Thermal degradation of poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) in drying treatment

This study examines the isothermal treatment of poly(3‐hydroxybutyrate) (PHB) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) powders and films. The PHB and PHBV crystallinities were determined using X‐ray diffractometry, and shown to increase with temperature (130–150°C) and then decreased from 55% to 45% at 180°C. The crystal morphology of crystal planes (101) and (111) became sharp at a high temperature. The weight average molecular weight (M_w) of PHB decreased from 1,028,000 to 41,800 g/mol when heated at 180°C for 30 min. The molecular weight of PHB decreased more rapidly than that of PHBV with time. No peak signal was observed in gel permeation chromatography after heating at 150°C because the solubility of PHB changed with crystallinity. The thermal behaviors of PHB and PHBV were analyzed by differential scanning calorimetry and thermogravimetric analysis. The roughness, contact angle, and surface morphology of PHB and PHBV films were also measured to determine the surface properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3659–3667, 2013     

Effects of Time and Temperature on the Viscoelastic Properties of Chinese Fir Wood

The effects of time and temperature on dynamic viscoelastic properties of Chinese fir (Cunninghamia lanceolata [Lamb.] Hook) were investigated using dynamic mechanical analysis in this study. The isothermal tests were applied to the small clear specimens with a moisture content of about 0.6% at constant temperatures ranging from 25 to 200°C for 550 min at atmospheric pressure. Changes in storage modulus and loss tangent with heating time were examined. The results indicated that heating time mainly resulted in thermal softening, thermal degradation of wood, and the reduction of wood stiffness. At more than 60°C, the reduction in storage modulus was accelerated generally as the wood was subjected to a higher temperature or longer heating time. At constant temperatures of 140 and 160°C, a relaxation phenomenon was observed with a slight change in weight, which could be attributed to the relocation of lignin molecules. At the temperature range of 140 to 180°C, the higher the heating temperatures, the earlier the tanδ peak appeared. It is suggested that the wood thermal softening occurs at higher temperatures with shorter heating times or at lower temperatures with longer heating times. At temperatures of 180 and 200°C, the loss of amorphous polysaccharides due to thermal degradation is considered to be the main factor affecting wood viscoelasticity.     

A two‐station embossing process for rapid fabrication of surface microstructures on thermoplastic polymers

An embossing strategy involving a hot station and a cold station for sequentially heating and cooling the embossing tool was investigated to reduce cycle times in hot embossing polymer microstructures. Experimental studies showed that aluminum stamps with a thickness of 1.4 mm can be rapidly heated from room temperature to 200°C in 3 s using contact heating against a hot station at 250°C. Microchannels and microlenses were successfully embossed onto high‐density polyethylene and acrylonitrile–butadiene–styrene substrates using a heating time less than 3 s and a total cycle time around 10 s. The two‐station embossing process for the microlens was also numerically studied. The simulated filling behavior agreed with the experimental observation and the predicted thermal and deformation history of the polymer offered a good explanation on the experimentally observed process characteristics. POLYM. ENG. SCI., 47:530–539, 2007. © 2007 Society of Plastics Engineers.     

Effect of short thermal treatment on cotton degradation

Cotton fabric was subjected to thermal treatment for durations ranging from 0.5 to 5 min at a temperature range of 160°C. In comparison with the untreated cotton, the copper number (measure of the aldehyde content) decreased after heating cotton for up to 3 min at 160°, 180°, and 190°C but increased when heating was prolonged to 5 min. Thermal treatment at 200°C or above caused an appreciable increase in the copper number. The carboxyl content increased with time of heating, attained a maximum, and then fell down to reach values which in some cases were lower than that of untreated cotton. Thermal treatment at 180°C caused a substantial reduction in the D. P.; this reduction increased with time of treatment. At the other temperatures there was no significant decrease in D. P. when cotton was heated up to 3 min. The D. P. decreased in these cases only when the thermal treatment was conducted for 5 min. The tensile strength remained practically unimpaired after thermal treatment of the cotton for up to 2 min, regardless of the temperature used within the range studied. A loss in tensile strength of ca. 9% and 13% was observed with fabrics treated for 5 min at 160° and 180°C, respectively. This contrasts with a loss of ca. 4% at 190°C, 7% at 200°C, and 8% at 220°C. The highest dye exhaustion was obtained on cotton which was thermally treated at 180°C prior to dyeing, while the lowest dye exhaustion was obtained on cotton heated at 220°C. Thermal treatment at 160°C left the susceptibility of cotton toward the dyestuff practically unaltered.     

