Titanium(IV)-EDTA complex - Kinetics of thermal decomposition by non-isothermal procedures

This work aims the evaluation of the kinetic triplets corresponding to the two successive steps of thermal decomposition of Ti(IV)-ethylenediaminetetraacetate complex. Applying the isoconversional Wall-Flynn-Ozawa method on the DSC curves, average activation energy: E=172.4 +/- 9.7 and 205.3 +/- 12.8 kJ mol(-1), and pre-exponential factor: logA = 16.38 +/- 0.84 and 18.96 +/- 1.21 min(-1) at 95% confidence interval could be obtained, regarding the partial formation of anhydride and subsequent thermal decomposition of uncoordinated carboxylate groups, respectively.From E and logA values, Dollimore and Malek methods could be applied suggesting PT (Prout-Tompkins) and R3 (contracting volume) as the kinetic model to the partial formation of anhydride and thermal decomposition of the carboxylate groups, respectively.

Non isothermal study of the devitrification kinetics of fluoroindate glasses

The kinetics of crystallization in an indium fluoride-based glass was studied by a non-isothermal method using differential scanning calorimetry. The experiments led to an Avrami's exponent of 4.6 for solid glass and 2.2 for a powdered sample. The apparent activation energy for crystallization was found to be 130 kJ/mol for solid glass and 354 kJ/mol for the powder. These results express the profound effect of glass particle size on those kinetic parameters, as different crystallization mechanisms take place during sample heating.

Application of non-isothermal cure kinetics on the interaction of poly(ethylene terephthalate) - Alkyd resin paints

Samples of paint (P), reused PET (PET-R) and paint/PET-R mixtures (PPET-R) were evaluated using DSC to verify their physical-chemical properties and thermal behavior. Films from paints and PPET-R are visually similar. It was possible to establish that the maximum amount of PET-R that can be added to paint without significantly altering its filming properties is 2%. The cure process (80-203°C) was identified through DSC curves. The kinetic parameters, activation energy (E a) and Arrhenius parameters (A) for the samples containing 0.5 to 1% of PET-R, were calculated using the Flynn-Wall-Ozawa isoconversional method. It was observed that for greater amounts of PET-R added, there is a decrease in the E a values for the cure process. A Kinetic compensation effect (KCE), represented by the equation InA=-2.70+0.31E a was observed for all the samples. The most suitable kinetic model to describe this cure process is the autocatalytic Šesták-Berggreen, model applied to heterogeneous systems. © 2007 Springer Science+Business Media, LLC.

Studies on the thermal decomposition behaviour, kinetics and electrical conductivity of the non-isothermal decomposition of pyridine mono carboxylic acids and some of their transition metal complexes

The thesis is divided into four chapters. They are: introduction, experimental, results and discussion about the free ligands and results and discussion about the complexes. The First Chapter, the introductory chapter, is a general introduction to the study of solid state reactions. The Second Chapter is devoted to the materials and experimental methods that have been used for carrying out tile experiments. TIle Third Chapter is concerned with the characterisations of free ligands (Picolinic acid, nicotinic acid, and isonicotinic acid) by using elemental analysis, IR spectra, X-ray diffraction, and mass spectra. Additionally, the thermal behaviour of free ligands in air has been studied by means of thermogravimetry (TG), derivative thermogravimetry (DTG), and differential scanning calorimetry (DSC) measurements. The behaviour of thermal decomposition of the three free ligands was not identical Finally, a computer program has been used for kinetic evaluation of non-isothermal differential scanning calorimetry data according to a composite and single heating rate methods in comparison with the methods due to Ozawa and Kissinger methods. The most probable reaction mechanism for the free ligands was the Avrami-Erofeev equation (A) that described the solid-state nucleation-growth mechanism. The activation parameters of the decomposition reaction for free ligands were calculated and the results of different methods of data analysis were compared and discussed. The Fourth Chapter, the final chapter, deals with the preparation of cobalt, nickel, and copper with mono-pyridine carboxylic acids in aqueous solution. The prepared complexes have been characterised by analyses, IR spectra, X-ray diffraction, magnetic moments, and electronic spectra. The stoichiometry of these compounds was ML2x(H20), (where M = metal ion, L = organic ligand and x = water molecule). The environments of cobalt, nickel, and copper nicotinates and the environments of cobalt and nickel picolinates were octahedral, whereas the environment of copper picolinate [Cu(PA)2] was tetragonal. However, the environments of cobalt, nickel, and copper isonicotinates were polymeric octahedral structures. The morphological changes that occurred throughout the decomposition were followed by SEM observation. TG, DTG, and DSC measurements have studied the thermal behaviour of the prepared complexes in air. During the degradation processes of the hydrated complexes, the crystallisation water molecules were lost in one or two steps. This was also followed by loss of organic ligands and the metal oxides remained. Comparison between the DTG temperatures of the first and second steps of the dehydration suggested that the water of crystallisation was more strongly bonded with anion in Ni(II) complexes than in the complexes of Co(II) and Cu(II). The intermediate products of decomposition were not identified. The most probable reaction mechanism for the prepared complexes was also Avrami-Erofeev equation (A) characteristic of solid-state nucleation-growth mechanism. The tempemture dependence of conductivity using direct current was determined for cobalt, nickel, Cl.nd copper isonicotinates. An activation energy (ΔΕ), the activation energy (ΔΕ ) were calculated.The ternperature and frequency dependence of conductivity, the frequency dependence of dielectric constant, and the dielectric loss for nickel isonicotinate were determined by using altemating current. The value of s paralneter and the value of'density of state [N(Ef)] were calculated. Keyword Thermal decomposition, kinetic, electrical conduclion, pyridine rnono~ carboxylic acid, cOlnplex, transition metal compJex.

