A kinetic study of the thermal and thermal oxidative degradations of new bridged POSS/PS nanocomposites

The thermal degradation of a series of three novel bridged polyhedral oligomeric silsesquioxanes (POSS)/polystyrene (PS) nanocomposites, at different POSS content (3%, 5% and 10%), was studied in both inert (flowing nitrogen) and oxidative (static air) atmospheres, in order to investigate the effects of this new dumbbell-shaped structure on the filler–polymer interaction and then on the thermal stability of the obtained materials. Nanocomposites were synthesized by in situ polymerization of styrene in the presence of POSS which has not polymerizable groups, aiming to obtain well dispersed POSS/PS systems. The actual filler concentration in the obtained nanocomposites was checked by ¹H NMR spectroscopy. Scanning electron microscopy (SEM) and FTIR spectroscopy evidenced the presence of filler–polymer interactions. Degradations were carried out into a thermobalance, in the scanning mode, at various heating rates, and the characteristic parameters of thermal stability, namely temperature at 5% mass loss (T₅%) and the activation energy (E_a) of degradation, of the various nanocomposites were determined. The results were discussed and interpreted.     

Kinetic study of the thermal and thermo-oxidative degradations of polylactide-modified films for food packaging

In this study, the thermal degradations of some commercial polylactide (PLA) films, pure and subjected to various superficial treatments, were investigated in both inert (flowing nitrogen) and oxidative (static air) atmospheres. Degradations were carried out in a thermobalance, in the scanning mode, at various heating rates, and the obtained thermogravimetric curves were discussed and interpreted. Experiments, performed in the temperature range of 35–700 °C, showed similar behavior in both the atmospheres used. The initial decomposition temperature (T _i) and the apparent activation energy (E _a) of degradation of the differently treated PLA films were determined and compared with each other and with those of untreated PLA. The E _a of degradation was obtained by Kissinger’s method, and the values were found increased linearly as a function of crystallinity percentage (%c) as well as the T _i values. The glass transition temperature (T _g) was also determined by differential scanning calorimetry. All the investigated parameters showed dependence on different treatments made to the films. The results obtained for the degradations of PLA films were compared with each other, and a classification of thermal stability in the studied environments were made.     

Thermal and rheological behaviours of some random aromatic amino-ended polyethersulfone/polyetherethersulfone copolymers

The thermal and rheological characterizations of seven random, low molecular weight (M_n ≅ 9500 g mol⁻¹), H₂N-ended polyethersulfone/polyetherethersulfone (PES/PEES) copolymers, at various PES/PEES ratios, were performed. The glass transition temperatures (T_g) were determined by DSC. Degradations were carried out in a thermobalance, under flowing nitrogen, in dynamic heating conditions from 35 °C to 650 °C. The initial decomposition temperatures (T_i) and the half decomposition temperatures (T_1/2) were directly determined by TG curves, while the apparent activation energies of degradation (E_a) were obtained by the Kissinger method. In addition, the complex viscosities (η^∗) of the molten polymers were determined in experimental conditions of linear viscoelasticity. T_g, E_a and η^∗ values increased linearly with PES% content, while T_i and T_1/2 values showed opposite behaviour. In every case both PES and PEES homopolymers felt outside linearity. The results obtained are discussed and interpreted, and compared with those of corresponding Cl-ended copolymers previously studied.     

Exploitation of introducing of catalytic centers into layer galleries of layered silicates and related epoxy nanocomposites. I. Epoxy nanocomposites derived from montmorillonite modified with catalytic surfactant‐bearing carboxyl groups

