Detailed kinetic modeling of pyrolysis of tetrabromobisphenol A

The thermal degradation of 4,4′-isopropylidenebis(2,6-dibromophenol), commonly known as tetrabromobisphenol A (TBBA), was studied by means of a semi-detailed kinetic model. TBBA is a widely adopted flame retardant. It decomposes in a temperature range between 200 °C and 500 °C, forming gaseous mixtures of HBr and harmful compounds such as bromine-containing phenols, the precursors of brominated dibenzo-p-dioxins (PBDDs) and dibenzofurans (PBDFs). These thermochemical characteristics constitute a significant risk of environmental contamination right throughout TBBA's whole life cycle. A kinetic model based on about 60 components (real and lumped species and radicals) and about 900 reactions satisfactorily reproduces the main aspects of TBBA degradation and volatilization. The model was validated by comparison with several thermogravimetric analyses, both isothermal and dynamic at 10 °C/min. The vaporization of pure TBBA, the formation of hydrogen bromide and of carbonaceous residue were all correctly predicted in quantitative terms right across the entire temperature range. Compared to conventional one-step global apparent degradation models, the proposed model spans much larger operating ranges, especially in predicting the gas phase products distribution. The results are encouraging and confirm the validity of the detailed kinetic model.     

Pyrolysis of textile wastes: I. Kinetics and yields

Thermal behavior of textile waste was studied by thermogravimetry at different heating rates and also by semi-batch pyrolysis. It was shown that the onset temperature of mass loss is within 104–156 °C and the final reaction temperature is within 423–500 °C. The average mass loss is 89.5%. There are three DTG peaks located at the temperature ranges of 135–309, 276–394 and 374–500 °C, respectively. The first two might be associated with either with decomposition of the hemicellulose and cellulose or with different processes of cellulose decomposition. The third peak is possibly associated to a synthetic polymer. At a temperature of 460 °C, the expected amount of volatiles of this waste is within 85–89%. The kinetic parameters of the individual degradation processes were determined by using a parallel model. Their dependence on the heating rate was also established. The pyrolysis rate is considered as the sum of the three reaction rates. The pyrolysis in a batch reactor at 700 °C and nitrogen flow of 60 ml/min produces 72 wt.% of oil, 13.5 wt.% of gas and 12.5 wt.% of char. The kinetic parameters of the first peak do not vary with heating rate, while those of the second and the third peak increase and decrease, respectively, with an increasing heating rate, proving the existence of complex reaction mechanisms for both cases.     

Thermal decomposition of zinc carbonate hydroxide

This study is devoted to the thermal decomposition of two zinc carbonate hydroxide samples up to 400 °C. Thermogravimetric analysis (TGA), boat experiments and differential scanning calorimetry (DSC) measurements were used to follow the decomposition reactions. The initial samples and the solid decomposition products were analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR) and laser particle size analyzer. Results showed that zinc carbonate hydroxide decomposition started at about 150 °C and the rate of decomposition became significant at temperatures higher than 200 °C. The apparent activation energies (E_a) in the temperature range 150–240 °C for these two samples were 132 and 153 kJ/mol. The XRD analyses of the intermediately decomposed samples and the DSC results up to 400 °C suggested a single-step decomposition of zinc carbonate hydroxide to zinc oxide with not much change in their overall morphologies.     

Catalytic effect of zinc oxide on the reduction of barium sulfate by methane

Reduction of barium sulfate by methane was investigated in this work. The thermogravimetric method was used to obtain kinetic parameters of the reaction in the temperature range of 900–975 °C at atmospheric pressure. The kinetics of the reaction has been studied both in the absence and presence of zinc oxide as a catalyst. The conversion–time data have been interpreted by using the grain model, and the effect of catalyst on the kinetic parameters has been elucidated. It was found that zinc oxide acted as fairly strong catalyst for the reaction, especially at higher temperatures. At about 975 °C the reaction rate constant was increased more than 7 times by using 2% of zinc oxide. This enhancement in the rate constant is valuable for industries.     

