923 resultados para metal trace analysis


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In this thesis, the applications of the recurrence quantification analysis in metal cutting operation in a lathe, with specific objective to detect tool wear and chatter, are presented.This study is based on the discovery that process dynamics in a lathe is low dimensional chaotic. It implies that the machine dynamics is controllable using principles of chaos theory. This understanding is to revolutionize the feature extraction methodologies used in condition monitoring systems as conventional linear methods or models are incapable of capturing the critical and strange behaviors associated with the metal cutting process.As sensor based approaches provide an automated and cost effective way to monitor and control, an efficient feature extraction methodology based on nonlinear time series analysis is much more demanding. The task here is more complex when the information has to be deduced solely from sensor signals since traditional methods do not address the issue of how to treat noise present in real-world processes and its non-stationarity. In an effort to get over these two issues to the maximum possible, this thesis adopts the recurrence quantification analysis methodology in the study since this feature extraction technique is found to be robust against noise and stationarity in the signals.The work consists of two different sets of experiments in a lathe; set-I and set-2. The experiment, set-I, study the influence of tool wear on the RQA variables whereas the set-2 is carried out to identify the sensitive RQA variables to machine tool chatter followed by its validation in actual cutting. To obtain the bounds of the spectrum of the significant RQA variable values, in set-i, a fresh tool and a worn tool are used for cutting. The first part of the set-2 experiments uses a stepped shaft in order to create chatter at a known location. And the second part uses a conical section having a uniform taper along the axis for creating chatter to onset at some distance from the smaller end by gradually increasing the depth of cut while keeping the spindle speed and feed rate constant.The study concludes by revealing the dependence of certain RQA variables; percent determinism, percent recurrence and entropy, to tool wear and chatter unambiguously. The performances of the results establish this methodology to be viable for detection of tool wear and chatter in metal cutting operation in a lathe. The key reason is that the dynamics of the system under study have been nonlinear and the recurrence quantification analysis can characterize them adequately.This work establishes that principles and practice of machining can be considerably benefited and advanced from using nonlinear dynamics and chaos theory.

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The thesis is an introduction to our attempts to evaluate the coordination behaviour of a few compounds of our interest. Semicarbazones and their metal complexes have been an active area of research during the past years because of the beneficial biological activities of these substances. Tridentate NNO semicarbazone systems formed from heterocyclic and aromatic carbonyl compounds and their transition metal complexes are well-authenticated compounds in this field and their synthesis and characterization are well desirable. Hence, we decided to develop a research program aimed at the synthesis and characterization of novel semicarbazones derived from 2-benzoylpyridine and 2-acetylpyridine and their transition metal complexes. In addition to various physicochemical methods of analysis, single crystal X—Ray diffraction studies were also used for the characterization of the complexes.

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Modern computer systems are plagued with stability and security problems: applications lose data, web servers are hacked, and systems crash under heavy load. Many of these problems or anomalies arise from rare program behavior caused by attacks or errors. A substantial percentage of the web-based attacks are due to buffer overflows. Many methods have been devised to detect and prevent anomalous situations that arise from buffer overflows. The current state-of-art of anomaly detection systems is relatively primitive and mainly depend on static code checking to take care of buffer overflow attacks. For protection, Stack Guards and I-leap Guards are also used in wide varieties.This dissertation proposes an anomaly detection system, based on frequencies of system calls in the system call trace. System call traces represented as frequency sequences are profiled using sequence sets. A sequence set is identified by the starting sequence and frequencies of specific system calls. The deviations of the current input sequence from the corresponding normal profile in the frequency pattern of system calls is computed and expressed as an anomaly score. A simple Bayesian model is used for an accurate detection.Experimental results are reported which show that frequency of system calls represented using sequence sets, captures the normal behavior of programs under normal conditions of usage. This captured behavior allows the system to detect anomalies with a low rate of false positives. Data are presented which show that Bayesian Network on frequency variations responds effectively to induced buffer overflows. It can also help administrators to detect deviations in program flow introduced due to errors.

