Kinetics of thermal degradation and thermal oxidative degradation of poly(p-dioxanone)

The kinetics of the thermal degradation and thermal oxidative degradation of poly(p-dioxanone) (PPDO) were investigated by thermogravimetric analysis. Kissinger method, Friedman method, Flynn-Wall-Ozawa method and Coats-Redfern method have been used to determine the activation energies of PPDO degradation. The results showed that the thermal stability of PPDO in pure nitrogen is higher than that in air atmosphere. The analyses of the solid-state processes mechanism of PPDO by Coats-Redfern method and Criado et al. method showed: the thermal degradation process of PPDO goes to a mechanism involving random nucleation with one nucleus on the individual particle (F₁ mechanism); otherwise, the thermal oxidative degradation process of PPDO is corresponding to a nucleation and growth mechanism (A₂ mechanism).     

Preparation, optimization and thermal characterization of a novel conductive thermoset nanocomposite containing polythiophene nanoparticles using dynamic thermal analysis

Polythiophene nanoparticles as a conductive filler was prepared with average diameter of 20-35 nm and its molecular structure was confirmed by the FT-IR, TEM, XRD and UV-vis analysis. A new conductive epoxy nanocomposite was synthesized by curing of diglycidyl ether of bisphenol A/4,4′-(4,4′ Isopropylidenediphenoxy) bis (Phthalic Anhydride) involving various percentages of polythiophene nanoparticles. DSC and DMTA studies revealed that low percentage of the polythiophene nanoparticles, i.e. 1%, results in improved crosslink density as evidenced by increasing in the glass transition temperature. The addition of polythiophene nanoparticles into the epoxy matrix resulted in a significant increment in the electrical conductivity, mechanical properties, thermal stability and activation energy of thermal degradation. The advanced isoconversional method is utilized to describe the curing behavior and thermal degradation process of the neat epoxy and epoxy nanocomposite. We have utilized the Coats-Redfern and Criado methods to find the solid state thermal degradation reaction mechanism. For the nanocomposite, the mechanism was recognized to be two-dimensional diffusion (D₂) reaction and it changes to a nucleation and growth (A₄) for pure epoxy system.     

Thermal decomposition of RDX/AP by TG–DSC–MS–FTIR

The method of TG–DSC–MS–FTIR simultaneous analysis has been used to study the thermal decomposition mechanism of the RDX/AP (1/2) mixture. TG–DSC showed that there were two mass loss processes for thermal decomposition of RDX/AP. The first one was mainly ascribed to the thermal decomposition of RDX. Addition of AP to RDX causes decomposition to take place abruptly, after melting, resulting in a very sharp and strong peak at lower temperature. The apparent activation energies, calculated by model-free Friedman method, of this process were negative. The second mass loss process of RDX/AP was confirmed to be the thermal decomposition of AP, catalyzed by RDX. This process can be divided into three stages, which were an nth-order autocatalytic and two one-dimensional diffusion stages, respectively. There was a competition among the formation reactions of N₂O, HNCO, and HCl for the first stage and between NO₂ and N₂O for the later two stages. The production of N₂O dominated in the second stage, while NO₂ did in the third stage.     

Thermal degradation mechanism of highly filled nano-SiO2 and polybenzoxazine

Effects of high nano-SiO₂ loading (up to 30 mass%) on polybenzoxazine (PBA-a) thermal degradation kinetics have been investigated using nonisothermal thermogravimetric analysis (TG). The DTG curves revealed three stages of thermal decomposition process in the neat PBA-a, while the first peak at low temperature was absent in its nanocomposites. As a consequence, the maximum degradation temperature of the nanocomposites shifted significantly to higher temperature as a function of the nano-SiO₂ contents. Moreover, the degradation rate for every degradation stage was found to decrease with the increasing amount of the nano-SiO₂. From the kinetics analysis, dependence of activation energy (E _a) of the nanocomposites on conversion (α) suggests a complex reaction with the participation of at least two different mechanisms. From Coats–Redfern and integral master plot methods, the average E _a and pre-exponential factor (A) of the nanocomposites showed systematically higher value than that of the PBA-a, likely from the shielding effect of the nanoparticles. The main degradation mechanism of the PBA-a was determined to be a random nucleation type with one nucleus on the individual particle (F1 model), while that of the PBA-a nanocomposite was the best described by diffusion-controlled reaction (D3 model).     

