Effect of physical aging on nucleation of amorphous indomethacin

Differential scanning calorimetry has been used to study glassy indomethacin aged at 0 and -10 degrees C for periods of time up to 109 and 210 days, respectively. The results demonstrate the emergence of a small melting peak of the alpha-polymorph after aging for 69 days at 0 degrees C and for 147 days at -10 degrees C (i.e., approximately 55 degrees C below the glass-transition temperature) that provides evidence of nucleation occurring in the temperature region of the beta-relaxation. The evolution of an endothermic recovery peak temperature features a plateau at longer annealing times that suggests that the glass has made significant progress toward reaching the supercooled liquid state. It has been found that the melting peaks become detectable after the recovery peak has reached the plateau. The results highlight the importance of studying physical aging in the temperature region of the beta-relaxation as a means of evaluating the physical stability of amorphous pharmaceutical materials.     

Kinetics of the Thermal and Thermo‐Oxidative Degradation of a Polystyrene–Clay Nanocomposite

Summary: Thermogravimetry and differential scanning calorimetry have been used to study the thermal and thermo‐oxidative degradation of polystyrene (PS) and a PS–clay nanocomposite. An advanced isoconversional method has been applied for kinetic analysis. Introduction of the clay phase increases the activation energy and affects the total heat of degradation, which suggests a change in the reaction mechanism. The obtained kinetic data permit a comparative assessment of the fire resistance of the studied materials.

The change in activation energy for the degradation of PS and the PS–clay nanocomposite with the extent of polymer conversion.     

Detecting Mechanochemical Degradation of Nitrocellulose by Combining Dynamic Mechanical Analysis with Mass Spectrometry

Summary: Dynamic mechanical analysis is combined with mass spectrometry to study nitrocellulose under oscillating strain. At a constant temperature (150–160 °C) and frequency (400–600 Hz) nitrocellulose fractures demonstrating a modulus drop and release of products with m/z: 30 and 44. At linear heating (2 °C · min⁻¹) and a frequency of 10–50 Hz similar products are released in two steps, the second of which demonstrates a modulus drop and a temperature increase indicating ignition.

Data for an isothermal dynamic mechanical analysis–mass spectrometry experiment performed at 160 °C.     

Use of Methods of Thermal Analysis in Studying Ceramic Materials on the Basis of Al2O3, ZrO2, Si3N4, SiC and Inorganic Binder

By thermoanalytical methods TG, DTG, DTA there have been investigated the processes occurring during the formation of ceramic materials on the basis of Al₂O₃, ZrO₂, Si₃N₄, SiC,and inorganic binder. IR spectroscopy has been an additional research method. It's been determined that with the use of H₃PO₄ as the binder for ceramic materials, the mechanisms of thermal decomposition are connected with the following processes: 1. removal of weakly tied and crystallized water in the temperature range of120–230°C, the removal being characterized by the endothermic effect, 2. interaction of the initial powder components of the ceramic materials with orthophosphoric acid conditioned by a strong exothermic effect on the DTA curve in the range of 230–530°C, 3. overlapping of endo- and exo-effects, testifying to a complex mechanism of thermal transformations, 4.oxidizing of the non-reacted silicon at the temperature of 720(760)°C, an increase of mass is observed on the TG curve as a result of the formation of SiO₂ – crystoballite. This revised version was published online in July 2006 with corrections to the Cover Date.     

Application of Thermal Analysis to the Study of Some Waste Agricultural Products for the Preparation of Active Carbons

TG, DTG and DTA methods were used for the investigation of some waste agricultural products, such as grape seeds, walnut shells, plum and peach stones, which can serve as raw materials for the production of active carbons. It was demonstrated that thermo analytical methods are appropriate to study the thermal characteristics of the above wastes and the data obtained can be applied to the technological processes of active carbon preparation. This revised version was published online in August 2006 with corrections to the Cover Date.     

