Evaluation of roof slope and exposure with different roofing materials in reduced models of animal production facilities in spring and summer

The present study was conducted at the Department of Rural Engineering and the Department of Animal Morphology and Physiology of FCAV/Unesp, Jaboticabal, SP, Brazil. The objective was to verify the influence of roof slope, exposure and roofing material on the internal temperature of reduced models of animal production facilities. For the development of the research, 48 reduced and dissemble models with dimensions 1.00 × 1.00 × 0.50 m were used. The roof was shed-type, and the models faced to the North or South directions, with 24 models for each side of exposure. Ceramic, galvanized-steel and fibro tiles were used to build the roofs. Slopes varied between 20, 30, 40 and 50% for the ceramic tile and 10, 30, 40 and 50% for the other two. Inside the models, temperature readings were performed at every hour, for 12 months. The results were evaluated in a general linear model in a nested 3 × 4 × 2 factorial arrangement, in which the effects of roofing material and exposure were nested on the factor Slope. Means were compared by the Tukey test at 5% of probability. After analyzing the data, we observed that with the increase in the slope and exposure to the South, there was a drop in the internal temperature within the model at the geographic coordinates of Jaboticabal city (SP/Brazil).

Non-linear analysis of laminated metal matrix composites by an integrated micro/macro-mechanical model

The present paper describes an integrated micro/macro mechanical study of the elastic-viscoplastic behavior of unidirectional metal matrix composites (MMC). The micromechanical analysis of the elastic moduli is based on the Composites Cylinder Assemblage model (CCA) with comparisons also draw with a Representative Unit Cell (RUC) technique. These "homogenization" techniques are later incorporated into the Vanishing Fiber Diameter (VFD) model and a new formulation is proposed. The concept of a smeared element procedure is employed in conjunction with two different versions of the Bodner and Partom elastic-viscoplastic constitutive model for the associated macroscopic analysis. The formulations developed are also compared against experimental and analytical results available in the literature.

The design, synthesis and characterization of new building blocks for the preparation of molecule-based magnetic materials /

Two new families of building blocks have been prepared and fully characterized and their coordination chemistry exploited for the preparation of molecule-based magnetic materials. The first class of compounds were prepared by exploiting the chemistry of 3,3'-diamino-2,2'-bipyridine together with 2-pyridine carbonyl chloride or 2-pyridine aldehyde. Two new ligands, 2,2'-bipyridine-3,3'-[2-pyridinecarboxamide] (Li, 2.3) and N'-6/s(2-pyridylmethyl) [2,2'bipyridine]-3,3'-diimine (L2, 2.7), were prepared and characterized. For ligand L4, two copper(II) coordination compounds were isolated with stoichiometrics [Cu2(Li)(hfac)2] (2.4) and [Cu(Li)Cl2] (2.5). The molecular structures of both complexes were determined by X-ray crystallography. In both complexes the ligand is in the dianionic form and coordinates the divalent Cu(II) ions via one amido and two pyridine nitrogen donor atoms. In (2.4), the coordination geometry around both Cu11 ions is best described as distorted trigonal bipyramidal where the remaining two coordination sites are satisfied by hfac counterions. In (2.5), both Cu(II) ions adopt a (4+1) distorted square pyramidal geometry. One copper forms a longer apical bond to an adjacent carbonyl oxygen atom, whereas the second copper is chelated to a neighboring Cu-Cl chloride ion to afford chloride bridged linear [Cu2(Li)Cl2]2 tetramers that run along the c-axis of the unit cell. The magnetic susceptibility data for (2.4) reveal the occurrence of weak antiferromagnetic interactions between the copper(II) ions. In contrast, variable temperature magnetic susceptibility measurements for (2.5) reveal more complex magnetic properties with the presence of ferromagnetic exchange between the central dimeric pair of copper atoms and weak antiferromagnetic exchange between the outer pairs of copper atoms. The Schiff-base bis-imine ligand (L2, 2.7) was found to be highly reactive; single crystals grown from dry methanol afforded compound (2.14) for which two methanol molecules had added across the imine double bond. The susceptibility of this ligand to nucleophilic attack at its imine functionality assisted via chelation to Lewis acidic metal ions adds an interesting dimension to its coordination chemistry. In this respect, a Co(II) quaterpyridine-type complex was prepared via a one-pot transformation of ligand L2 in the presence of a Lewis acidic metal salt. The rearranged complex was characterized by X-ray crystallography and a reaction mechanism for its formation has been proposed. Three additional rearranged complexes (2.13), (2.17) and (2.19) were also isolated when ligand (L2, 2.7) was reacted with transition metal ions. The molecular structures of all three complexes have been determined by X-ray crystallography. The second class of compounds that are reported in this thesis, are the two diacetyl pyridine derivatives, 4-pyridyl-2,6-diacetylpyridine (5.5) and 2,2'-6,6'-tetraacetyl-4,4'-bipyridine (5.15). Both of these compounds have been designed as intermediates for the metal templated assembly of a Schiff-base N3O2 macrocycle. From compound (5.15), a covalently tethered dimeric Mn(II) macrocyclic compound of general formula {[Mn^C^XJCl-FkO^Cl-lO.SFbO (5.16) was prepared and characterized. The X-ray analysis of (5.16) reveals that the two manganese ions assume a pentagonal-bipyramidal geometry with the macrocycle occupying the pentagonal plane and the axial positions being filled by a halide ion and a H2O molecule. Magnetic susceptibility data reveal the occurrence of antiferromagnetic interactions between covalently tethered Mn(II)-Mn(II) dimeric units. Following this methodology a Co(II) analogue (5.17) has also been prepared which is isostructural with (5.16).

