Thermal degradation of biomedical polyurethanes—A kinetic study using high‐resolution thermogravimetry

The kinetics of thermal degradation of polyurethanes (PUR) has been studied by means of high‐resolution and constant heating rate thermogravimetry (TG), under nitrogen and synthetic air atmospheres. The high‐resolution TG provided a way to increase resolution with decreasing the time of data acquisition. In this mode, the heating rate is dynamically varied to maximize resolution. A method to calculate the kinetic parameters from this technique was used. The TG curves showed two or three decomposition steps, depending on the atmosphere employed. The parameters calculated for the PUR decomposition were the activation energy, reaction order, and preexponential factor. A method to estimate the polymer lifetime was also used. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 910–919, 2001     

High‐resolution thermogravimetry of cellulose esters

Cellulose dinitrate (CDN), cellulose diacetate (CDA), and cellulose triacetate (CTA) were subjected to high‐resolution thermogravimetry (TG) at a variable heating rate in air. The TG curves, the derivative TG curves, the second derivative TG curves, and heating rate curves are discussed. The thermal degradation temperature and kinetic parameters are presented and compared to those obtained with traditional TG at a constant heating rate. The degradation process of the cellulose esters is speculated. Among the three cellulose esters, CDN exhibits the lowest degradation temperature of (213°C) but the largest degradation activation energy of (237–269 kJ/mol). © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 573–578, 1999     

High‐resolution thermogravimetry of poly(2,6‐dimethyl‐1,4‐phenylene oxide)

The thermal degradation and kinetics of poly(2,6‐dimethylphenylene oxide) (PPO) were studied by high‐resolution thermogravimetry. The thermogravimetry measurements were conducted at an initial heating rate of 50°C min⁻¹, resolution 4.0, and sensitivity 1.0 in both nitrogen and air from room temperature to 900°C. A two‐step degradation process was clearly revealed in air at the temperatures of 430°C and 521°C. The thermal degradation temperatures and kinetic parameters of the PPO appear to be higher in air than in nitrogen, indicative of a higher thermostability in air. The temperature, activation energy, order, and frequency factor of the thermal degradation of the PPO in nitrogen are 419°C, 100–120 kJ mol⁻¹, 0.5, and 13–17 min⁻¹, respectively. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1887–1892, 1999     

High‐resolution thermogravimetry of poly(4‐methyl‐1‐pentene)

Thermal degradation and kinetics of poly(4‐methyl‐1‐pentene) were investigated by nonisothermal high‐resolution thermogravimetry at a variable heating rate. Thermal degradation temperatures are higher, but the maximum degradation rates are lower in nitrogen than in air. The degradation process in nitrogen is quite different from that in air. The average activation energy and frequency factor of the first stage of thermal degradation for the poly(4‐methyl‐1‐pentene) are 2.4 and 2.8 times greater in air than those in nitrogen, respectively. Poly(4‐methyl‐1‐pentene) exhibits almost the same decomposition order of 2.0 and char yield of 14.3–14.5 wt % above 500°C in nitrogen and air. The isothermal lifetime was estimated based on the kinetic parameters of nonisothermal degradation and compared with the isothermal lifetime observed experimentally. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2201–2207, 1999     

Thermal degradation of bisphenol A polycarbonate by high-resolution thermogravimetry

Thermal degradation of bisphenol A polycarbonate (PC) has been studied in nitrogen and air from room temperature to 900 °C by high-resolution thermogravimetry (TG) with a variable heating rate in response to changes in the sample's degradation rate. A three-step (in nitrogen) or four-step (in air) degradation process of the PC, which was hardly ever revealed by traditional TG, has been found. The initial thermal degradation temperature of the PC is higher in nitrogen than in air, but the three kinetic parameters (activation energy E, decomposition order n, frequency factor Z) of the major degradation process are slightly lower in nitrogen. The average E, n and lnZ values determined by three methods in nitrogen are 154 KJ mol⁻¹, 0.8 and 21 min⁻¹, respectively, which are almost the same as those calculated by traditional TG measurements. © 1999 Society of Chemical Industry     

Structure and high‐resolution thermogravimetry of liquid‐crystalline copoly(p‐oxybenzoate‐ethylene terephthalate‐p‐benzamide)

