The non-isothermal kinetics analysis of the thermal decomposition of kaolinite by Effluent Gas Analysis technique

The thermal decomposition of kaolin with high-content of the medium ordered kaolinite was studied by Effluent Gas Analysis (EGA) under non-isothermal conditions. This technique enables to distinguish two overlaying processes during the thermal decomposition of kaolin: oxidation of organic compounds and dehydroxylation. The kinetic of non-isothermal dehydroxylation of kaolinite is controlled by the rate of the third-order reaction. For the given reaction mechanism, the overall activation energy (E_A) and pre-exponential (frequency) factor (A) values are 242 kJ mol⁻¹ and 2.21 × 10⁸ s⁻¹, respectively.     

Water density effects on methanol oxidation in supercritical water at high pressure up to 100 MPa

Reaction kinetics of methanol oxidation in supercritical water at high pressure condition (420 °C; 34-100 MPa; ρ = 300-660 kg/m³) was investigated. Pseudo-first order rate constant for methanol decomposition increased with increasing water density. Effects of supercritical water on the reaction kinetics were investigated using a detailed chemical kinetics model. Incorporating the effect of diffusion in a reduced model revealed that overall kinetics for SCWO of methanol is not diffusion-limited. Roles of water as a reactant were also investigated. The dependence of sensitivity coefficient for methanol concentration and rate of production of OH radical on water density indicated that a reaction, HO₂ + H₂O = OH + H₂O₂, enhanced the OH radical production and thereby facilitated the decomposition of methanol. It is presumed that concentration of key radicals could be controlled by varying pressure intensively.     

In situ ATR-FT-IR study of the thermal decomposition of diethyl peroxydicarbonate in supercritical carbon dioxide

The thermal decomposition of the organic free-radical initiator, diethyl peroxydicarbonate (DEPDC), was monitored by in situ ATR-FT-IR in heptane, and in the green solvent supercritical carbon dioxide (scCO₂) both with and without supercritical ethylene. It was observed that the characteristic peaks of DEPDC at 1802-1803 and 1194-1203 cm⁻¹ decreased significantly upon heating corresponding to the decomposition of DEPDC, while two new intense peaks simultaneously appeared at 1747 and 1262 cm⁻¹ in heptane, and similarly at 1756 and 1250 cm⁻¹ in scCO₂. The changes in the absorbance intensity of the characteristic peaks of the initiator during the decomposition were used for the measurement of the decomposition rate constant (k_d) of DEPDC. It was found that the thermal decomposition of DEPDC at low concentration in either heptane under atmospheric N₂ or scCO₂ under high pressure was via the first-order kinetics of unimolecular decomposition. The activation energy of the thermal decomposition of DEPDC was found to be 115 kJ/mol in heptane from 40 to 74 °C and 118 kJ/mol in scCO₂ from 40 to 60 °C. These new peaks revealed the formation of carboxyl groups contained in the decomposed products, indicating incomplete decarboxylation. During removal of CO₂ after the reaction in scCO₂, the instable intermediate monoethyl carbonate was decarboxylated and converted into the major end product, ethanol.     

Insights into fry-drying process of wood through a simplified approach of heat and mass transport phenomena

Fry-drying process of wood involves intense water vaporization. The pressure at a sample core increases over 250 kPa. Under such pressure conditions, vapour transport driven by Darcy's law should be considered as the prevailing phenomenon in a simplified heat and mass transport model. The latter was developed in the absence of mechanical deformation and oil penetration, in a 2D rectangular geometry and solved numerically with commercial finite element software. Free and bound water were distinguished in the energy equation. Despite the directions of vapour flux being orthogonal to the simulation plane, the use of only two adjusted permeabilities (9 × 10⁻¹⁵ and 9 × 10⁻¹⁶ m²) allowed the characterisation of a large amount of wood, regardless of sample size and permeability variability. The model was experimentally validated with local pressure and temperature measurements at the core, temperature alone at three locations and with overall water loss. Beech (Fagus silvatica), oak (Quercus pedonculae) and maritime pine (Pinus pinaster) were considered at both laboratory (0.3 m in length) and industrial (2 m in length) scales in the temperature range from 103 to 180 °C. Evidence of mechanical degrade or cracks was observed at 180 °C due to the sudden decrease in water boiling point and by fluctuations in temperature kinetics.     

