Thermal analysis of a model bio-membrane

Thermal properties of some shedded snake skins in comparison with human skins are represented by thermogravimetry (TG), derivative thermogravimetry (DTG), and differential thermal analysis (DTA) to predict process condition as dermal pathway for administration of drugs or it be used as model membranes for permeation studies. Thermal behavior by TG/DTG and DTA curves for four kinds of shedded snake skins as Boelens Python (BP), Eastern Indigo Snake (EIS), Emerald Tree Boa (ETB), and Cascavel (CBR) were similar in relation to their decomposition temperatures at 100 °C and 230–400 °C of its constituents, however, their properties were different in the residue content (inorganic or carbonaceous substances). Similar thermal properties were also exhibited by human skins’ samples, however, they presented different residue and constituents’ content.     

Thermal behaviour of cephalexin in different mixtures

The thermoanalytical curves (TA), i.e. TG, DTG and DTA for pure cephalexin and its mixtures with talc, magnesium stearate, starch and microcrystalline cellulose, respectively, were drawn up in air and nitrogen at a heating rate of 10 °C min⁻¹. The thermal degradation was discussed on the basis of EGA data obtained for a heating rate of 20 °C min⁻¹. Until 250 °C, the TA curves are similar for all mixtures, up this some peculiarities depending on the additive appears. These certify that between the pure cephalosporin and the excipients do not exists any interaction until 250 °C. A kinetic analysis was performed using the TG/DTG data in air for the first step of cephalexin decomposition at four heating rates: 5, 7, 10 and 12 °C min⁻¹. The data processing strategy was based on a differential method (Friedman), an integral method (Flynn–Wall–Ozawa) and a nonparametric kinetic method (NPK). This last one allowed an intrinsic separation of the temperature, respective conversion dependence on the reaction rate and less speculative discussions on the kinetic model. All there methods had furnished very near values of the activation energy, this being an argument for a single thermooxidative degradation at the beginning (192–200 °C).     

Synthesis and characterization of hydroxyapatite obtained from different organic precursors by sol–gel method

The synthesis of four types of hydroxyapatite synthesized from calcium chloride and four different organic phosphites is presented. The method of synthesis chosen is the sol–gel route, which has a number of advantages compared to other methods, like the intimate contact between reactants and the milder synthesis conditions. The samples were thermally treated, the TG/DTG/DTA curves being obtained at four heating rates, namely: 7, 10, 12 and 15 °C min⁻¹. The samples were characterized before and after the thermal treatment using FT-IR analysis. The FT-IR spectra certified that the formed compounds represent hydroxyapatite. Based on the information from the TG curves and IR spectra interpretation, a reaction mechanism was proposed.     

Thermal evolution of a slate

The thermal evolution of a slate rock sample (Berja, Almería, Spain) has been studied. The phase minerals identified in this sample were mica (illite), chlorite (clinochlore) and quartz as major components, with minor microcline, iron oxide and a mixed-layer or interstratified phase (montmorillonite-chlorite). This slate is highly silico-aluminous (48.33 mass% silica, 22.04 mass% alumina), and ca. 20 mass% of other elements, mainly Fe₂O₃ (8.35 mass%), alkaline-earths and alkaline oxides. Two main endothermic DTA effects, centered at 640 and 730°C, were observed. The more important contribution of total mass loss (7.15 mass%) was found between 500–900°C, with two DTG peaks detected at 630 and 725°C. All these effects were associated to the dehydroxylation of structural OH groups of 2:1 layered silicates mixed in the slate. The dehydroxylation of the layered silicates evidenced by dilatometry, produced a rapid increase of expansion between 600–800°C. The thermal evolution of the slate upper 800°C indicated the first sintering effects associated to shrinkage, which is also favoured by its low particle size (average 23 μm) and the presence of a liquid or vitreous phase as increasing the heating temperature. The application of thermal diffractometry to the slate sample allowed to study the formation of dehydroxylated crystalline phases from the layered silicates after heating. At 1000°C, β-quartz, dehydroxylated illite, iron oxide, relicts of microcline and the vitreous phase were present in the sample. All these results are interesting to know the thermal behaviour of a complex mineral mixture as identified in the slate.     