Thermotropic liquid‐crystalline copoly(ester‐amide)s consisting of three units of p‐oxybenzoate (B), ethylene terephthalate (E) and p‐benzamide (A) were studied by proton nuclear magnetic resonance at 200 and 400 MHz, wide‐angle X‐ray diffraction, and high‐resolution thermogravimetry to ascertain their molecular and supermolecular structures, thermostability and kinetics parameters of thermal decomposition in both nitrogen and air. The assignments of all resonance peaks of [¹H]NMR spectra for the copoly(ester‐amide)s are given and the characteristics of X‐ray equatorial and meridional scans are discussed. Overall activation energy data of the first major decomposition have been evaluated through three calculating techniques. The thermal degradation occurs in three steps in nitrogen and air. The degradation temperatures are higher than 447 °C in nitrogen and 440 °C in air and increase with increasing B‐unit content at a fixed A‐unit content of 5 mol%. The temperatures at the first maximum weight‐loss rate are higher than 455 °C in nitrogen and 445 °C in air and also increase with an increase in B‐unit content. The first maximum weight‐loss rates range between 11.1 and 14.5%min⁻¹ in nitrogen and between 11.9 and 13.5%min⁻¹ in air. The char yields at 500 °C in both nitrogen and air range from 45.8 to 54.3 wt% and increase with increasing B‐unit content. But the char yields at 800 °C in nitrogen and air are quite irregular with the variation of copolymer composition and testing atmosphere. The activation energy and Ln (pre‐exponential factor) for the first major decomposition are usually higher in nitrogen than in air and increase slightly with an increase in B‐unit content at a given A‐unit content of 5 mol%. The activation energy, decomposition order, and Ln (pre‐exponential factor) of the thermal degradation for the copoly(ester‐amide)s in two testing atmospheres, are situated in the ranges of 210–292 kJmol⁻¹, 2.0–2.8, 33–46 min⁻¹, respectively. The three kinetic parameters of the thermal degradation for the aromatic copoly(ester‐amide)s obtained by high‐resolution thermogravimetry at a variable heating rate are almost the same as those by traditional thermogravimetry at constant heating rate, suggesting good applicability of kinetic methods developed for constant heating rate to the variable heating‐rate method. These results indicate that the copoly(ester‐amide)s exhibit high thermostability. The isothermal decomposition kinetics of the copoly(ester‐amide)s at 450 and 420 °C are also discussed and compared with the results obtained based on non‐isothermal high‐resolution thermogravimetry. © 1999 Society of Chemical Industry     

Thermal degradation of high‐temperature fluorinated polyimide and its carbon fiber composite

High‐temperature polymers are being used for a broad range of applications, such as composite matrices for structural applications (e.g., high speed aircraft). Polyimides are a special class of polymers that meet the thermal and oxidative stability requirements for high temperature composite aerospace applications. A weight loss study was performed on a fluorinated polyimide resin and its carbon fiber composite in an effort to determine its thermal stability and degradation mechanisms. Experiments were conducted using a preheated oven and thermogravimetric analysis to obtain the weight loss. Regardless of the method used, the resin and composite exhibited excellent thermal stability (less than 1% weight loss) below 430°C, regardless of 2–20 min of exposure. After 20 min of exposure at 510°C, the composite remained relatively stable with only 5.3% weight loss using the oven technique, whereas the neat polyimide sustained 12.6%. When degradation occurred, it was found to be the result of thermolysis and oxidation (to a lesser extent). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

High‐resolution thermogravimetry of polyphenylene sulfide film under four atmospheres

Thermal degradation of polyphenylene sulfide (PPS) film was investigated in air, nitrogen, helium, and argon with different physical and reactive characteristics from room temperature to 790°C by a high‐resolution thermogravimetry (TG) at a variable heating rate in response to the changes in the sample's weight‐loss rate. In nitrogen and argon, only a single‐step degradation process of the PPS was observed, but in helium, a two‐step degradation process of PPS was found. Notably, in air a four‐step degradation process of the PPS, which was hardly ever revealed by a traditional TG, was found in this investigation. The initial thermal degradation temperature T_d and temperature at the first maximum weight‐loss rate T_dm1 of the PPS increased in the following order: in helium < in nitrogen < in argon < in air. The first maximum weight‐loss rate also increased with the variation of atmosphere in the order: nitrogen < air < argon < helium. The char yield at 700°C increased in the order: in air < in helium < in nitrogen < in argon. The activation energy of the major degradation process of PPS calculated based on the high‐resolution TG data was very high, increasing in the order: in nitrogen < in argon < in helium < in air. The thermal decomposition parameters of the PPS determined by the high‐resolution TG were systematically compared with those by traditional TG at a constant heating rate. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2053–2059, 2002     

High‐resolution thermogravimetry of poly(phenylene sulfide) film under four atmospheres

