Thermal Stability and Degradation Kinetics of Poly(Methyl Methacrylate)/Sepiolite Nanocomposites by Direct Melt Compounding

Poly(methyl methacrylate) (PMMA) nanocomposites based on sepiolite modified with trimethyl hydrogenated tallow amine by an adsorption process were prepared by melt compounding using a corotating twin screw extruder. The morphology and dispersion of sepiolite in the PMMA were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Thermal stability and the activation energies were investigated by thermogravimetric analysis/differential thermogravimetric (TGA/DTG). The XRD and TEM results show that the sepiolite was dispersed homogeneously in the PMMA matrix at a nanometer scale. The TGA analysis revealed that the addition of sepiolite improved the thermal stability of PMMA. The apparent activation energies were calculated by the method of Flynn–Wall–Ozawa in nitrogen at four different heating rates, showing that sepiolite increased the apparent activation energies by about 20 kJ/mol within the degree of conversion (α) of 0.35–0.9, as compared with the reference PMMA sample.     

Characteristics and Kinetics of Thermal Degradation of Fluoroether Rubber

An advanced, heat-resistant fluoroether rubber (FM-20) was subjected to dynamic thermogravimetric analysis (TGA) in the air atmosphere. The results suggested that its thermal degradation process can be divided into two parts. As the heating rate increased, the initial decomposition temperature and degradation temperature would move to higher ranges. The apparent activation energy of thermal decomposition, calculated by the Kissinger, Friedman and Flynn-Wall-Ozawa methods were 209, 240, and 211kJ/mol, respectively. Furthermore, the probable thermal degradation mechanism was also analyzed by the Coats-Redfern method. As a result, the most reasonable thermal degradation mechanism of FM-20 was g (α) = α^3/2     

A Kinetic Study on the Thermal Degradation of Polypropylene/Attapulgite Nanocomposites

In this work, a polypropylene (PP)/attapulgite nanocomposite was prepared via melt blending using a novel organically modified attapulgite (OATP). The thermal stability of PP/clay nanocomposites compared to pure PP was examined in nitrogen using a kinetic analysis. The kinetic parameters, including reaction order and activation energy (A and E _a) of the degradation process were determined by applying the Flynn‐Wall‐Ozawa method using derivative thermogravimetric (DTG) curves. At the same time, the effect of organic attapulgite on thermal decomposition of polypropylene matrix was analyzed. As a result, PP/OATP nanocomposites have slightly higher degradation temperature than that of the pure PP. The values of the reaction order of PP and PP/OATP nanocomposites are close to 1 in the nonisothermal degradation process. The activation energies of PP/OATP nanocomposites also increase slightly compared to the pure PP, thus it is suggested that the org‐attapulgite has little effect on the thermal stability of the pure PP.     

Thermal Degradation Behavior and Kinetics of Polybenzoxazine Based on Bisphenol-S and Allylamine

The thermal degradation behavior of polybenzoxazine based on bisphenol-S/allylamine was studied by Fourier transform–infrared spectroscopy and thermogravimetry–mass spectrometry. The reaction proceeded through detaching of Schiff bases and cleavage of aromatic C–S bonds and the Mannich bridge structures; the scission temperature of the aromatic C–S bond was lower than those of C–N and C–C bonds. The activation energy of the thermal degradation was evaluated with the Flynn–Wall–Ozawa method.     

Basic Mechanisms of Thermal Degradation of the Compositions of Synthetic Restoration Polymers With Metal Oxides

Using the method of diffuse reflection spectroscopy, we studied thermal degradation of the compositions of white pigments with a number of synthetic polymers intended for restoration of paint layers of paintings. It has been established that, starting with 340 K, the heating of polymer compositions with TiO₂, regardless of the polymer type, induces absorption in the pigment at 2.88 and 2.50 eV, which can be referred to color centers (CC) fixed to oxygen vacancies. In the spectra of the compositions of fluorine-containing polymers with MgO and Al₂O₃, absorption bands in the blue region, which are induced when T > 315–320 K, can be ascribed to the hole color centers in oxides. The measurement of temperature dependences for the rate of increase in the absorption bands in programmed heating permitted determination of the activation energies of thermal degradation E _td. The dependence of E _td on the polymer type is attributed to the fact that reactions on the surface of pigments are limited by the activation of bonds in adsorbed macromolecules.     

Thermal Degradation Kinetics of Plasticized Poly (Vinyl Chloride) with Six Different Plasticizers