Etude de la formation d'un complexe de surface graphite-eau relation avec la reaction d'oxydation

Using a gas flow apparatus under atmospheric pressure with infrared CO and CO₂ detection and an apparatus operating under low pressure with a mass spectrometer for analysis, we have found the following: The chemisorption of water becomes appreciable above 200°C. The water chemisorbed on graphite previously degassed at 1000°C forms a surface complex which on raising the temperature decomposes with simultaneous evolution of CO and H₂, thus showing that hydrogen enters into the composition of the complex. The programmed thermal decomposition of the complex shows two peaks. The first peak corresponds to the sites which disappear with the degassing of the CO and H₂; these sites are formed by the ‘labile’ carbon atoms created by the prior degassing. The second peak corresponds to the sites which are constantly renewed after degassing the CO molecules, and which are therefore formed by graphite atoms normally linked to the graphite lattice. The reaction rate of the oxidation of graphite by water shows two transient rates before attaining a stationary value. Correlations between the CO thermo-desorption and these reaction rates are found which indicate that the formation of a surface complex is a necessary step in graphite-H₂O reaction.     

Theoretical evaluation and the effect of thermal degradation on the Time–Temperature–Transformation (TTT) diagram of bisphenol A epoxies

A brief discussion about the Time–Temperature–Transformation (TTT) diagram is presented. Using diamino diphenylsulfone‐cured diglycidyl bisphenol A as a representative example, its TTT diagram is completed by including the thermal degradation. The theoretical diagram as obtained from the kinetics of curing and thermal degradation is compared with experimental data. The agreement is good, slight deviations are observed only in the time to vitrify above 150°C and the maximum available glass temperature, which is due to side reactions and onset of thermal degradation during curing. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3894–3896, 2003     

Vertical flame spread on charring materials at different ambient temperatures

A new flame spread apparatus for the measurement of flame spread rates at different ambient temperatures is presented. A 2‐m long sample is pre‐heated with air to the desired temperature and ignited from its lower end with a small propane burner. The flame spread is traced with thermocouples in contact with the sample surface. The features and function of the new apparatus are described, as well as series of vertical flame spread experiments on cylindrical birch rods and electrical cables made of polyvinylchloride (PVC) and flame retardant non‐corrosive (FRNC) materials. Vertical flame spread rates 6–62 mm/s (temperature range 22–271 °C) were determined for birch samples, 3–24 mm/s (22–190 °C) for PVC cable samples, and 0–4 mm/s (22–293 °C) for FRNC cable samples. Small‐scale experiments with thermogravimetric analysis and cone calorimeter were performed to characterize the sample materials in terms of their thermal and fire behaviour. Copyright © 2012 John Wiley & Sons, Ltd.     

Thermal Stability and Early Degradation Mechanisms of High‐Density Polyethylene,Polyamide 6 (Nylon 6), and Polyethylene Terephthalate

The thermal stability and degradation mechanisms of three semicrystalline polymers (polyethylene terephthalate [PET], high‐density polyethylene [HDPE], and polyamide 6 [nylon 6]) were studied. Thermogravimetric traces were acquired first at heating rates of 1°C/min and 10°C/min, and it was determined that the heating rate significantly affected the thermal decay curves of the three polymers. The results allowed the selection of specific temperatures at which to carry out heating and cooling cycles from room temperature to the molten state. The thermal behaviors of HDPE, nylon 6, and PET each had particular characteristics. HDPE showed the highest thermal resistance, whereas nylon 6 displayed the lowest. PET had the lowest activation energy for degradation, 93.5 kJ/mol, and retained 14 wt% after thermal recycling with no influence of molecular weight. Thermal cycling also revealed gradual morphological changes in HDPE, nylon 6, and PET, and their crystals changed from regular to branched spherulites with variations in the nucleation patterns. Fourier‐transform infrared spectroscopy measurements allowed us to explain the early stages of degradation for each polymer. POLYM. ENG. SCI., 59:2016–2023, 2019. © 2019 Society of Plastics Engineers     

The influence of thermal history on the properties of poly(3-hydroxybutyrate-co-12%-3-hydroxyvalerate)

The influence of thermal history on the properties of commercial P(3HB-co-12%-3HV) was studied. Thermogravimetric analysis and differential scanning calorimetry revealed that the plasticizer evaporated at 140°C or higher. The loss of plasticizer during thermal treatment at 170 and 180°C resulted in a slight increase of the melting temperature of the polymer. The processing time and temperature, as well as the cooling procedure influenced the thermal behaviour of the material. A decrease in molecular weight with time was found at the temperatures investigated and this significantly affected the mechanical properties of the polymer prepared at 180 and 200°C. The rate constant k_d of thermal degradation was slightly higher for samples during a shape-forming process in a Minimax apparatus than during a quiescent heating process (DSC) and its value increased with temperature. Limiting the processing at 170°C to 2 min gave a material with useful properties but increasing the residence time resulted in a decrease in strength, elongation at break, molecular weight and viscosity although it did not significantly influence the modulus of elasticity. Materials prepared at 180 or 200°C were more brittle and longer residence times resulted in a deterioration of the mechanical properties. © 1996 John Wiley & Sons, Inc.     

