Thermal degradation and fire behaviour of unsaturated polyesters filled with metallic oxides

Nano-alumina and submicron alumina trihydrate particles were incorporated into an unsaturated polyester resin at various loadings. The morphologies of composites showed that only nano-alumina was correctly dispersed. The thermal degradation behaviour of the composites was studied using thermogravimetric analysis and Py-GC/MS, while their fire behaviour was investigated using cone calorimeter and pyrolysis combustion flow microcalorimeter. Synergistic effects on thermal stability and heat release rate were observed for combinations between both submicron filler and nanofiller. The best result for fire behaviour was obtained for a global loading of 10wt% with an equal mass ratio for both kind of particles. Mass loss curves also showed increased char yield. The interest of combining particles with different sizes has been discussed as well as the role of water release, regarding activations energies of degradation processes.     

Branching ratios in the hydroxyl reaction with propene

The branching ratios for the reactions of attachment of hydroxyl radical to propene and hydrogen-atom abstraction were measured at 298 K over the buffer gas pressure range 60-400 Torr (N(2)) using a subatmospheric pressure turbulent flow reactor coupled with a chemical ionization quadrupole mass spectrometer. Isotopically enriched water H(2)(18)O was used to produce (18)O-labeled hydroxyl radicals in reaction with fluorine atoms. The β-hydroxypropyl radicals formed in the attachment reactions 1a and 1b , OH + C(3)H(6) → CH(2)(OH)C(?)HCH(3) (eq 1a ) and OH + C(3)H(6) → C(?)H(2)CH(OH)CH(3) (eq 1b ), were converted to formaldehyde and acetaldehyde in a sequence of secondary reactions in O(2)- and NO-containing environment. The (18)O-labeling propagates to the final products, allowing determination of the branching ratio for the attachment channels of reaction 1. The measured branching ratio for attachment is β(1b) = k(1b)/(k(1a) + k(1b)) = 0.51 ± 0.03, independent of pressure over the 60-400 Torr pressure range. An upper limit on the hydrogen-abstraction channel, OH + C(3)H(6) → H(2)O + C(3)H(5) (eq 1c ), was determined by measuring the water yield in reactions of OH and OD radicals (produced via H(D) + NO(2) → OH(OD) + NO reactions) with C(3)H(6) as k(1c)/(k(1a) + k(1b) + k(1c)) < 0.05 (at 298 K, 200 Torr N(2)).     

Thermal behaviour of montmorillonite pillared with different metal oxides

Natural montmorillonite was pillared by various polyhydroxy cations. The resulting pillared layer clays (PILCs) were characterized by X-ray fluorescence, X-ray diffraction (XRD) and infrared (IR) spectroscopies. The thermal behaviour of Al-PILC was investigated in detail by a combonation of XRD, derivatography IR spectroscopy and a comparison to natural montmorillonite is given. It was found that thermal stability of Al-PILC is lower than that of natural montmorillonite. However, heat treatment in the stability region results in significant sintering of natural montmorillonite, while the interlayer spacing of Al-PILC is hardly affected.     

Thermal and mechanical behaviour of flexible poly(vinyl chloride) mixed with some saturated polyesters

Four saturated polyesters poly(hexamethylene adipate), poly(ethylene adipate), poly(hexamethylene terephthalate) and poly(ethylene terephthalate) were prepared. The resulting materials were characterized by IR and ¹H NMR, end group analysis and gel permeation chromatography. The effect of blending these polyesters (5 and 10%) with poly(vinyl chloride) (PVC) in the melt was investigated in terms of changes in the thermal behaviour of PVC by studying the weight loss after 50 min at 180 °C, colour changes of the blend before and after aging for one week at 90 °C, the variation in glass transition temperature and the initial decomposition temperature. The results gave proof for the stabilizing role played by the investigated polyesters against the thermal degradation of PVC. The best results are obtained when PVC is mixed with 5% aliphatic polyesters rather than with aromatic ones. This is well illustrated not only from the increase in the initial decomposition temperature (IDT), but also from the decrease of % weight loss and from the lower extent of discolouration of PVC, which is a demand for the application of the polymer. It was also found that blending PVC with 5% of the four investigated polyesters before and after aging for one week at 90 °C gave better mechanical properties even than that of the unaged PVC blank.     

