Thermal behavior of polymethacrylonitrile

The intramolecular cyclization by heating and the thermal degradation of polymethacrylonitrile samples prepared with various initiators, AIBN (A), BPO (B), BuLi (C), Et₂Mg (D), and methacrylonitrile–methacrylic acid copolymer (E), were investigated by DTA, TGA, and infrared spectroscopy. The rate of formation of ? C?N? linkages determined by IR was in the order of E > C > D > B > A. An endothermic peak of DTA thermogram due to thermal degradation was observed at approximately 345°C for the ionically initiated samples, whereas two endothermic peaks were observed at approximately 315°C and 365°C for the radically initiated ones. In the TGA thermograms, although the ionically initiated samples decomposed continuously in a single stage, the radically initiated ones showed weight loss in two steps, with an inflection point at about 330°C. The first stage of thermal degradation of radically initiated samples was concluded to be initiated at the terminal double bonds formed as a result of termination by disproportionation, and the second one at higher temperatures is initiated at random in the polymer. The ionically initiated samples without terminal double bond decompose exclusively by random scission.     

Synthesis and characterization of poly(vinyl 2,4,6‐trinitrophenylacetal) as a new energetic binder

Poly(vinyl alcohol) was modified by an aldehyde acetal reaction with 2,4,6‐trinitrophenylacetaldehyde to give a new energetic polymer poly(vinyl 2,4,6‐trinitrophenylacetal) (PVTNP). The structure of PVTNP was characterized by elemental analysis, ultraviolet–visible spectroscopy, Fourier transform infrared spectroscopy, and nuclear magnetic resonance spectra. The glass‐transition temperature of PVTNP was evaluated by differential scanning calorimetry (DSC), and the thermal stability of PVTNP was tested by differential thermal analysis (DTA) and thermogravimetric analysis (TGA). DSC traces showed that the PVTNP polymer had one single glass‐transition temperature at 105.3°C. DTA and TGA curves showed that the thermooxidative degradation of PVTNP in air was a three‐step reaction, and the percentage of degraded PVTNP reached nearly 100% at 650°C. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Kinetics of thermal degradation and fire retardant efficiency of polyesters

Seven polyesters having different amounts of halogen were studied for kientics of degradation and fire retardant efficiency. Out of them, the polyesters number 1, 2, 3, and 4 had the molar ratios of chlorendic acid to isophthalic acid of 0.25, 0.67, 1.5, and 4.0 respectively. The polyesters number 5, 6, and 7 were based on dimethyl-di-(p-oxyacetoxymethylphenyl)-methane, dimethyl-di-(3,5-dichloro-4-oxyacetoxymethylphenyl) methane and dimethyl-di-(3,5-dibromo-4-oxyacetoxymethylphenyl)-methane respectively. These studies were done with the help of thermogravimetric analysis (TGA), differential thermal analysis (DTA), infra-red spectroscopy and glow rod apparatus. The thermal stability of these polyesters decreased in the following order: 5 > 6 > 7 > 1 > 2 > 3 > 4, taking the threshold temperature as a measure of the thermal stability. The 50% weight loss temperature determined from TGA curves supported this to some extent. These studies further revealed that these polyesters degrade in two stages. The first stage of degradation ranged from 250–450°C. The second stage of degradation is in the range of 450–600°C. In the first stage, the range of temperature for degradation is constricted by increasing the halogen content. Bromination is more effective than chlorination. The activation energy for degradation of these polyesters showed the same trend as the thermal stability. But the flame resistance is somewhat in the reverse order of thermal stability. These studies also confirm a cyclic mechanism for flame retardancy.     

Thermogravimetric and differential thermal analysis of cellulose,hemicellulose, and lignin

The thermal degradation of samples of cellulose, hemicellulose, and lignin have been investigated using the techniques of thermogravimetric analysis (TGA) and differential thermal analysis (DTA) between room temperature and 600°C. The results calculated from static and dynamic TGA indicated that the activation energy E for thermal degradation for different cellulosic, hemicellulose, and lignin samples is in the range 36–60, 15–26, and 13–19 kcal/mole, respectively. DTA of all the wood components studied showed an endothermic tendency around 100°C in an atmosphere of flowing nitrogen and stationary air. However, in the presence of flowing oxygen this endothermic effect was absent. In the active pyrolysis temperature range in flowing nitrogen and stationary air atmospheres, thermal degradation of Avicel cellulose occurred via a sharp endothermic and a sharp exothermic process, the endothermic nadir and exothermic peak being at 320° and 360°C, respectively. In the presence of oxygen, combustion of Avicel cellulose occurred via two sharp exothermic processes. DTA studies of different cellulose samples in the presence of air showed that the shape of the curve depends on the sources from which the samples were prepared as well as on the presence of noncellulosic impurities. Potassium xylan recorded a sharp exothermic peak at 290°C in a nitrogen atmosphere, and in a stationary air atmosphere it yielded an additional peak at 410°C, while in the presence of oxygen the curve showed two sharp exothermic peaks. DTA traces of periodate lignin in flowing nitrogen and air were the same and showed two exothermic peaks at 320° and 410°C, while in the presence of oxygen there were two exothermic peaks in the temperature range 200°–500°C.     