Investigation of the composition of linear alkylbenzenes with emphasis on the identification and quantitation of some trace compounds using GS/MS system in both electron impact and chemical ionization modes

Linear alkylbenzenes, LAB, formed by the Alel3 or HF catalyzed alkylation of benzene are common raw materials for surfactant manufacture. Normally they are sulphonated using S03 or oleum to give the corresponding linear alkylbenzene sulphonates In >95 % yield. As concern has grown about the environmental impact of surfactants,' questions have been raised about the trace levels of unreacted raw materials, linear alkylbenzenes and minor impurities present in them. With the advent of modem analytical instruments and techniques, namely GCIMS, the opportunity has arisen to identify the exact nature of these impurities and to determine the actual levels of them present in the commercial linear ,alkylbenzenes. The object of the proposed study was to separate, identify and quantify major and minor components (1-10%) in commercial linear alkylbenzenes. The focus of this study was on the structure elucidation and determination of impurities and on the qualitative determination of them in all analyzed linear alkylbenzene samples. A gas chromatography/mass spectrometry, (GCIMS) study was performed o~ five samples from the same manufacturer (different production dates) and then it was followed by the analyses of ten commercial linear alkylbenzenes from four different suppliers. All the major components, namely linear alkylbenzene isomers, followed the same elution pattern with the 2-phenyl isomer eluting last. The individual isomers were identified by interpretation of their electron impact and chemical ionization mass spectra. The percent isomer distribution was found to be different from sample to sample. Average molecular weights were calculated using two methods, GC and GCIMS, and compared with the results reported on the Certificate of Analyses (C.O.A.) provided by the manufacturers of commercial linear alkylbenzenes. The GC results in most cases agreed with the reported values, whereas GC/MS results were significantly lower, between 0.41 and 3.29 amu. The minor components, impurities such as branched alkylbenzenes and dialkyltetralins eluted according to their molecular weights. Their fragmentation patterns were studied using electron impact ionization mode and their molecular weight ions confirmed by a 'soft ionization technique', chemical ionization. The level of impurities present i~ the analyzed commercial linear alkylbenzenes was expressed as the percent of the total sample weight, as well as, in mg/g. The percent of impurities was observed to vary between 4.5 % and 16.8 % with the highest being in sample "I". Quantitation (mg/g) of impurities such as branched alkylbenzenes and dialkyltetralins was done using cis/trans-l,4,6,7-tetramethyltetralin as an internal standard. Samples were analyzed using .GC/MS system operating under full scan and single ion monitoring data acquisition modes. The latter data acquisition mode, which offers higher sensitivity, was used to analyze all samples under investigation for presence of linear dialkyltetralins. Dialkyltetralins were reported quantitatively, whereas branched alkylbenzenes were reported semi-qualitatively. The GC/MS method that was developed during the course of this study allowed identification of some other trace impurities present in commercial LABs. Compounds such as non-linear dialkyltetralins, dialkylindanes, diphenylalkanes and alkylnaphthalenes were identified but their detailed structure elucidation and the quantitation was beyond the scope of this study. However, further investigation of these compounds will be the subject of a future study.

