Thermal behaviour of fumaric acid, sodium fumarate and its compounds with light trivalent lanthanides in air atmosphere

Characterization, thermal stability and thermal decomposition of light trivalent lanthanide fumarates, as well as, the thermal behaviour of fumaric acid and its sodium salt were investigated employing simultaneous thermogravimetry and differential thermal analysis, differential scanning calorimetry, Fourier transform infrared spectroscopy (FTIR), TG?CFTIR techniques, elemental analysis and complexometry. On heating, sublimation of fumaric acid is observed, while the thermal decomposition of the sodium fumarate occurs with the formation of a mixture of sodium carbonate and carbonaceous residue. The thermal decomposition of light trivalent lanthanide fumarates occurs in consecutive and/or overlapping steps with the formation of the respective oxides: CeO₂, Pr₆O₁₁, and Ln₂O₃ (Ln?=?La, Nd, Sm, Eu, Gd).     

Thermal and spectroscopic studies of solid oxamate of light trivalent lanthanides

Solid-state LnL₃·1.25H₂O compounds, where L is oxamate and Ln is light trivalent lanthanides, have been synthesized. Simultaneous thermogravimetry and differential scanning calorimetry (TG–DSC), experimental and theoretical infrared spectroscopy, TG–DSC coupled to FTIR, elemental analysis, complexometry, and X-ray powder diffractometry were used to characterize and to study the thermal behavior of these compounds. The results led to information about the composition, dehydration, thermal stability, thermal decomposition, and gaseous products evolved during the thermal decomposition of these compounds in dynamic air atmosphere. The dehydration occurs in a single step and through a slow process. The thermal decomposition of the anhydrous compounds occur in a single (Ce), two (Pr), and three (La, Nd to Gd) steps with the formation of the respective oxides, CeO₂, Pr₆O₁₁, and Ln₂O₃ (Ln = La, Nd to Gd). The theoretical and experimental spectroscopic study suggests that the carboxylate group and amide carbonyl group of oxamate are coordinate to the metals in a bidentate chelating mode.     

Synthesis,characterization, and thermal study of solid-state alkaline earth metal mandelates,except beryllium and radium

Characterization, thermal stability, and thermal decomposition of alkaline earth metal mandelates, M(C₆H₅CH(OH)CO₂)₂, (M = Mg(II), Ca(II), Sr(II), and Ba(II)), were investigated employing simultaneous thermogravimetry and differential thermal analysis or differential scanning calorimetry, (TG–DTA or TG–DSC), infrared spectroscopy (FTIR), complexometry, and TG–DSC coupled to FTIR. All the compounds were obtained in the anhydrous state and the thermal decomposition occurs in three steps. The final residue up to 585 °C (Mg), 720 °C (Ca), and 945 °C (Sr) is the respective oxide MgO, CaO, and SrO. For the barium compound the final residue up to 580 °C is BaCO₃, which is stable until 950 °C and above this temperature the TG curve shows the beginning of the thermal decomposition of the barium carbonate. The results also provide information concerning the thermal behavior and identification of gaseous products evolved during the thermal decomposition of these compounds.     

Use of thermal analysis techniques for evaluation of the stability and chemical properties of papaya biodiesel (<Emphasis Type="Italic">Carica Papaya</Emphasis> L.) at low temperatures

Solid state Ln₂–L₃ compounds, where Ln stands for light trivalent lanthanides (lanthanum to gadolinium), except promethium, and L is folate (C₁₉H₁₇N₇O₆), have been synthesized. Simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), X-ray powder diffractometry, infrared spectroscopy (FTIR), TG coupled to FTIR, elemental analysis and complexometry were used to characterize and to study the thermal behaviour of these compounds. The results provided information concerning the stoichiometry, crystallinity, ligand’s denticity, thermal stability, thermal behaviour and identification of the gaseous products evolved during the thermal decomposition of these compounds.     