Thermal properties of thermotropic polyesters with rigid chains

The relationship between chemical structure and thermal properties of three polyesters composed of rigid backbone units, and here X = Br (A), Y = Cl (B), and Y = Methyl (C), was studied by differential scanning calorimetry, x-ray diffraction, and polarized-light microscopy. The effect of annealing on the polyesters was also investigated. Polymer A forms an anisotropic melt phase at temperatures above 280°C, but decomposes at temperatures in the range of the anisotropic melt phase. The thermal properties of polymer B are very similar to those of polymer C. Anisotropic-isotropic melt transitions were observed at temperatures below 400°C in both heating and cooling runs for polymers B and C. These two polymers do not decompose thermally up to 400°C. A polymer with chlorine as a substituent on the hydroquinone ring in the main chain shows a wider range of temperatures at which the anisotropic melt phase exists. Quenched films of the polymers are very poorly crystalline or almost amorphous. Textures observed in anisotropic melt phases are largely preserved in the quenched films. The temperatures of the crystal-anisotropic melt and anisotropic-isotropic melt phase transitions become higher with annealing.     

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).     

Facile synthesis of Cu-LDH with different Cu/Al molar ratios: application as antibacterial inhibitors

Research on Chemical Intermediates - A range of Cu-LDHs has been synthesized by co-precipitation using metal nitrate precursors and sodium carbonate under varying molar ratios Cu/Al...     

Thermal behavior of silicophosphate gels obtained from different precursors

Phosphosilicate glasses are of great interest in important fields, such as optical active systems, energy generating systems, humidity sensors, and as materials for biomedical applications. Many studies were accomplished to establish the influence of different reaction parameters on the evolution and final structure of sol–gel prepared phosphosilicate gels. In the present work, we studied the thermal behavior of the silicophosphate gels obtained starting with different phosphorous precursors, the influence of these precursors on the composition and structure of the resultant gels, and their evolution with thermal treatment. By Fourier transform infrared spectroscopy (FT-IR), thermogravimetric and thermodifferential analysis (DTA/TG), and Differential Scanning calorimetry coupled with Mass Spectrometry (DSC-MS), it was established that the type of the precursors essentially influences the composition and structure and consequently the thermal behavior of the obtained gels. In the case of triethylphosphate precursor, all used methods of investigation have shown that the ester is trapped in the silica matrix and it is eliminated during the thermal treatment. Triethylphosphite partially hydrolizes and reacts with the silica network during post-preparation thermal treatment. Only in the case of H₃PO₄, an interaction with TEOS takes place and leads to Si–O–P bond formation. By thermal treatment, the gels with different composition and structure lead to materials with different properties.     

Thermal analysis of zeolite ZSM-5 precursors with different Si/Al ratios

The thermal analysis of crystalline zeolite ZSM-5 precurcors with different Si/Al ratios was carried out in a nitrogen atmosphere. Different interactions between tetrapropylammonium species and the zeolitic environment were evidenced, depending on the Al content of the crystalline precursors. The results support the mechanism of ZSM-5 formation through a condensation process from the liquid phase.

---

Zusammenfassung Thermische Analysen kristalliner Zeolith- (ZSM-5) Vorprodukte mit unterschiedlichen Verhältnissen Si/Al wurden in Stickstoffatmosphäre ausgeführt. Verschiedene Wechselwirkungen zwischen den Tetrapropylammonium-Spezies und ihrer zeolithischen Umgebung wurden nachgewiesen, die vom Aluminiumgehalt der kristallinen Vorprodukte abhängen. Die Ergebnisse sprechen für einen Bildungsmechanismus des ZSM-5 über einen Kondensationsprozess aus der flüssigen Phase.

---

ZSM-5 . . ZSM-5 .

---

---

This work was carried out with the financial support of the Italian National Research Council Progetto Finalizzato Energetica 2.     

Kinetics of complex formation of poly-n-vinyl carbazole and n-ethyl carbazole with electron acceptors at different molar ratios

The rates of complex formation for poly-N-vinyl carbazole and its saturated low molecular analogue, N-ethyl carbazole, with tetracyanoethylene, chloranil, trinitrobenzene and picric acid in chloroform solution have been investigated at molar ratios of donor to acceptor, D/A = 1, 2, 4, 8 and 10. The reaction rate was studied by the “stopped flow” method. At mole ratio D/A > 1 the complex forming reactions follow kinetics of first order. The apparent rate constants were calculated by the least squares method. The complex formation rate constants for the monomer analogue are higher than those for the polymer. They also depend on the electron affinity of the acceptor. The reaction rate rises with increase of the electron affinity of the acceptor.     