Plasticized PVC formulated with different kinds of normally used plasticizers, including bis(2-ethylhexyl) phthalate (DOP), dioctyl terephthalate (DOTP), acetyl tri-n-butyl citrate (ATBC), acetyl trioctyl citrate (ATOC), trioctyl trimellitate (TOTM), and a new vegetable devived plasticizer, isosorbide ester (ID-37), were prepared by a melt blending method. The effect of plasticizer on the thermal degradation behavior of plasticized PVC was investigated by thermal gravimetric analysis (TGA). The activation energies were calculated by three well known methods, developed by Flynn-Wall-Ozawa (FWO), Friedman and Kissinger, respectively. The TGA conducted in N₂ atmosphere showed that the type of plasticizer had an obvious influence on the thermal stability of plasticized PVC. It was found that the peak temperatures (T_P) of the thermal degradation processes shifted to higher temperature with the increase of the heating rate, with two processes being shown. The activation energy of the first thermal decomposition process (E₁), calculated by the Kissinger method, was between 118 and 130 kJ/mol, while the activation energy of the second thermal decomposition process (E₂) was between 261 and 305 kJ/mol, except 499 kJ/mol for the PVC/TOTM formulation. The corresponding values of E₁ and E₂ obtained by the Flynn-Wall-Ozawa method were similar to the above data. E of the sample with TOTM also showed a higher value than the others; the results demonstrated that the PVC plasticized with TOTM was more thermally stable than with the others. The activation energies for certain conversion degrees were calculated by the Friedman method and the FWO method. The value of activation energy for 20%, 50%, and 80% conversion calculated by the Friedman method, exhibited an apparent difference from that calculated by the Flynn-Wall-Ozawa method; the results showed that the value of E obtained by the Friedman method was much more reasonable than that obtained by the Flynn-Wall-Ozawa method.     

Nonisothermal Degradation Kinetics and Life Prediction of the Pendent Phenyl-Containing Polyarylate

The nonisothermal degradation kinetics of a pendent phenyl-containing polyarylate (PAR-P)were studied using different kinetic models, including the Kissinger method, Flynn–Wall–Ozawa (FWO) method, and Coats–Redfern (CR) method. The “three kinetic factors” of degradation, namely, activation energy (E), pre-exponential factor (A), and the reaction mechanism function (f(α)) were determined by these methods. Moreover, the lifetime equations of PAR-P were deduced, and its lifetime was predicted. The Kissinger method could be used to describe the nonisothermal degradation of PAR-P, and the results indicated that PAR-P could be degraded more easily in air than in nitrogen. The FWO method was expected to give more reliable values of the activation energy (209.71 kJ·mol^?1 in nitrogen and 176.22 kJ·mol^?1 in air) due to not having to introduce the reaction mechanism function during the calculation. According to the results of the CR method, the thermal degradation reaction mechanism was probably the R1 model in nitrogen, while it was likely to be the F2 model in air. The long-term and short-term use temperatures of PAR-P in air were 260°C and 300°C, respectively. The lifetime of PAR-P in nitrogen was much longer than that in air at low temperature, but had little difference when the use temperature exceeded 260°C. Although the lifetime of PAR-P obtained from the present work was unrealistic due to probable contributions from other unconsidered factors and being determined by a single factor method, it still could play a guiding role for designing the structure and determining the use conditions of the material.     

Kinetics Study of the Thermal Decomposition of Post-consumer Poly(Ethylene Terephthalate) in an Argon Atmosphere

The thermal decomposition of post-consumer samples of a carbonated water bottle made of poly(ethylene terephthalate), PC-PET, was examined by linear temperature programing under an argon atmosphere to determine its mass loss kinetics. A simple kinetic model, called the first order pseudo single-component model, was used. The total weight-loss of each sample assumed to be in two periods, with each period corresponding to a one step decomposition of the PC-PET to volatiles. Three methods for determining the kinetic parameters by thermal gravimetric analysis were examined: differential analysis at a constant heating rate (differential), temperatures of a given conversion at a number of heating rates (isoconversional), and the maximum rate at multiple heating rates (peak temperature). The latter two multiple heating rates methods results were comparable to each other but they were not in agreement with the results from the differential method. The results of the differential method were insensitive to the heating rate and consistent with kinetics data reported in the literature for PET.     

A Kinetic Study of the Thermal Degradation of Nylon-6/Attapulgite Nanocomposites

The thermal degradation behavior of nylon-6 (PA6) and PA6/attapulgite (ATP) nanocomposites was investigated by thermogravimetric analysis under non-isothermal conditions at various heating rates in nitrogen. It is suggested that during thermal degradation, ATP, as a protective barrier, can slow down degradation of polymer, but the catalytic effects of structural water and hydroxyl groups may accelerate the degradation of PA6. The combination of these two effects determined the final thermal stability of nanocomposites. The apparent activation energies of the samples were evaluated by the Kissinger and Flynn–Wall–Ozawa methods. The results showed that the presence of ATP adversely affected the thermal stability of PA6. The degradation activation energies of PA6/ATP nanocomposites decreased monotonically with increase in ATP content; thus, it is suggested that the ATP has a disadvantageous effect on the thermal stability of PA6.     

Thermal Field-Flow Fractionation of Initially Dilute Polymer Solutions as a Shear Degradation Model. Scaling Model of Macromolecule Degradation at Concentrations Exceeding the Critical Entanglement Value

Experimental data are presented on thermal field-flow fractionation (TFFF) of anionic polystyrene (PS) samples in the range M = (4–12)·10⁶. They show extensive degradation of macromolecular chains at relatively low rate gradients (G < 30 s^?1). The possibility of the influence of relaxation effects on the shape of fractograms and the elution volumes of the samples was taken into account. Mean concentrations in accumulative zones were evaluated. It was shown that, in all cases when degradation was observed, the accumulative zones are the layers of entangled macromolecules. The use of the scaling approach made it possible to simulate layer extension toward the channel center under the influence of the rate gradient. It was shown that, during stretching, the layer is destroyed into blobs, the size of which is determined by experimental conditions. An expression for the critical gradient leading to layer degradation was derived. Quantitative evaluations of fragment sizes and critical gradients obtained from the model are in good agreement with experimental data. The model developed for specific experimental conditions confirms the proposed general mechanism of the so-called shear degradation of macromolecules. The physical picture of degradation in the TFFF channel was considered.     