Thermogravimetric analysis of olive-oil residue in air atmosphere

In olive-oil producing countries, large amounts of waste material are generated as by-product for which there is no ready use and in some cases may have a negative value because of the cost of disposal. Most of these countries depend on fossil fuels for their energy uses, and olive-oil residue can be used to supplement such energy sources using thermochemical conversion processes. However, efficient operation of thermochemical conversion systems requires a thorough understanding of the influence of the composition and thermal properties of these by-products on their behaviour during the conversion process. In this study, the thermal behaviour of two olive-oil residue samples (non-leached and water-leached olive-oil residue) was examined at three heating rates (10, 20, and 50 °C min^− 1) in air atmosphere using the technique of thermogravimetric analysis. The thermal degradation rate in active and passive zones, the initial degradation temperature, and the residual weight at 700 °C were determined. Increasing the heating rate increased the thermal degradation rate, the residual weight at 700 °C, and the initial degradation temperature. The thermal degradation rate and the initial degradation temperature increase with the cellulosic content of the olive-oil residue. Also, higher ash content in the olive residue resulted in higher residual weight at 700 °C.     

Synthesis and characterization of epoxy film cured with phosphorous‐containing phenolic resin

Through the electrophilic addition reaction of ? P(O)? H and C?C, a series of novel phosphorus‐containing phenolic resins bearing maleimide (P‐PMFs) were synthesized and used as curing agent for preparing high performance and flame retardancy epoxy resins. The structure of the resin was confirmed with FTIR and elemental analysis. Thermal properties and thermal degradation behaviors of the thermosetted resin was investigated by using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The epoxy resins exhibited high glass transition temperature (143–156°C), goof thermal stability (>330°C) and retardation on thermal degradation rates. High char yields (700°C, 52.9%) and high limited oxygen indices (30.6–34.8) were observed, indicating the resins' good flame retardance for the P‐PMFs/CNE cured resins. The developed resin may be used potentially as environmentally preferable products in electronic fields. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3813–3817, 2007     

Effect of zeolite filler on the thermal degradation kinetics of polypropylene

In this study, the thermal degradation behavior of polypropylene (PP) and PP–zeolite composites was investigated. Clinoptilolite, a natural zeolitic tuff, was used as the filler material in composites. The effects of both pure clinoptilolite and silver‐ion‐exchanged clinoptilolite on the thermal degradation kinetics of the PP composites was studied with differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Polymer degradation was evaluated with DSC at heating rates of 5, 10, and 20°C/min from room temperature to 500°C. The silver concentration (4.36, 27.85, and 183.8 mg of Ag/g of zeolite) was the selected parameter under consideration. From the DSC curves, we observed that the heat of degradation values of the composites containing 2–6% silver‐exchanged zeolite (321–390 kJ/kg) were larger than that of the pure PP (258 kJ/kg). From the DSC results, we confirmed that the PP–zeolite composites can be used at higher temperatures than the pure PP polymer because of its higher thermal stability. The thermal decomposition activation energies of the composites were calculated with both the Kissinger and Ozawa models. The values predicted from these two equations were in close agreement. From the TGA curves, we found that zeolite addition into the PP matrix slowed the decomposition reaction; however, silver‐exchanged zeolite addition into the matrix accelerated the reaction. The higher the silver concentration was, the lower were the thermal decomposition activation energies we obtained. As a result, PP was much more susceptible to thermal decomposition in the presence of silver‐exchanged zeolite. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 143–148, 2006     

