Thermal decomposition of methylxanthines

The thermal decomposition of theophylline, theobromine, caffeine, diprophylline and aminophylline were evaluated by calorimetrical, thermoanalytical and computational methods. Calorimetrical studies have been performed with aid of a heat flux Mettler Toledo DSC system. 10 mg samples were encapsulated in a 40 μL flat-bottomed aluminium pans. Measurements in the temperature range form 20 to 400°C were carried out at a heating rate of 10 and 20°C min⁻¹ under an air stream. It has been established that the values of melting points, heat of transitions and enthalpy for methylxanthines under study varied with the increasing of heating rate. Thermoanalytical studies have been followed by using of a derivatograph. 50, 100 and 200 mg samples of the studied compounds were heated in a static air atmosphere at a heating rate of 3, 5, 10 and 15°C min⁻¹ up to the final temperature of 800°C. By DTA, TG and DTG methods the influence of heating rate and sample size on thermal destruction of the studied methylxanthines has been determined. For chemometric evaluation of thermoanalytical results the principal component analysis (PCA) was applied. This method revealed that first of all the heating rate influences on the results of thermal decomposition. The most advantageous results can be obtained taking into account sample masses and heating rates located in the central part of the two-dimensional PCA graph. As a result, similar data could be obtained for 100 mg samples heated at 10°C·min⁻¹ and for 200 mg samples heated at 5°C min⁻¹.     

Polymeric Schiff Bases. VII. Some Parameters in the Evaluation of the Thermal Stability of Poly(p-Xylylidene-p-phenylenediamine)

Thermogravimetric analyses of poly(p-xylylidene-p-phenylenediamine) in nitrogen, helium, and air yield stability values substantially identical to values obtained from tests in vacuo. The respective thermal stability values in nitrogen and in air are unchanged over a fourfold change in gas flow rates. Slightly lower values are found at heating rates of 5–15°C/min than at 30°C/min. Thermal stabilities are lower in oxygen than in air, but the values are still relatively high. Higher apparent thermal stability values are observed when a powder sample of 10 mg is evaluated as a single mass rather than as a fine powder. Calorimetric measurements indicate that Schiff base polymers which have been heated in nitrogen to 1000–1200°C have not been converted to graphite-type polymers. The Schiff base polymers are resistant to radiation; their stability is shown to be independent of dose rate and of the nature of the ionizing radiation.     

Structural evolution of turbostratic carbon: Implications in H2 storage

Structural evolution of turbostratic carbon samples as a function of annealing temperature has been investigated in detail using small angle X-ray scattering (SAXS), solid state nuclear magnetic resonance (NMR) and Raman spectroscopic techniques. From these studies, it is established that, samples heated at lower temperatures (700 °C and 800 °C) consist carbon particles with rough surfaces forming structure of surface fractal in nature. Whereas the sample heated at higher temperature (900 °C) consists of larger clusters with nearly smooth surface as well as smaller size particles forming dense mass fractal structure. For this sample, solid state NMR and Raman Spectroscopic studies indicate an increased extent of overlapping of 2p_z orbital of carbon atoms due to improved long range ordering and clustering. Hydrogen adsorption studies further substantiated that energetically more homogeneous surface exists for particles of 900 °C heated sample as compared to those of 700 °C and 800 °C heated samples. A highest hydrogen storage capacity of 0.152 H/M has been observed at 123 K and 45 bar pressure for the sample heated at 900 °C.     

Heating effect on the DSC melting curve of flaxseed oil

Flaxseed oil is rich in the alpha-linolenic acid. The effect of heating on the thermal properties of flaxseed oil extracted from flax seeds has been investigated. The flaxseed oils were heated at a certain temperature (75, 105, and 135 °C, respectively) for 48 h. The melting curve (from ?75 to 100 °C) of flaxseed oil was determined by differential scanning calorimetry (DSC) at intervals of 4 h. Three DSC parameters of exothermic event and endothermic event, namely, peak temperature (T _peak), enthalpy, and temperature range were determined. The initial flaxseed oil exhibited an exothermic peak, two endothermic peaks, and two endothermic shoulders between ?68 and ?5 °C in the melting profile. Heating temperature had a significant influence on the oxidative deterioration of flaxseed oil. The melting curve and parameters of flaxseed oil were almost not changed when flaxseed oil was heated at 75 °C. However, the endothermic peaks of melting curve decreased dramatically with the increasing of heating time when heating temperature was above 105 °C. There is almost no change of melting heat flow of flaxseed oil when heating time exceeded 32 h at 135 °C. The preliminary results suggest that the DSC melting profile can be used as a fast and direct way to assess the deterioration degree of flaxseed oil.     