Catalytic effects of NaOH and ZrO2 for partial oxidative gasification of n-hexadecane and lignin in supercritical water☆

Partial oxidative gasification of n-hexadecane (n-C₁₆) and organosolv-lignin (lignin) was studied by use of a batch type reactor in supercritical water: 673 K, 0.52 cm⁻³ of water density (40 MPa of water pressure at 673 K), and 0.3 of O/C ratio for the n-C₁₆ experiments; 673 K, 0.35 cm⁻³ of water density (30 MPa of water pressure at 673 K), and 1.0 of O/C ratio for the lignin experiments. The experiments without O₂ were also conducted for lignin (lignin decomposition). For all the cases (n-C₁₆ partial oxidation, lignin decomposition, lignin partial oxidation), NaOH or zirconia (ZrO₂) was added in the system as catalysts. Through n-C₁₆ studies, the catalytic effect of NaOH and ZrO₂ on partial oxidation in supercritical water were examined. In the case of lignin partial oxidation, we studied the possibility of partial oxidation in supercritical water for gasification technique of wastes. The yield of H₂ from n-C₁₆ and lignin with zirconia was twice as same as that without catalyst at the same condition. The H₂ yield with NaOH was 4 times higher than that without catalyst. Thus, a base catalyst has a positive effect on partial oxidation of n-C₁₆ and lignin to produce H₂. The catalytic effect of NaOH and ZrO₂ was found to be enhancement of decomposition of intermediate (aldehyde and ketone) into CO, through n-C₁₆ studies. In the case of lignin studies, the enhancement of decomposition of the carbonyl compounds by catalytic effect of NaOH and ZrO₂ inhibit char formation and promotes CO and thus H₂ formation.     

PEG-directed microwave-assisted hydrothermal synthesis of spherical α-Ni(OH)2 and NiO architectures

Spherical α-Ni(OH)₂ architectures were synthesized by the microwave-assisted hydrothermal technique using PEG-6000 as the surfactant. NiO architectures with similar morphology were obtained by a simple thermal decomposition process of the precursor α-Ni(OH)₂ at 400 °C for 2 h and were confirmed by the X-ray diffraction (XRD) analysis. Scanning electron microscopy (SEM) revealed that the synthesized spherical α-Ni(OH)₂ and NiO architectures were composed of stacked lamellar sheets and transmission electron microscopy (TEM) showed that the α-Ni(OH)₂ and NiO architectures were polycrystalline. The effect of the PEG-6000 concentration on particle size was investigated and it was found that the average particle size of α-Ni(OH)₂ architectures decreased from 4.689 μm at C_PEG=2 mmol L⁻¹ to 3.907 μm at C_PEG=4 mmol L⁻¹, and the corresponding average particle size of NiO decreased from 2.818 μm to 2.492 μm. The optical absorption band gap of NiO architectures was determined to be about 2.7–3.0 eV by UV–vis spectroscopy.     

Decomposition of MgSiN2 in nitrogen atmosphere

Magnesium silicon nitride MgSiN₂ was prepared by direct nitridation of Si/Mg₂Si/Mg/Si₃N₄ powder compact in a temperature range 1350-1420 °C. The thermal stability examination showed that MgSiN₂ is stable up to 1400 °C at 0.1 MPa N₂ pressure. The activation energy of decomposition of MgSiN₂ calculated from the temperature dependence of mass loss in the range of 1400-1650 °C is ΔH = 501 kJ mol⁻¹. The time dependence and nitrogen pressure dependence of MgSiN₂ decomposition was also investigated at constant temperature. MgSiN₂ is stable at 1560 °C in 0.6 MPa nitrogen atmosphere. Using these experimental data together with the heat capacity published in a literature the Gibbs energy of formation of MgSiN₂ was calculated in a temperature range 25-2200 °C.     

Measurements of methane hydrate heat of dissociation using high pressure differential scanning calorimetry

The methane hydrate heat of decomposition was directly measured up to 20 MPa and 292 K using a high pressure differential scanning calorimeter (DSC). The methane hydrate sample was formed ex-situ using granular ice particles and subsequently transferred into the DSC cell under liquid nitrogen. The ice and water impurities in the hydrate sample were reduced by converting any dissociated hydrate into methane hydrate inside the DSC cell before performing the thermal properties measurements. The methane hydrate sample was dissociated by raising the temperature (0.5-1.0 K/min) above the hydrate equilibrium temperature at a constant pressure. The measured methane hydrate heat of dissociation (H→W+G), ΔH_d, remained constant at 54.44±1.45 kJ/mol gas (504.07±13.48 J/gm water or 438.54± 13.78 J/gm hydrate) for pressures up to 20 MPa. The measured ΔH_d is in agreement with the Clapeyron equation predictions at high pressures; however, the Clausius-Clapeyron equation predictions do not agree with the heat of dissociation data at high pressures. In conclusion, it is recommended that the Clapeyron equation should be used for hydrate heat of dissociation estimations at high pressures.     