Thermal characterization of usnic acid/collagen-based films

The purpose of this study was to evaluate the physical–chemical properties of collagen (CL) and usnic acid/collagen-based (UAC) films, using differential thermal analysis (DTA), thermogravimetry (TG/DTG), infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). Both films were prepared by casting process using polyethylene glycol 1500 (PEG 1500) as plasticizer. In the spectrum of UAC, similar bands of the usnic acid are observed, indicating that the polymerization (film formation) did not affect the stability of the drug. Distinctly, DTA curve of UAC did not show an endothermic peak at 201 °C, indicative that the drug was incorporated into the polymeric system. These results were corroborated by the scanning electron microscopy (SEM). The TG/DTG curves of UAC presented a different thermal decomposition profile compared to the individual compounds and CL. These findings suggest the occurrence of molecular dispersion or solubilization of the drug in the collagen film.     

Thermal characterization of hydrotalcite used in the transesterification of soybean oil

Hydrotalcite was synthesised by co-precipitation method, calcined and characterized by XRD, BET, IR and TG/DTA/DTG analyses and tested as solid base catalyst in the transesterification of soybean oil with methanol, achieving a methyl ester content of 99.5%. The thermal decomposition of hydrotalcite calcined occurred in four mass loss steps at 28, 105, 203 and 400 °C. The hydrotalcite was recovered and through a simple evaluation by TG/DTA/DTG techniques it was found that at 500 °C is the temperature, where the organic matter should be eliminated from the catalyst. This study shows the importance of thermal analysis in the evaluation of the recovery temperature of hydrotalcite.     

Compatibility and decomposition kinetics studies of prednicarbate alone and associated with glyceryl stearate

In this work, TG/DTG and DSC techniques were used to the determination of thermal behavior of prednicarbate alone and associated with glyceryl stearate excipient (1:1 physical mixture). TG/DTG curves obtained for the binary mixture showed a reduction of approximately 37 °C to the thermal stability of drug ( T_{\textdm/\textdt = 0 \textDTG}^\textMax T_{{{\text{d}}m/{\text{d}}t = 0\,{\text{DTG}}}}^{\text{Max}} ). The disappearance of stretching band at 1280 cm⁻¹ (ν_as C–O, carbonate group) and the presence of streching band with less intensity at 1750 cm⁻¹ (ν_s C–O, ester group) in IR spectrum obtained to the binary mixture submitted at 220 °C, when compared with IR spectrum of drug submitted to the same temperature, confirmed the chemical interaction between these substances due to heating. Kinetics parameters of decomposition reaction of prednicarbate were obtained using isothermal (Arrhenius equation) and non-isothermal (Ozawa) methods. The reduction of approximately 45% of activation energy value (E _a) to the first step of thermal decomposition reaction of drug in the 1:1 (mass/mass) physical mixture was observed by both kinetics methods.     

Thermal behavior of verapamil in pure and in solid dosage forms

Verapamil is a phenyl-alchil-amine type pharmaceutical largely used as a specific calcium antagonist. Knowledge of drug-excipient compatibility represents an important phase in development of different dosage forms. Hyphenated techniques are versatile for obtaining such necessary information’s. The TG/DTG/DTA curves were obtained in air at different heating rates and in nitrogen. The IR spectra of pure compound and its char at 400 °C (by U-ATR technique) and the IR identification of Evolved Gasses allowed some discussions on the thermally induced events. In the solid dosage forms verapamil was mixed with talc, magnesium stearate, starch, and cellulose, and the corresponding thermoanalytical curves were compared with that one of pure I. No physical or chemical interactions were observed till 250 °C. A kinetic analysis was performed for TG step of verapamil between 250 and 350 °C. The data at four heating rates (7, 10, 12, 15 °C min⁻¹) were processed on a strategy using at last three different kinetic methods. For these, the NPK method seems to be less speculative, allowing an objective determination of the kinetic parameters.     