Natural convection from a plane vertical porous surface in non-isothermal surroundings

In this paper, laminar natural convection flow from a permeable and isothermal vertical surface placed in non-isothermal surroundings is considered. Introducing appropriate transformations into the boundary layer equations governing the flow derives non-similar boundary layer equations. Results of both the analytical and numerical solutions are then presented in the form of skin-friction and Nusselt number. Numerical solutions of the transformed non-similar boundary layer equations are obtained by three distinct solution methods, (i) the perturbation solutions for small � (ii) the asymptotic solution for large � (iii) the implicit finite difference method for all � where � is the transpiration parameter. Perturbation solutions for small and large values of � are compared with the finite difference solutions for different values of pertinent parameters, namely, the Prandtl number Pr, and the ambient temperature gradient n.

Conduction-radiation effect on natural convection flow in a fluid-saturated non-Darcy porous medium enclosed by non-isothermal walls

The effect of conduction-convection-radiation on natural convection flow of Newtonian optically thick gray fluid, confined in a non-Darcian porous media square cavity is numerically studied. For the gray fluid consideration is given to Rosseland diffusion approximation. Further assuming that (i) the temperature of the left vertical wall is varying linearly with height, (ii) cooled right vertical and top walls and (iii) the bottom wall is uniformly-heated. The governing equations are solved using the Alternate Direct Implicit method together with the Successive Over Relaxation technique. The investigation of the effect of governing parameters namely the Forschheimer resistance (Γ), the Planck constant (Rd), and the temperature difference (Δ), on flow pattern and heat transfer characteristics has been carried out. It was seen that the reduction of flow and heat transfer occurs as the Forschheimer resistance is increased. On the other hand both the strength of flow and heat transfer increases as the temperature ratio, Δ, is increased.

Effect of ionic temperature on propagation of ion-acoustic solitary waves in a collisionless plasma of warm-ion fluid and non-isothermal electrons

Using a perturbation technique, we derive Modified Korteweg—de Vries (MKdV) equations for a mixture of warm-ion fluid (γ i = 3) and hot and non-isothermal electrons (γ e> 1), (i) when deviations from isothermality are finite, and (ii) when deviations from isothermality are small. We obtain stationary solutions for these equations, and compare them with the corresponding solutions for a mixture of warm-ion fluid (γ i = 3) and hot, isothermal electrons (γ i = 1).

Crystallization kinetics of SrBi2B2O7 glasses by non-isothermal methods

Transparent glasses of SrBi2B2O7 (SBBO) were fabricated via the conventional melt-quenching technique. The amorphous and the glassy nature of the as-quenched samples were, respectively, confirmed by X-ray powder diffraction (XRD) and differential scanning calorimetry (DSC). The glass transition (T (g)) and the crystallization parameters [crystallization activation energy (E (cr)) and Avrami exponent (n)] were evaluated under non-isothermal conditions using DSC. There was a close agreement between the activation energies for the crystallization process determined by Augis and Bennet and Kissinger methods. The variation of local activation energy [E (c)(x)] that was determined by Ozawa method, decreased with the fraction of crystallization (x). The Avrami exponent (n(x)) increased with the increase in fraction of crystallization (x) suggesting that there was a change over in the crystallization process from the surface to the bulk.

Design of temperature-compensated reference electrodes for non-isothermal galvanic sensors

The criterion for the design of a temperature-compensated reference electrode for non-isothermal galvanic sensors is deduced from the basic flux equations of irreversible thermodynamics. It is shown that when the Seebeck coefficient of the non-isothermal cell using a solid oxygen ion-conducting electrolyte under pure oxygen is equal to the relative partial molar entropy of oxygen in the reference electrode divided by 4F, then the EMF of the non-isothermal cell is the same as that of an isothermal cell with the same electrodes operating at the higher temperature. By measuring the temperature of the melt alone and the EMF of the non-isothermal galvanic sensor, one can derive the chemical potential or the concentration of oxygen in a corrosive medium. The theory is experimentally checked using sensors for oxygen in liquid copper constructed with various metal+oxide electrodes and fully stabilised (CaO)ZrO2 as the electrolyte. To satisfy the exact condition for temperature compensation it is often necessary to have the metal or oxide as a solid solution in the reference electrode.