Linear block copolymers of L–lactide and 2–dimethylaminoethyl methacrylate : synthesis and properties

Part of the research described in this thesis is conducted in collaboration with Centre d' étude et de Recherche sur les Macromolécules (CERM), Université de Liège, Sart-Tilman, Belgium

Studies on Thermoplastic Elastomer Based on Linear Low-Density Polyethylene and Latex Product Waste Modified with Thiocarbanilide

Latex waste like glove waste was effectively modified using a new reclaiming agent, thiocarbanilide. This modified waste was blended with linear low-density polyethylene (LLDPE) to develop a novel thermoplastic elastomer. Both uncrosslinked and dynamically crosslinked blends were prepared and their properties were studied. The results were found to be comparable to those of conventional thermoplastic elastomers.

Mathematical Modelling of the Dynamics of Granular Materials in a Rotating Cylinder

The current study is aimed at the development of a theoretical simulation tool based on Discrete Element Method (DEM) to 'interpret granular dynamics of solid bed in the cross section of the horizontal rotating cylinder at the microscopic level and subsequently apply this model to establish the transition behaviour, mixing and segregation.The simulation of the granular motion developed in this work is based on solving Newton's equation of motion for each particle in the granular bed subjected to the collisional forces, external forces and boundary forces. At every instant of time, the forces are tracked and the positions velocities and accelarations of each partcle is The software code for this simulation is written in VISUAL FORTRAN 90 After checking the validity of the code with special tests, it is used to investigate the transition behaviour of granular solids motion in the cross section of a rotating cylinder for various rotational speeds and fill fraction.This work is hence directed towards a theoretical investigation based on Discrete Element Method (DEM) of the motion of granular solids in the radial direction of the horizontal cylinder to elucidate the relationship between the operating parameters of the rotating cylinder geometry and physical properties ofthe granular solid.The operating parameters of the rotating cylinder include the various rotational velocities of the cylinder and volumetric fill. The physical properties of the granular solids include particle sizes, densities, stiffness coefficients, and coefficient of friction Further the work highlights the fundamental basis for the important phenomena of the system namely; (i) the different modes of solids motion observed in a transverse crosssection of the rotating cylinder for various rotational speeds, (ii) the radial mixing of the granular solid in terms of active layer depth (iii) rate coefficient of mixing as well as the transition behaviour in terms of the bed turnover time and rotational speed and (iv) the segregation mechanisms resulting from differences in the size and density of particles.The transition behaviour involving its six different modes of motion of the granular solid bed is quantified in terms of Froude number and the results obtained are validated with experimental and theoretical results reported in the literature The transition from slumping to rolling mode is quantified using the bed turnover time and a linear relationship is established between the bed turn over time and the inverse of the rotational speed of the cylinder as predicted by Davidson et al. [2000]. The effect of the rotational speed, fill fraction and coefficient of friction on the dynamic angle of repose are presented and discussed. The variation of active layer depth with respect to fill fraction and rotational speed have been investigated. The results obtained through simulation are compared with the experimental results reported by Van Puyvelde et. at. [2000] and Ding et at. [2002].The theoretical model has been further extended, to study the rmxmg and segregation in the transverse direction for different particle sizes and their size ratios. The effect of fill fraction and rotational speed on the transverse mixing behaviour is presented in the form of a mixing index and mixing kinetics curve. The segregation pattern obtained by the simulation of the granular solid bed with respect to the rotational speed of the cylinder is presented both in graphical and numerical forms. The segregation behaviour of the granular solid bed with respect to particle size, density and volume fraction of particle size has been investigated. Several important macro parameters characterising segregation such as mixing index, percolation index and segregation index have been derived from the simulation tool based on first principles developed in this work.