Preparation and characterisation of carbon-coated ceramic foams for organic vapour adsorption

Ceramic foam substrates of various porosities were coated with novolak resin, which was then subsequently carbonised and activated to develop a pore structure. The carbon forming the layer was characterised by thermal analysis, TPD and N₂, CO₂ and hexane vapour adsorption. It was found to be microporous with a high surface area (up to 1400 m² g⁻¹), which made it a good adsorbent for hexane vapour at ambient temperature. The carbon-ceramic interface was examined using SEM. The coated foams displayed a reduced pressure drop compared to carbon granules and had good dynamic hexane vapour adsorption characteristics. Depending on the foam architecture, hexane breakthrough was delayed for up to 78 min.     

Specific signatures of α-alumina powders prepared by calcination of boehmite or gibbsite

The specific signatures of α-Al₂O₃ powders by a combination of X-ray diffraction (Rietveld analysis), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, thermal analysis (TG-DTA) and cathodoluminescence (CL) were investigated. Thus, α-alumina was prepared by calcination of boehmite or gibbsite at 1573 K for 24 h. The size of α-alumina crystallites obtained using boehmite precursor was smaller than that obtained using gibbsite precursor. The difference in oxygen vacancies (F⁺-centers) amount between α-Al₂O₃ powder obtained by calcination of gibbsite and boehmite was confirmed by CL spectra. Furthermore, the Ti³⁺ emission at 1.71 eV is absent in α-Al₂O₃ powder obtained by calcination of gibbsite. CL has been demonstrated as a possible method for differentiation between the various α-alumina powders.     

Anomalous reduction in surface area during mechanical activation of boehmite synthesized by thermal decomposition of gibbsite

Mechanical activation of boehmite (γ-AlOOH), synthesized by thermal decomposition of gibbsite, has been carried out in a planetary mill up to 240 min. After an initial decrease in particle size up to 15 min, the particle size shows an increase with further milling; the median size (d₅₀) has increased from 1.8 to 5 μm during 15 to 240 min of milling. Quite unexpectedly, the BET specific surface area of the sample (N₂ adsorption method) decreases continuously from 264 m²/g to 67 m²/g with milling. A detailed analysis of N₂ adsorption/desorption isotherms has indicated that the decrease in surface area is associated with: (a) change in narrow slit like pores with microporosity to slit shaped pores originating from loose aggregate of platelet type particles; and (b) shift of maxima in pore size distribution plot at ~ 2 nm and ~ 4 nm to dominantly ~ 23 nm size pores. Scanning electron microscopy (SEM) studies have revealed that during milling, initial breakage is followed by agglomeration/fusion of particles with consequent loss in porosity. Amorphisation, decrease in microcrystallite dimension (MCD) and increase in microstrain (ε) are indicated from a detailed analysis of X-ray powder diffraction patterns and Fourier Transform Infrared (FTIR) spectra. Reactivity of samples, expressed in terms of increase in dissolution in alkali (in 8 M NaOH at 90 °C) and decrease in boehmite to γ-Al₂O₃ transformation temperature, increases with milling time. The nature of correlations between reactivity and physico-chemical changes during milling has been analyzed and discussed.     

Structural studies of oriented carbon nanotubes in alumina channels using high energy X-ray diffraction

Structural studies of multi-wall carbon nanotubes prepared by template pyrolytic carbon deposition from thermal decomposition of propylene at 800 °C inside channels of an alumina membrane have been performed using X-ray diffraction. The two-dimensional diffraction pattern of the deposited carbon nanotubes, recorded directly within the alumina template using an image plate detector, exhibits two dark arcs corresponding to the (0 0 2) graphitic reflection. The anisotropic scattering distribution indicates alignment of the nanotubes. The diffracted intensity was measured for the powdered samples after removing the alumina membrane using a point detector. A maximum scattering vector of K_max = 20 Å⁻¹ yielded the radial distribution function, providing evidence that the investigated nanotubes form a distorted hexagonal network that implies the presence of five-membered rings.     