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Polymer supports are efficient reagents,substrates and catalysts and they are extensively used for carrying out reactions at controlled rates.Tailor-made polymer supports are highly versatile which have opened an excellent area of research.Now polymer supported chemistry is being exploited at an amazing rate and it seems to join the routine world of organic synthesis.Polymer supported ligands are found to be efficient complexing agents whose high selectivity enables the analysis and removal of heavy metal ions which are toxic to all the living organisms of land and sea.polymer supported membranes function as ion selective potentiometric sensors which allow the exchange of specific ions among other ions of the same charge.In this investigation three series of polymeric schiff bases and three series of metal complexes have been prepared.An attempt is done to develop optimum conditions for the removal of heavy metal ions using polymeric schiff bases.A novel copper sensor electrode have also been prepared from polymer supported metal complex.

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The thesis is an introduction to evaluate the coordination behaviour of a few compounds of our interest. The crucial aim of these investigations was to synthesize and characterize some transition metal complexes using the ligands benzaldehyde, 2-hydroxybenzaldehyde and 4-methoxybenzaldehyde N(4)-ring incorporated thiosemicarbazones.The study involves a brief foreword of the metal complexes of thiosemicarbazones including their bonding, stereochemistry and biological activities.The different analytical and spectroscopic techniques used for the analysis of the ligands and their complexes are discussed.It also deals with the synthesis and spectral characterization of the thiosemicarbazones and single crystal X-ray diffraction study of one of them.Chapter 3 describes the synthesis, spectral characterization, single crystal X-ray diffraction studies of copper(ll) complexes with ONS/NS donor thiosemicarbazones. Chapter 4 deals with the synthesis, spectral characterization and single crystal X-ray diffraction studies of nickel(II) complexes. Chapter 5 contains the synthesis, structural and spectral characterization of the cobalt(III) complexes. Chapters 6 and 7 include the synthesis, structural and spectral characterization of zinc(II) and cadmium(ll) complexes with ONS/NS donor thiosemicarbazones.

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Natural systems are inherently non linear. Recurrent behaviours are typical of natural systems. Recurrence is a fundamental property of non linear dynamical systems which can be exploited to characterize the system behaviour effectively. Cross recurrence based analysis of sensor signals from non linear dynamical system is presented in this thesis. The mutual dependency among relatively independent components of a system is referred as coupling. The analysis is done for a mechanically coupled system specifically designed for conducting experiment. Further, cross recurrence method is extended to the actual machining process in a lathe to characterize the chatter during turning. The result is verified by permutation entropy method. Conventional linear methods or models are incapable of capturing the critical and strange behaviours associated with the dynamical process. Hence any effective feature extraction methodologies should invariably gather information thorough nonlinear time series analysis. The sensor signals from the dynamical system normally contain noise and non stationarity. In an effort to get over these two issues to the maximum possible extent, this work adopts the cross recurrence quantification analysis (CRQA) methodology since it is found to be robust against noise and stationarity in the signals. The study reveals that the CRQA is capable of characterizing even weak coupling among system signals. It also divulges the dependence of certain CRQA variables like percent determinism, percent recurrence and entropy to chatter unambiguously. The surrogate data test shows that the results obtained by CRQA are the true properties of the temporal evolution of the dynamics and contain a degree of deterministic structure. The results are verified using permutation entropy (PE) to detect the onset of chatter from the time series. The present study ascertains that this CRP based methodology is capable of recognizing the transition from regular cutting to the chatter cutting irrespective of the machining parameters or work piece material. The results establish this methodology to be feasible for detection of chatter in metal cutting operation in a lathe.

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The research work which was carried out to Synergic Reactions in the Estuarine Environment leading to Modulation of Aluminium metal during Transport Processes (in Cochin Estuary)Estuaries are considered as sink or source for terrestrial and various anthropogenically generated materials. These include naturally occurring elements Al, Si, Fe or trace inorganics or industrial pollutants of different types. There have been reports on both positive and negative impacts by the introduction of above materials into the ecosystem.This thesis deals with the trace metal Aluminium (Al) whose average concentration (about 8%) in the earths crust is surpassed only by that of Oxygen and Silicon. There can be no doubt that most of the land derived materials reaches the ocean through rivers via estuaries. An important aspect noticed here is that the concentration of dissolved Al is much lower in sea water than in river water.On critically analysing Cochin estuary, for the entire cycles, covering monsoon, postmonsoon and premonsoon, the following salient features are documented as hereunder. Dissolved Al exhibits high and variable trends in Cochin estuary, the influencing parameters being salinity, SPM, pH and dissolved Si. A general profile showed removal in upper/mid estuary followed by regeneration in the mid/lower estuary and further decrease seawards in the southern/northem arms.Distribution appears to be a function of freshwater input, the monsoon season exhibiting very high concentrations throughout the estuary. As the river discharge decreased with the progress of seasons, dissolved Al concentration also decreased, the metal limiting itself to the upper and mid estuary.