Montmorillonite (MMT) was modified with the acidified cocamidopropyl betaine (CAB) and the resulting organo‐montmorillonite (O‐MMT) was dispersed in an epoxy/methyl tetrahydrophthalic anhydride system to form epoxy nanocomposites. The intercalation and exfoliation behavior of the epoxy nanocomposites were examined by X‐ray diffraction and transmission electron microscopy. The curing behavior and thermal property were investigated by in situ Fourier transform infrared spectroscopy and DSC, respectively. The results showed that MMT could be highly intercalated by acidified CAB, and O‐MMT could be easily dispersed in epoxy resin to form intercalated/exfoliated epoxy nanocomposites. When the O‐MMT loading was lower than 8 phr (relative to 100 phr resin), exfoliated nanocomposites were achieved. The glass‐transition temperatures (T_g's) of the exfoliated nanocomposite were 20 °C higher than that of the neat resin. At higher O‐MMT loading, partial exfoliation was achieved, and those samples possessed moderately higher T_g's as compared with the neat resin. O‐MMT showed an obviously catalytic nature toward the curing of epoxy resin. The curing rate of the epoxy compound increased with O‐MMT loading. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1192–1198, 2004     

Thermal and rheological behaviour of some random aromatic polyethersulfone/polyetherethersulfone copolymers

The thermal and rheological behaviour of seven random Cl-ended aromatic PES/PEES copolymers (M_n ≈ 9500 g mol⁻¹), at various PES/PEES repeating unit ratios, was studied. The glass transition temperatures (T_g), determined by DSC experiments, showed a dependence on copolymer composition significantly different from the ideal linear behaviour expected on the basis of Fox equation. Degradations were carried out in the scanning mode, under flowing nitrogen, in the temperature range 35-650 °C and a single degradation stage was observed for all copolymers. The initial decomposition temperatures (T_i) and the half decomposition temperatures (T_1/2) were directly determined by TG curves, while the apparent activation energies of degradation (E_a) were obtained by the Kissinger method. In addition, the complex viscosity (η^∗) of molten copolymers was determined in experimental conditions of linear viscoelasticity. T_i, T_1/2, E_a, and η^∗ values were depending on copolymer composition, showing a trend similar to that of T_g values. The results obtained were discussed and interpreted.     

Observation of Regime III Crystallization in Polyethylene/Montmorillonite Nanocomposites

Summary: Exfoliated and intercalated polyethylene/montmorillonite (PE/MMT) nanocomposites with high MMT content were prepared by in situ polymerization. The isothermal crystallization kinetics of the nanocomposites were analyzed with Lauritzen–Hoffman regime theory. Regime III crystallization, which is difficult to observe in linear polyethylene, appears in the PE/MMT nanocomposites. The broader temperature range of regime III crystallization in PE/MMT nanocomposites shows that the mobility and reptation ability of the PE chains are greatly reduced by the MMT, especially in the intercalated nanocomposite.

Plots of ln K/n + U*/R(T_c − T₀) against 1/T_c(ΔT)f for the intercalated and exfoliated PE/MMT nanocomposites.     

Evaluation of the thermal degradation of PC/ABS/montmorillonite nanocomposites

Polycarbonate (PC)/acrylonitrile‐butadiene‐styrene (ABS) polymer alloy/montmorillonite (MMT) nanocomposites were prepared using a direct melt intercalation technique. The pyrolytic degradation and the thermo‐oxidative degradation of the polymer alloy and the nanocomposites were studied by thermogravimetric analysis (TGA). The kinetic evaluations were performed by the model‐free kinetic analysis and the multivariate non‐linear regression. Apparent kinetic parameters for the overall degradation were calculated. The results show that PC/ABS/MMT nanocomposites have high thermal stability and low flammability. Their pyrolytic degradation and the thermo‐oxidative degradation model are different. The pyrolytic degradation reaction of the polymer is a two‐step parallel reaction model: nth‐order reaction model, and ath‐degree autocatalytic reaction with an nth‐order reaction autocatalytic reaction, whereas the thermal oxidative degradation reaction of the polymer is a two‐step following reaction model: A → B → C of nth‐order reaction model, and autocatalytic reaction model. Copyright © 2005 John Wiley & Sons, Ltd.     