Synthesis, characterization and thermal behaviour of solid-state compounds of folates with some bivalent transition metals ions

Solid-state M–L compounds, where M stands for bivalent Mn, Co, Ni, Cu and Zn and L is folate (C₁₉H₁₇N₇O₆)_, have been synthesized. Simultaneous thermogravimetry and differential scanning calorimetry (TG–DSC), X-ray powder diffractometry, infrared spectroscopy (FTIR), TG–DSC coupled to FTIR, elemental analysis and high-resolution continuum source flame atomic absorption spectrometry technique (HR-CS FAAS) were used to characterize and to study the thermal behaviour of these compounds. The results provided information concerning the composition, dehydration, thermal stability and thermal decomposition.     

Studies on the thermal decomposition kinetics and mechanism of ammonium niobium oxalate

Ammonium niobium oxalate was prepared and characterized by elemental analysis, XRD and FTIR spectroscopy analysis, which confirmed that the molecular formula of the complex is NH₄(NbO(C₂O₄)₂(H₂O)₂)(H₂O)₃. Dynamic TG analysis under air was used to investigate the thermal decomposition process of synthetic ammonium niobium oxalate. It shows that the thermal decomposition occurs in three stages and the corresponding apparent activation energies were calculated with the Ozawa–Flynn–Wall and the Friedman methods. The most probable kinetic models of the first two steps decomposition of the complex have been estimated by Coats–Redfern integral and the Achar–Bridly–Sharp differential methods.     

Thermal investigation of solid 2-methoxycinnamylidenepyruvate of some bivalent transition metal ions

Solid-state M-2-MeO-CP compounds, where M represents bivalent Mn, Fe, Co, Ni, Cu, Zn and 2-MeO-CP is 2-methoxycinnamylidenepyruvate, were synthesized for the first time. Simultaneous thermogravimetry and differential thermal analysis, differential scanning calorimetry, X-ray powder diffractometry, infrared spectroscopy, TG-FTIR system, elemental analysis and complexometry have been used to characterize and to study the thermal behaviour of the compounds. The dehydration in all the compounds, except for iron occurs in a single step. The thermal decomposition of the anhydrous compounds occurs in two or three steps with the formation of the respective oxides, Mn₃O₄, Fe₂O₃, Co₃O₄, NiO, CuO and ZnO, as final residue. The results also provided information concerning the thermal behaviour and identification of the gaseous products evolved during the heating of these compounds.     

Solid-state 2-methoxybenzoates of light trivalent lanthanides

Solid-state LnL₃ compounds, where L is 2-methoxybenzoate and Ln is light trivalent lanthanides, have been synthesized. Thermogravimetry (TG), differential scanning calorimetry (DSC), X-ray powder diffractometry, infrared spectroscopy and elementary analysis were used to characterize and to study the thermal behaviour of these compounds. The results led to information on the composition, dehydration, thermal stability and thermal decomposition of the isolated compounds. On heating these complexes decompose in three (Ce, Pr) or five (La, Nd, Sm) steps with the formation of the respective oxide: CeO₂, Pr₆O₁₁ and Ln₂O₃ (Ln=La, Nd, Sm) as final residues. The theoretical and experimental spectroscopic study suggests predominantly the ionic bond between the ligand and metallic center.     

The influence of the nanofiller on thermal properties of thermoplastic polyurethane elastomers