Thermal conductivity and electrical resistivity of poco grade AXF-Q1 graphite to 3300° K

Thermal conductivity and electrical resistivity of Poco Grade AXF-Q1 Graphite are presented from 110 to 3300°K. The temperature range was covered by two steady state techniques: (a) a comparative rod apparatus and (b) a radial inflow apparatus. Above 500°K the thermal conductivity data are represented quite well by a T^?1 type function, that is characteristic of Umklapp scattering processes which give rise to the thermal resistivity. We have further shown that the lattice conduction accounts for about 80 per cent of the heat transport even at 3300°K. For more highly graphitized graphite and other cokes, the results can be different. Our results are at variance with some literature that indicate a ‘strongly’ decreasing thermal conductivity above 3000°K or a ‘constant’ thermal conductivity with a ‘strong’ electronic conduction at up to 3300 °K.     

Amorphous state transitions in butadiene–acrylonitrile copolymers

Differential thermal analysis, creep measurements, and gas permeation rates are used to confirm the existence of a transition zone in three butadiene acrylonitrile copolymers in a temperature region that starts at roughly 15° to 25°C above the main glass transition temperatures of the copolymers and extends over a broad temperature range. The change appears to be slightly endothermic and softens the copolymers upon heating. It is speculated that the copolymers are in a mesomorphic state above their main glass temperature in which there is either a degree of ordering or a low-grade crystallinity of polybutadiene units along the copolymer chains. It is not until the copolymers are 50° to 75°C above their main glass temperature that they become truly amorphous.     

High‐Temperature Isothermal Oxidation of Ultra‐High Temperature Ceramics Using Thermal Gravimetric Analysis

Oxidation of ZrB₂ + SiC composites is investigated using isothermal measurements to study the effects of temperature, time, and gas flow on oxidation behavior and microstructural evolution. A test method called dynamic nonequilibrium thermal gravimetric analysis (DNE‐TGA), which eliminates oxidation during the heating ramp, has been developed to monitor mass change from the onset of an isothermal hold period (15 min) as a function temperature (1000°C–1600°C) and gas flow (50 and 200 mL/min). In comparing isothermal to nonisothermal TGA measurements, the scale thicknesses from isothermal tests are up to 4 times greater, indicating that oxidation kinetics are faster for isothermal testing, where the oxide scale thickness is 110 μm after 15 min at 1600°C in air. Isothermal oxidation followed parabolic kinetics with a mass gain that is temperature dependent from 1000°C–1600°C. The mass gain increased from ~5 to 45 g/m² and parabolic rate constants increased from 0.037 to 2.2 g²/m⁴·s over this temperature range. The effect of flow velocity on oxidation is not significant under the given laminar flow environment where the gas boundary layer is calculated to be 4 mm. These values are consistent with diffusion of oxygen through the glass‐ceramic surface layer as rate limiting.     

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     

Étude Théorique et Expérimentale de la Formation d'une Couche Limite par Convection Libre dans une Eau à Basse Température

A study, both analytical and experimental, has been made on the natural convection induced by an isothermal vertical plate immersed in a large volume of water at a temperature which was close to its freezing point. A particular attention has been paid to the effects resulting from the non-linearity existing between the density of water and its temperature. when the latter was close to 4°C. The plate temperature (T_w) was in the range from 8.0°C to 27.2°C, while the water temperature (T_i) varied between 0°C and 22.2°C. The Prandtl numbers for the flow were in the range from 6.4 to 13.7. An excellent agreement between the theoretical solution and the experimental data has been observed.     

Étude théorique et expérimentale de la formation d'une couche Limite par convection libre dans une eau à basse température

A study, both analytical and experimental, has been made on the natural convection induced by an isothermal vertical plate immersed in a large volume of water at a temperature which was close to its freezing point. A particular attention has been paid to the effects resulting from the non-linearity existing between the density of water and its temperature. when the latter was close to 4°C. The plate temperature (T_w) was in the range from 8.0°C to 27.2°C. while the water temperature (T_i) varied between 0°C and 22.2°C. The Prandtl numbers for the flow were in the range from 6.4 to 13.7. An excellent agreement between the theoretical solution and the experimental data has been observed.     