Linear and nonlinear optical characteristics of ZnO-SiO2 nanocomposites.

We present the spectral and nonlinear optical properties of ZnO-SiO2 nanocomposites prepared by colloidal chemical synthesis. Obvious enhancement of ultraviolet (UV) emission of the samples is observed, and the strongest UV emission of a typical ZnO-SiO2 nanocomposite is over three times stronger than that of pure ZnO. The nonlinearity of the silica colloid is low, and its nonlinear response can be improved by making composites with ZnO. These nanocomposites show self-defocusing nonlinearity and good nonlinear absorption behavior. The observed nonlinear absorption is explained through two photon absorption followed by weak free carrier absorption and nonlinear scattering. The nonlinear refractive index and the nonlinear absorption increase with increasing ZnO volume fraction and can be attributed to the enhancement of exciton oscillator strength. ZnO-SiO2 is a potential nanocomposite material for the UV light emission and for the development of nonlinear optical devices with a relatively small limiting threshold.

Laser Spectroscopy: TDLAS instrumentation and NIR analysis of some organic materials

Near-infrared spectroscopy can be a workhorse technique for materials analysis in industries such as agriculture, pharmaceuticals, chemicals and polymers. A near-infrared spectrum represents combination bands and overtone bands that are harmonics of absorption frequencies in the mid-infrared. Near-infrared absorption includes a combination-band region immediately adjacent to the mid-infrared and three overtone regions. All four near-infrared regions contain "echoes" of the fundamental mid-infrared absorptions. For example, vibrations in the mid-infrared due to the C-H stretches will produce four distinct bands in each of the overtone and combination regions. As the bands become more removed from the fundamental frequencies they become more widely separated from their neighbors, more broadened and are dramatically reduced in intensity. Because near-infrared bands are much less intense, more of the sample can be used to produce a spectra and with near-infrared, sample preparation activities are greatly reduced or eliminated so more of the sample can be utilized. In addition, long path lengths and the ability to sample through glass in the near-infrared allows samples to be measured in common media such as culture tubes, cuvettes and reaction bottles. This is unlike mid-infrared where very small amounts of a sample produce a strong spectrum; thus sample preparation techniques must be employed to limit the amount of the sample that interacts with the beam. In the present work we describe the successful the fabrication and calibration of a linear high resolution linear spectrometer using tunable diode laser and a 36 m path length cell and meuurement of a highly resolved structure of OH group in methanol in the transition region A v =3. We then analyse the NIR spectrum of certain aromatic molecules and study the substituent effects using local mode theory

Exploring oligo(p-phenylenevinylene) gelators as sensors and stimuli responsive materials

Gelation provides a unique medium, which often induces organization of molecules resulting in the modulation of their optical, morphological and electronic properties thereby opening a new world of fascinating materials with interesting physical properties at nano- meso- and macroscopic levels. Supramolecular gels based on linear π-systems have attracted much attention due to their inherent optical and electronic properties which find application in organic electronics, light harvesting and sensing. They exhibit reversible properties due to the dynamic nature of noncovalent forces. As a result, studies on such soft materials are currently a topic of great interest. Recently, researchers are actively involved in the development of sensors and stimuli-responsive materials based on self-assembled π-systems, which are also called smart materials. The present thesis is divided into four chapters