Pure Fe₃O₄ and Mn-doped Fe₃O₄ nanoparticles were synthesized by simple wet chemical reduction technique using nontoxic precursors. Manganese doping of two concentrations, 10 and 15%, were employed. All the three synthesized nanoparticles were characterized by stoichiometry, crystal structure, and surface morphology. Thermal studies on as-synthesized nanoparticles of pure ferrite (Fe₃O₄) and manganese (Mn) doped ferrites were carried out. The thermal analysis of the three as-synthesized nanoparticles was done by thermogravimetric (TG), differential thermogravimetric, and differential thermal analysis techniques. All the thermal analyses were done in nitrogen atmosphere in the temperature range of 308–1233 K. All the thermocurves were recorded for three heating rates of 10, 15, and 20 K min^?1. The TG curves showed three steps thermal decomposition for Fe₃O₄ and two steps thermal decompositions for Mn-doped Fe₃O₄ nanoparticles. The kinetic parameters of the three as-synthesized nanoparticles were evaluated from the thermocurves employing Kissinger–Akahira–Sunose (KAS) method. The thermocurves and evaluated kinetic parameters are discussed in this paper.     

Thermal analysis of ammonium,mono-, di- and triethanolammonium alginates

Thermal behaviour of ammonium (NH₄alg), mono- (MEAalg), di- (DEAalg) and triethanolammonium (TEAalg) salts of alginic acid (Halg) was investigated by thermogravimetry (TG) and differential scanning calorimetry (DSC). Salts were prepared by the direct reaction of alginic acid with the ammonium hydroxide and with the respective ethanolamines. After preparation the compounds were lyophilized during 24 h and characterized by FTIR spectroscopy and elemental analysis (C, H and N). Under air the compounds exhibited three successive thermal decomposition steps: dehydration, decomposition of the polymeric matrix and finally, burning of carbonaceous residue. Under nitrogen two steps (dehydration and decomposition) were observed. The stability order of this series of compounds was: TEAalg this series of compounds was: TEAalg<DEAalg<NH₄alg<Halg≈MEAalg. DSC curves between –50 and 150°C did not show any thermal events suggesting that after lyophilization probably non-freezing type water is present in the system.     

Thermal and spectroscopic studies on solid Ketoprofen of lighter trivalent lanthanides

Solid-state Ln(L)₃ compounds, where Ln stands for trivalent La, Ce, Pr, Nd, Sm, Eu, and L is ketoprofen have been synthesized. Thermogravimetry (TG), differential thermal analysis (DTA), differential scanning calorimetry (DSC) as well as X-ray diffraction powder (DRX) patterns, Fourier transformed infrared spectroscopy (FTIR), and other methods of analysis were used to study solid Ketoprofen of lighter trivalent lanthanides. The results provided information of the composition, dehydration, coordination mode, structure, thermal behavior, and thermal decomposition. The theoretical and experimental spectroscopic study suggests that the carboxylate group of ketoprofen is coordinate to metals as bidentate bond.     

Using TG–FTIR and TG–MS to study thermal degradation of metal hypophosphites

Three typical metal hypophosphite flame retardants La(H₂PO₂)₃·H₂O (LHP), Ce(H₂PO₂)₃·H₂O (CHP), and Al(H₂PO₂)₃ (AHP) were synthesized and characterized by Fourier transform infrared spectroscopy (FTIR), X-ray powder diffraction, scanning electron microscopy, thermogravimetric analysis (TG), derivative thermogravimetric analysis, and differential thermal analysis. The thermal degradation products from the synthesized metal hypophosphites were also investigated using thermogravimetry coupled with Fourier transform infrared spectroscopy (TG–FTIR) and thermogravimetry coupled with mass spectrometry (TG–MS). The synthesized metal hypophosphites were also used as flame retardants for poly (1,4-butylene terephthalate) (PBT), and the combustion properties of flame-retarded PBT were evaluated using the limiting oxygen index and UL-94 tests. The results showed that the metal hypophosphites LHP, CHP, and AHP can be used as effective flame retardants for PBT, and these compounds can be obtained through a simple precipitation method. TG–FTIR and TG–MS results showed that the degradation process of AHP involves two steps, corresponding to the removal PH₃ reaction and the further dehydration reaction of the hydrogen phosphate aluminum. While LHP and CHP have three degradation steps, the additional step is due to that LHP and CHP which will loss the crystal water at lower temperature.     