Efficient electrochemical decomposition of perfluorocarboxylic acids by the use of a boron-doped diamond electrode

The electrochemical decomposition of environmentally persistent perfluorooctanoic acid (PFOA) was achieved by the use of a boron-doped diamond (BDD) electrode. The PFOA decomposition follows pseudo-first-order kinetics, with an observed rate constant (k₁) of 2.4 × 10^− 2 dm³ h^− 1. Under the present reaction conditions, k₁ increased with increasing current density and saturated at values over 0.60 mA cm^− 2. Therefore, the rate-limiting step for the electrochemical decomposition of PFOA was the direct electrochemical oxidation at lower current densities. In the proposed decomposition pathway, direct electrochemical oxidation cleaves the C-C bond between the C₇F₁₅ and COOH in PFOA and generates a C₇F₁₅ radical and CO₂. The C₇F₁₅ radical forms the thermally unstable alcohol C₇F₁₅OH, which undergoes F⁻ elimination to form C₆F₁₃COF. This acid fluoride undergoes hydrolysis to yield another F⁻ and the perfluorocarboxylic acid with one less CF₂ unit, C₆F₁₃COOH. By repeating these processes, finally, PFOA was able to be totally mineralized to CO₂ and F⁻. Moreover, whereas the BDD surface was easily fluorinated by the electrochemical reaction with the PFOA solution, medium pressure ultraviolet (MPUV) lamp irradiation in water was able to easily remove fluorine from the fluorinated BDD surface.     

A numerical study of particle wall-deposition in a turbulent square duct flow

The deposition of dense solid particles in a downward, fully developed turbulent square duct flow at Re_τ = 360, based on the mean friction velocity and the duct width, is studied using large eddy simulations of the fluid flow. The fluid and the particulate phases are treated using Eulerian and Lagrangian approaches, respectively. A finite-volume based, second-order accurate fractional step scheme is used to integrate the incompressible form of the unsteady, three-dimensional, filtered Navier-Stokes equations on an 80 × 80 × 128 grid. A dynamic subgrid kinetic energy model is used to account for the unresolved scales. The Lagrangian particle equation of motion includes the drag, lift, and gravity forces and is integrated using the fourth-order accurate Runge-Kutta scheme. Two values of particle to fluid density ratio (ρ_p/ρ_f = 1000 and 8900) and five values of dimensionless particle diameter (d_p/δ × 10⁶ = 100, 250, 500, 1000 and 2000, δ is the duct width) are studied. Two particle number densities, consisting of 10⁵ and 1.5 × 10⁶ particles initially in the domain, are examined.Variations in the probability distribution function (PDF) of the particle deposition location with dimensionless particle response time, i.e. Stokes number, are presented. The deposition is seen to occur with greater probability near the center of the duct walls, than at the corners. The average streamwise and wall-normal deposition velocities of the particles increase with Stokes number, with their maxima occurring near the center of the duct wall. The computed deposition rates are compared to previously reported results for a circular pipe flow. It is observed that the deposition rates in a square duct are greater than those in a pipe flow, especially for the low Stokes number particles. Also, wall-deposition of the low Stokes number particles increases significantly by including the subgrid velocity fluctuations in computing the fluid forces on the particles. Two-way coupling and, to a greater extent, four-way coupling are seen to increase the deposition rates.     

Impedance analysis of Sr-substituted CePO4 with mixed protonic and p-type electronic conduction

Members of the solid-solution series Ce_1−xSr_xPO_4−δ (x = 0, 0.01, 0.02) with mixed protonic and electronic transport have been synthesized by a nitrate-decomposition method followed by sintering at 1450 °C. Impedance spectroscopy is employed to estimate the bulk electrical conductivity in wet (∼0.03 atm) and dry atmospheres of O₂ and 10%H₂:90%N₂. Conductivity increases with dopant concentration (x), oxygen partial pressure (pO₂) and water vapour partial pressure (pH₂O) reaching ∼3.5 × 10⁻³ S cm⁻¹ at 600 °C for x = 0.02 in wet O₂. Activation energies (E_a) for the bulk conductivity of Ce_0.98Sr_0.02PO_4−δ below 650 °C are 0.44 and 0.78 eV for wet oxidising and wet reducing conditions, respectively. A moderate but positive pO₂⁺ⁿ power-law dependence (n < 1/10) of conductivity is exhibited in the pO₂ range 10^−2.5 to 10⁻¹ atm, consistent with mixed ionic and p-type electronic transport. Thermogravimetric analysis indicates that the Sr-doped materials are stable in a CO₂ atmosphere in the temperature range 25–1200 °C.     