Synthesis,characterization, and thermal stability of poly (lactic acid)/zinc oxide pillared organic saponite nanocomposites via ring‐opening polymerization of d,l‐lactide

Poly (lactic acid) (PLA) was synthesized using d , l ‐lactide monomer and zinc oxide (ZnO) pillared organic saponite as the green catalyst, through ring‐opening polymerization. The effects of stoichiometry of catalyst and polymerization conditions on molecular weight of PLA were evaluated by orthogonal experiment. The optimum polymerization parameters were: 0.5 wt% ZnO pillared organic saponite and reaction conditions of 170°C for 20 hr. Fourier transform infrared spectroscopy and ¹H nuclear magnetic resonance spectroscopy confirmed the PLA structure. Gel permeation chromatography showed that the average molecular weight of PLA was 48,442 g/mol, and its polydispersity index was 1.875. Differential scanning calorimetry, X‐ray diffraction, and polarized optical microscopy showed that ZnO pillared organic saponite improved the crystallinity of PLA. Thermal gravimetric analysis showed improved thermal stability of PLA because of ZnO pillared organic saponite. Thermal decomposition kinetics of PLA/ZnO pillared organic saponite nanocomposites was also studied. The activation energies (E_a) for thermal degradation of PLA and PLA/ZnO pillared organic saponite nanocomposites were evaluated by the Kissinger and Ozawa methods, which demonstrated that ZnO pillared organic saponite enhanced E_a of thermal degradation of PLA and significantly improved its thermal stability. Copyright © 2015 John Wiley & Sons, Ltd.     

Preparation and Characterization of the Nanocomposites SiO2/H-Bond Hydrogensulphate (Hydrogenselenate)

The nanocomposites representing interesting H-bond compounds (Na₃H(SO₄)₂, RbHSO₄, RbHSeO₄, and Rb₃H(SeO₄)₂) in the silica matrix were prepared by the sol-gel method. Resulting samples were characterised by X-ray diffraction, IR spectroscopy and electron microscopy. Transition temperatures of the nanocomposites were determined using DSC and compared with the T _C of the pure bulk active compounds. The shifts of the T _C towards lower temperatures or the disappearing of the certain effects in the case nanocomposites were observed. A possible explanation of these phenomena was proposed using the analogy with the superparamagnetic compounds.     

Preparation and properties of organo‐modifier free PET/MMT nanocomposites via monomer intercalation and in situ polymerization

In order to prevent the properties, especially transparency, color and health security, of PET/clay nanocomposites from being deteriorated due to the thermal degradation of clay organo‐modifer, we had directly modified sodium montmorillonite (Na⁺‐MMT) with PET's monomer, bis (hydroxyethyl) terephthalate (BHET) which had a degradation temperature higher than 400°C, and successfully prepared the hybrids via in situ polymerization. Nanodispersion of clay and the intercalated morphology were determined, and compared with PET/Na⁺‐MMT hybirds in which Na⁺‐MMT was directly added without any treatment. Improved mechanical properties and T_g were observed for the prepared PET/ BHET‐modified clay composites. More importantly, the film produced from the composites had the same transparency as that of pure PET even when 2 wt% of clay was added. Non‐isothermal and isothermal crystallization experiments showed a very good neculation capability of the nano‐dispersed clay, particularly at higher crystallization temperatures. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of nanosilica on the kinetics of cure reaction and thermal degradation of epoxy resin

Nanocomposites from nanoscale silica particles(NS),diglycidylether of bisphenol-A based epoxy(DGEBA),and 3,5-diamino-N-(4-(quinolin-8-yloxy) phenyl) benzamide(DQPB) as curing agent were obtained from direct blending of these materials.The effect of nanosilica(NS) particles as catalyst on the cure reaction of DGEBA/DQPB system was studied by using non-isothermal DSC technique.The activation energy(E_a) was obtained by using Kissinger and Ozawa equations. The E_a value of curing of DGEBA/DQPB/10%NS system showed a decrease of about 10 kJ/mol indicating the catalytic effect of NS particles on the cure reaction.The E_a values of thermal degradation of the cured samples of both systems were 148 kJ/mol and 160 kJ/mol,respectively.The addition of 10%of NS to the curing mixture did not have much effect on the initial decomposition temperature(T_i) but increased the char residues from 20%to 28%at 650℃.     

