Behavior of geopolymer concrete exposed to elevated temperatures

The research in the area of geopolymer is gaining momentum during the past 20 years. Studies confirm that geopolymer concrete has good compressive strength, tensile strength, flexural strength, modulus of elasticity and durability. These properties are comparable with OPC concrete.There are many occasions where concrete is exposed to elevated temperatures like fire exposure from thermal processor, exposure from furnaces, nuclear exposure, etc.. In such cases, understanding of the behaviour of concrete and structural members exposed to elevated temperatures is vital. Even though many research reports are available about the behaviour of OPC concrete at elevated temperatures, there is limited information available about the behaviour of geopolymer concrete after exposure to elevated temperatures. A preliminary study was carried out for the selection of a mix proportion. The important variable considered in the present study include alkali/fly ash ratio, percentage of total aggregate content, fine aggregate to total aggregate ratio, molarity of sodium hydroxide, sodium silicate to sodium hydroxide ratio, curing temperature and curing period. Influence of different variables on engineering properties of geopolymer concrete was investigated. The study on interface shear strength of reinforced and unreinforced geopolymer concrete as well as OPC concrete was also carried out. Engineering properties of fly ash based geopolymer concrete after exposure to elevated temperatures (ambient to 800 °C) were studied and the corresponding results were compared with those of conventional concrete. Scanning Electron Microscope analysis, Fourier Transform Infrared analysis, X-ray powder Diffractometer analysis and Thermogravimetric analysis of geopolymer mortar or paste at ambient temperature and after exposure to elevated temperature were also carried out in the present research work. Experimental study was conducted on geopolymer concrete beams after exposure to elevated temperatures (ambient to 800 °C). Load deflection characteristics, ductility and moment-curvature behaviour of the geopolymer concrete beams after exposure to elevated temperatures were investigated. Based on the present study, major conclusions derived could be summarized as follows. There is a definite proportion for various ingredients to achieve maximum strength properties. Geopolymer concrete with total aggregate content of 70% by volume, ratio of fine aggregate to total aggregate of 0.35, NaOH molarity 10, Na2SiO3/NaOH ratio of 2.5 and alkali to fly ash ratio of 0.55 gave maximum compressive strength in the present study. An early strength development in geopolymer concrete could be achieved by the proper selection of curing temperature and the period of curing. With 24 hours of curing at 100 °C, 96.4% of the 28th day cube compressive strength could be achieved in 7 days in the present study. The interface shear strength of geopolymer concrete is lower to that of OPC concrete. Compared to OPC concrete, a reduction in the interface shear strength by 33% and 29% was observed for unreinforced and reinforced geopolymer specimens respectively. The interface shear strength of geopolymer concrete is lower than ordinary Portland cement concrete. The interface shear strength of geopolymer concrete can be approximately estimated as 50% of the value obtained based on the available equations for the calculation of interface shear strength of ordinary portland cement concrete (method used in Mattock and ACI). Fly ash based geopolymer concrete undergoes a high rate of strength loss (compressive strength, tensile strength and modulus of elasticity) during its early heating period (up to 200 °C) compared to OPC concrete. At a temperature exposure beyond 600 °C, the unreacted crystalline materials in geopolymer concrete get transformed into amorphous state and undergo polymerization. As a result, there is no further strength loss (compressive strength, tensile strength and modulus of elasticity) in geopolymer concrete, whereas, OPC concrete continues to lose its strength properties at a faster rate beyond a temperature exposure of 600 °C. At present no equation is available to predict the strength properties of geopolymer concrete after exposure to elevated temperatures. Based on the study carried out, new equations have been proposed to predict the residual strengths (cube compressive strength, split tensile strength and modulus of elasticity) of geopolymer concrete after exposure to elevated temperatures (upto 800 °C). These equations could be used for material modelling until better refined equations are available. Compared to OPC concrete, geopolymer concrete shows better resistance against surface cracking when exposed to elevated temperatures. In the present study, while OPC concrete started developing cracks at 400 °C, geopolymer concrete did not show any visible cracks up to 600 °C and developed only minor cracks at an exposure temperatureof 800 °C. Geopolymer concrete beams develop crack at an early load stages if they are exposed to elevated temperatures. Even though the material strength of the geopolymer concrete does not decrease beyond 600 °C, the flexural strength of corresponding beam reduces rapidly after 600 °C temperature exposure, primarily due to the rapid loss of the strength of steel. With increase in temperature, the curvature at yield point of geopolymer concrete beam increases and thereby the ductility reduces. In the present study, compared to the ductility at ambient temperature, the ductility of geopolymer concrete beams reduces by 63.8% at 800 °C temperature exposure. Appropriate equations have been proposed to predict the service load crack width of geopolymer concrete beam exposed to elevated temperatures. These equations could be used to limit the service load on geopolymer concrete beams exposed to elevated temperatures (up to 800 °C) for a predefined crack width (between 0.1mm and 0.3 mm) or vice versa. The moment-curvature relationship of geopolymer concrete beams at ambient temperature is similar to that of RCC beams and this could be predicted using strain compatibility approach Once exposed to an elevated temperature, the strain compatibility approach underestimates the curvature of geopolymer concrete beams between the first cracking and yielding point.