Thermal behavior of drugs

Data on the thermal stability of drugs was required to obtain information for handling, storage, shelf life and usage. In this study, the thermal stability of two nonsteroidal anti-inflammatory drugs (NSAIDs) was determined by differential scanning calorimetry (DSC) and simultaneous thermogravimetery/differential thermal analysis (TG/DTA) techniques. The results of TG analysis revealed that the main thermal degradation for the naproxen and celecoxib occurs in the temperature ranges of 196–300 and 245–359 °C, respectively. The TG/DTA analysis of compounds indicates that naproxen melts (at about 158.1 °C) before it decomposes. However, the thermal decomposition of the celecoxib started about 185 °C after its melting. The influence of the heating rate (5, 10, 15, and 20 °C min⁻¹) on the DSC behavior of the both drug samples was verified. The results showed that, as the heating rate was increased, decomposition temperatures of the compounds were increased. Also, the kinetic parameters such as activation energy and frequency factor for the compounds were obtained from the DSC data by non-isothermal methods proposed by ASTM E696 and Ozawa. Based on the values of activation energy obtained by various methods, the following order for the thermal stability was noticed: naproxen > celecoxib. Finally, the values of ΔS ^#, ΔH ^#, and ΔG ^# of their decomposition reaction were calculated.     

Thermal degradation of poly(lactic acid) measured by thermogravimetry coupled to Fourier transform infrared spectroscopy

Thermogravimetric (TG), differential thermal analysis (DTA) and thermal degradation kinetics, FTIR and X-ray diffraction (XRD) analysis of synthesized glycine–montmorillonite (Gly–MMT) and montmorillonite bound dipeptide (Gly–Gly–MMT) along with pure Na–MMT samples have been performed. TG analysis at the temperature range 25–250 °C showed a mass loss for pure Na–MMT, Gly–MMT and Gly–Gly–MMT of about 8.0%, 4.0% and 2.0%, respectively. DTA curves show the endothermic reaction at 136, 211 and 678 °C in pure Na–MMT whereas Gly–MMT shows the exothermic reaction at 322 and 404 °C and that of Gly–Gly–MMT at 371 °C. The activation energies of the first order thermal degradation reaction were found to be 1.64 and 9.78 kJ mol⁻¹ for Gly–MMT and Gly–Gly–MMT, respectively. FTIR analyses indicate that the intercalated compounds decomposed at the temperature more than 250 °C in Gly–MMT and at 250 °C in Gly–Gly–MMT.     

Thermal behaviour and characterization of cement composites with burnt kaolin sand

The kaolin sand containing 36 wt% of kaolinite was thermally transformed at 650 °C/L h to the burnt kaolin sand (BKS) with relevant content of metakaolinite. Thermal behaviour of composites with substitution of Portland cement (PC) by the BKS containing 0, 5, 10 and 15 wt% of metakaolinite and water-to-solid ratio of 0.5 kept for 90 days in 20 ± 1 °C water was studied by thermal analysis. TG/DTA/DTG studies concerned calciumsilicate hydrate and calciumaluminate hydrate formation, portlandite dehydroxylation and calcite decarbonation. The influence of curing time and metakaolinite content were estimated. The reduction in portlandite content was observed in PC–BKS composites opposite to that found in the reference PC system. Compressive strength uptakes were observed in PC–BKS composites relative to that of reference PC system. BKS is characterized as effective pozzolanic material giving cement composites of high performance. The above findings were confirmed by X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM) results.     

Effect of particle size on pyrolysis characteristics of Elbistan lignite

In this study, the relationship between particle size and pyrolysis characteristics of Elbistan lignite was examined by using the thermogravimetric (TG/DTG) and differential thermal analysis (DTA) techniques. Lignite samples were separated into different size fractions. Experiments were conducted at non-isothermal conditions with a heating rate of 10°C min⁻¹ under nitrogen atmosphere up to 900°C. Pyrolysis regions, maximum pyrolysis rates and characteristic peak temperatures were determined from TG/DTG curves. Thermogravimetric data were analyzed by a reaction rate model assuming first-order kinetics. Apparent activation energy (E) and Arrhenius constant (A _r) of pyrolysis reaction of each particle size fraction were evaluated by applying Arrhenius kinetic model. The apparent activation energies in the essential pyrolysis region were calculated as 27.36 and 28.81 kJ mol⁻¹ for the largest (−2360+2000 μm) and finest (−38 μm) particle sizes, respectively.     