Investigations on Nonlinear and Radiative Properties of Certain Phatonic Materials

Light in its physical and philosophical sense has captured the imagination of human mind right from the dawn of civilization. The invention of lasers in the 60’s caused a renaissance in the field of optics. This intense, monochromatic, highly directional radiation created new frontiers in science and technology. The strong oscillating electric field of laser radiation creates a. polarisation response that is nonlinear in character in the medium through which it passes and the medium acts as a new source of optical field with alternate properties. It was in this context, that the field of optoelectronics which encompasses the generation, modulation, transmission etc. of optical radiation has gained tremendous importance. Organic molecules and polymeric systems have emerged as a class of promising materials of optoelectronics because they offer the flexibility, both at the molecular and bulk levels, to optimize the nonlinearity and other suitable properties for device applications. Organic nonlinear optical media, which yield large third-order nonlinearities, have been widely studied to develop optical devices like high speed switches, optical limiters etc. Transparent polymeric materials have found one of their most promising applicationsin lasers, in which they can be used as active elements with suitable laser dyes doped in it. The solid-matrix dye lasers make possible combination of the advantages of solid state lasers with the possibility of tuning the radiation over a broad spectral range. The polymeric matrices impregnated with organic dyes have not yet widely used because of the low resistance of the polymeric matrices to laser damage, their low dye photostability, and low dye stability over longer time of operation and storage. In this thesis we investigate the nonlinear and radiative properties of certain organic materials and doped polymeric matrix and their possible role in device development

Investigations on TiO2 Based Nanocomposites as Potential Photonic Materials

This Study overviews the basics of TiO2with respect to its structure, properties and applications. A brief account of its structural, electronic and optical properties is provided. Various emerging technological applications utilising TiO2 is also discussed.Till now, exceptionally large number of fundamental studies and application-oriented research and developments has been carried out by many researchers worldwide in TiO2 with its low-dimensional nanomaterial form due to its various novel properties. These nanostructured materials have shown many favourable properties for potential applications, including pollutant photocatalytic decomposition, photovoltaic cells, sensors and so on. This thesis aims to make an in-depth investigation on different linear and nonlinear optical and structural characteristics of different phases of TiO2. Correspondingly, extensive challenges to synthesise different high quality TiO2 nanostructure derivatives such as nanotubes, nanospheres, nanoflowers etc. are continuing. Here, different nanostructures of anatase TiO2 were synthesised and analysed. Morphologically different nanostructures were found to have different impact on their physical and electronic properties such as varied surface area, dissimilar quantum confinement and hence diverged suitability for different applications. In view of the advantages of TiO2, it can act as an excellent matrix for nanoparticle composite films. These composite films may lead to several advantageous functional optical characteristics. Detailed investigations of these kinds of nanocomposites were also performed, only to find that these nanocomposites showed higher adeptness than their parent material. Fine tuning of these parameters helps researchers to achieve high proficiency in their respective applications. These innumerable opportunities aims to encompass the new progress in studies related to TiO2 for an efficient utilization in photo-catalytic or photo-voltaic applications under visible light, accentuate the future trends of TiO2-research in the environment as well as energy related fields serving promising applications benefitting the mankind. The last section of the thesis discusses the applicability of analysed nanomaterials for dye sensitised solar cells followed by future suggestions.