The thermal degradation of poly(phenylene sulfide) (PPS) film is investigated in air, nitrogen, helium, and argon with different physical and reactive characteristics at room temperature to 790°C as ascertained by high‐resolution thermogravimetry (TG) at a variable heating rate in response to the changes in the sample's weight‐loss rate. Only a one‐step degradation process of the PPS is observed in nitrogen and argon, but a two‐step degradation process of PPS is found in helium. A four‐step degradation process of the PPS, which is hardly ever revealed by traditional TG, is found in this investigation, especially in air. The initial thermal degradation temperature and temperature at the first maximum weight‐loss rate of the PPS increase in the following order: helium < nitrogen < argon < air. The first maximum weight‐loss rate also increases with the variation of the atmosphere in the order nitrogen < air < argon < helium. The char yield at 700°C increases in the order air < helium < nitrogen < argon. The activation energy of the major degradation process of PPS, as calculated based on the high‐resolution TG data, is very high and increases in the order nitrogen < argon < helium < air. The thermal decomposition parameters of the PPS determined by the high‐resolution TG are systematically compared with those by traditional TG at a constant heating rate. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1940–1946, 2002     

Thermogravimetric kinetics of thermotropic copolyesters containing p‐oxybenzoate unit by multiple heating‐rate methods

Two series of thermotropic liquid crystalline copolyesters containing mainly the p‐oxybenzoate unit were studied by thermogravimetry to ascertain the kinetic parameters of their thermal degradation by six multiple heating‐rate techniques for the first time. The two copolyesters are (1) poly(p‐oxybenzoate‐co‐ethylene terephthalate‐co‐vanillate) and (2) poly(p‐oxybenzoate‐co‐2,6‐oxynaphthoate). The effect of copolymer composition, degradation stage, and test atmosphere on the three kinetic parameters of the thermal degradation in the weight loss range from 5 to 70% is discussed. Comparison of the multiple heating‐rate techniques with single heating‐rate techniques for calculating the kinetic parameters of thermal degradation was made. The respective activation energy, order, and natural logarithm of the frequency factor of the thermal degradation in nitrogen for the poly(p‐oxybenzoate‐co‐ethylene terephthalate‐co‐vanillate)s are between 180 and 230 kJ/mol, between 2.0 and 5.0, and between 28 and 38 min⁻¹ for the first degradation step and between 250 and 390 kJ/mol, between 6.4 and 7.6, and between 38 and 64 min⁻¹ for the second degradation step of the poly(p‐oxybenzoate‐co‐ethylene terephthalate‐co‐vanillate)s with the unit‐B content in the range of 70–75 mol %. The respective activation energy, order, and natural logarithm of frequency factor of the first degradation stage for the poly(p‐oxybenzoate‐co‐2,6‐oxynaphthoate) (Vectra) are between 380 and 570 kJ/mol, between 2.0 and 3.1, and between 55 and 68 min⁻¹ in nitrogen and between 160 and 210 kJ/mol, between 0.8 and 1.8, and between 25 and 32 min⁻¹ in air. The best methods of calculating the kinetic parameters of the thermal degradation for the copolymers are suggested. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2016–2028, 1999     

Thermal degradation kinetics of thermotropic poly(p‐oxybenzoate‐co‐p,p′‐biphenylene terephthalate) fiber

An advanced heat‐resistant fiber (trade name Ekonol) spun from a nematic liquid crystalline melt of thermotropic wholly aromatic poly(p‐oxybenzoate‐p,p′‐biphenylene terephthalate) has been subjected to a dynamic thermogravimetry in nitrogen and air. The thermostability of the Ekonol fiber has been studied in detail. The thermal degradation kinetics have been analyzed using six calculating methods including five single heating rate methods and one multiple heating rate method. The multiple heating‐rate method gives activation energy (E), order (n), frequency factor (Z) for the thermal degradation of 314 kJ mol⁻¹, 4.1, 7.02 × 10²⁰ min⁻¹ in nitrogen, and 290 kJ mol⁻¹, 3.0, 1.29 × 10¹⁹ min⁻¹ in air, respectively. According to the five single heating rate methods, the average E, n, and Z values for the degradation were 178 kJ mol⁻¹, 2.1, and 1.25 × 10¹⁰ min⁻¹ in nitrogen and 138 kJ mol⁻¹, 1.0, and 6.04 × 10⁷ min⁻¹ in air, respectively. The three kinetic parameters are higher in nitrogen than in air from any of the calculating techniques used. The thermostability of the Ekonol fiber is substantially higher in nitrogen than in air, and the decomposition rate in air is higher because oxidation process is occurring and accelerates thermal degradation. The isothermal weight‐loss results predicted based on the nonisothermal kinetic data are in good agreement with those observed experimentally in the literature. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1923–1931, 1999     