Growth and thermal behavior of lead Iodate crystals grown in silica gel

The Pb(IO₃)₂ crystals have been grown in sodium meta silicate gel using the single diffusion method at room temperature. The grown crystals were characterized by thermo analytical techniques (TG, DTA, and DTG), X-ray powder diffraction (XRD), and FTIR spectroscopy. The crystal system is confirmed to be orthorhombic having lattice parameters a = 6.09 Å, b = 16.68 Å, and c = 5.58 Å by powder X-ray diffraction analysis. FTIR study reveals that lead iodate crystal is anhydrous. TG, DTA, and DTG analysis shows a remarkable thermal stability.     

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.     

Thermal analysis of dehydroxylation of Algerian kaolinite

Thermal analysis techniques remain important tools amongst the large variety of methods used for analysis of the dehydroxylation of kaolinite. In the present study, the kinetics of dehydroxylation of Algerian kaolinite, wet ball milled for 5 h followed by attrition milling for 1 h, was investigated using differential thermal analysis (DTA) and thermogravimetry (TG). Experiments were carried out between room temperature and 1350 °C at heating rates of 5, 10 and 20 °C min⁻¹. The temperature of dehydroxylation was found to be around 509 °C. The activation energy and frequency parameter evaluated through isothermal DTA treatment were 174.69 kJ mol⁻¹ and 2.68 × 10⁹ s⁻¹, respectively. The activation energies evaluated through non-isothermal DTA and TG treatments were 177.32 and 177.75 kJ mol⁻¹, respectively. Growth morphology parameters n and m were found to be almost equal to 1.5.     

Study of Kinetic Parameters of Reject/Clay/Composites by Thermal Analysis

Thermal degradation of granite and marble industry reject (GMIR), a red clay (RC)and their composites were studied by non-isothermal thermogravimetry (TG/DTG) in nitrogen atmosphere, differential thermal analysis (DTA) and derivative thermogravimetry(DTG) in air atmosphere. Measurements were made in the temperature range of 25–1000,25–1200 and 25–1400°C. The kinetic parameters were determined by Flynn–Wall and Kissinger's methods. The results indicate the absent dominance of one mechanism of reaction, and the composites show smaller values of kinetic parameters than GMIR or RC. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal decomposition of metal methanesulfonates in air

The thermal decompositions of dehydrated or anhydrous bivalent transition metal (Mn, Fe, Co, Ni, Cu, Zn, Cd) and alkali rare metal (Mg, Ca, Sr, Ba) methanesulfonates were studied by TG/DTG, IR and XRD techniques in dynamic Air at 250–850 °C. The initial decomposition temperatures were calculated from TG curves for each compound, which show the onsets of mass loss of methanesulfonates were above 400 °C. For transition metal methanesulfonates, the pyrolysis products at 850 °C were metal oxides. For alkali rare metal methanesulfonates, the pyrolysis products at 850 °C of Sr and Ba methanesulfonates were sulphates, while those of Mg and Ca methanesulfonate were mixtures of sulphate and oxide.     

Thermal degradation behaviour of some metal chelate polymer compounds with bis(bidentate) ligand by TG/DTG/DTA