Thermogravimetric analysis of aluminised E-glass fibre reinforced unsaturated polyester composites

Novel aluminised E-glass fibre reinforced unsaturated polyester composites, originally formulated for enhanced thermal and electrical shielding properties were evaluated in terms of their thermal performance. The thermal degradation of these specimens was analysed using a thermogravimetric analyser (TGA). The samples were heated from ambient temperature to 500 °C at a heating rate of 20 °C/min. All specimens were decomposed under dry nitrogen (N₂) at a flow rate of 40 ml/min to yield gases and solid char. Aluminised E-glass composites were compared alongside the unmetallised E-glass and unreinforced composite. The major weight loss occurred between 200 and 400 °C. The unreinforced polyester had a maximum weight loss, 1.25%/°C, occurring at 360 °C. For the aluminised and unmetallised E-glass composites, the maximum rate of weight loss was 0.34 and 0.55%/°C, respectively. Experimental results show the degradation of the aluminised E-glass composites obtained from TGA tests is higher compared to those of unmetallised E-glass fibre and unreinforced polyester composite. This improvement is correlated to the aluminium coating.     

Isothermal kinetic analysis of the thermal decomposition of magnesium hydroxide using thermogravimetric data

In the present study, the kinetics of the thermal decomposition of magnesium hydroxide is investigated, using isothermal methods of kinetic analysis. For this purpose, experiments in thermogravimetric analyser were carried out in standard values of temperature (350°, 400°, 450° and 500°C) which resulted in weight loss percent as a function of time. The data were further modified to give fraction reacted ‘' versus time to be tested in various forms of ‘' functions. In order to determine the mechanism of the magnesium hydroxide decomposition and the form of the conversion function which governs the dehydroxylation of Mg(OH)₂, four different methods of isothermal kinetic analysis were used. Applying each of these methods to the data, it was concluded that the nucleation mechanism predominates the Mg(OH)₂, decomposition for all values of temperature tested; at 350°C the kinetic model which represents the experimental data is that of reaction at phase boundaries (random nucleation), F₁: ln(1−)=kt) while for the higher temperatures 400°, 450° and 500°C the kinetic equation of nucleation and development in two dimensions, A₂: [−ln (1−)]^1/2=kt was found to fit better the experimental results. The activation energy was evaluated applying two alternative methods; the Arrhenius plot, using maximum rates of reaction, from which the activation energy was evaluated to be 20.54 kcal/mol. An alternative method based on plots of ln t versus 1/T corresponding to the same value of ‘' gave values of 10.72, 13.82 and 16.31 kcal/mol for ‘' values of 0.25, 0.50 and 0.75, respectively.     

An investigation on the solid state pyrolytic decomposition of bimetallic oxalate precursors of Ca, Sr and Ba with cobalt: A mechanistic approach

The mixed metal oxalate precursors, calcium(II)bis(oxalato)cobaltate(II)hydrate (COC), strontium(II)bis(oxalato)cobaltate(II)pentahydrate (SOC) and barium(II)bis(oxalato)cobaltate(II)octahydrate (BOC) have been synthesized and their thermal stability was investigated. The complexes were characterized by elemental analysis, IR spectral and X-ray powder diffraction studies. Thermal decomposition studies (TG, DTG and DTA) in air showed that the compound COC decomposed mainly to CaC₂O₄ and Co₃O₄ at 340 °C, and a mixture of CaCO₃ and Co₃O₄ identified at 510 °C. A mixture of CaCO₃ and Ca₃Co₂O₆ along with the oxides and carbides of both the cobalt and calcium were attributed at 1000 °C as end products. DSC study in nitrogen ascertained the formation of a mixture of CaO and CoO along with a trace of carbon at 550 °C. The mixture species, SrC₂O₄, CoC₂O₄ and Co₃O₄ were generated at 255 °C in case of SOC in air, which ultimately changed to CoSrO₃, SrCO₃ and oxides of strontium and cobalt at 1000 °C. The several mixture species also generated as intermediate at 332 and 532 °C. The DSC study in nitrogen indicated the formation of CoSrO_x (0.5 < x < 1) as end product. In case of BOC in air, a mixture of BaCoO₂, BaO, CoO and carbides are identified as end product at 1000 °C through the generation of several intermediate species at 350 and 530 °C. A mixture of BaO and CoO is identified as end product in DSC study in nitrogen. The kinetic parameters have been evaluated for all the dehydration and decomposition steps of all the three compounds using four non-mechanistic equations. Using seven mechanistic equations, the kind of dominance of kinetic control mechanism of the dehydration and decomposition steps are also inferred. The kinetic parameters, ΔH and ΔS of all the steps are explored from the DSC studies. Some of the decomposition products are identified by IR and X-ray powder diffraction studies.     