Formation and characterisation of indium selenide thin films by elemental evaporation

This thesis deals with preparing stoichiometric crystalline thin films of InSe and In2Se3 by elemental evapouration and their property investigation.In the present study three temperature( or Elemental evapouration) method is utilized for the deposition of crystalline thin films . The deposition mechanism using three temperature method deals’ with condensation of solids on heated surfaces when the critical supersaturation of the vapour phase exceeds a certain limit. The critical values of the incident flux are related to substrate temperature and the interfacial energies of the involved vapours. At a favorable presence of component atoms in the vapour phase these can react and condense onto a substrate even at a elevated temperature. In the studies conducted the most significant factor is the formation of single compositional film namely indium mono selenide in the In –se system of compounds .Further this work shows the feasibility of thin film photovoltaic junctions of the schottky barrier type

Design and study of self-assembled functional organic and hybrid systems for biological applications

The focus of self-assembly as a strategy for the synthesis has been confined largely to molecules, because of the importance of manipulating the structure of matter at the molecular scale. We have investigated the influence of temperature and pH, in addition to the concentration of the capping agent used for the formation of the nano-bio conjugates. For example, the formation of the narrower size distribution of the nanoparticles was observed with the increase in the concentration of the protein, which supports the fact that γ-globulin acts both as a controller of nucleation as well as stabiliser. As analyzed through various photophysical, biophysical and microscopic techniques such as TEM, AFM, C-AFM, SEM, DLS, OPM, CD and FTIR, we observed that the initial photoactivation of γ-globulin at pH 12 for 3 h resulted in small protein fibres of ca. Further irradiation for 24 h, led to the formation of selfassembled long fibres of the protein of ca. 5-6 nm and observation of surface plasmon resonance band at around 520 nm with the concomitant quenching of luminescence intensity at 680 nm. The observation of light triggered self-assembly of the protein and its effect on controlling the fate of the anchored nanoparticles can be compared with the naturally occurring process such as photomorphogenesis.Furthermore,our approach offers a way to understand the role played by the self-assembly of the protein in ordering and knock out of the metal nanoparticles and also in the design of nano-biohybrid materials for medicinal and optoelectronic applications. Investigation of the potential applications of NIR absorbing and water soluble squaraine dyes 1-3 for protein labeling and anti-amyloid agents forms the subject matter of the third chapter of the thesis. The study of their interactions with various proteins revealed that 1-3 showed unique interactions towards serum albumins as well as lysozyme. 69%, 71% and 49% in the absorption spectra as well as significant quenching in the fluorescence intensity of the dyes 1-3, respectively. Half-reciprocal analysis of the absorption data and isothermal titration calorimetric (ITC) analysis of the titration experiments gave a 1:1 stoichiometry for the complexes formed between the lysozyme and squaraine dyes with association constants (Kass) in the range 104-105 M-1. We have determined the changes in the free energy (ΔG) for the complex formation and the values are found to be -30.78, -32.31 and -28.58 kJmol-1, respectively for the dyes 1, 2 and 3. Furthermore, we have observed a strong induced CD (ICD) signal corresponding to the squaraine chromophore in the case of the halogenated squaraine dyes 2 and 3 at 636 and 637 nm confirming the complex formation in these cases. To understand the nature of interaction of the squaraine dyes 1-3 with lysozyme, we have investigated the interaction of dyes 1-3 with different amino acids. These results indicated that the dyes 1-3 showed significant interactions with cysteine and glutamic acid which are present in the side chains of lysozyme. In addition the temperature dependent studies have revealed that the interaction of the dye and the lysozyme are irreversible. Furthermore, we have investigated the interactions of these NIR dyes 1-3 with β- amyloid fibres derived from lysozyme to evaluate their potential as inhibitors of this biologically important protein aggregation. These β-amyloid fibrils were insoluble protein aggregates that have been associated with a range of neurodegenerative diseases, including Huntington, Alzheimer’s, Parkinson’s, and Creutzfeldt-Jakob diseases. We have synthesized amyloid fibres from lysozyme through its incubation in acidic solution below pH 4 and by allowing to form amyloid fibres at elevated temperature. To quantify the binding affinities of the squaraine dyes 1-3 with β-amyloids, we have carried out the isothermal titration calorimetric (ITC) measurements. The