Seven novel divalent transitional metal chelate polymers compounds (commonly known as chelate compounds or metal coordination complexes or polymer complexes) have been characterized by thermogravimetry (TG), differential thermal gravimetry (DTG) and differential thermal analysis (DTA) methods. Thermal decomposition behaviour of Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) polymers with terphthaoyl-bis(p-methoxyphenylcarbamide) has been investigated by thermogravimetric analysis (TGA) at heating rate 10 °C min^?1 under nitrogen atmosphere. TG/DTA of chelate compounds were shown to be a stable compound against thermal decomposition which was measured on the basis of final decomposing temperature, but it is observed in some curves that decomposition takes place at low temperature due to the lattice water, which is always placed at outer coordination sphere of the central metal ion. The presence of both lattice and coordinated water were noteworthy investigated in Co(II), Ni(II) and Cu(II) chelate polymer compounds, whereas lattice water found in Zn(II), Cd(II) and Hg(II). However, Mn(II) showed only coordinated water. Thermal stabilities for release of lattice water, coordinated water and organic moiety that occur in sequential decomposition of chelate compounds are explained on the basis of ionic size effect and electronegativity. The processes of thermal degradation taking place in seven chelate polymers were studied comparatively by TG/DTG/DTA curves which indicating the difference in the thermal decomposition. Coats–Redfern integral method is used to determine the kinetic parameters for the successive steps in the decomposition sequence of TG curves. Scanning electron microscope images of some chelate polymers were shown in previous publication revealed that particle sizes of chelate polymers were found to be of nanomaterial level therefore, resulting chelate compounds might be called as nanomaterial.     

Mass spectra of gliclazide drug at various ion sources temperature

Gliclazide (GL, C₁₅H₂₁N₃O₃S) drug is used as non-insulin-dependant diabetes mellitus. The drug was investigated using thermal analysis (TA) measurements (TG/DTG) and electron impact mass spectral (EI–MS) fragmentation at 70 eV techniques. The mass spectra of GL at different values of ion source temperatures (400, 416, 425, and 440 K) are recorded and investigated. Semiempirical MO calculation, using PM3 procedure, has been carried out on neutral molecule and positively charged species. These calculations included bond length, bond order, bond strain, partial charge distribution, ionization energy, and heats of formation (ΔH _f). PM3 procedure provides a basis for fine distinction among sites of initial bond cleavage, which is crucial to the rationalization of subsequent fragmentation of the molecule. The primary fragmentation pathway in both TA and MS (at different values of ion source temperature) is initiated by S–N bond rupture. TA and DTG show one main weight loss at 250.38 °C and four peaks at 271.6, 360.99, 427.93 and 479.17 °C in DTA, which may be attributed to various fragments. Also, the rate constant (K′) of thermal degradation has been tested isothermally at 210 and 600 °C. The calculated rate values are 9.6 × 10⁻³ and 0.33 × 10⁻³ s⁻¹, respectively, and discussed. In MS, the effect of ion source temperature on mass spectral fragmentation processes is discussed on the basis of energy considerations using quasi equilibrium theory.     

Thermal behaviour,surface properties and vibrational spectroscopic studies of the synthesized Co3xNi3−3x(PO4)2·8H2O (0 ≤ x ≤ 1)

Co_3xNi_3−3x(PO₄)₂·8H₂O (x = 1, 0.8, 0.6, 0.4, 0.2, and 0) were synthesized via simple wet chemical reaction and energy saving route method. The final decomposition products of hydrates are corresponding anhydrous tri(cobalt nickel) diphosphates. The metal and water contents of the synthesized hydrates were confirmed by AAS and TG/DTG/DTA techniques, respectively. The observed metal and water contents agree well with the formula of the title compounds. The crystal structures and lattice parameters as well as crystallite sizes of the studied compounds were determined using XRD data. The results from XRD and TG/DTG/DTA techniques confirmed that Co_3xNi_3−3x(PO₄)₂·8H₂O at all ratios were the single phase. The FTIR spectra of studied compounds were recorded and assigned. The thermal behaviours of single and binary tri(cobalt nickel) diphosphate octahydrates were studied for the first time. The morphologies of the studied compounds were investigated by using the SEM technique. The micrographs of all studied compounds exhibited the thin plated morphology. The surface area and the pore size data of anhydrous forms were measured by N₂ adsorption at −190 °C according to the BET method. The anhydrous forms of binary metal phosphate at x = 0.8, Co_2.4Ni_0.6(PO₄)₂, exhibits the highest surface area and expects to improve the catalytic activity.