribution profiles and four-point bending tests were applied to evaluate the mechanical performance of both conventional and graded composites. The results show that grading PVA fiber content is an effective way to produce functionally graded fiber cement, which allows for a reduction of the total fiber volume without a significant reduction on modulus of rupture of composite. TG tests were found adequate to assess the fiber content at different points in functionally graded fiber cements. (C) 2009 Elsevier Ltd. All rights reserved.

Short-term experimental data of drying shrinkage of ground granulated blast-furnace slag cement concrete

This paper presents results of laboratory testing of unrestrained drying shrinkage during a period of 154 days of different concrete mixtures from the Brazilian production line that utilize ground granulated blast-furnace slag in their compositions. Three concrete mixtures with water/cement ratio of 0.78(M1), 0.41(M2), and 0.37(M3) were studied. The obtained experimental data were compared with the analytical results from prediction models available in the literature: the ACI 209 model (ACI), the B3 model (B3), the Eurocode 2 model (EC2), the GL 2000 model (GL), and the Brazilian NBR 6118 model (NBR), and an analysis of the efficacy of these models was conducted utilizing these experimental data. In addition, the development of the mechanical properties (compressive strength and modulus of elasticity) of the studied concrete mixtures was also measured in the laboratory until 126 days. From this study, it could be concluded that the ACI and the GL were the models that most approximated the experimental drying shrinkage data measured during the analyzed period of time.

Reaction rate and product morphology in carbon composite iron ore pellets with and without Portland cement

The aim of this work is to study the reaction rate and the morphology of intermediate reaction products during iron ore reduction when iron ore and carbonaceous materials are agglomerated together with or without Portland cement. The reaction was performed at high temperatures, and used small size samples in order to minimise heat transfer constraints. Coke breeze and pure graphite were the carbonaceous materials employed. Portland cement was applied as a binder, and pellet diameters were in the range 5.6-6.5 mm. The experimental technique involved the measurement of the pellet weight loss, as well as the interruption of the reaction at different stages, in order to submit the partially reduced pellet to scanning electron microscopy. The experimental temperature was in the range 1423-1623 K, and the total reaction time varied from 240 to 1200 s. It was observed that above 1523 K the formation of liquid slag occurred inside the pellets, which partially dissolved iron oxides. The apparent activation energies obtained were 255 kJ mol(-1) for coke breeze containing pellets, and 230 kJ mol(-1) for those pellets containing graphite. It was possible to avoid heat transfer control of the reaction rate up to 1523 K by employing small composite pellets.

Drying and autogenous shrinkage of pastes and mortars with activated slag cement

Activated slag cement (ASC) shows significantly higher shrinkage than ordinary Portland cement agglomerates. Cracking generated by shrinkage is one of the most critical drawbacks for broader applications of this promising alternative binder. This article investigates the relationship between ASC hydration, unrestrained drying and autogenous shrinkage of mortar specimens. The chemical and microstructure evolution due to hydration were determined on pastes by thermogravimetric analysis, conduction calorimetry and mercury porosimetry. Samples were prepared with ground blast furnace slag (BFS) activated with sodium silicate (silica modulus of 1.7) with 2.5, 3.5 and 4.5% of Na2O, by slag mass. The amount of activator is the primary influence on drying and autogenous shrinkage, and early hydration makes a considerable contribution to the total result, which increases with the amount of silica. Drying shrinkage occurred in two stages, the first caused by extensive water loss when the samples were exposed to the environment, and the second was associated with the hydration process and less water loss. Due to the refinement of ASC porous system, autogenous shrinkage is responsible for a significant amount of the total shrinkage. (C) 2007 Elsevier Ltd. All rights reserved.

Long-term aging of fiber-cement corrugated sheets - The effect of carbonation, leaching and acid rain

This paper studies the performance of fiber-cement corrugated sheets exposed to long-term weathering, exploring the effect of different environments on fiber-cement degradation. Fiber-cement corrugated sheets that had been exposed to weathering, and in place for more than 30-years, were collected from two different Brazilian cities (Sao Paulo and Criciuma). Mechanical properties (MOR, MOE and fracture toughness) were tested on samples removed from the corrugated sheets. Microstructure was evaluated by X-ray diffraction, SEM with EDS analysis, MIP and TG. The results show that the 37-year-old asbestos-cement corrugated sheets from Sao Paulo presented similar characteristics to those of the non-aged asbestos-cement readily available on the market place. Conversely, deterioration of the asbestos-cement from the industrial area of Criciuma is related to acidic attack, along with carbonation and leaching as a consequence of continued exposition to acid rain during several decades. This process resulted in higher porosity and lower mechanical strength, revealing that leaching mechanisms can have important effect on the performance of thin fiber-cement sheets. (c) 2007 Elsevier Ltd. All rights reserved.