Thermal behaviour of lyocell fibres

Fourier-transform infrared (FTIR) spectroscopy has been applied in combination with wide-angle X-ray diffraction and measurements of strength, fluidity, yellowness, birefringence, and moisture regain to detect microstructural changes in lyocell fibres, a regenerated cellulose fibre, subjected to direct heat and annealing treatments. TMA, and SEM were used to show the effect of direct heat and annealing on lyocell fibres. The FTIR spectroscopy results show that a decrease in intermolecular hydrogen bonding occurs at 70 and 80 °C for annealed and directly heated samples, respectively. The results demonstrate increase of the intensity of O–H stretching vibrations, this associated with hydrogen bonds reforming around 130 °C. Lyocell fibres shrink with direct heating in the temperature range 130–160 °C. The crystallinity decreases gradually with increasing temperature. There is no significant change in colour of the samples annealed up to 150 °C. A continuous increase in the fluidity occurs for the annealed samples in the range 150–230 °C. The tenacity and breaking extension of heated samples decrease with increasing temperature. The lower annealing temperatures cause no observable change in the smooth and void-free surface, but in the annealing temperature range 170–230 °C, substantial non-uniformity is apparent on the surface of the fibres.     

Kinetics of isothermal thermooxidative degradation of poly(vinyl chloride)/chlorinated polyethylene blends

The thermooxidative degradation of poly(vinyl chloride)/chlorinated polyethylene blends of different compositions was investigated by means of isothermal thermogravimetry in flowing atmosphere of synthetic air at temperatures 240–270 °C. The main degradation processes are dehydrochlorination of PVC and CPE. For calculation of the apparent activation energy and apparent pre-exponential factor two kinetic methods were used: isoconversional method and Prout–Tompkins method. True compensation dependency between Arrhenius parameters, obtained using Prout–Tompkins model, was found. Calculated kinetic parameters of isothermal thermooxidative degradation are close to those from non-isothermal degradation and confirm the assumption of the main degradation process in PVC/CPE blends.     

Small-angle neutron scattering study on microstructure of poly(N-isopropylacrylamide)-block-poly(ethylene glycol) in water

By employing small-angle neutron scattering (SANS), we investigated the microstructures of, poly(N-isopropylacrylamide) (PNIPA)-block-poly(ethylene glycol) (PEG) (NE) in deuterated water D₂O, as related to macroscopic behaviors of fluidity, turbidity and synerisis. SANS revealed following results: (i) microphase separation occurs at around above 17 °C in a temperature range of transparent sol below 30 °C. In the microdomain appeared in the transparent sol state, both block chains of PNIPA and PEG are swollen by water; (ii) for the NE solution of polymer concentration W_p > 3.5% (w/v), corresponding to opaque gel above 30 °C, a percolated structure, i.e., network-like domain is formed by NE as a result of macrophase separation due to dehydration of the PNIPA chains. As the temperature increases toward 40 °C, the network domain is squeezed along a direction parallel to the NE interface, which leads to increase of the interfacial thickness given by swollen PEG chains and to the macroscopic synerisis behavior.     

Sunna 535-nm photo-fluorescent film dosimeter response to different environmental conditions

Evaluations on the influence of environmental variabilities on the red fluorescence component of the Sunna Model γ photo-fluorescent dosimeter^TM have previously been reported. This present paper describes the environmental effects on the response of the green fluorescence component of the same dosimeter, which is manufactured using the injection molding technique. The results presented include temperature, relative humidity, and light influences both during and after irradiation. The green fluorescence signal shows a significant dependence on irradiation temperature below room temperature at 1%/°C. Above room temperature (approximately 24–60°C), the irradiation temperature effect varies from −0.1%/°C to 1.0%/°C, depending on the absorbed dose level. For facilities with irradiation temperatures between 30°C and 60°C and absorbed dose levels above 10 kGy, irradiation temperature effects are minimal. Light-effects results indicate that the dosimeter is influenced by ultraviolet and blue wavelengths during irradiation as well as during the post-irradiation stabilization period (approximately 22 h), requiring the use of light-tight packaging. Results also show that the dosimeter exhibits negligible effects from ambient moisture during and after irradiation when in the range of 33–95% relative humidity.     