Variously substituted phenyl hepta cyclopentyl-polyhedral oligomeric silsesquioxane (ph,hcp-POSS)/polystyrene (PS) nanocomposites

A comparative study concerning the thermal stability of polystyrene (PS) and six POSS/PS nanocomposites of general formula R₇R′(SiO_1.5)₈/PS (where R = cyclopentyl and R′ = phenyl, 4-methoxyphenyl, 4-tolyl, 3,5-xilyl, 4-fluorophenyl, and 2,4-difluorophenyl) was carried out in both inert (flowing nitrogen) and oxidative (static air) atmospheres. Nanocomposites were prepared by in situ polymerization of styrene in the presence of 5 % w/w of POSS, but the actual filler concentration in the obtained nanocomposites, determined by ¹H NMR spectroscopy, was in all cases slightly higher than that in the reactant mixtures. FTIR spectra of nanocomposites evidenced the presence of filler-polymer interactions. Inherent viscosity (η _inh) determinations indicated that the average molar mass of polymer in methylated and fluorinated derivatives was lower than neat PS, and were in agreement with calorimetric glass transition temperature (T _g) measurements. Degradations were performed into a thermobalance, in the scanning mode, at 10 °C min^?1, and the temperatures at 5 % mass loss (T _5 %), of various nanocomposites were determined. The effects of various substituents of the POSS phenyl group on the thermal stability of nanocomposites were evaluated. The results were discussed and interpreted.     

Differential Pulse Polarography for a First‐Order EC Process and Its Diagnostic Parameters

Theoretical expressions for differential pulse polarography (DPP) for a reversible electron transfer coupled with an irreversible follow‐up first‐order chemical reaction (E_rC_i) is derived approximately. The peaks as given by the current expressions are analyzed in terms of several parameters such as a ratio of anodic‐to‐cathodic peak‐currents (i_p^a/i_p^c), a separation of peak‐potentials (E_p^c?E_p^a), and a ratio of anodic‐to‐cathodic half‐peak‐widths (W_1/2^a/W_1/2^c) in order to characterize the E_rC_i process and distinguish it from other types of electrode processes. The anodic peak is found to be more susceptible to the post kinetics than the cathodic peak. The new parameter of W_1/2^a/W_1/2^c ratio is much more sensitive to the post kinetics than the peak separation (E_p^c?E_p^a). The peak current ratio (i_p^a/i_p^c) and the peak‐width ratio (W_1/2^a/W_1/2^c) have comparable sensitivities to the kinetics. Hence, W_1/2^a/W_1/2^c ratio is a better diagnostic parameters than (E_p^c?E_p^a) which has a poor sensitivity. This phenomenon is different from cyclic voltammetry (CV) in which E_p^c?E_p^a is as sensitive as i_p^a/i_p^c. The new criteria for EC with DPV is tested and successfully applied to several Co(III) complex systems, including coenzyme B₁₂. The homogeneous rate constant (k) for the follow‐up step is estimated from the measurements of the experimental values of the parameters. The present treatment is valid quantitatively at lower values of k, yielding relatively larger errors for higher k values (k>10 s^?1).     

Thermal properties and kinetics of new-generation posterior bulk fill composite cured light-emitting diodes

In this study, the thermal behavior in terms of glass transition (T _g), degradation, and thermal stability of four commercial new-generation posterior bulk fill composites (Surefill SDR, Dentsply; Quixfill, Dentsply; Xtrabase, Voco; and Xtrafill, Voco) activated by light-emitting diodes (LEDs) was analyzed by thermogravimetric analysis (TG), differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA). The activation energies (E _a) for the decomposition of the dental resins were calculated based on the Kissinger and Doyle kinetic models from the peaks of the endothermic curves obtained when the specimens were heated at four different temperatures (5, 10, 15, and 20 °C min^?1) during DSC. The results show that the Xtrabase composite displayed the highest T _g (120 °C at a 5 °C min^?1 heating rate) and E _a (157.64 kJ mol^?1) values associated with thermal degradation from the main chain of the polymer.     