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The present study is an attempt at investigating the intercompartmental exchange of trace metals (copper, cadmium, zinc, lead and nickel) in the Cochin estuary. The nature and extent of distribution in the different compartments with special reference to the transport from environmental compartments to biological compartments have been dealt with in detail. The suitability of the shells of Villorita cyprinoides var cochinensis (Hanely) in pollution monitoring activities has been assessed. A mathematical model (SAAMPLE - Shells in the Assessment of Aquatic Metal Pollution Levels) based on kinetic laws that govern the intercompartmental exchange has been proposed.

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Thiosemicarbazones have recently attracted considerable attention due to their ability to form tridentate chelates with transition metal ions through either two nitrogen and sulfur atoms, N–N–S or oxygen, nitrogen and sulfur atoms, O–N–S. Considerable interest in thiosemicarbazones and their transition metal complexes has also grown in the areas of biology and chemistry due to biological activities such as antitumoral, fungicidal, bactericidal, antiviral and nonlinear optical properties. They have been used for metal analyses, for device applications related to telecommunications, optical computing, storage and information processing.The versatile applications of metal complexes of thiosemicarbazones in various fields prompted us to synthesize the tridentate NNS-donor thiosemicarbazones and their metal complexes. As a part of our studies on transition metal complexes with these ligands, the researcher undertook the current work with the following objectives. 1. To synthesize and physico-chemically characterize the following thiosemicarbazone ligands: a. Di-2-pyridyl ketone-N(4)-methyl thiosemicarbazone (HDpyMeTsc) b. Di-2-pyridyl ketone-N(4)-ethyl thiosemicarbazone (HDpyETsc) 2. To synthesize oxovanadium(IV), manganese(II), nickel(II), copper(II), zinc(II) and cadmium(II) complexes using the synthesized thiosemicarbazones as principal ligands and some anionic coligands. 3. To study the coordination modes of the ligands in metal complexes by using different physicochemical methods like partial elemental analysis, thermogravimetry and by different spectroscopic techniques. 4. To establish the structure of compounds by single crystal XRD studies

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Mangroves are considered to play a significant role in global carbon cycling. Themangrove forests would fix CO2 by photosynthesis into mangrove lumber and thus decrease the possibility of a catastrophic series of events - global warming by atmospheric CO2, melting of the polar ice caps, and inundation of the great coastal cities of the world. The leaf litter and roots are the main contributors to mangrove sediments, though algal production and allochthonous detritus can also be trapped (Kristensen et al, 2008) by mangroves due to their high organic matter content and reducing nature are excellent metal retainers. Environmental pollution due to metals is of major concern. This is due to the basic fact that metals are not biodegradable or perishable the way most organic pollutants are. While most organic toxicants can be destroyed by combustion and converted into compounds such as C0, C02, SOX, NOX, metals can't be destroyed. At the most the valance and physical form of metals may change. Concentration of metals present naturally in air, water and soil is very low. Metals released into the environment through anthropogenic activities such as burning of fossils fuels, discharge of industrial effluents, mining, dumping of sewage etc leads to the development of higher than tolerable or toxic levels of metals in the environment leading to metal pollution. Of course, a large number of heavy metals such as Fe, Mn, Cu, Ni, Zn, Co, Cr, Mo, and V are essential to plants and animals and deficiency of these metals may lead to diseases, but at higher levels, it would lead to metal toxicity. Almost all industrial processes and urban activities involve release of at least trace quantities of half a dozen metals in different forms. Heavy metal pollution in the environment can remain dormant for a long time and surface with a vengeance. Once an area gets toxified with metals, it is almost impossible to detoxify it. The symptoms of metal toxicity are often quite similar to the symptoms of other common diseases such as respiratory problems, digestive disorders, skin diseases, hypertension, diabetes, jaundice etc making it all the more difficult to diagnose metal poisoning. For example the Minamata disease caused by mercury pollution in addition to affecting the nervous system can disturb liver function and cause diabetes and hypertension. The damage caused by heavy metals does not end up with the affected person. The harmful effects can be transferred to the person's progenies. Ironically heavy metal pollution is a direct offshoot of our increasing ability to mass produce metals and use them in all spheres of existence. Along with conventional physico- chemical methods, biosystem approachment is also being constantly used for combating metal pollution

