Singlet Oxygen in Microporous Silica Xerogel:Quantum Yield and Oxidation at the Gas–Solid Interface

The quantum yields of singlet oxygen production and lifetimes at the gas–solid interface in silica gel material are determined. Different photosensitizers (PS) are encapsulated in parallelepipedic xerogel monoliths (PS-SG). PS were chosen according to their known photooxidation properties: 9,10-dicyanoanthracene (DCA), 9,10-anthraquinone (ANT), and a benzophenone derivative, 4-benzoyl benzoic acid (4BB). These experiments are mainly based on time-resolved 1O2 phosphorescence detection, and the obtained FD and tD values are compared with those of a reference sensitizer for production, 1H-phenalen-1- one (PN), included in the same xerogel. The trend between their ability to oxidize organic pollutants in the gas phase and their efficiency for production is investigated through photooxidation experiments of a test pollutant dimethylsulfide (DMS). The FD value is high for DCA-SG relative to the PN reference, whereas it is slightly lower for 4BB-SG and for ANT-SG. FD is related to the production of sulfoxide and sulfone as the main oxidation products for DMS photosensitized oxidation. Additional mechanisms, leading to C!S bond cleaveage, appear to mainly occur for the less efficient singlet oxygen sensitizers 4BB-SG and ANTSG.

Assessment of Energy Conservation in Indian Cement Industry and Forecasting of Co2 Emissions

Cement industry ranks 2nd in energy consumption among the industries in India. It is one of the major emitter of CO2, due to combustion of fossil fuel and calcination process. As the huge amount of CO2 emissions cause severe environment problems, the efficient and effective utilization of energy is a major concern in Indian cement industry. The main objective of the research work is to assess the energy cosumption and energy conservation of the Indian cement industry and to predict future trends in cement production and reduction of CO2 emissions. In order to achieve this objective, a detailed energy and exergy analysis of a typical cement plant in Kerala was carried out. The data on fuel usage, electricity consumption, amount of clinker and cement production were also collected from a few selected cement industries in India for the period 2001 - 2010 and the CO2 emissions were estimated. A complete decomposition method was used for the analysis of change in CO2 emissions during the period 2001 - 2010 by categorising the cement industries according to the specific thermal energy consumption. A basic forecasting model for the cement production trend was developed by using the system dynamic approach and the model was validated with the data collected from the selected cement industries. The cement production and CO2 emissions from the industries were also predicted with the base year as 2010. The sensitivity analysis of the forecasting model was conducted and found satisfactory. The model was then modified for the total cement production in India to predict the cement production and CO2 emissions for the next 21 years under three different scenarios. The parmeters that influence CO2 emissions like population and GDP growth rate, demand of cement and its production, clinker consumption and energy utilization are incorporated in these scenarios. The existing growth rate of the population and cement production in the year 2010 were used in the baseline scenario. In the scenario-1 (S1) the growth rate of population was assumed to be gradually decreasing and finally reach zero by the year 2030, while in scenario-2 (S2) a faster decline in the growth rate was assumed such that zero growth rate is achieved in the year 2020. The mitigation strategiesfor the reduction of CO2 emissions from the cement production were identified and analyzed in the energy management scenarioThe energy and exergy analysis of the raw mill of the cement plant revealed that the exergy utilization was worse than energy utilization. The energy analysis of the kiln system showed that around 38% of heat energy is wasted through exhaust gases of the preheater and cooler of the kiln sysetm. This could be recovered by the waste heat recovery system. A secondary insulation shell was also recommended for the kiln in the plant in order to prevent heat loss and enhance the efficiency of the plant. The decomposition analysis of the change in CO2 emissions during 2001- 2010 showed that the activity effect was the main factor for CO2 emissions for the cement industries since it is directly dependent on economic growth of the country. The forecasting model showed that 15.22% and 29.44% of CO2 emissions reduction can be achieved by the year 2030 in scenario- (S1) and scenario-2 (S2) respectively. In analysing the energy management scenario, it was assumed that 25% of electrical energy supply to the cement plants is replaced by renewable energy. The analysis revealed that the recovery of waste heat and the use of renewable energy could lead to decline in CO2 emissions 7.1% for baseline scenario, 10.9 % in scenario-1 (S1) and 11.16% in scenario-2 (S2) in 2030. The combined scenario considering population stabilization by the year 2020, 25% of contribution from renewable energy sources of the cement industry and 38% thermal energy from the waste heat streams shows that CO2 emissions from Indian cement industry could be reduced by nearly 37% in the year 2030. This would reduce a substantial level of greenhouse gas load to the environment. The cement industry will remain one of the critical sectors for India to meet its CO2 emissions reduction target. India’s cement production will continue to grow in the near future due to its GDP growth. The control of population, improvement in plant efficiency and use of renewable energy are the important options for the mitigation of CO2 emissions from Indian cement industries