Stability of phospholipid vesicles studied by asymmetrical flow field-flow fractionation and capillary electrophoresis

The stability of zwitterionic phosphatidylcholine vesicles in the presence of 20 mol% phosphatidyl serine (PS), phosphatidic acid (PA), phosphatidyl inositol (PI), and diacylphosphatidyl glycerol (PG) phospholipid vesicles, and cholesterol or calcium chloride was investigated by asymmetrical flow field-flow fractionation (AsFlFFF). Large unilamellar vesicles (LUV, diameter 100 nm) prepared by extrusion at 25 °C were used. Phospholipid vesicles (liposomes) were stored at +4 and −18 °C over an extended period of time. Extruded egg yolk phosphatidylcholine (EPC) particle diameters at peak maximum and mean measured by AsFlFFF were 101 ± 3 nm and 122 ± 5 nm, respectively. No significant change in diameter was observed after storage at +4 °C for about 5 months. When the storage period was extended to about 8 months (250 days) larger destabilized aggregates were formed (172 and 215 nm at peak maximum and mean diameters, respectively). When EPC was stored at −18 °C, large particles with diameters of 700–800 nm were formed as a result of dehydration, aggregation, and fusion processes. In the presence of calcium chloride, EPC alone did not form large aggregates. Addition of 20 mol% of negatively charged phospholipids (PS, PA, PI, or PG) to 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphatidylcholine (POPC) vesicles increased the electrostatic interactions between calcium ion and the vesicles and large aggregates were formed. In the presence of cholesterol, large aggregates of about 250–350 nm appeared during storage at +4 and −18 °C for more than 1 day.

The effect of liposome storage temperature on phospholipid coatings applied in capillary electrophoresis (CE) was studied by measuring the electroosmotic flow (EOF). EPC coatings with and without cholesterol, PS, or calcium chloride, prepared from liposomes stored at +25, +4, and −18 °C, were studied at 25 °C. The performances of the coatings were further evaluated with three uncharged compounds. Only minor differences were observed between the same phospholipid coatings, showing that phospholipid coatings in CE are relatively insensitive to storage at +25, +4 °C or −18 °C.     

Measurement of glass transition temperature by mechanical (DMTA), thermal (DSC and MDSC), water diffusion and density methods: A comparison study

Glass transition measured by DMTA from the change in slope in storage modulus was 55 °C, which was 10.5 °C lower than the value measured by tan δ peak. Initial glass transition measured by DSC, increased exponentially and reached a constant value of 55 °C at or higher heating rate of 30 °C/min. Transition temperature, measured by MDSC, remained constant up to heating rate 15 °C/min and then decreased. The glass transition values determined from reversible heat flow was 60 °C. The break in diffusivity and density (i.e. volume) was observed at 50 °C below the glass transition temperature measured by thermal and mechanical methods.     

Thermal decomposition temperatures and kinetic parameters of copolymers from N-phenylmaleimide and oxazoline derivatives

The thermal stabilities of 15 copolymers of varying comonomer structure based on N-phenylmaleimide and oxazoline derivatives have been studied by programmed thermogravimetric analysis over a temperature range from 20 to 500°C under a flow of nitrogen. All the copolymers are stable below 130°C. Only three of the copolymers undergo degradation in two stages.

Kinetic parameters such as the pre-exponential factor, activation energy and reaction order were evaluated. All the reactions were found to be zero order under the experimental conditions used. Possible effects of copolymer composition on the kinetic parameters are discussed.     