没食子酸铋锆的制备、表征及其燃烧催化作用

以没食子酸、硝酸铋和硝酸氧锆为原料, 首次合成出了双金属有机盐——没食子酸铋锆, 采用有机元素分析、X射线荧光(XRF)光谱和傅里叶变换红外(FTIR)光谱对其进行了表征. 在程序升温条件下, 利用热重(TG)分析、差示扫描量热法(DSC)、固相原位反应池/FTIR 联用技术, 研究了没食子酸铋锆的热行为和热分解机理,描述了没食子酸铋锆的热分解过程, 分析得出其最终分解产物为Bi₂O₃、ZrO₂和C. 利用螺压工艺制备了含没食子酸铋锆的推进剂样品, 研究了没食子酸铋锆对双基(DB)推进剂燃烧性能的影响, 分析了其燃烧催化作用. 结果表明, 没食子酸铋锆对双基推进剂的燃烧具有良好的催化作用, 是一种高效的燃烧催化剂; 没食子酸铋锆热分解的最终产物是催化燃烧的主要物质, 锆和碳则起辅助催化的作用.     

Synthesis, characterization and thermal studies on solid compounds of 2-chlorobenzylidenepyruvate of heavier trivalent lanthanides and yttrium(III)

Solid-state compounds of general formula LnL_3⋅nH₂O, where Ln represents heavier lanthanides and yttrium and L is 2-chlorobenzylidenepyruvate, have been synthesized. Chemical analysis, simultaneous thermogravimetry-differential analysis (TG-DTA), differential scanning calorimetry (DSC), X-ray powder diffractometry, elemental analysis and infrared spectroscopy have been employed to characterize and to study the thermal behaviour of these compounds in dynamic air atmosphere. On heating these compounds decompose in four (Gd, Tb, Ho to Lu, Y) or five (Eu, Dy) steps. They lose the hydration water in the first step and the thermal decomposition of the anhydrous compounds up to 1200°C occurs with the formation of the respective oxide, Tb₄O₇ and Ln₂O₃ (Ln=Eu, Gd, Dy to Lu and Y) as final residue. The dehydration enthalpies found for these compounds (Eu, to Lu and Y) were: 65.77, 55.63, 86.89, 121.65, 99.80, 109.59, 131.02, 119.78, 205.46 and 83.11 kJ mol^-1, respectively.     

Kinetic and thermodynamic study of the Na4(UO2)2(OH)4(C2O4)2 complex

The synthesis, the characterization, and the thermal decomposition of the dioxouranium(VI) ternary complex of formula Na₄(UO₂)₂(OH)₄(C₂O₄)₂, has been studied. The identification of the compound was performed by chemical analysis and by infrared spectrometry. Thermal decomposition of the compound occurs in several steps due to the decomposition of the salt to Na₂O and UO₃ oxides. The stoichiometry of the steps, hypothesized by means of the thermodynamic and kinetic parameters, is confirmed by the evolved gas analysis studied by FTIR spectrometer coupled to TG/DSC apparatus. Model‐fitting and model‐free kinetic methods have been used in kinetic analysis. The latter allows determining kinetic scheme. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 661–669, 2003     

Thermal decomposition of novel rare-earth selenites

TG and DTA have been carried out on new anhydrous rare-earth selenites R₂Se_aO_3+2a (a=3.5,4) in order to establish their stability. Decomposition occurs in three steps attributed to successive losses of SeO₂. The first process gives rise to other new group of selenites of composition R₂Se₃O₉, which crystallize in two different forms depending on the rare-earth element. The second process leads to isomorphous compounds R₂SeO₅. The final product of thermal degradation is R₂O₃. All products were characterized by chemical analysis and X-ray powder diffraction methods.     