Influence of fullerene on the kinetics of thermal and thermo-oxidative degradation of high-density polyethylene by capturing free radicals

The influence of fullerene (C₆₀) on the thermal and thermal-oxidative degradation of high-density polyethylene (HDPE) was studied using non-isothermal thermogravimetric analysis under nitrogen (N₂) and air atmosphere. Kinetic parameters of the degradation were evaluated using the Flynn–Wall–Ozawa method, which does not require the knowledge of the reaction mechanism. The results showed that the addition of C₆₀ enhanced the thermal stability of HDPE and increased the activation energy both in N₂ and air atmosphere and especially affected the initial stage of degradation. In N₂, C₆₀-trapped carbon-centered radical originated from the degradation of HDPE to improve the thermal stability and increase the activation energy. While in air, C₆₀ trapped the alkyl radicals and alkyl peroxide radicals to inhibit the hydrogen abstraction (especially the initial stage of thermo-oxidative degradation) and form more stable species, which improved the thermal stability and increased the activation energy during the thermal degradation of HDPE. Comparing with that of pure HDPE, the changes of activation energy for HDPE/C₆₀ nanocomposites were higher in air than in N₂, especially in the initial stage.     

Mechanism and kinetics of thermal degradation of insulating materials developed from cellulose fiber and fire retardants

The mechanism and kinetics of thermal degradation of materials developed from cellulose fiber and synergetic fire retardant or expandable graphite have been investigated using thermogravimetric analysis. The model-free methods such as Kissinger–Akahira–Sunose (KAS), Friedman, and Flynn–Wall–Ozawa (FWO) were applied to measure apparent activation energy (E_α). The increased E_α indicated a greater thermal stability because of the formation of a thermally stable char, and the decreased E_α after the increasing region related to the catalytic reaction of the fire retardants, which revealed that the pyrolysis of fire retardant-containing cellulosic materials through more complex and multi-step kinetics. The Friedman method can be considered as the best method to evaluate the E_α of fire-retarded cellulose thermal insulation compared with the KAS and FWO methods. A master-plots method such as the Criado method was used to determine the possible degradation mechanisms. The degradation of cellulose thermal insulation without a fire retardant is governed by a D3 diffusion process when the conversion value is below 0.6, but the materials containing synergetic fire retardant and expandable graphite fire retardant may have a complicated reaction mechanism that fits several proposed theoretical models in different conversion ranges. Gases released during the thermal degradation were identified by pyrolysis–gas chromatography/mass spectrometry. Fire retardants could catalyze the dehydration of cellulosic thermal insulating materials at a lower temperature and facilitate the generation of furfural and levoglucosenone, thus promoting the formation of char. These results provide useful information to understand the pyrolysis and fire retardancy mechanism of fire-retarded cellulose thermal insulation.

     

A facile route of polythiophene nanoparticles via Fe3+‐catalyzed oxidative polymerization in aqueous medium

We have demonstrated that unsubstituted thiophene can be polymerized by Fe³⁺‐catalyzed oxidative polymerization inside nanosized thiophene monomer droplets, that is, nanoreactors, dispersed in aqueous medium, which can be performed under acidic solution conditions with anionic surfactant. Besides, we proposed a synthetic mechanism for the formation of the unsubstituted polythiophene nanoparticles in aqueous medium. This facile method includes a FeCl₃/H₂O₂ (catalyst/oxidant) combination system, which guarantees a high conversion (ca. 99%) of thiophene monomers with only a trace of FeCl₃. The average particle size was about 30 nm, within a narrow particle‐size distribution (PDI = 1.15), which resulted in a good dispersion state of the unsubstituted polythiophene nanoparticles. Hansen solubility parameters were introduced to interpret the dispersion state of the polythiophene nanoparticles with various organic solvents. The UV–Visible absorption and photoluminescence (PL) spectrum were measured to investigate the light emitting properties of the prepared unsubstituted polythiophene nanoparticle emulsions. According to non‐normalized PL analysis, the reduced total PL intensity of the polythiophene nanoparticle emulsions can be rationalized by self‐absorption in a wavelength range less than 500 nm. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2097–2107, 2008     