Non-linear mechanical behavior of the elastomer polydimethylsiloxane (PDMS) used in the manufacture of microfluidic devices

Polydimethylsiloxane (PDMS) is the elastomer of choice to create a variety of microfluidic devices by soft lithography techniques (eg., [1], [2], [3], [4]). Accurate and reliable design, manufacture, and operation of microfluidic devices made from PDMS, require a detailed characterization of the deformation and failure behavior of the material. This paper discusses progress in a recently-initiated research project towards this goal. We have conducted large-deformation tension and compression experiments on traditional macroscale specimens, as well as microscale tension experiments on thin-film (≈ 50µm thickness) specimens of PDMS with varying ratios of monomer:curing agent (5:1, 10:1, 20:1). We find that the stress-stretch response of these materials shows significant variability, even for nominally identically prepared specimens. A non-linear, large-deformation rubber-elasticity model [5], [6] is applied to represent the behavior of PDMS. The constitutive model has been implemented in a finite-element program [7] to aid the design of microfluidic devices made from this material. As a first attempt towards the goal of estimating the non-linear material parameters for PDMS from indentation experiments, we have conducted micro-indentation experiments using a spherical indenter-tip, and carried out corresponding numerical simulations to verify how well the numerically-predicted P(load-h(depth of indentation) curves compare with the corresponding experimental measurements. The results are encouraging, and show the possibility of estimating the material parameters for PDMS from relatively simple micro-indentation experiments, and corresponding numerical simulations.

Case based reasoning as an extension of fault dictionary methods for linear electronic analog circuits diagnosis

El test de circuits és una fase del procés de producció que cada vegada pren més importància quan es desenvolupa un nou producte. Les tècniques de test i diagnosi per a circuits digitals han estat desenvolupades i automatitzades amb èxit, mentre que aquest no és encara el cas dels circuits analògics. D'entre tots els mètodes proposats per diagnosticar circuits analògics els més utilitzats són els diccionaris de falles. En aquesta tesi se'n descriuen alguns, tot analitzant-ne els seus avantatges i inconvenients. Durant aquests últims anys, les tècniques d'Intel·ligència Artificial han esdevingut un dels camps de recerca més importants per a la diagnosi de falles. Aquesta tesi desenvolupa dues d'aquestes tècniques per tal de cobrir algunes de les mancances que presenten els diccionaris de falles. La primera proposta es basa en construir un sistema fuzzy com a eina per identificar. Els resultats obtinguts son força bons, ja que s'aconsegueix localitzar la falla en un elevat tant percent dels casos. Per altra banda, el percentatge d'encerts no és prou bo quan a més a més s'intenta esbrinar la desviació. Com que els diccionaris de falles es poden veure com una aproximació simplificada al Raonament Basat en Casos (CBR), la segona proposta fa una extensió dels diccionaris de falles cap a un sistema CBR. El propòsit no és donar una solució general del problema sinó contribuir amb una nova metodologia. Aquesta consisteix en millorar la diagnosis dels diccionaris de falles mitjançant l'addició i l'adaptació dels nous casos per tal d'esdevenir un sistema de Raonament Basat en Casos. Es descriu l'estructura de la base de casos així com les tasques d'extracció, de reutilització, de revisió i de retenció, fent èmfasi al procés d'aprenentatge. En el transcurs del text s'utilitzen diversos circuits per mostrar exemples dels mètodes de test descrits, però en particular el filtre biquadràtic és l'utilitzat per provar les metodologies plantejades, ja que és un dels benchmarks proposats en el context dels circuits analògics. Les falles considerades son paramètriques, permanents, independents i simples, encara que la metodologia pot ser fàcilment extrapolable per a la diagnosi de falles múltiples i catastròfiques. El mètode es centra en el test dels components passius, encara que també es podria extendre per a falles en els actius.

Enhanced second order non-linear optical properties of silica sol-gel thin films through photo-induced poling

Sol-gel derived inorganic materials are of interest as hosts for non-linear optically active guest molecules and they offer particular advantages in the field of non-linear optics. Orientationally ordered glasses have been prepared using a sol-gel system based on tetramethoxysilane, methyltrimethoxysilane and a non-linear optical chromophore Disperse Red 1. The novel technique of photo-induced poling was used to generate enhanced levels of polar order. The level of enhancement is strongly dependent on the extent of gelation and an optimum preparation time of ∼100 h led to an enhancement factor of ∼5. Films prepared in this manner exhibited a high stability of the polar order.