The Thermal Degradation of Waterborne Polyurethanes with Catalysts of Different Selectivity

The thermal stability of waterborne polyurethanes was measured by use of the thermogravimetric analysis. Waterborne polyurethanes (wbPUR) with catalysts of different selectivity were characterized using dynamic heating. In the dynamic method, heating rates with increments of 0.5, 1, 2, 5, and 10°C min^?1 were used in the range of 30–500°C, to achieve degradations of 0.025, 0.05, and 0.10, respectively. By using more selective catalysts, the resulting total time of decomposition was increased in all cases of degradation degrees for given initial temperature of waterborne polyurethanes. This paper shows how the dynamic method based on thermogravimetric analysis can be used to calculate the thermal stabilities of waterborne polyurethanes, using catalysts of different selectivity.     

Flammability of polyacrylonitrile and its copolymers II. Thermal behaviour and mechanism of degradation

Homopolymeric polyacrylonitrile and fibre-forming copolymers containing either vinyl acetate or methyl acrylate comonomer have been studied by thermal analysis (DSC, TGA and DTG) at various heating rates (10–100 K min^?1) and under air and nitrogen. Three well-defined pyrolysis stages have been observed which occur over the temperature ranges 250–350°C, 350–550°C and above 550°C. Each stage involves a competition between volatilisation and cyclisation or char-forming reactions which depends on heating rate and the presence or absence of oxygen. The well-established dominance of cyclisation in the 250–350°C temperature range obtained during carbon fibre production from acrylic precursors occurs only at low heating rates. At high heating rates, volatilisation dominates and this explains why acrylic polymers have high flammabilities when heating rapidly. The full pyrolysis mechanism has been semi-quantitatively analysed and the role that comonomers play discussed. This has enabled a fuller understanding of the potential burning behaviour of these polymers to be developed.     

Carbonization and CO<Subscript>2</Subscript> activation of scrap tires: Optimization of specific surface area by the Taguchi method

This research demonstrates the production of activated carbon from scrap tires via physical activation with carbon dioxide. A newly constructed apparatus was utilized for uninterrupted carbonization and activation processes. Taguchi experimental design (L16) was applied to conduct the experiments at different levels by altering six operating parameters. Carbonization temperature (550–700 °C), activation temperature (800–950 °C), process duration (30–120 min), CO₂ flow rate (400 and 600 cc/min) and heating rate (5 and 10 °C/min) were the variables examined in this study. The effect of parameters on the specific surface area (SSA) of activated carbon was studied, and the influential parameters were identified employing analysis of variance (ANOVA). The optimum conditions for maximum SSA were: carbonization temperature=650 °C, carbonization time=60 min, heating rate=5 °C/min, activation temperature= 900 °C, activation time=60 min and CO₂ flow rate=400 cc/min. The most effective parameter was activation temperature with an estimated impact of 49%. The activated carbon produced under optimum conditions was characterized by pore and surface structure analysis, iodine adsorption test, ash content, scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The process yield for optimized activated carbon was 13.2% with the following properties: specific surface area=437 m²/g, total pore volume=0.353 cc/g, iodine number=404.7 mg/g and ash content=13.9% along with an amorphous structure and a lot of oxygen functional groups. These properties are comparable to those of commercial activated carbons.     

Thermal Behavior of Howlite,Ca<Subscript>2</Subscript>B<Subscript>5</Subscript>SiO<Subscript>9</Subscript>(OH)<Subscript>5</Subscript>

The thermal behavior of natural borosilicate howlite, Ca₂B₅SiO₉(OH)₅, is studied by the methods of high-temperature X-ray diffraction and differential thermal analysis in the temperature range of 30–1100°C. The thermal expansion is anisotropic (α_max/α_min = 3.6); the degree of anisotropy increases (α_max/α_min = 4.3) with a temperature increase up to 480°C (360–480°C).     

Thermal Degradation Kinetics of Carotenoids in Palm Oil

In the present work, a detailed study is performed for carotene thermal degradation in palm oil at four temperatures ranging from 170 to 230 °C. The heating process was carried out with injection of nitrogen, and the samples were collected every 20 min during a total heating period of 140 min. HPLC analysis was conducted to monitor the carotenoids and tocols variations over the heating time at each temperature. The experimental data were then compared to literature data concerning carotenoids thermal degradation. The thermal degradation kinetics of carotenoids in palm oil followed an order superior to 1. The dependence of constant rates with temperature obeyed the Arrhenius relationship. The activation energy for the carotenoids thermal degradation in palm oil was found to be 109.4 kJ/mol.