Thermal Degradation of Poly(Allyl Methacrylate) by Mass Spectroscopy and TGA

Allyl methacrylate, AMA was polymerized in CCl₄ solution by α,α′‐azoisobutyronitrile at 50°C. The thermal degradation mechanism of PAMA was characterized by MS, TGA‐FT‐IR and FT‐IR‐ATR methods. The mass spectrum and TGA thermogram showed two stage degradation. The first stage of degradation was mostly linkage type degradation for the fragmentation of pendant allyl groups at 225–350°C. In the second stage, at 395–515°C, the degradation is random scission and depolymerization types. This was also supported by direct thermal pyrolysis of polymer under vacuum. The degradation fragments of MS and TGA were in agreement. In the degradation process, monomer degraded further to CO, CO₂, allyl and ether groups. No strong monomer peak was observed in mass spectrum.     

A comparative study of thermal properties of sinocalamus affinis and moso bamboo

Moso bamboo (Phyllostachys pubescens) and sinocalamus affinis (Phyllostachys heterocycla) were used in the research. Thermogravimetry (TG), a combination of TG and Fourier transform infrared spectrometer (TG–FTIR), X-ray diffraction (XRD), and differential thermal analysis (DTA) were used to investigate thermal decomposition of bamboo. The calorific value and smoke release process of both bamboos were also tested, respectively. The results from TG indicated that degradation process of sinocalamus affinis and moso bamboo was similar, but their degradation temperatures were different. The main decomposition occurred in the second step and about 68.70 and 64.63% masses degraded for sinocalamus affinis and moso bamboo, whose temperature of maximum mass loss was 319 and 339 °C, respectively. DTA curve showed that the thermal decomposition of both bamboos was an absorbance heat process. TG–FTIR analysis showed that the main pyrolysis products of both bamboos were similar, including absorbed water (H₂O), methane gas (CH₄), carbon dioxide (CO₂), acids and aldehydes, ammonia gas (NH₃). The calorific value of moso bamboo (19,291 J g^?1 K^?1) was higher than that of sinocalamus affinis (18,082 J g^?1 K^?1). The initial time of smoke release process of moso bamboo was later, and its maximum smoke density was higher than that of sinocalamus affinis. The difference was probably attributed to different compositions and structure of sinocalamus affinis and moso bamboo. The results from this research are very helpful to better design manufacturing process of bio-energy, made from bamboo, by gasification and pyrolysis methods.     

Thermal degradation kinetics of polyimide containing 2,6-benzobisoxazole units

A novel polyimide (PI) based on 2,6-bis(p-aminophenyl)-benzo[1,2-d;5,4-d′]bisoxazole has been synthesized via a conventional two-stage procedure with bis(ether anhydrides) (HQDPA). The intermediate poly(amic acid) had inherent viscosities of 1.70 dl/g and could be thermally converted into light yellow polyimide film. The resulted polyimide showed excellent thermal stability, and the glass transition temperatures (T_g) were above 283 °C, the 5% weight loss temperature of the polymer was at 572 °C in N₂. The thermal degradation of the polyimide was studied by thermogravimetric analysis (TGA) in order to determine the actual reaction mechanisms of the decomposition process. The activation energy of the solid-state process was determined using Flynn-Wall-Ozawa method, which does not require knowledge of the reaction mechanism, which resulted to be 361.36 kJ/mol. The activation energy of different mechanism models and pre-exponential factor (A) were determined by Coats-Redfern method. Compared with the value obtained from the Ozawa method, the actual reaction mechanism obeyed nucleation and growth model, Avrami-Erofeev function (A₃) with integral form g(X) = [−ln(1−X)]³.     