Physical stability and relaxation of amorphous indomethacin

The alpha- and beta-relaxation processes in amorphous indomethacin have been studied by using differential scanning calorimetry. The beta-process has been detected as a small endothermic peak that emerges before the glass transition step when reheating samples previously annealed in the temperature region -20 to +5 degrees C. The activation energy of the beta-process is approximately 57 kJ mol(-1), and shows an increase with increasing temperature as it approaches the glass transition region. In the glass transition region, the effective activation energy of relaxation decreases with increasing temperature from 320 to 160 kJ mol(-1). Heat capacity measurements have allowed for the evaluation of the cooperatively rearranging region in terms of the linear size (3.4 nm) and the number of molecules (90). The beta-relaxation fades below -30 degrees C, which provides a practical estimate for the lower temperature limit of physical instability in indomethacin. It is demonstrated experimentally that nucleation of indomethacin takes place in the temperature region of the beta-relaxation.     

Thermoanalytical study of some salts of3d metals withd-tartaric acid

The processes of dehydration and decomposition of the Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II) salts ofd-tartaric acid were studied by using TG, DTG and DTA methods in air or in argon, and also IR-spectroscopy. The equations of thermal decomposition were established. For the dehydration processes, the kinetic parametersn, E andInA were determined.     

Variation of the Effective Activation Energy Throughout the Glass Transition

Summary: An advanced isoconversional method has been applied to determine the effective activation energies (E) for the glass transition in polystyrene (PS), poly(ethylene terephthalate) (PET), and boron oxide (B₂O₃). The values of E decrease from 280 to 120 kJ · mol⁻¹ in PS, from 1 270 to 550 kJ mol⁻¹ in PET, and from 290 to 200 kJ mol⁻¹ in B₂O₃. It is suggested that a significant variation in E should be observed for the fragile glasses that typically include polymers.

Variation in the effective activation energy of PS, PET, and B₂O₃ with temperature.     

Thermal regeneration of activated carbons saturated with ortho- and meta-chlorophenols

Activated carbons (ACs) made from peach and plum stones were oxidized and impregnated with salts of Cu(II), Fe(III), Ni(II) and Cr(III). The chemically modified ACs, along with a commercial AC (S208c), were saturated with ortho- (OCP) and meta-chlorophenol (MCP) to investigate the potential for thermally regenerating the spent ACs. The thermal regeneration process was monitored by thermal analysis (TGA/DSC), gas chromatography and mass spectrometry (GC/MS). Thermal desorption profiles showed that in most cases weight losses occur in two steps (weak physisorption at ∼220 °C and strong chemisorption at ∼620 °C). Intermediate steps at ∼400 °C appeared in samples whose chemical treatments successfully weakened the interactions between strongly chemisorbed chlorophenol (CP) molecules and AC surfaces. The type and quantity of products of OCP and MCP desorption during the thermal regeneration of a spent AC depend on the chemical modification given to the AC prior to its use as CP adsorbent. Besides the original chlorophenols, thermal regeneration products can include chlorobenzene, dichloro-dibenzofuran, phenol, aliphatic and aromatic hydrocarbons, water, chlorides, carbon oxides, hydrogen, and char deposits. Mechanisms for the formation of these compounds are discussed. The char deposits built during this study did not appear to diminish the surface area or porosity of the chemically modified ACs following their thermal regeneration.     

Utilization of Thermal Analysis to Establish the Optimal Conditions for Regeneration of Activated Carbons

Thermoanalytical methods (TG, DTG and DTA) were used to determine the temperature interval (140–350°C) in which p-nitroaniline undergoes thermal desorption from the surface of activated carbons obtained from the shells of oxidized plum stones and impregnated with aqueous solutions of Cu, Fe and Ti salts, which simulate the processes of activated carbon regeneration. It was established that the impregnation of the activated carbons facilitated the regeneration processes in the sense that they can occur at lower temperatures: 135–320 (Cu), 150–340 (Ti) and 130–320°C (Fe). The utilized activated carbons were preliminarily characterized by BET surface area, DSC and scanning electron microscopic methods. This revised version was published online in July 2006 with corrections to the Cover Date.