Thermogravimetric analysis of cellulose insulation and determination of activation energy of its thermo‐oxidation using non‐isothermal,model‐free methods

The aim of the work was to determine the effect of heating rate on initial decomposition temperature and phases of thermal decomposition of cellulose insulation. The activation energy of thermo‐oxidation of insulation was also determined. Individual samples were heated in the air flow in the thermal range of 100°C to 500°C at rates from 1.9°C min^?1 to 20.1°C min^?1. The initial temperatures of thermal decomposition ranged from 220°C to 320°C, depending on the heating rate. Three regions of thermal decomposition were observed. The maximum rates of mass loss were measured at the temperatures between 288°C and 362°C. The activation energies, which achieved average values between 75 and 80.7 kJ mol^?1, were calculated from the obtained results by non‐isothermal, model‐free methods. Copyright © 2014 John Wiley & Sons, Ltd.     

Analysis of degradation products by thermal volatilization analysis at subambient temperatures

In the subambient thermal volatilization analysis (TVA) technique, degradation products initially at ?196°C are allowed to warm up to ambient temperature in a controlled manner under vacuum conditions, and volatilization from the sample tube to a trap at ?196°C is monitored by means of a Pirani gauge. The technique is discussed in relation to earlier TVA work in which volatilization from a heated polymer sample was followed. Design and operation of a subambient TVA system are described, and examples of the application of the technique to the study of the degradation products of seven polymers are considered.     

Thermal transformations of lead oxides

Differential scanning calorimetry, differential thermogravimetry, X-ray analysis and electronic microscopic studies of thermal transformations of PbO₂ were carried out. Formation of fine dispersed (less than 100 nm) particles of α-PbO was observed at PbO₂ thermal decomposition at heating to 580°C. Reverse reaction of Pb₃O₄ formation from PbO was found at cooling and annealing at 400°C in air. At heating of α-PbO to 650°C the particle growth to 1 μm with formation of β-PbO took place. Thermal decomposition with formation of β-PbO particles with size from 0.3 to 1 μm at PbO₂ heating to 650°C was observed. Transition from PbO to Pb₃O₄ at cooling of sample heated to 650°C was not detected. Interpretation of observed phenomena from the point of view of particle size influences on the shift of α-PbO↔β-PbO phase transition temperature and on the chemical activity of phases are presented.     

Thermal hazard analysis of ALA nightclub fire debris

The fire that occurred at ALA nightclub was the deadliest nightclub fire in Taiwan. This study used the ALA nightclub fire as a case study and conducted a burning test based on the official fire investigation report. Fireworks that had been used during the performance were the cause of fire. Their heat release rate is approximately 180 kW, and the flame temperature is 300 °C. Soundproof foam collected from the fire debris was used to conduct a thermal analysis experiment under two different heating rates. In addition, related studies were referenced. It was found that when the sample was heated to between 45 and 55 °C, pyrolysis reaction started and the sample started to release harmful substances. The burning behavior of soundproof foam is considered ultrafast. When the heating temperature reaches between 225 and 370 °C, the sample releases 1,819.09–2,894.59 J g^?1 of heat. It is evident that it poses a serious degree of thermal hazard. Finally, it is recommended that the emergency egress time in entertainment establishments such as nightclubs should be kept between 60 and 90 s or less as a reference for fire safety strategies for nightclubs.     