Investigation of the thermal degradation of fully aromatic regular polyesters: Poly(oxy-1,4-phenyleneoxy-fumaroyl-bis-4-oxybenzoate)

The thermal behaviour and degradation mechanism of fully aromatic polyester, poly(oxy-1,4-phenyleneoxy-fumaroyl-bis-4-oxybenzoate), were studied by pyrolysis-gas chromatography and pyrolysis-gas chromatography/mass spectrometry at 500-700 °C, and by thermogravimetry. The influence of fullerene C₆₀ additives on thermal behaviour and thermal degradation was investigated. On the basis of pyrolysis products determined, the origin of the main degradation products (maleic anhydride, phenol, hydroquinone, phenyl ether, p-hydroxybenzoate-p′-phenol, etc.) was estimated. The fullerene is a well-known efficient acceptor of radicals and its presence influences the thermal degradation process of polymers shifting the decomposition from a radical pathway to a non-radical mechanism. Thermal degradation mechanism of poly(oxy-1,4-phenyleneoxy-fumaroyl-bis-4-oxybenzoate) is discussed in detail.     

Kinetics of thermal degradation of poly(aryl ether)s containing phthalazinone and life estimation

New special engineering thermoplastics, poly(phthalazinone ether sulfone) (PPES) and poly(phthalazinone ether sulfone ketone) (PPESK), containing phthalazinone are synthesized through step-polymerization. The kinetics of thermal degradation of PPES and PPESK (1/1) in nitrogen is investigated at several heating rates by thermogravimetry (TG). It is concluded that, based on using Satava’s theory, the thermal degradation mechanism of PPESK (1/1) is nucleation and growth, the order of reaction of the degradation process is one (n = 1). In contrast, the thermal degradation mechanism of PPES is a phase boundary controlled reaction and the order of the reaction is two (n = 2). The kinetic parameters, including reaction energy and frequency factor of thermal degradation reaction for PPES and PPESK (1/1) are analyzed using isoconversional Friedman, Kissinger–Akahira–Sunose (K–A–S) and Ozawa method. In addition, the study focus on the influence of heating rate and ratio of ketone/sulfone on thermal stability and the life estimation are described.     

Determination of kinetic triplet of the synthesized Ni3(PO4)2·8H2O by non-isothermal and isothermal kinetic methods

The nickel phosphate octahydrate (Ni₃(PO₄)₂·8H₂O) was synthesized by a simple procedure and characterized by FTIR, TG/DTG/DTA, AAS, and XRD techniques. The morphologies of the title compound and its decomposition product were studied by the SEM method. The dehydration process of the synthesized hydrate occurred in one step over the temperature range of 120–250 °C, and the thermal decomposition product at 800 °C was found to be Ni₃(PO₄)₂. The kinetic parameters (E and A) of this step were calculated using the Ozawa–Flynn–Wall and Kissinger–Akahira–Sunose methods. The iterative methods of both equations were carried out to determine the exact values of E, which confirm the single-step mechanism of the dehydration process. The non-isothermal kinetic method was used to determine the mechanism function of the dehydration, which indicates the contracting disk mechanism of R₁ model as the most probable mechanism function and agrees well with the isothermal data. Besides, the isokinetic temperature value (T _i) was calculated from the spectroscopic data. The thermodynamic functions of the activated complex (ΔS ^≠, ΔH ^≠, and ΔG ^≠) of the dehydration process were calculated using the activated complex theory of Eyring. The kinetic parameters and thermodynamic functions of the activated complex for the dehydration process of Ni₃(PO₄)₂·8H₂O are reported for the first time.     