Biosensor analysis for the kinetic study of polyphenols deterioration during the forced thermal oxidation of extra-virgin olive oil

The process of artificial rancidification of extra-virgin olive oil due to heating in an oxidizing atmosphere was studied by testing an actual kinetic model of the process and monitoring the thermal oxidative degradation of the polyphenols contained in it. To this end, a series of oxidative degradation experiments were carried out on extra-virgin olive oil samples under isothermal conditions at 98, 120, 140, 160, and 180 °C using a thermostatic silicon oil bath. The experimental procedure used in this study carefully followed the recommendations regarding the study of olive oil rancidification set out in the AOM procedure. The change in polyphenol concentration with time was monitored at selected temperatures using a tyrosinase biosensor operating in an organic phase (n-hexane). The activation energy for the polyphenol degradation process determined using the MacCallum method was found to be practically constant throughout most of the process.

Furthermore, the application of the so-called “model-fitting” method to this process enabled the specific constant rates to be determined at the above-mentioned selected temperatures. In addition, a confirmation of the activation energy value was obtained by the “model-fitting” method and the algorithm of the kinetic model equation best-fitting the experimental curve representing the whole process was checked.

Finally, further very interesting observations were made, for instance, the half-life concentration values of polyphenols at selected temperatures between 98 and 180 °C.     

Effects of heat on physicochemical properties of whey protein-stabilised emulsions

The effect of heating has been studied for whey protein-stabilised oil-in-water emulsions (25.0% (w/w) soybean oil, 3.0% (w/w) whey protein isolate, pH 7.0). These emulsions were heated between 55 and 95 °C as a function of time and the effect on particle size distribution, adsorbed protein amount, protein conformation and rheological properties was determined. Heating the emulsions as a function of temperature for 25 min resulted in an increase of the mean diameter (d₃₂) and shear viscosity with a maximum at 75 °C. Heating of the emulsions at different temperatures as a function of time in all cases resulted in a curve with a maximum for d₃₂. A maximum increase of d₃₂ was observed after about 45 min at 75 °C and after 6–8 min at 90 °C. Similar trends were observed with viscosity measurements. Confocal scanning laser micrographs showed that after 8 min of heating at 90 °C large, loose aggregates of oil droplets were formed, while after 20 min of heating compact aggregates of two or three emulsion droplets remained. An increase of the adsorbed amount of protein was found with increasing heating temperature. Plateau values were reached after 10 min of heating at 75 °C and after 5 min of heating at 90 °C. Based on these results we concluded that in the whole process of aggregation of whey protein-stabilised emulsions an essential role is played by the non-adsorbed protein fraction, that the kinetics of the aggregation of whey protein-stabilised emulsions follow similar trends as those for heated whey protein solutions and that upon prolonged heating rearrangements take place leading to deaggregation of initially formed large, loose aggregates of emulsion droplets into smaller, more compact ones.     

The effect of humidity on dehydration behavior of nitrofurantoin monohydrate studied by humidity controlled simultaneous instrument for X-ray Diffractometry and Differential Scanning Calorimetry (XRD–DSC)

The dependence of thermal dehydration behavior of nitrofurantoin monohydrate on humidity was studied. Difference in observed crystallinity of resulting anhydrates under three humidity conditions is discussed in relation to the effect of water vapor molecules. Thermal dehydration of nitrofurantoin monohydrate was measured using a humidity controlled simultaneous measurement instrument for X-ray Diffractometry (XRD) and Differential Scanning Calorimetry (DSC) in dry, 27 °C 91% RH and 60 °C 90% RH nitrogen. Dehydration of nitrofurantoin in dry nitrogen gave a mixture of crystalline and amorphous anhydrates in the temperature range of 124–180 °C followed by crystallization around 185–190 °C. Whereas, dehydration in high humidity atmosphere (60 °C 90% RH or 17.7% H₂O–82.3% N₂) gave well crystallized anhydrate at 140 °C soon after dehydration. Dehydration in low humidity nitrogen (27 °C 91% RH or 3.2% H₂O–96.8% N₂) gave not totally crystalline anhydrate, which became pure crystalline at around 190 °C. The effect of high humidity on dehydration and crystallinity of the resulting anhydrate can be attributed to the role of water vapor molecules in two ways such as the acceleration of molecular mobility and high molecular diffusion rate of nitrofurantoin anhydrate, and the formation of hydrogen bonding bridges quickly connecting dehydrated molecules to one another.     