Preparation,characterization and compatibility studies of poly(DFAMO/AMMO)

Poly(3-difluoroaminomethyl-3-methyl oxetane (DFAMO)/3-azidomethyl-3-methyl oxetane (AMMO)) (PDA) can be used as an energetic pre-polymer in the binder systems of solid propellants and polymer-bonded explosives (PBXs). The cationic solution polymerization affords PDA using butane diol (BDO) and boron trifluride etherate (TFBE) as initiator and catalyst, separately. Its molecular structure is characterized and thermal decomposition behavior is investigated by thermogravimetric analysis (TG), differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR). The copolymer has good thermal stability and exhibits a three-step mass-loss process with the first two steps mainly belonging to the thermal decomposition of difluoroamino and azido groups, respectively. DSC method is performed to evaluate the compatibility of PDA with some energetic components and inert materials. More than half of the selected materials are compatible with PDA, which including cyclotrimethylenetrinitramine (RDX), 2,4,6-trinitrotoluene (TNT), 1,3,5-triamino-2,4,6-trinitrobenzene (TATB), pentaerythritol tetranitrate (PETN), ammonium perchlorate (AP), ammonium nitrate (AN), potassium nitrate (KNO₃), aluminum powder (Al), aluminum oxide (Al₂O₃), 2-nitrodiphenylamine (NDPA) and 1,3-diethyl-1,3-diphenyl urea (C₁).     

Thermal and spectroscopic data to investigate the oxamic acid,sodium oxamate and its compounds with some bivalent transition metal ions

Synthesis, characterization, and thermal behavior of transition metal oxamates, M(NH₂C₂O₃)₂·nH₂O (M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II)), as well as the thermal behavior of oxamic acid and its sodium salt (NaNH₂C₂O₃) were investigated employing simultaneous thermogravimetry and differential scanning calorimetry (TG-DSC), experimental and theoretical infrared spectroscopy, TG-DSC coupled to FTIR, elemental analysis and complexometry. The results led to information about the composition, dehydration, thermal stability, thermal decomposition, as well as of the gaseous products evolved during the thermal decomposition of these compounds in dynamic air and N₂ atmospheres.     

TG and DSC studies on Sm(III) and Tb(III) tartrates

The tartrate monohydrates of Sm(III) and Tb(III), Sm₂C₁₂H₁₂O₁₈·H₂O and Tb₂C₁₂H₁₂O₁₈·H₂O, were prepared and characterized on the basis of their elemental analysis and IR spectral studies. The thermal decompositions of these compounds, studied by TG and DSC methods, were found to follow an almost uniform pattern. Decomposition occurs in four steps. The first step involves dehydration, accompanied by partial decomposition to the oxalate, followed by conversion to the carbonate. The ultimate product in each case is the oxide M₂O₃, whereM=Sm or Tb. Reflectance spectra of the terbium compound were recorded at various stages of decomposition. The kinetics of the first decomposition step was studied by the non-isothermal method. TG and DSC data for this step were analysed for the evaluation of various kinetic parameters. Reasonable values ofE, Z, andΔS ⁺ were obtained.α vs. T curves were drawn on the basis of the TG and DSC data. The results suggest that the mechanism involves random nucleation.     

Thermal behavior of tetradentate Schiff base chromium(III) complexes

Thermal analytical behavior of eight chromium(III) complexes with N,N′-bis(salicylidene)ethylenediamine (salen) Schiff bases, Cr(salen), has been investigated regarding their thermal stability and thermal decomposition pathways. Thus, the ligands and the respective chromium(III) complexes of salen-type Schiff bases derived from salicylaldehyde and its 5-chloro, 5-bromo, 5-methoxy, 5-nitro, 3,5-dicloro, 3,5-dibromo, and 3,5-diiodosalicylaldehyde were synthesized, characterized, and submitted to TG/DTG, DTA, and TG–FTIR evolved gas analysis. The number of steps and, in particular, the starting temperature of decomposition of these complexes was dependent of the ligand nature. The gaseous products evolved during the thermal decomposition of these compounds were identified by TG–FTIR.