Electrical conductivity and ion-exchange kinetic studies of polythiophene Sn(VI)phosphate nano composite cation-exchanger

A polymeric hybrid nanocomposite, namely polythiophene tin(IV)phosphate (PTh–SnP), was expediently synthesized by incorporating polythiophene (PTh) in tin phosphate (SnP) to enhance the conducting behavior and sorption of heavy metal ions by porous polymeric cation exchanger. Composite was characterized by Fourier Transform-Infra Red and Transmission Electron Microscopy. The dc electrical conductivity studies carried out on the composite, showed conductivity within the range of 4.0 × 10⁻²–1.0 × 10⁻³ S/cm⁻¹; measured by a 4-in line-probe dc electrical conductivity measuring technique. Ion-exchange kinetics for few divalent metal ions was evaluated by particle diffusion-controlled ion-exchange phenomenon at four different temperatures. The particle diffusion mechanism is confirmed by the linear τ (dimensionless time parameter) vs t (time) plots. The exchange processes thus controlled by the diffusion within the exchanger particle for the systems studies herein. Some physical parameters like self-diffusion coefficient (D₀)_, energy of activation (E_a) and entropy (ΔS°) have been evaluated under conditions favoring a particle diffusion-controlled mechanism.     

Crystalline properties and decomposition kinetics of cellulose fibers in wood pulp obtained by two pulping processes

In this study two cellulose fibers, Eucalyptus grandis (CEG) and Pinus taeda (CPT), obtained through the kraft and sulfite pulping processes, respectively, were characterized. Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) and thermogravimetric analysis (TGA) were carried out. From the XRD analysis the interplanar distance, crystallite size and crystallinity index were calculated and the degradation kinetics parameters were determined by TGA at heating rates of 5, 10, 20 and 40 °C min⁻¹ using the Avrami, Flynn-Wall-Ozawa (FWO) and Criado methods. The results obtained by FTIR showed that the composition of the fibers is similar, while from the XRD analysis slight differences in the crystallinity were observed. The thermogravimetric analysis showed higher thermal stability for CPT than CEG while the values for the activation energy (E_a) were higher for CEG than CPT. The results obtained by Avrami and Criado methods showed that the degradation mechanism in the CEG samples involves a diffusion process while in the case of CPT the degradation process is a phase boundary controlled reaction. The degradation mechanisms demonstrated that the difference between thermal stability and E_a may be due to differences in the type of crystalline structure of the samples obtained through the two pulping processes.     

Enhanced thermal properties and flame retardancy of unsaturated polyester‐based hybrid materials containing phosphorus and silicon

A phosphorus and silicon containing liquid monomer (9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene 10‐oxide–vinyltrimethoxysilane (DOPO–VTS)) was synthesized by the reaction between DOPO and VTS. DOPO–VTS and methacryloxypropyltrimethoxylsilane were introduced into unsaturated polyester resin to prepare flame retardant UPR/SiO₂ (FR‐UPR/SiO₂) hybrid materials by sol–gel method and curing process. DOPO–VTS contributes excellent flame retardancy to UPR matrix, which was confirmed by the limiting oxygen index and microscale combustion calorimeter results. The thermogravimetric analysis (TGA) results indicate that the FR‐UPR/SiO₂ hybrid materials possess higher thermal stability and residual char yields than those of pure UPR at high temperature region. The thermal degradation of materials was investigated by TGA/infrared spectrometry (TG‐IR) and real‐time infrared spectrometry (RT‐IR), providing insight into the thermal degradation mechanism. Moreover, scanning electron microscopy (SEM) and X‐ray photoelectron spectroscopy (XPS) were used to explore the morphologies and chemical components of the residual char. Copyright © 2013 John Wiley & Sons, Ltd.     

Temperature dependence of the thermophysical properties of polycrystallene chalcogenide glasses

The specific heat (C _p), thermal conductivity (λ), thermal diffusivity (a), and electrical conductivity (σ) were measured for polycrystalline HgS and Sb₂S₃ in the temperature range 300–600 K. The measurements were performed with an experimental apparatus based on a socalled flash method. The results showed that the mechanism of heat transfer is mainly due to phonons, whereas the contribution of electrons and bipolars is very small indeed. The energy gap of the samples was also calculated.     