Measurements and particle resolved modelling of the thermo- and fluid dynamics of a packed bed

The objective of this study is to investigate experimentally and numerically into heat-up, drying and pyrolysis of a packed bed consisting of large single particles. The novelty of the current approach is that the numerical model contrary to continuum mechanic approaches considers a packed bed as an ensemble of a finite number of particles, which may have different material properties or sizes. The heat-up, drying and pyrolysis process of each particle is described sufficiently accurate by a set of one-dimensional and transient differential conservation equations for mass and energy. Applying this model to all particles, including interactions between them, of a packed bed forms the entire backed bed process as a sum of individual particle processes. The arrangement of particles within a bed defines a void space between the particles. The flow through the void space of a packed bed is modelled as a flow through a porous media taking into account interaction between the solid and the gaseous phase by heat and mass transfer. Experiments for drying and pyrolysis of a packed bed were carried out for validation in a temperature range of T=120–530 °C. The temperatures and the mass loss due to drying and pyrolysis were recorded during the experiments. The measured mass loss of the packed bed due to drying were well predicted by the constant evaporation temperature model of the particles and thus, indicating, that the drying process is transport limited by heat transfer for large wood particles in a temperature range of T=120–530 °C. A comparison between experiments and predictions of pyrolysis yielded reasonable agreement for temperatures above T=300 °C. For temperatures of T≈200 °C the deviations were not acceptable. However, the results show, that a particle resolved approach is well suited to describe packed bed processes.     

Zirconia-supported phosphotungstic acid as catalyst for alkylation of phenol with benzyl alcohol

The liquid-phase alkylation of phenol with benzyl alcohol was carried out using zirconia-supported phosphotungstic acid (PTA) as catalyst. The catalysts with different PTA loadings (5–20 wt.% calcined at 750 °C) and calcination temperature (15 wt.% calcined from 650 to 850 °C) were prepared and characterized by ³¹P MAS NMR and FT-IR pyridine adsorption spectroscopy. The catalyst with optimum PTA loading (15%) and calcination temperature (750 °C) was prepared in different solvents. ³¹P MAS NMR spectra of the catalysts showed two types of phosphorous species, one is the Keggin unit and the other is the decomposition product of PTA and the relative amount of each depends on PTA loading, calcination temperature and the solvent used for the catalyst preparation. The catalysts with 15% PTA on zirconia calcined at 750 °C showed the highest Brönsted acidity. At 130 °C and phenol/benzyl alcohol molar ratio of 2 (time, 1 h), the most active catalyst, 15% PTA calcined at 750 °C gave 98% benzyl alcohol conversion with 83% benzyl phenol selectivity.     

On the thermodynamic equilibrium between ice and electrolyte solutions in the conditions of confined geometry

For a small volume (of about 10⁻⁶ cm³) of NaCl and other electrolyte solutions (C = 0.1 and 1 M) in thin (r = 5/10 μm) single quartz capillaries, dependencies of the column length l of frozen solutions on the temperature t were measured using comparator IZA-2 in a thermostated chamber. At temperatures range t > −4 °C (for C = 0.1 M) and t > −8 °C (for C = 1 M) the l(t) dependencies are reversible and therefore correspond to establishment of an equilibrium between ice-1 and the solution.

From the constants mass condition of the dissolved salt in a frozen column, the l(t) expression was derived, which includes thermodynamic relation between solution concentration in an equilibrium with ice, C_s, and the temperature t for bulk systems. Deviations from the data known for bulk solutions were observed in thin capillaries when temperature t decreased to −3 °C (for 0.1 M NaCl) and to −6 °C for 1 M NaCl solution.

This effect may be a result of strong adhesion of the ice column to capillary walls. In this case, some internal stresses arise in frozen solution resulting in a deviation from thermodynamic equilibrium conditions for bulk systems. When approaching the temperature of ice melting, adhesion forces decrease due to formation of a thin non-freezing water interlayer on the capillary wall. In this temperature range the experimental data are in agreement with the predictions for bulk systems. It was supposed that the observed deviation in thin capillaries may be caused by formation of an amorphous ice phase with higher density as compared with the ice-1 during rapid freezing, or by an effect of ice microlenses formation. Both effects will result in a deviation from the phase diagram corresponding to a bulk solution.