Spectroscopic analysis of electrically polarized polyacrylonitrile

Electrically polarized and unpolarized films of polyacrylonitrile (PAN) have been investigated by both infrared attenuated total reflection (ATR) and thermally stimulated discharge (TSD). ATR analysis of PAN films has been aimed at explaining the molecular origin of thermally stimulated currents, and consequently that of phenomena contributing to electrical polarization in this material. Preferred orientation of nitrile dipoles along the thickness direction (applied electric field direction) has been detected by ATR in both polarized and unpolarized films. It is suggested that dipolar alignment in unpolarized solvent-cast films could result from internal electric fields associated with space charges. The observed orientational anisotropy is found to disappear gradually as films (both polarized and unpolarized) are heated from ambient temperature to 100°C and rotational motion in the backbone is thermally activated. TSD currents observed in this thermal range are thus associated with randomization of molecular dipoles. TSD currents observed above 100°C are suggested to originate from drift of space charges, since both an isotropic orientation of dipoles and onset of considerable diffusion are detected by ATR in this temperature range. PAN films polarized by high-intensity electric fields (5 × 10⁵Vcm^?1, as opposed to 5 × 10⁴Vcm^?1) are found to retain orientational anisotropy above 100°C, and this is believed to be associated with a structural rearrangement induced by electrical polarization.     

Catalysis and reaction mechanisms of N-formylation of amines using Fe(III)-exchanged sepiolite

This study presents a rapid, economical and “green” N-formylation of anilines with formic acid (FA) using Fe(III)-exchanged sepiolite (IES) as a catalyst. The IES exhibited excellent catalytic properties and the reactions were complete within 20.90 min to afford products with high yields. The adsorption mechanism of FA on the IES sample was studied by infrared (IR) spectroscopy at a temperature range of 120–400°C. The thermal desorption of pyridine was detected by the IR technique to estimate the acidity of IES. Lewis acid-bound pyridine bands at 1618–1631 cm^-1 and 1443–1445 cm^-1 were observed even after the IES sample was heated above 400°C.     

Structural changes in poly(L-alanine) induced by heat treatment

Structural changes in poly(L -alanine)(PLA), a model compound related to tussah silk fibroin, induced by heat treatment have been studied by differential thermal analysis, x-ray diffraction, and infrared spectroscopy. PLA heated below 300°C shows x-ray patterns very similar to those of the α-helix crystalline phase, in addition to the diffraction patterns due to the β structure. Samples heated at 368°C exhibit predominantly the diffraction patterns due to the β crystalline phase. From infrared spectra, PLA samples heated below 280°C are found to be composed of all three molecular conformations: β sheet, random coil, and α helix. The intensity of the infrared absorption at 650 cm^?1 (amide V) assigned to the random coil conformation is decreased by heat treatment above 325°C. The content of the β-sheet structure remains almost constant when the specimen is heated below 325°C, and increases abruptly on heating to around 335°C, while the random coil content is decreased abruptly by heat treatment above 335°C. The α-helix content does not change, regardless of heat treatment. It is suggested therefore that the random coil conformation of PLA transforms directly into the β sheet on heat treatment above 335°C.     

Effect of Partially Hydrolyzed Kappa-Casein on Physicochemical and Sensory Properties of Heated Milk

The chemical, physical, and sensory characteristics of renneted skim milk (RSM) containing partially hydrolyzed κ-casein were assessed and compared with skim milk (control). Rennet was added to heated milk (60°C for 15 minutes) at seven concentrations from 0.1 to 0.7 mL rennet/100 mL milk followed by heating to 63°C for 30 minutes in order to inactivate the rennet. The RSM samples had higher viscosity as well as whiter, yellower, and greener color in comparison with control sample. The range of size distribution of casein aggregates was larger than that of skim milk, while being within the range of fat mimetics.     

Recovery and determination of tritium produced in lithium-aluminium alloy by neutron irradiation

Neutron-irradiated Li−Al alloy was heated at 800°C in He flow. The tritiated species released from the sample were oxidized to H₂O(T) by passing them through a CuO column heated at 800°C and completely trapped in water scrubbers. The tritium was determined by liquid scintillation counting. The amount of tritium determined by this method was consistent with that calculated by the method of WESTCOTT et al.     