Effect of cupric ion on thermal degradation of chitosan

The thermal degradation of chitosan and chitosan–cupric ion compounds in nitrogen was studied by thermogravimetry analysis and differential thermal analysis (DTA) in the temperature range 30–600°C. The effect of cupric ion on the thermal degradation behaviors of chitosan was discussed. Fourier transform-infrared (FTIR) and X-ray diffractogram (XRD) analysis were utilized to determine the micro-structure of chitosan–cupric ion compounds. The results show that FTIR absorbance bands of  N H,  C N ,  C O C etc. groups of chitosan are shifted, and XRD peaks of chitosan located at 11.3, 17.8, and 22.8° are gradually absent with increasing weight fraction of cupric ion mixed in chitosan, which show that there are coordinating bonds between chitosan and cupric ion. The results of thermal analysis indicate that the thermal degradation of chitosan and chitosan–cupric ion compounds in nitrogen is a two-stage reaction. The first stage is the deacetylation of the main chain and the cleavage of glycosidic linkages of chitosan, and the second stage is the thermal destruction of pyranose ring of chitosan and the decomposition of residual carbon, in which both are exothermic. The effect of cupric ion on the thermal degradation of chitosan is significant. In the thermal degradation of chitosan–cupric ion compounds, the temperature of initial weight loss (T_st), the temperature of maximal weight loss rate (T_max), that is, the peak temperature on the DTG curve, and the peak temperature (T_p) on the DTA curve decrease, and the reaction activation energy (E_a) varies with increasing weight fraction of cupric ion. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Pyrolysis kinetics of Athabasca bitumen using a TGA under the influence of reservoir sand

Pyrolysis kinetics of thermal decomposition of bitumen was investigated by thermogravimetric analysis (TGA). TGA experiments were conducted at multiple heating rates of 5, 10, 20°C min^–1 up to 800°C to obtain the pyrolysis characteristics of bitumen. Weight loss curve from TGA shows that two different stages occurred during bitumen pyrolysis. Differential method has been used for determining the kinetic parameters and the best fit for the order of reaction was found based on the R² values. Kinetics results confirm the presence of two different stages in bitumen pyrolysis with varying kinetic parameters. The average activation energy for the first and second stage was 29 and 60 kJ mol^?1 and the average order of the reaction was 1.5 and 0.25, respectively. Experiments have been conducted with different reservoir sand. The effect of different source of sand reveals no effect on the pyrolysis behaviour of bitumen. A considerable difference was found with the pyrolysis of bitumen–sand mixtures and bitumen alone based on coke yield and activation energy. © 2011 Canadian Society for Chemical Engineering     

Thermal and morphological studies of chemically prepared emeraldine‐base‐form polyaniline powder

In this study, emeraldine base (EB)‐form polyaniline (PANI) powder was chemically prepared in 1M HNO₃ aqueous solution. The thermal characteristics and chemical structures of this powder were studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), and X‐ray diffraction (XRD). A polarizing optical microscope was also used to examine the crystalline morphology of this sample. The results indicated that the EB‐form PANI powder had a discernible moisture content. Moreover, in the first run of DSC thermal analysis, the exothermic peak at 170–340°C was due to the crosslinking reaction occurring among the EB‐form PANI molecular chains. FTIR and XRD examinations further confirmed the chemical crosslinking reaction during thermal treatment. TGA results illustrated that there were two major stages for weight loss of the EB‐form PANI powder sample. The first weight loss, at the lower temperature, resulted from the evaporation of moisture. The second weight loss, at the higher temperature, was due to the chemical structure degradation of the sample. The degradation temperature of the EB‐form PANI powder was around 420–450°C. The degradation temperature of emeraldine salt (ES)‐form PANI powder was lower (around 360–410°C) than that of the EB form (around 420–450°C). From the TGA results, I roughly estimated that 2.74 aniline repeat units, on average, were doped with 1 HNO₃ molecule in the ES‐form PANI. I found a single crystalline morphology of EB‐form PANI, mostly like a conifer leaf. More complex, multilayered dendritic structures were also found. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2142–2148, 2003     

Synthesis,characterization, and kinetic study of functional polystyrenes

In this study, functionalization of polystyrene (PS) (M_n = 2.5 × 10⁵) was carry out with maleic anhydride in the presence of boron trifluoride dietyhletherade (BF₃ OEt₂) as catalyst and then functional PS was subjected to condensation reaction with phenyl hydrazine. The structures of both of them were determined by using FTIR, ¹H‐NMR, elemental analysis, thermogravimetric analysis (TGA) and differential thermal analysis (DTA) techniques. Some physical properties of these two products were investigated and the kinetic parameters of solid state decomposition reactions were determined from TGA curves. The intrinsic viscosity [η] values of modified PS and condensation products (cPs) found to be 1.024 and 0.7036 dL g^?1, respectively. According to TGA, the weight losses of modified PS and cPs were found to be 84.03 and 81.86%, respectively, at 500°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Thermal degradation kinetics of rigid polyurethane foams blown with water