association constants were determined and are found to be 1.2 × 105, 3.6× 105 and 3.2 × 105 M-1 for the dyes, 1-3, respectively. To gain more insights into the amyloid inhibiting nature of the squaraine dyes under investigations, we have carried out thioflavin assay, CD, isothermal titration calorimetry and microscopic analysis. The addition of the dyes 1-3 (5μM) led to the complete quenching in the apparent thioflavin fluorescence, thereby indicating the destabilization of β-amyloid fibres in the presence of the squaraine dyes. Further, the inhibition of the amyloid fibres by the squaraine dyes 1-3, has been evidenced though the DLS, TEM AFM and SAED, wherein we observed the complete destabilization of the amyloid fibre and transformation of the fibre into spherical particles of ca. These results demonstrate the fact that the squaraine dyes 1-3 can act as protein labeling agents as well as the inhibitors of the protein amyloidogenesis. The last chapter of the thesis describes the synthesis and investigation of selfassembly as well as bio-imaging aspects of a few novel tetraphenylethene conjugates 4-6.Expectedly, these conjugates showed significant solvatochromism and exhibited a hypsochromic shift (negative solvatochromism) as the solvent polarity increased, and these observations were justified though theoretical studies employing the B3LYP/6-31g method. We have investigated the self-assembly properties of these D-A conjugates though variation in the percentage of water in acetonitrile solution due to the formation of nanoaggregates. Further the contour map of the observed fluorescence intensity as a function of the fluorescence excitation and emission wavelength confirmed the formation of J-type aggregates in these cases. To have a better understanding of the type of self-assemblies formed from the TPE conjugates 4-6, we have carried out the morphological analysis through various microscopic techniques such as DLS, SEM and TEM. 70%, we observed rod shape architectures having ~ 780 nm in diameter and ~ 12 μM in length as evidenced through TEM and SEM analysis. We have made similar observations with the dodecyl conjugate 5 at ca. 70% and 50% water/acetonitrile mixtures, the aggregates formed from 4 and 5 were found to be highly crystalline and such structures were transformed to amorphous nature as the water fraction was increased to 99%. To evaluate the potential of the conjugate as bio-imaging agents, we have carried out their in vitro cytotoxicity and cellular uptake studies though MTT assay, flow cytometric and confocal laser scanning microscopic techniques. Thus nanoparticle of these conjugates which exhibited efficient emission, large stoke shift, good stability, biocompatibility and excellent cellular imaging properties can have potential applications for tracking cells as well as in cell-based therapies. In summary we have synthesized novel functional organic chromophores and have studied systematic investigation of self-assembly of these synthetic and biological building blocks under a variety of conditions. The investigation of interaction of water soluble NIR squaraine dyes with lysozyme indicates that these dyes can act as the protein labeling agents and the efficiency of inhibition of β-amyloid indicate, thereby their potential as anti-amyloid agents.

Behaviour of laterised normal and self compacting concrete subjected to elevated temperatures

Concrete is a universal material in the construction industry. With natural resources like sand and aggregate, fast depleting, it is time to look for alternate materials to substitute these in the process of making concrete. There are instances like exposure to solar radiation, fire, furnaces, and nuclear reactor vessels, special applications like missile launching pads etc., where concrete is exposed to temperature variations In this research work, an attempt has been made to understand the behaviour of concrete when weathered laterite aggregate is used in both conventional and self compacting normal strength concrete. The study has been extended to understand the thermal behaviour of both types of laterised concretes and to check suitability as a fire protection material. A systematic study of laterised concrete considering parameters like source of laterite aggregate, grades of Ordinary Portland Cement (OPC) and types of supplementary cementitious materials (fly ash and GGBFS) has been carried out to arrive at a feasible combination of various ingredients in laterised concrete. A mix design methodology has been proposed for making normal strength laterised self compacting concrete based on trial mixes and the same has also been validated. The physical and mechanical properties of laterised concretes have been studied with respect to different variables like exposure temperature (200°C, 400°C and 600°C) and cooling environment (air cooled and water cooled). The behaviour of ferrocement elements with laterised self compacting concrete has also been studied by varying the cover to mesh reinforcement (10mm to 50mm at an interval of 10mm), exposure temperature and cooling environment.