Study on the PMMA/GO nanocomposites with good thermal stability prepared by in situ Pickering emulsion polymerization

Graphene oxide (GO) is used as a stabilizer in the Pickering emulsion polymerization of methyl methacrylate (MMA) to prepare PMMA/GO nanocomposites. Transmission electron microscope studies of the emulsion polymerization products showed that the average diameter of nanocomposite particles was about 150 nm, the transparent GO flakes covered the surface of the particles, and were well dispersed in polymer matrix. The influence of GO on the thermal stability of PMMA was investigated by thermogravimetry analysis and differential scanning calorimetry. The results showed that the thermal stability and the glass transition temperature (T _g) of PMMA/GO nanocomposites were improved obviously compared with PMMA. The apparent activation energy (E _a) for the degradation process of PMMA/GO nanocomposites was evaluated by Kissinger method, which indicated that their E _a s were much higher than those of PMMA both in nitrogen and air atmosphere.     

Effect of nanoclay and barium sulfate nanoparticles on the thermal and morphological properties of polyvinylidene fluoride nanocomposites

The thermal, morphological and optical studies of BaSO₄ and MMT (nanoclay) embedded in PVDF were investigated. Nanocomposites samples of PVDF–BaSO₄–MMT were prepared by varying the loadings (1–4 mass%) in case of BaSO₄ and MMT nanomaterials, respectively. Polyvinylidene fluoride–barium sulfate-montmorillonite (PVDF–BaSO₄–MMT) nanocomposites were prepared by solvent-mixing technique. Nanoparticles were synthesized by in situ deposition technique with the help of nonionic polymeric surfactant, and the particle size of nanoparticles was recognized by scanning electron microscopy (SEM) analysis which confirms that the particle has diameter of 80–90 nm. As prepared, nanocomposites films (thickness, 25 μm) were characterized by Fourier transform infrared microscopy (FTIR), SEM and electron diffraction spectroscopy (EDS). FTIR shows that all the chemical constituents were present in the nanocomposites, whereas SEM analysis suggested that the nanofillers dispersed well in polymer matrix and EDS showed the elemental composition of nanocomposite samples. Thermal properties of nanocomposites were studied by using TG/DTA/DTG. TG/DTA studies showed decomposition temperature of pure PVDF is 473.5 °C. The decomposition temperature (T _d) of nanocomposites was increased by 93 °C in case of nanocomposites with addition of both BaSO₄ and MMT nanomaterials. The difference in the thermal degradation temperature was found to be 1.2% higher in case of addition of BaSO₄ nanoparticle as compared to nanoclay. The obtained transparent nanocomposite films were characterized by using UV–Vis spectrophotometer which shows that transparencies of nanocomposites are maintained in visible region, the intensity of absorption band in UV region is increased with the addition of BaSO₄ nanoparticles, while in case of addition of nanoclay the UV region does not show drastic changes. Addition of both nanoparticle and nanoclay shows higher absorption in comparison with the individual samples. But further, doubling the amount of nanoparticle and nanoclay shows decrease in UV absorption. Overall, the results of thermal studies show that the incorporation of BaSO₄ and MMT could significantly improve the thermal properties of nanocomposites.     

Effect of different nanoparticles on thermal decomposition of poly(propylene sebacate)/nanocomposites: Evaluation of mechanisms using TGA and TG–FTIR–GC/MS

In the present study poly(propylene sebacate) (PPSeb) nanocomposites containing 2 wt% of fumed silica nanoparticles (SiO₂) or multiwalled carbon nanotubes (MWCNTs), or montmorillonite (MMT) were prepared by in situ polymerization. The thermal degradation of nanocomposites was studied using thermogravimetric analysis (TGA). It was found that the addition of MWCNTs and MMT enhances the thermal stability of the polymer, while SiO₂ nanoparticles do not affect it. From the variation of the activation energy (E) with increasing degree of conversion it was found that the decomposition of nanocomposites proceeded with a complex reaction mechanism with the participation of at least two different steps. To evaluate the thermal decomposition mechanisms and mainly the effect of nanoparticles on the thermal decomposition of PPSeb, TGA/FTIR and a combination of TG-gas chromatography–mass spectrometry (TG/GC–MS) were used. From mass ions detection of the formed decomposition compounds it was found that the decomposition of PPSeb and its nanocomposites, takes place mainly through β-hydrogen bond scission and, secondarily, through α-hydrogen bond scission. The main decomposition products were aldehydes, alcohols, allyl, diallyl, and carboxylic acids.     