Thermal stability of aluminium hydroxycarbonates with monovalent cations

Dawsonite-type compounds of formula MAl(OH)₂CO₃ (M = Na. K, NH₄) as well as a laminar hydrotalcite-type hydroxycarbonate of composition [Al₂Li(OH)₆]₂CO₃·4H₂O. have been hydrothermally synthesized The thermal decomposition of these compounds was monitored by DTA and TG, and the resulting products have been studied by X-ray and IR techniques. Sodium and potassium dawsonites are destroyed at 335°C. yielding a poorly crystalline compound in which part of the overall carbonate is present; the remaining carbonate is lost between 600 and 700°C, yielding NaAlO₂ and KAlO₂, respectively Ammonium dawsonite and lithium hydrotalcite are less stable, their thermal decomposition occurring at about 240°C. The ammonium dawsonite heated at 680°C shows the presence of A1₂O₃ with a poorly ordered structure, while lithium hydrotalcite yields poorly crystalline γ-Al₂O₃ at 500°C and a mixture of γ-LiAlO₂ and LiAl₅O₈ when the compound is heated at higher temperatures ( ~ 1000°C).     

Degradation studies of some polyesters and polycarbonates—2. Polylactide: Degradation under isothermal conditions,thermal degradation mechanism and photolysis of the polymer

The thermal degradation of polylactide has been studied at several temperatures in the range 230–440°C and the variation of product distribution with temperature has been examined. From experiments at 240–270°C, an energy of activation of 28·5 kcal mol^?1 (119 kJ mol^?1) has been calculated. Mass spectra have been obtained for polylactide and for the cold ring fraction of degradation products in TV A experiments. Both lactide and polylactide have also been heated under closed system conditions and the products have been identified.A mechanism is presented for the thermal degradation, based upon a hydroxyl end-initiated ester interchange process giving cyclic oligomers, lactide, acetaldehyde and carbon monoxide, together with a series of reactions at somewhat higher temperatures dependent upon chain homolysis, giving the same products and also carbon dioxide and methylketene.The photolysis of polylactide at 30°C, using the medium pressure mercury lamp, has been briefly examined.     

Quantitative analysis of phase transition of heated Portland cement paste

This paper studies Portland cement paste heated up to different temperatures ranging from 105 to 1,000 °C by X-ray diffraction. The heated cement paste samples are kept isothermal in furnace for 6 h and cooled down to 100 °C. Then the samples are picked out and grinded into fine powders. 10 % Corundum is blended with cement paste powders as an internal standard. Quantitative phase analysis of cement paste samples is performed by Rietveld method. With the addition of a crystalline standard, the mass fractions of all crystalline phases as well as amorphous calcium silicate hydrate (C–S–H) are determined. The Rietveld analysis results are compared with independent measurements of the same material by thermal analysis (TG/DSC). The phase transition of Portland cement paste is discussed. An empirical relationship between the dehydration degree of C–S–H and the crystallization degree of C–S–H is derived.     

Poly(Aryl ethers) by nucleophilic aromatic substitution. II. Thermal stability

The thermal stability and degradation process for a specific poly(aryl ether) system have been studied. In particular, the polymer which is available from Union Carbide Corporation as Bakelite polysulfone has been examined in detail. Polysulfone can be prepared from 2,2-bis(4-hydroxyphenyl)propane and 4,4′-dichlorodiphenyl sulfone by nucleophilic aromatic substitution. Because of a low-temperature transition at ? 100°C. and a glass transition at 195°C., polysulfone retains useful mechanical properties from ?100°C. to 175°C. A number of experimental methods were utilized to study the thermal decomposition process for this polymer system. Polysulfone gradually degraded in vacuum above 400°C. as demonstrated by mass spectrometry. Thermogravimetric analysis in argon, air, or high vacuum indicated that rapid decomposition began above 460°C. From gas chromatography, mass spectrometry and repeated laboratory pyrolyses, a number of products from polymer decompositions were identified. The most important degradation process in vacuum or inert atmosphere was loss of sulfur dioxide. Several model compounds representative of portions of poly(aryl ether) molecules were synthesized and the relative thermal stabilities determined. Possible mechanisms for pure thermal decomposition of polysulfone were derived from the product analyses, model studies, and consideration of bond dissociation energies.     