Mixed convection adjacent to non-isothermal vertical surfaces

Study of laminar boundary layer in mixed convection from vertical plates is carried out. The surface temperature along the vertical plate is assumed to vary arbitrarily with vertical distance. Perturbation technique is used to solve the governing boundary layer equations. The differentials of the wall temperature are used as perturbation elements, which are functions of vertical distance, to obtain universal functions. The universal functions are valid for any type of vertical wall temperature variation. Heat transfer rates and fluid velocity inside the boundary layer can be expressed and calculated using these universal functions. Heat transfer rates are obtained for the special cases of power-law variation of the wall temperature. The effect of the governing parameter (Gr(y)/Re-y(2)) and the power index of the power-law wall temperature variation on heat transfer rates is studied. For the purpose of validation, the mixed convection results obtained by the present technique pertaining to the special cases of isothermal vertical wall are compared with those obtained by similarity analysis reported in literature, and the agreement is found to be good. (C) 2012 Elsevier Ltd. All rights reserved.

Numerical modeling of the non-isothermal liquid droplet impact on a hot solid substrate

The heat transfer from a solid phase to an impinging non-isothermal liquid droplet is studied numerically. A new approach based on an arbitrary Lagrangian-Eulerian (ALE) finite element method for solving the incompressible Navier Stokes equations in the liquid and the energy equation within the solid and the liquid is presented. The novelty of the method consists in using the ALE-formulation also in the solid phase to guarantee matching grids along the liquid solid interface. Moreover, a new technique is developed to compute the heat flux without differentiating the numerical solution. The free surface and the liquid solid interface of the droplet are represented by a moving mesh which can handle jumps in the material parameter and a temperature dependent surface tension. Further, the application of the Laplace-Beltrami operator technique for the curvature approximation allows a natural inclusion of the contact angle. Numerical simulation for varying Reynold, Weber, Peclet and Biot numbers are performed to demonstrate the capabilities of the new approach. (C) 2014 Elsevier Ltd. All rights reserved.

Formation of Prestellar Cores via Non-Isothermal Gas Fragmentation

Sheet-like clouds are common in turbulent gas and perhaps form via collisions between turbulent gas flows. Having examined the evolution of an isothermal shocked slab in an earlier contribution, in this work we follow the evolution of a sheet-like cloud confined by (thermal) pressure and gas in it is allowed to cool. The extant purpose of this endeavour is to study the early phases of core-formation. The observed evolution of this cloud supports the conjecture that molecular clouds themselves are three-phase media (comprising viz. a stable cold and warm medium, and a third thermally unstable medium), though it appears, clouds may evolve in this manner irrespective of whether they are gravitationally bound. We report, this sheet fragments initially due to the growth of the thermal instability (TI) and some fragments are elongated, filament-like. Subsequently, relatively large fragments become gravitationally unstable and sub-fragment into smaller cores. The formation of cores appears to be a three stage process: first, growth of the TI leads to rapid fragmentation of the slab; second, relatively small fragments acquire mass via gas-accretion and/or merger and third, sufficiently massive fragments become susceptible to the gravitational instability and sub-fragment to form smaller cores. We investigate typical properties of clumps (and smaller cores) resulting from this fragmentation process. Findings of this work support the suggestion that the weak velocity field usually observed in dense clumps and smaller cores is likely seeded by the growth of dynamic instabilities. Simulations were performed using the smooth particle hydrodynamics algorithm.

Modeling of the non-isothermal liquid droplet impact on a heated solid substrate with heterogeneous wettability

A comprehensive numerical investigation on the impingement and spreading of a non-isothermal liquid droplet on a solid substrate with heterogeneous wettability is presented in this work. The time-dependent incompressible Navier-Stokes equations are used to describe the fluid flow in the liquid droplet, whereas the heat transfer in the moving droplet and in the solid substrate is described by the energy equation. The arbitrary Lagrangian-Eulerian (ALE) formulation with finite elements is used to solve the time-dependent incompressible Navier-Stokes equation and the energy equation in the time-dependent moving domain. Moreover, the Marangoni convection is included in the variational form of the Navier-Stokes equations without calculating the partial derivatives of the temperature on the free surface. The heterogeneous wettability is incorporated into the numerical model by defining a space-dependent contact angle. An array of simulations for droplet impingement on a heated solid substrate with circular patterned heterogeneous wettability are presented. The numerical study includes the influence of wettability contrast, pattern diameter, Reynolds number and Weber number on the confinement of the spreading droplet within the inner region, which is more wettable than the outer region. Also, the influence of these parameters on the total heat transfer from the solid substrate to the liquid droplet is examined. We observe that the equilibrium position depends on the wettability contrast and the diameter of the inner surface. Consequently. the heat transfer is more when the wettability contrast is small and/or the diameter of inner region is large. The influence of the Weber number on the total heat transfer is more compared to the Reynolds number, and the total heat transfer increases when the Weber number increases. (C) 2015 Elsevier Ltd. All rights reserved.