The thermal decomposition behavior of rigid polyurethane foams blown with water was studied by dynamic thermogravimetric analysis (TGA) in both nitrogen and air atmosphere at several heating rates ranging from room temperature to 800°C. The kinetic parameters, such as activation energy (E), degradation order (n), and pre‐exponential factor (A) were calculated by three single heating rate techniques of Friedman, Chang, and Coats–Redfern, respectively. Compared with the decomposition process in nitrogen, the decomposition of foams in air exhibits two distinct weight loss stages. The decomposition in nitrogen has the same mechanism as the first stage weight loss in air, but the second decomposition stage in air appears to be dominated by the thermo‐oxidative degradation. The heating rates have insignificant effect on the kinetic parameters except that the kinetic parameters at 5°C/min have higher values in nitrogen and lower values in air, indicating different degradation kinetics in nitrogen and air. The kinetic parameters of foam samples blown with different water level in formulation decline firstly and then increase when water level increases from 3.0 to 7.0 pph. According to the prediction for lifetime and half‐life time of foams, water‐blown rigid foams have excellent thermostability, when used as insulation materials below 100°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:4149–4156, 2006     

Thermal behavior of some homogeneously polymethyl methacrylate (PMMA)‐grafted high α‐cellulose products

The graft copolymerization of methyl methacrylate (MMA) onto high α‐cellulose was carried out homogeneously in an N,N‐dimethyl acetamide/lithium chloride solvent system by using benzoyl peroxide as radical initiator. The rate of grafting was evaluated as a function of concentrations of initiator and monomer, reaction time, and temperature. The grafted products were characterized with the help of infrared spectroscopy, whereas the thermal decomposition of optimum PMMA‐grafted high α‐cellulose was studied using TGA, DTG, and DTA techniques at two heating rates, 10 and 20°C/min, in nitrogen atmosphere in the range of room temperature to 650°C. Three major decomposition steps were identified and the relative thermal stabilities of the PMMA‐grafted high α‐cellulose products were assessed. The kinetic parameters for the three decomposition steps were estimated with the help of two well‐known methods. The thermal stability of the grafted products decreased with the increase of graft yield (GY). Crystallinity or peak intensity of wide‐angle X‐ray diffraction patterns decreased with the increase of GY. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3471–3478, 2004     

Function of sulfur dioxide in the kinetic mechanism of oxidation of carbon

Retardation of the gasification reaction of carbon with oxygen by SO₂ was observed. Rates of oxidation were determined by thermal gravimetric analysis (TGA) of a nuclear graphite in the temperature range of 550–700°C, and of a coconut charcoal in the temperature range of 400–505°C. The oxidant gases were dry air containing 0–6% SO₂. Reduction of the rate by SO₂ varied with burn-off. Differential thermal analysis (DTA) was also applied to detect the retardation effect of SO₂. The technique of infrared internal reflection spectroscopy (IRS) was used to examine the surface species of reacted charcoal samples. Absorption bands were assigned to surface carbonyls, lactones, and a chemisorbed SO₂ in the form of sulfate. Chemisorption of SO₂ was attributed to cause the retardation of the oxidation reaction.     

Influence of polyhedral oligomeric silsesquioxanes on thermal and mechanical properties of polycarbonate/POSS hybrid composites

Two types of silsesquioxanes were synthesized by hydrolytic condensation reaction, and then were incorporated into polycarbonate (PC) matrix by melt blending to prepare PC/POSS hybrid composites. The study of morphology of the composites showed that octaphenylsilsesquioxane (PH‐POSS) exhibited partial compatibility with PC matrix, while 3‐glycidyloxypropylsilsesquioxane (EP‐POSS) could react with phenolic hydroxyl groups of matrix. Thermal and mechanical properties were studied by DSC, TGA, and DMA. The result showed that the incorporation of POSS not only improved thermal stabilities of PC composites, but also retarded their thermal degradation. Si O fractions left during POSS degradations were the key factor governing the formation of a gel network layer on the exterior surface. This layer possessed more compact structures, higher thermal stabilities, and some thermal insulation. In addition, percentage residues at 700°C (C₇₀₀) significantly increased from 10.8 to 15.5–22.8% in air. The storage modulus of two series of composites was slightly improved up to 90°C; furthermore, the temperature range of the rubbery state of them shifted to high temperature. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Thermal studies on kraft black liquor

Kraft black liquor and lignin from the same batch were subjected to thermal analysis (DTA and TGA) under an inert atmosphere and also in an oxidising atmosphere to simulate conditions which might be encountered in the recovery furnace. Gasification studies were carried out by rapidly heating the sample under helium. Results showed that the thermal decomposition of black liquor can be divided into four characteristic steps: drying up to 200°C, pyrolysis between 200 and 550°C, inorganic sodium salt formation between 550 and 800°C and salt fusion between 800 and 1000°C. Gases evolved during gasification of black liquor are rich in flammable compounds while those from the lignin sample are rich in CO₂.     