Applications of cardanol in rubber processing

This research project explores the utilization of cardanol in various capacities for rubber processing. Cardanol is a phenol with a long side chain in the meta position of the benzene ring. It is obtained by the vacuum distillation of cashew Hut shell liquid (CNSL) which is a cheap agro-byproduct. In this study, the plasticizer property of cardanol was investigated in silica filled and HAF black filled NR, NBR, EPDM and CR by comparing cure characteristics and mechanical properties of vulcanizates containing conventional plasticizer with those containing cardanol as plasticizer. The co-activator, antioxidant and accelerator properties were investigated in gum samples of NR, NBR, EPDM and CR by comparing the properties of vulcanizates which contain conventional co-activator, antioxidant and accelerator with those in which each of them was replaced by cardanol. The general effectiveness of cardanol was investigated by determination of cure time , measurement of physical and mechanical properties, ageing studies, crosslink density, extractability, FTIR spectra, TGA etc.The results show that cardanol can be a substitute for aromatic oil in both silica filled and HAF black filled NR. Again, it can replace dioctyl phthalate in both silica filled and HAF black filled NBR. Similarly, cardanol Can replace naphthenic oil in silica filled as well as HAF black filled EPDM and CR. The cure characteristics and mechanical properties are comparable in all the eight cases. The co-activator property of cardanol is comparable to stearic acid in all the four rubbers. The cure characteristics and mechanical properties in this case are also comparable. The antioxidant ,property of cardanol is comparable to TQ in all the four rubbers. The antioxidant property of cardanol is comparable to TQ in all the four case of NBR and EPDM.The accelerator property of cardarlol is comparable with CBS in the case of NBR and EPDM. No accelerator property is observed in the case of NR. The accelerator property of cardanol in CR is not negligible when compared with TMTD.

Modelling of Ultraviolet and Vissible Emissions in Comets

Comets are the spectacular objects in the night sky since the dawn of mankind. Due to their giant apparitions and enigmatic behavior, followed by coincidental calamities, they were termed as notorious and called as `bad omens'. With a systematic study of these objects modern scienti c community understood that these objects are part of our solar system. Comets are believed to be remnant bodies of at the end of evolution of solar system and possess the material of solar nebula. Hence, these are considered as most pristine objects which can provide the information about the conditions of solar nebula. These are small bodies of our solar system, with a typical size of about a kilometer to a few tens of kilometers orbiting the Sun in highly elliptical orbits. The solid body of a comet is nucleus which is a conglomerated mixture of water ice, dust and some other gases. When the cometary nucleus advances towards the Sun in its orbit the ices sublimates and produces the gaseous envelope around the nucleus which is called coma. The gravity of cometary nucleus is very small and hence can not in uence the motion of gases in the cometary coma. Though the cometary nucleus is a few kilometers in size they can produce a transient, extensive, and expanding atmosphere with size several orders of magnitude larger in space. By ejecting gas and dust into space comets became the most active members of the solar system. The solar radiation and the solar wind in uences the motion of dust and ions and produces dust and ion tails, respectively. Comets have been observed in di erent spectral regions from rocket, ground and space borne optical instruments. The observed emission intensities are used to quantify the chemical abundances of di erent species in the comets. The study of various physical and chemical processes that govern these emissions is essential before estimating chemical abundances in the coma. Cameron band emission of CO molecule has been used to derive CO2 abundance in the comets based on the assumption that photodissociation of CO2 mainly produces these emissions. Similarly, the atomic oxygen visible emissions have been used to probe H2O in the cometary coma. The observed green ([OI] 5577 A) to red-doublet emission ([OI] 6300 and 6364 A) ratio has been used to con rm H2O as the parent species of these emissions. In this thesis a model is developed to understand the photochemistry of these emissions and applied to several comets. The model calculated emission intensities are compared with the observations done by space borne instruments like International Ultraviolet Explorer (IUE) and Hubble Space Telescope (HST) and also by various ground based telescopes.

Design, Fabrication and Characterization of Passive and Active Polymer Photonic Devices

The rapid developments in fields such as fibre optic communication engineering and integrated optical electronics have expanded the interest and have increased the expectations about guided wave optics, in which optical waveguides and optical fibres play a central role. The technology of guided wave photonics now plays a role in generating information (guided-wave sensors) and processing information (spectral analysis, analog-to-digital conversion and other optical communication schemes) in addition to its original application of transmitting information (fibre optic communication). Passive and active polymer devices have generated much research interest recently because of the versatility of the fabrication techniques and the potential applications in two important areas – short distant communication network and special functionality optical devices such as amplifiers, switches and sensors. Polymer optical waveguides and fibres are often designed to have large cores with 10-1000 micrometer diameter to facilitate easy connection and splicing. Large diameter polymer optical fibres being less fragile and vastly easier to work with than glass fibres, are attractive in sensing applications. Sensors using commercial plastic optical fibres are based on ideas already used in silica glass sensors, but exploiting the flexible and cost effective nature of the plastic optical fibre for harsh environments and throw-away sensors. In the field of Photonics, considerable attention is centering on the use of polymer waveguides and fibres, as they have a great potential to create all-optical devices. By attaching organic dyes to the polymer system we can incorporate a variety of optical functions. Organic dye doped polymer waveguides and fibres are potential candidates for solid state gain media. High power and high gain optical amplification in organic dye-doped polymer waveguide amplifier is possible due to extremely large emission cross sections of dyes. Also, an extensive choice of organic dye dopants is possible resulting in amplification covering a wide range in the visible region.