An experimental and theoretical mechanistic analysis of thermal degradation of polypropylene/polylactic acid/clay nanocomposites

Polypropylene/polylactic acid (PP/PLA) blends containing 5 wt% of nanoclay in presence and absence of an ethylene‐butylacrylate‐glycidyl methacrylate terpolymer as compatibilizer were prepared by melt‐mixing process. A matrix‐droplet–type morphology confirmed by transmission electron microscope (TEM) and scanning electron microscopy (SEM) studies is formed in presence and absence of the compatibilizer in which the clay platelets were mainly localized in the polylactic acid (PLA) dispersed phase. Degradation studies by means of thermogravimetry analysis (TGA) and analysis of degradation activation energy (E_a), T_max (maximum degradation temperature), and ΔT (difference between initial and final degradation temperatures) parameters for each polymer component of the system revealed that incorporation of less stable PLA phase to polypropylene (PP) decreases E_a and T_max parameters, and hence, reduces the thermal stability of PP phase, while incorporation of clay nanoplatelets to the neat blend further reduces its thermal stability attributed to their lack of localization in PP phase. Compatibilization of the filled system results in migration of clay nanoplatelets toward PP and improves E_a and T_max of PP phase. On the other hand, the E_a and T_max of PLA phase of the blend were increased with incorporation of clay and its localization within that phase, while compatibilization of the filled system slightly reduces thermal stability of PLA phase due to migration of clay toward PP. A correlation was found between E_a and intensity of the thermogravimetry analysis Fourier‐transform infrared spectroscopy (TGA‐FTIR) peaks of the evolved products. Using the Criado method, a detailed analysis on degradation mechanism of each component was performed, and the changes in the degradation mechanism of the developed systems were determined.     

Thermal and thermo-oxidative degradations of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO)/copoly(aryl ether sulfone) P(ESES-co-EES) block copolymers: a kinetic study

The thermal degradation of a series of three novel ABA block copolymers of different molar mass (M _n), were the block A is a poly(2,6-dimethyl-1,4-phenylene oxide) (PPO), while the block B is a random copoly(aryl ether sulfone) P(ESES-co-EES), was studied in both inert (flowing nitrogen) and oxidative (static air) atmospheres, to investigate the effects of M _n of the central block on the thermal stability. Copolymers were synthesized with a two step method: in the first stage, a linking molecule is selectively attached as end group to the P(ESES-co-EES) which reacts in the second step with the phenolic hydroxyl group of PPO. Degradations were carried out into a thermobalance, in the scanning mode, at various heating rates, and the characteristic parameters of thermal stability, namely initial decomposition temperature (T _i) and the activation energy (E _a) of degradation, of the various copolymers were determined. Both T _i and degradation E _a values increased exponentially as a function of M _n of copolymers. The results were discussed and interpreted.     

Effect of montmorillonite content and the type of its modifier on the thermal properties and flammability of polyimideamide nanocomposite fibers

The effects of montmorillonite (MMT) content (1, 3, 5%) and the type of its modifiers on the thermal properties and flammability of PIA nanocomposite fibers have been assessed. Sodium montmorrilonite was modified with aminododecane acid and octadecylamine. Samples of PIA nanocomposite containing commercial MMT: Nanomer PGW from Nanocor were also included in the comparative analysis. It has been found that the glass transition temperature (T _g) of the fibers under investigation depends on the type of MMT’s modifier. On the other hand this parameter does not affect the thermal stability of fibers defined with T ₅ and T ₅₀ indicators since the thermal decomposition of modifiers takes place at lower temperatures.