Thermal degradation of poly(p‐phenylenebenzobisoxazole) and poly(p‐phenylenediamine terephthalamide) fibres

This study investigates the thermal stability of poly(p‐phenylenediamine‐terephtalamide) (PPT) and poly(p‐phenylenebenzobisoxazole) (PBO) fibres. Excellent behaviour of PBO is shown in comparison to that of PPT. The thermal stability (under pyrolytic or thermo‐oxidative conditions) of PBO is 150 °C higher than that of PPT. Moreover, the strong influence of oxygen, which plays the role of an initiator of degradation, on the degradation of fibres is shown. Using the invariant kinetic parameter (IKP) method, it is shown that the degradation rate of PBO is strongly reduced in comparison with that of PPT. It provides a simulation of the ‘fuel flow’ able to feed the flames, which can explain the high fire performance of PBO compared to PPT. © 2001 Society of Chemical Industry     

聚乙烯的热降解动力学研究

采用三种不同的动力学分析方法,即Freeman方法、Flynn-Wall-Ozawa以及Kissinger方法对不同类型聚乙烯的热分解动力学进行了探讨。结果表明,Flynn-Wall-Ozawa法I、Friedman法的测试结果与三者聚乙烯的结构特征较吻合,不同聚乙烯降解活化能的大小顺序为HDPE>LLDPE>LDPE。     

Kinetics of thermal degradation of thermotropic poly(p‐oxybenzoate‐co‐ethylene‐2,6‐naphthalate) by single heating rate methods

The kinetics of thermal degradation of thermotropic liquid crystalline poly(p‐oxybenzoate‐co‐ethylene‐2,6‐naphthalate) (PHB/PEN) with the monomer ratio of 60 : 40 and PEN in nitrogen was studied by dynamic thermogravimetry (TG). The kinetic parameters, including the activation energy E_a, the reaction order n, and the frequency factor ln(Z) of the degradation reaction for PHB/PEN (60 : 40) and PEN were analyzed by the single heating rate methods of Friedman and Chang. The effects of the heating rate and the calculating method on the thermostable and degradation kinetic parameters are systematically discussed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91:3915–3920, 2004     

Thermal degradation of cellulose and cellulose esters

Cellulose, cellulose diacetate (CDA), cellulose triacetate (CTA), cellulose nitrate (CN), and cellulose phosphate (CP) were subjected to dynamic thermogravimetry in nitrogen and air. The thermostability of the cellulose and its esters was estimated, taking into account the values of initial thermal degradation temperature T_d, the temperature at the maximum degradation rate T_dm, and char yield at 400°C. The results show that these polymers may be arranged in the following order of increasing thermostability: CN < CP < regenerated cellulose < filter cotton < CDA < CTA. The activation energy (E), order (n), and frequency factor (Z) of their degradation reactions were obtained following the Friedman, Chang, Coats–Redfern, Freeman–Carroll, and Kissinger methods. The dependence of T_d, T_dm, E, n, Ln Z, and char yield at 400°C on molecular weight and test atmosphere is also discussed. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:293–304, 1998     

Two‐step degradation of high‐density polyethylene during multiple extrusion

Ensuing our recent studies on polyethylene stabilization,^1,2 further multiple extrusion experiments were carried out with a high‐density polyethylene (HDPE) polymer containing various amounts of a sterically hindered phenolic antioxidant. Discoloration, thermoxidative stability, and melt flow index (MFI) retention were measured by standard techniques; the functional group content of the polymer was determined by Fourier transform infrared (FTIR) spectroscopy, and rheological, as well as mechanical properties, were also measured. The results indicated that degradation and stabilization reactions take place according to two different mechanisms in the first and subsequent processing steps, respectively. Color development could be described well by the simple first‐order overall reaction kinetics proposed earlier, and color change could be related to the stability of the polymer. The existence of general correlations among the properties proved that all chemical reactions are interrelated. The reactions of the stabilizer lead to color development, while those of the polymer to a modification of its molecular architecture, which determines the rheological and mechanical characteristics of the product. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1596–1605, 1999     

Thermal stability and kinetics analysis of rubber‐modified epoxy resin by high‐resolution thermogravimetric analysis