The effect of fullerene on the resistance to thermal degradation of polymers with different degradation processes

Investigations were made about the effect of fullerene (C₆₀) on the resistance to thermal degradation of high density polyethylene (HDPE), polypropylene (PP), polymethyl methacrylate (PMMA), and bisphenol A polycarbonate (PC) matrix by using thermogravimetric analysis coupled to Fourier transform infrared spectroscopy. The results showed that the influences of C₆₀ on the resistance to the thermal degradation of different polymers were dependent on their thermal degradation mechanism. The resistance to the thermal degradation of HDPE, PP, and PMMA were improved with the addition of C₆₀, especially for HDPE matrix, which indicated that the radical trapping played a dominant role. PP and PMMA released more gaseous products at high temperature by the random scission of C–C backbone; owing to the lower bond dissociation energy of C–C in the backbone for the existence of side chains. Meanwhile, the steric hindrance of side chains also made the radicals hard to recombine with each other and accelerated the random scission, leading to the less effect on the resistance to the thermal degradation of PP and PMMA. However, few changes of resistance to the thermal degradation were found in PC matrix with the addition of C₆₀ for its non-radical degradation mechanism.     

Comparison of oxidation polymerization methods of thiophene in aqueous medium and its mechanism

Precipitation method of oxidation polymerization for preparing polythiophene was carried out as well as dispersion and emulsion methods in aqueous medium by using (NH₄)₂S₂O₈ and CuCl₂ as the oxidant and catalyst, respectively. In precipitation method, ethanol was served as an auxiliary solvent to water. The effective conjugated length (ECL) of the obtained polythiophene was demonstrated to be evaluated by the UV absorption spectrum. The ECL of the polythiophene gradually increases with the rise of the content of ethanol in the mixed solvent in precipitation polymerization, and it was higher comparing to the ECL of the product prepared by aqueous dispersion or emulsion method. An electron transition mechanism of the oxidation polymerization of thiophene was suggested.     

Free-radical degradation of solid poly(methyl methacrylate) initiated by photoreduction of the chloride complexes of Fe3+. Kinetics and mechanism

The kinetics have been studied quantitatively and a mechanism proposed for the free-radical degradation of solid PMMA initiated by photoreduction of the chloride complexes of Fe³⁺. The polymer was exposed in an inert atmosphere at 77 and 293 K to light of various spectral compositions with γ > 300 nm, not absorbed by the polymer. The rate of the build-up of the double isolated and conjugated bonds, formed as a result of thermal transformations of the PMMA macroradicals at 293 K, has been studied. It is shown that the isolated double bonds are generated at a rate equal to the initiation rate W, and the conjugated double bonds are generated at the rate of 0.3 W_i. A mechanism is proposed closely describing the observed regularities. It has been found that the degradation of PMMA irradiated at 77 K results from the thermal decomposition of macroradicals on heating the samples and is dependent upon the spectral composition of the light. The probability of degradation is 0.16 per photoreduced Fe³⁺ ion for light γ < 370 nm and decreases to only 0.009 for light with γ > 390 nm. It is concluded that macrochain breaking under these conditions is due to the thermal decomposition of the macroradicals ～CH₂C(CH₃)CH₂～ . At 293 K the photoinitiated PMMA degradation is a free-radical, but not a chain, process independent of the intensity and spectral composition of the light (in the wavelength range 313–390 nm), molecular mass of the polymer and film thickness. Degradation in an inert atmosphere is characterised by a probability factor per photoreduced Fe³⁺ ion (α) which increases with the degree of conversion of the initiators. The rate of degradation in an atmosphere of HCl is directly proportional to the initiation rate W_i. It is concluded that, at 293 K in an enert atmosphere, the rupture of macromolecules is due to the thermal decomposition of both the primary macroradicals ～C(CH₃)(COOCH₃)?H-C(CH₃)(COOCH₃)～ and the radicals ～CH₂-?(CH₃)CH₂～ formed by addition of low-molecular radicals to the radical reaction products in this system, i.e. the isolated middle double bonds.