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Environmental persistence, fate and interactive effects with living organisms - beneficial or toxic - of trace elements are directly related to the physico-chemical forms in which they occur. Knowledge on the association of trace metals with different environmental compartments in an aquatic system are, therefore, essential for monitoring the trace metal pollution as well as transport, fate and bio-geochemical cycles of trace metals. This thesis is a modest attempt in assessing the trace metal levels and their behaviour in the aquatic environment of Kuttanad, an aquatic system that is severely affected by man's intervention on natural processes, by seriously evaluating the levels of trace metals in dissolved and particulate phases and also in the different chemical fractions of the sediments.

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The role of the bridging ligand on the effective Heisenberg coupling parameters is analyzed in detail. This analysis strongly suggests that the ligand-to-metal charge transfer excitations are responsible for a large part of the final value of the magnetic coupling constant. This permits us to suggest a variant of the difference dedicated configuration interaction (DDCI) method, presently one of the most accurate and reliable for the evaluation of magnetic effective interactions. This method treats the bridging ligand orbitals mediating the interaction at the same level than the magnetic orbitals and preserves the high quality of the DDCI results while being much less computationally demanding. The numerical accuracy of the new approach is illustrated on various systems with one or two magnetic electrons per magnetic center. The fact that accurate results can be obtained using a rather reduced configuration interaction space opens the possibility to study more complex systems with many magnetic centers and/or many electrons per center.

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This thesis deals with the studies on the synthesis and characterisation of the complexes of embelin with manganese (II), cobalt(II), nickel (II), copper (II), zinc (II), cadmium (II), chromium (III), iron (III) lanthanum(III), praseodymium (III) neodymium (III) Samarium (III), gadolinium (III) dysprosium (III), yttrium (III) thorium (IV) and uranium (VI). Elemental analysis as well as spectral, thermal and magnetic data were used to ascertain the composition of the complexes and to establish the structures of the metal complexes. Wherever possible, the electronic spectra and magnetic data were used to predict the stereochemistry of the complexes.The thesis is divided into four chapters.

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This thesis is an attempt by the author to assess the suitability of Metapenaeus dobsoni (Miers), an economically important crustacean species as a sentinel organism of trace metal pollution. The results of detailed investigations on seasonal variation, bioassay, accumulation and depuration of three metals viz., mercury, copper and zinc are presented and discussed. The importance of trace metals in the aquatic environment and their present status in the study area - Cochin backwaters, the significance of crustacean fisheries, the species M. dobsoni and the objectives of the present studies are described in Chapter 1. The methodology adopted during the investigation is given in Chapter 2. Chapter 3 delineates the seasonal variation of Hg, Cu and Zn in the edible and non-edible parts of M. dobsoni collected from Cochin backwaters for a period of one year (June 1984-May 1985). The results of bioassay experiments are given in Chapter 4. Kinetics of accumulation ,retention and depuration of trace metals, their biological half-life, the influence of size group and environmental factors are given in Chapter 5. The effect of these metals on the physiological response of M. dobsoni viz. oxygen consumption is included in Chapter 6. A summary and list of references are also appended.

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The present work is focused on the organelle and biochemical responses to heavy metal exposure in the fish Oreochromis mossambicus giving particular importance to the metal detoxifying machinery of the organism. The thesis is an outcome of the effort aimed at developing practicable monitoring techniques to deliver guidelines for biological effect monitoring and the need for specific biochemical methods to detect biological effects of heavy metals that can be interpreted in terms of the health status of the individual organism and eventually alterations in vital processes as growth and reproduction. The efficiency of the metal detoxifying metallothioneins which is an attractive tool for biological monitoring, their role as scavengers of trace metal ions and thus in relieving the biological machinery from their toxicity effects are important themes of this study. Efforts have also been made to test the reliability of the spill over hypothesis of the action of metallothioneins (Winge et a1.,1973) and their use as a biological barometer of heavy metal stress.