A dynamic heating rate mode of high‐resolution thermogravimetric analysis was used to study the thermal and thermal‐oxidative stability, as well as kinetics analyses, of a model liquid rubber‐modified epoxy resin, Ep/CTBN, made up of bisphenol A diglycidyl ether‐based epoxy and carboxyl‐terminated butadiene acrylonitrile rubber (CTBN). Results show that the thermal degradation of Ep/CTBN resin in nitrogen and air consists of two and three independent steps, respectively. Moreover, Ep/CTBN has a higher initial degradation temperature and higher activation energy than those of pure epoxy resin in both gases, indicating that the addition of CTBN to epoxy can improve the thermal and thermal‐oxidative stability of pristine epoxy resin. Kinetic parameters such as activation energy, reaction order, and preexponential factor of each degradation step of both Ep/CTBN and pure epoxy resins in air and nitrogen were calculated. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3594–3600, 2003     

Thermal aging of a blend of high‐performance fibers

The focus of this work is the study of the thermal aging of high‐performance fibers used in the making of fire protective garments. Accelerated thermal aging tests were carried out on fabric samples made up of a blend of Kevlar® (poly p‐phenylene terephthalamide) and PBI (poly benzimidazole) staple fibers, as well as on yarns pulled from this fabric, by means of exposure to elevated temperatures, comprised between 190°C and 320°C. All samples underwent loss of breaking force retention. The material thermal life, defined as the time required for the fibers to attain a 50% reduction of the original breaking force, ranged between a dozen of days at the lowest exposure temperature, to less than an hour at the highest. Breaking force data were fitted using the Arrhenius model following two different approaches, namely the extrapolated thermal life value and the shift factors yielded by the time‐temperature superposition (TTS). The Arrhenius model seemed to describe appropriately the overall aging process, as inferred from the excellent fit obtained when using both approaches, although activation energies provided from both approaches are different. To follow the chemical evolution of the material with thermal aging, Fourier‐transform infrared (FTIR) analyses were conducted. The qualitative analysis of the FTIR spectra showed little evidence of chemical changes between the aged and the nonaged samples, indicating either that the aging process carries on without significant modification of the chemical structure of the fibers, or that FTIR is not an appropriate method to spot such a modification. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

High‐resolution thermogravimetry of polyethersulfone chips in four atmospheres

Thermal degradation and kinetics of polyethersulfone (PES) chips were studied in air, nitrogen, helium, and argon from room temperature to 790°C by high‐resolution thermogravimetry (TG) at a variable heating rate in response to changes in the sample's degradation rate. In the four atmospheres, a two‐step degradation process in air, argon, and helium or a three‐step degradation process in nitrogen of the PES were found in this investigation. In particular, the three‐step degradation process in nitrogen of the PES revealed by the high‐resolution TG was hardly ever observed by a traditional TG. The initial thermal degradation temperature of the PES increases with the testing atmosphere in the following order: air < argon < helium < nitrogen but the activation energy of the first major degradation of PES increases in a different order: argon < nitrogen < helium < air. The degradation temperature, the temperature at the maximum weight‐loss rate, the maximum weight‐loss rate [(dα/dT)_m1 and (dα/dT)_m2], char yield at 790°C, and activation energy of the first major degradation process obtained by the high‐resolution TG were compared with those by traditional TG. The PES exhibits the largest (dα/dT)_m1 and the greatest char yield at 790°C in helium but the largest (dα/dT)_m2 and smallest char yield in air. A significant dependency of the thermal decomposition of the polymers on the physicochemical properties (density, thermal conductivity, and oxidative ability) of the testing atmospheres is elaborated for the first time. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3631–3637, 2003     

Improvement of adhesion of Kevlar fiber to epoxy by chemical modification

Kevlar 149 fibers were surface-modified by chlorosulfonation and subsequent reaction of -SO₂O with some reagents (e.g. glycine, water, ethylenediamine, and 2-butanol) to improve the adhesion to epoxy resin. The mechanical properties and surface topography of the modified fibers were investigated at different reaction times and reagent concentrations. The surface functional groups introduced into the surface of the fibers were identified by X-ray photoelectron spectroscopy (XPS) and static secondary ion mass spectroscopy (SIMS). The interfacial shear strength (IFSS) between the fibers and epoxy resin was measured by the microbond test. The results showed that the IFSS was markedly improved (by a factor of 2.25) by the chlorosulfonation/glycine treatment and that the fiber strength was not affected. Scanning electron microscopy (SEM) was also used to study the surface topography of fibers pulled from the epoxy resin. Furthermore, energy dispersive X-ray (EDX) spectroscopy was used to qualitatively examine the amount of sulfur in the fiber surfaces and in the fracture surfaces of fibers from microbond pull-out specimens. The results of EDX examination were consistent with a change of the fracture mode from the interface between the fiber and the epoxy resin to a location within the fiber and/or epoxy resin as observed by SEM.