The high-temperature degradation of poly(2,6-dimethyl-1,4-phenylene ether)

The thermal degradation of poly(2,6-dimethyl-1,4-phenylene ether) has been investigated to 1000°C in an inert atmosphere. X-ray diffraction, thermogravimetric analysis, and differential scanning calorimetry were employed to study the physical changes in the polymer, and vapor-phase chromatography, infrared spectroscopy, and mass spectrometric thermal analysis were used to elucidate the chemical aspects of the degradation process. It was found that degradation occurs in two steps: (1) a rapid exothermic process occurs between 430 and 500°C, leading to the evolution of phenolic products, water, and a black, highly crosslinked residue, and (2) a slower, char-forming process occurs above 500°C, characterized by the evolution of methane, carbon monoxide, and hydrogen. The chars formed in process 2 were found by x-ray analysis to be amorphous. The infrared spectrum of a sample heated to 510°C is nearly identical with that of the starting polymer, indicating that oxidative reactions are not important in the first process. The data for the low-temperature process are consistent with a thermal degradation scheme based on the radical-redistribution reaction of polyphenylene ethers and/or the degradation of o-benzylphenols formed by the thermal rearrangement of o-methyl diphenyl ethers. The char-forming process is best explained by simultaneous operation of the Szwarc mechanism of toluene pyrolysis, producing hydrogen and methane and reactions that cleave the aromatic rings and produce carbon monoxide.     

A differential scanning calorimeter study of the crystal forms and polymerization kinetics of 2,4-hexadiynyl-1,6-bis(p-toluenesulfonate)

The thermal properties of 2,4-hexadiynyl-1,6-bis(p-toluenesulfonate) have been explored by program temperature and isothermal differential calorimetry. The heat of fusion for the rapidly heated pure solid was 8254 cal/mole (34,540 J/mole) at 367.1°K (93.8°C). This amounts to an entropy change of 22.5 cal/mole °K (94.1 J/mole °K). The energy of activation for the thermal polymerizations was 18.97 kcal/mole (79.37 kJ/mole). The thermal polymerization appears to follow a solid–solid phase transition which proceeds by random homogeneous nucleation throughout the process. The kinetics were simple first order over 70% of the reaction. Programmed temperature studies indicate that during the first 10% of the polymerization a new high temperature (mp 375.4°K) solid phase is formed which acts as the monomer form during the bulk of the reaction.     

Principal component analysis of thermal decomposition of magnesium salts used as drugs

Thermal decomposition of magnesium salts of organic acids used in medicine (Mg acetate, Mg valproate, Mg lactate, Mg citrate, Mg hydrogen aspartate, Zn hydrogen aspartate) was analyzed by thermoanalytical, calorimetrical, and computational methods. Thermoanalytical studies were performed with aid of a derivatograph. 50-, 100-, and 200-mg samples were heated in a static air atmosphere at a heating rate of 3, 5, 10, and 15 °C min⁻¹ up to the final temperature of 700–900 °C. By differential thermal analysis (DTA), thermogravimetry (TG), and derivative thermogravimetry (DTG) methods, it has been established that thermal decomposition of the salts under study occurs via two stages. The first stage (dehydratation) was distinctly marked on the thermoanalytical curves. Calorimetrical studies were carried out by using of a heat-flux Mettler Toledo differential scanning calorimetry (DSC) system. Ten milligram samples of compounds under study were heated in the temperature range from 20 to 400 °C at a heating rate of 10 and 20 °C min⁻¹ under an air stream. The studies showed that the values of transitions heats and enthalpies of dehydration for investigated salts varied with the increasing of heating rate. For chemometric evaluation of thermoanalytical results, the principal component analysis (PCA) was applied. This method revealed that points on PC1 versus PC2 diagrams corresponding to the compounds of similar chemical constitution are localized in the similar ranges of the first two PC’s values. This proves that thermal decomposition reflects similarity in the structure of magnesium salts of organic acids.