Study on preparation of chlorinated natural rubber from latex and its thermal stability

The effects of pH value of reaction system, reaction time, and reaction temperature on the chlorination reaction in the preparation of chlorinated natural rubber (CNR) from natural rubber latex were discussed. It has been found from the thermal analysis that the thermal degradation of CNR in nitrogen is a one-step reaction, and 30% carbonide with a stable structure remained at 360 to 700°C; whereas the thermo-oxidative degradation of CNR in air is a multistep reaction, and the thermal degradation ratio reaches to 100% at 560°C. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2863–2867, 1999     

Characterization of reworkable high-temperature adhesives for MCM-D application

The need to have a high-temperature adhesive that can withstand temperatures in excess of 350°C for MCM-D silicon substrate process application, yet which can be reworkable at slightly high temperature ∼ 400°C for the removal from the glass pallet, is important. A novel, reworkable, high-temperature adhesive based on polyimide–amide–epoxy (PIAE) copolymer was developed and investigated using modulated differential scanning calorimetry (MDSC), thermal gravimetric analysis (TGA), Fourier Transform Infrared Spectroscopy (FTIR) and solid-probe pyrolysis mass spectroscopy (MS). Compared with commercial polyimide–amide (PIA) adhesives, FTIR spectra reveal that the thermally degradative ester groups contribute to the reworkability of the PIAE adhesive at a specific temperature (400°C), yet they remain thermally stable at a lower working temperature (350°C). FTIR spectrum comparison of the residuals of PIAE and PIA are similar after exposure to 400°C. MS spectra of outgassed products identify that the components of radical fragmentation from PIAE are due to polymeric chain degradation at 400°C, while only volatile trace water and N-methyl pyrolidone (NMP) are evolved from the commercial PIA adhesive. TGA results suggest a complementary explanation for the variation of total ion current (TIC) curves on these two adhesives. MDSC curves further verify that the reworkable PIAE adhesive is a copolymer. Furthermore, a reasonable thermal degradation mechanism is presented on the adhesive reworkability. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 997–1005, 1999     

Effect of preparation methods on thermal properties of poly(acrylic acid)/silica composites

Poly(acrylic acid)-silica composites have been prepared by two different methods and thermally characterized. The glass transition temperature (T_g) of the PAA-SiO₂ system prepared by mixture method was found to be 120°C irrespective of the type and amounts of silica involved in this work. However, the T_g varied between 132°C and 113°C in the systems prepared by polymerization reaction depending upon the type of silica and percentage conversion. The composites prepared by mixture and polymerization method have been investigated by using thermogravimetry (TGA) to follow the kinetics of anhydride formation and thermal degradation reactions. The activation energy of thermal anhydride formation and thermal degradation reaction was not found to change very much with ratio of PAA-SiO₂ when the composites were prepared by simple mixing. For the composites prepared by polymerization method the activation energy of anhydride formation and thermal degradation reaction were observed to change with percentage conversion. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 891–895, 1998     

Kinetics of Curing and Thermal Degradation of POSS Epoxy Resin/DDS System

Polyhedral oligomeric silsesquioxanes epoxy resin (POSSER) was prepared from 3-glycidypropyl-trimethoxysilane (GTMS) and tetramethylammonium hydroxide (TMAH) by hydrolytic condensation. POSSER was characterized using Fourier-transformed infrared spectroscopy (FTIR), ¹H-NMR, and liquid chromagraphy/mass spectrometry (LC/MS). The epoxy value of POSSER is 0.50 mol/100 g. The LC/MS analysis indicated that T₁₀ is the majority and contain some amount of T₈, besides, a trace T₉ also exists. The curing kinetics of POSSER with 4,4′-diaminodipheny sulfone (DDS) as a curing agent was investigated by means of differential scanning calorimetry (DSC). The curing reaction order n is 0.8841 and the activation energy Ea is 61.06 kJ/mol from dynamic DSC analysis. Thermal stability and kinetics of thermal degradation were also studied by thermal gravimetric analysis (TGA). TGA results indicated that the temperature of POSSE/DDS system 5% weight loss is approximately 377.0°C, which is higher by 12.6°C than that of pure POSSER, and the primary degradation reaction (300–465°C) followed first order kinetics; the activation energy of degradation reaction is 75.81 kJ/mol.