Comparison of experimental pressure gradient and experimental relationships for the low density spherical capsule train with slurry flow relationships

In the experimental part of this study, pressure drops that occur in the flow of a low density spherical capsule train conveyed by water in a horizontal pipe were found to be 5-30% of the capsule transport concentrations. The developed experimental relations were compared with well-known relations used for slurry flow. Experimental variables (i.e. bulk velocity, diameter of particle or capsule, diameter of pipe, concentration of particle, density of particle, etc.) were applied to the pressure gradient expressions developed for the slurry flow (asymmetric suspension flow), so that the pressure gradients calculated for a concentration by 5% and 10% were compared with the experimental findings and with the developed mathematical model. It was observed that the pressure gradient expressions of the slurry flow did not simulate the experimental results of the capsule flow. However, a comparison of the empirical expression developed for the pressure drops of the spherical capsule train flow in region (2.5 × 10⁴ < Re < 1.5 × 10⁵) with the experimental findings revealed an average deviation of 3.37%.     

Thermal breakthrough analysis for determination of energy equilibrium data in a fluidized bed

The aim of this work was to predict energy equilibrium values in a bench-scale fluidized bed (FB: 105 × 200 mm), using a thermal breakthrough analysis (TBA). For this purpose, a simple “unsteady state” energy balance was proposed by harnessing dynamic model approach on the basis of heat exchange between the bed and the gas. To investigate thermal behavior of the bed, low temperature runs at different flow rates (5.2 ≤ Q₀, m³ h⁻¹ ≤ 7.4) and heating rates (97 ≤ q, kJ h⁻¹ ≤ 765) were carried out. FB was heated by means of an electrical heater (10 × 50 mm) horizontally immersed into the bed particles for heating period and then the power input was terminated for cooling period. The bed temperatures (T_B) were continuously measured for obtaining thermal breakthrough curves for all periods. Temperature-time data were used for extracting bed-to-gas heat transfer film coefficients (h_BG) from linear forms of proposed model. The model was also employed for calculating amounts of shared energies by fluidized bed phases (q_y − q_x). A good agreement between experimental values and model values of T_B was found. The results were thus confirmed by proposed model. The latter may be successfully used to predict energy equilibrium data for e.g. drying or combustion.     

Pyrolysis of wheat straw in a thermogravimetric analyzer: Effect of particle size and heating rate on devolatilization and estimation of global kinetics

The influence of different parameters such as particle size, initial weight of the sample, and heating rate on the devolatilization of wheat straw particles have been studied using thermogravimetric analysis. In addition, the variations in proximate analysis with different particle sizes of wheat straw have also been investigated. Results show that the curves corresponding to the third stage of pyrolysis differ for variations in particle size, initial weight, and heating rate of the pyrolysis process. A devolatilization model with three parallel nth-order reactions has been considered to determine the global kinetic parameters using thermogravimetric data. The kinetic parameters such as activation energy (kJ/mol), frequency factor (1/min), and order of the reaction for the three stages considered in devolatilization model were E₁ = 69, E₂ = 78, E₃ = 80; k₀₁ = 2.57 × 10¹², k₀₂ = 3.97 × 10⁷, k₀₃ = 3.17 × 10⁶; and n₁ = 2.3, n₂ = 0.65, n₃ = 2.7, respectively. It was noted from the order of the reaction that the second stage of the pyrolysis curve corresponds to the degradation of cellulose and hemicellulose, and the third stage to the lignin degradation.     

Properties of BaTiO3 synthesized from barium titanyl oxalate

In order to enhance the tetragonality of BaTiO₃ derived from barium titanyl oxalate (BTO), various treatments were carried out by considering the thermal decomposition mechanism of BTO in air. A multi-step heat treatment process and the addition of carbon black, as a particle growth inhibitor, were effective in increasing the tetragonality, whilst maintaining a particle size smaller than 200 nm. The synthesized BaTiO₃ powder with a mean particle size of 177 nm showed a tetragonality and K-factor of 1.0064 and approximately 3, respectively.     

Preparation, characterization and dielectric properties of CaCu3Ti4O12 ceramics

CaCu₃Ti₄O₁₂ nano-sized powders were successfully prepared by sol-gel technique and calcination at 600-900 °C. The thermal decomposition process, phase structures and morphology of synthesized powders were characterized by IR, DSC-TG, XRD, TEM, respectively. It was found that the main weight-loss and decomposition of precursors occurred below 450 °C and the complex perovskite phase appeared when the calcination temperature was higher than 700 °C. Using above synthesized powders as starting materials, CCTO-based ceramics with excellent dielectric properties (?₂₅ = 5.9 × 10⁴, tan δ = 0.06 at 1.0 kHz) were prepared by sintering at 1125 °C. According to the results, a conduction mechanism was proposed to explain the origin of giant dielectric constant in CCTO system.