Thermal behaviour of Estonian phosphorites from different deposits

Journal of Thermal Analysis and Calorimetry - Thermal behaviour of shelly Estonian phosphorite ores from Iru, Toolse, Ülgase deposits and their concentrates have been studied. The...     

Binding properties of 2,4,5-trichlorophenoxyacetic acid-imprinted polymers prepared with different molar ratios between template and functional monomer

Several molecularly-imprinted polymers binding the herbicide 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) were prepared with a molar ratio between the functional monomer and the template molecule in the pre-polymerisation mixture set between 1+2 and 20+1. The functional monomer used was 4-vinylpyridine (4-VP), the cross-linker was ethylene dimethacrylate, and the porogenic solvent was a mixture of methanol–water 3+1 (v/v). The polymers obtained were grinded, sieved and packed in 100 mm×3.9 mm HPLC columns. The effects of the mobile phase composition were evaluated by eluting the columns with acetonitrile–water mixtures. The results obtained indicate that column capacity, selectivity factor and the imprinting effect are controlled by ion-pair and hydrophobic interactions between the analyte and the stationary phase. In the full range of ratios considered, column capacity, selectivity factor and imprinting effect are inversely proportional to the molar ratio between the template molecule and the functional monomer.     

Thermal analysis of synthetic (near-chabazite) zeolites with different Si/Al ratios

The thermal behaviour of synthetic K-G type zeolites (near-chabazites of Barrer) depends on their chemical composition. Samples with a Si/Si + Al fraction between 0.5 and 0.55 and consequently with a high potassium content, show a limited reversible dehydration between room temperature and 180°C. Above 180°C, after breakdown of the crystal structure, irreversible dehydration proceeds readily, with a sharp maximum near 270°C.Samples with a Si/Si + Al fraction greater than 0.57 and a lower potassium content dehydrate continuously over the whole range between room temperature and 450°C.     

Thermal stability evaluation of methylic biodiesel obtained for different oilseeds

Biodiesel is defined as a mixture of mono- or di-alquil esters of vegetable oil or animal fats. During long-term storage, oxidation caused by contact with air (autoxidation) presents a legitimate concern in relation to monitoring and maintaining fuel quality. Extensive oxidative degradation may compromise the quality by adversely affecting kinematic viscosity, acid value, or peroxide value. The oxidation susceptibility of biodiesel, due to the presence of triacilglycerides of poly-unsaturated fatty acids, was evaluated in this study. Samples of sunflower, castor, and soybean biodiesels were obtained through the transesterification reaction, with the intention of achieving the thermal stability study through thermogravimetrical analyses and differential scanning calorimetry high pressure. It was furthermore observed through thermogravimetry and pressure differential scanning calorimetry curves that castor biodiesel exhibited the highest thermal and oxidative stability.     

Synthesis of aromatic polyesters having pendant carboxyl groups in the side chains and conversion of the carboxyl groups to other reactive groups

Aromatic polyester, copolyester, and poly(ester-amide-thioester) having pendant carboxyl groups are directly synthesized by the organic phase/water phase interfacial polyconden-sation using low-molecular and polymeric phase transfer catalysts. Spectral analysis of the resulting polymers indicates that the nucleophilicity of salts of phenols to diacid chloride is far higher than that of salts of carboxylic acids and chemoselective esterification occurs in a 100% yield. Even if the polymeric catalyst having amino acid moiety as a nucleophilic group is used in the polycondensation, the polymers do not contain anhydride groups. The polyester can be almost quantitatively converted to polymers with different reactive groups by reacting the pendant carboxyl groups with alkyl halides in a DMA_c-H₂O mixture con-taining K₂CO₃. A bifunctional catalytic mechanism is proposed for the chemical modification of the polyesters. © 1995 John Wiley & Sons, Inc.     

Thermal behaviour of lignins extracted from different raw materials

The thermal degradation of lignins extracted from bagasse, rice straw, corn stalk and cotton stalk, have been investigated using the techniques of thermogravimetric analysis (TG) and differential thermal analysis (DTA), between room temperature and 600°C. The actual pyrolysis of all samples starts above 200°C and is slow. The results calculated from TG curves indicated that the activation energy, Efor thermal degradation for different lignins lies in the range 7.949–8.087 kJ mol^?1. The DTA of all studied lignins showed an endothermic tendency around 100°C. In the active pyrolysis temperature range, thermal degradation occurred via two exothermic process at about 320 and 480°C, and a large endothermic pyrolysis region between 375 and 450°C. The first exothermic peak represents the main oxidation and decomposition reaction, the endothermic effect represents completion of the decomposition and the final exothermic peak represents charring.