Effect of Polyborosiloxane on the Flame Retardancy and Thermal Degradation of Intumescent Flame Retardant Polypropylene

A novel synergistic flame retardant agent containing boron and silicon, namely polyborosiloxane (PBSil), was prepared via the condensation reaction of boric acid (BA), tetraethoxysilane (TEOS), and octamethyl cyclotetrasiloxane (OMCTS). The obtained PBSil was then combined with an intumescent flame retardant (IFR) to flame retard polypropylene (PP), and the effects of PBSil on the flame retardancy and thermal degradation of the PP/IFR composite were investigated. It was found that PBSil could improve the compatibility between the IFR and the PP matrix, thereby improving the mechanical properties of the composite. Compared with zinc borate, zeolite, and nano-silica, PBSil showed much better flame retardancy and smoke suppression in the PP/IFR composite. When the content of PBSil was 3.0 wt%, the limiting oxygen index (LOI) value of the flame retardant PP was increased from 29.0% to 35.0%, and the UL-94 rating was improved from V-1 to V-0 rating. Simultaneously, the heat release rate (HRR) and smoke production rate (SPR) of the composite were decreased dramatically. The thermogravimetric (TG) analysis, Fourier transform infrared (FTIR), and thermogravimetry-Fourier transform infrared spectrometry (TG-FTIR) results showed that, PBSil could enhance the thermostability of the IFR, and promote the char formation. Furthermore, the compactness and thermostability of the intumescent char were significantly improved, contributing to the improvement of the flame retardancy of the composite.     

Mechanistic Study of the Flame Retardancy of Epoxy Resin With a Novel Phosphorus and Silicon-Containing Flame Retardant

Abstract

An epoxy resin (EP) composite with a novel phosphorus and silicon-containing flame retardant (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-polyvinylsilicone-polyphenylaminosilicone, DOPO-V-PA) was prepared in this study. From the cone calorimeter measurements, it was confirmed that the EP/DOPO-V-PA (FREP) composite had relatively better flame retardancy than pure EP. The activation energy was calculated with the Kissinger and Ozawa–Flynn–Wall methods. The results showed that the activation energies of pure EP had slightly higher values than the FREP composite in the early and middle degradation stage (conversion ≤ 90% spaces), which indicated that the earlier degradation of the DOPO-V-PA at low temperature accelerated the degradation of the EP matrix. However, the activation energy values of the FREP were higher than those of pure EP in the final stage, which are attributed to the thermal stabilization effect of the DOPO-V-PA through the promoting of EP char formation.     

Kinetic Evaluation of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide as a Flame Retardant for Epoxy Resins

Abstract

In this investigation the flame-retardant effect of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) on an epoxy resin (EP) was studied. The results showed that the peak of heat release rate (PHRR) and total heat release (THR) of EP/DOPO (FREP) with 5phr DOPO during cone calorimeter measurements were only 67.4% and 75.3% of those of pure EP, respectively. The thermal degradation behavior of FREP was analyzed by the Kissinger and Flynn-Wall-Ozawa methods, both of which indicated that the activation energy of the FREP thermal degradation was lower than that of pure EP. This was attributed to the addition of DOPO into the resin, which promoted the thermal degradation of the EP composite.     

On a multistable competitive network model in the case of an inhomogeneous growth rate spectrum: With an application to priming

A stability analysis of a network model proposed by Haken is carried out for the case of an inhomogeneous spectrum of growth rates. The degree of multistability as a function of the coupling strength between network units is determined. An application to priming shows that the network can reconstruct the fundamental phenomenon that primed items have shorter recall latencies than non-primed items when assuming that learning affects the inhomogeneity of the growth rate spectrum.     

On the performance of an ArF and a KrF laser as a function of the preionisation timing and the excitation mode

An X-ray preionised ArF and KrF excimer laser has been studied with three different spiker-sustainer excitation circuits. We observed large differences in the laser performance, when the preionisation delay timing was varied on a nanosecond timescale. The behaviour of both lasers was found to be equivalent. The observations can be understood by considering the effect of the discharge excitation technique on the preionisation process. An excitation mode with a prepulse well above the steady-state voltage V_SS with a subsequent reversed overshoot voltage for initiating the discharge, in combination with a well-timed preionisation pulse is found to give the best results. Optimum output energies of 50 mJ with ArF and 175 mJ with KrF were obtained from an active volume of 60×1.5×1.2 cm in the so-called swing mode, with the preionisation applied 60 ns before the discharge breakdown. Received: 23 February 1999 / Revised version: 4 June 1999 / Published online: 16 September 1999