Thermooxidative degradation of methyl methacrylate‐graft‐natural rubber

The thermooxidative degradation of methyl methacrylate‐graft‐natural rubber (MG) at different heating rates (B) has been studied with thermogravimetric analysis in an air environment. The results indicate that the thermooxidative degradation of MG in air is a one‐step reaction. The degradation temperatures increase with B. The initial degradation temperature (T_o) is 0.697B + 350.7; the temperature at the maximum degradation rate, that is, the peak temperature on a differential thermogravimetry curve (T_p), is 0.755B + 368.8; and the final degradation temperature (T_f) is 1.016B + 497.4. The degradation rates at T_p and T_f are not affected by B, and their average values are 46.7 and 99.7%, respectively. The maximum thermooxidative degradation reaction rate, that is, the peak height on a differential thermogravimetry curve (R_p), increases with B. The relationship between B and R_p is R_p = 2.12B + 7.28. The thermooxidative degradation kinetic parameters are calculated with the Doyle model. The reaction energy (E) and frequency factor (A) change with an increasing reaction degree, and the variational trends of the two kinetic parameters are similar. The values of E and A increase remarkably during the initial stage of the reaction, then keep relevantly steady, and finally reach a peak during the last stage. The velocity constants of the thermooxidative degradation vary with the reaction degree and increase with the reaction temperature. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1227–1232, 2003     

Thermogravimetric analysis of methyl methacrylate‐graft‐natural rubber

The thermal degradations of methyl methacrylate‐graft‐natural rubber (MG) at different heating rates (B) in nitrogen were studied by thermogravimetric analysis. The results indicate that the thermal degradation of MG in nitrogen is a one‐step reaction. The degradation temperatures increase along with the increment of heating rates. The temperature of initial degradation (T₀) is 0.448B + 362.4°C, the temperature at maximum degradation rate, that is, the peak temperature on a differential thermogravimetric curve (T_p) is 0.545B + 380.7°C, and the temperature of final degradation (T_f) is 0.476B + 409.4°C. The degradation rate at T_p is not affected by B, and its average value is 48.9%; the degradation rate at T_f is not affected by B either, and its average value is 99.3%. The reaction order (n) is 2.1 and is not affected by B. The reaction activation energy (E) and the frequency factor (A) increase along with B, and the apparent reaction activation energy (E₀) is 254.6 kJ/mol. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2952–2955, 2002     

Thermooxidative decomposition and its kinetics on chlorinated natural rubber from latex

Thermooxidative decomposition and its kinetics on chlorinated natural rubber (CNR) from latex are studied by thermal gravimetry (TG) analysis and TG coupled with FTIR spectroscopy. The thermooxidative decomposition of CNR is a two‐step reaction. The first step is the reaction of dehydrochlorination of which the reaction order (n) is 1.1; the reaction activation energy (E) increases linearly with the increment of the heating rate (B), and the apparent activation energy (E₀) is 101.7 kJ/mol. The initial temperature of weight loss (T₀) is 1.29B + 248.7, the final temperature of weight loss (T_f) is 0.86B + 312.4, and the temperature at the maximum weight loss ratio (T_p) is 1.05B + 286.2. The decomposition ratio at T_p (C_p) is not affected by B, and its average value is 38%. The decomposition ratio at T_f (C_f) is also not affected by B, and its average value is 60%. The second step is an oxidative decomposition reaction of the molecular main chain. The value of n is 1.1, E increases linearly with the increment of B, E₀ is 125.0 kJ/mol, the relation between B and T is similar to that of the first step, and C_f approaches 100%. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1305–1309, 2001     

Thermogravimetric analysis of poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)

The thermal degradation of poly(3‐hydroxybutyrate) (PHB) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) [P(HB‐HV)] was studied using thermogravimetry (TG). In the thermal degradation of PHB, the temperature at the onset of weight loss (T_o) was derived by T_o = 0.97B + 259, where B represents the heating rate (°C/min). The temperature at which the weight loss rate was maximum (T_p) was T_p = 1.07B + 273, and the final temperature (T_f) at which degradation was completed was T_f = 1.10B + 280. The percentage of the weight loss at temperature T_p (C_p) was 69 ± 1% whereas the percentage of the weight loss at temperature T_f (C_f) was 96 ± 1%. In the thermal degradation of P(HB‐HV) (7:3), T_o = 0.98B + 262, T_p = 1.00B + 278, and T_f = 1.12B + 285. The values of C_p and C_f were 62 ± 7 and 93 ± 1%, respectively. The derivative thermogravimetric (DTG) curves of PHB confirmed only one weight loss step change because the polymer mainly consisted of the HB monomer only. The DTG curves of P(HB‐HV), however, suggested multiple weight loss step changes; this was probably due to the different evaporation rates of the two monomers. The incorporation of 10 and 30 mol % of the HV component into the polyester increased the various thermal temperatures (T_o, T_p, andT_f) by 7–12°C (measured at B = 20°C/min). © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2237–2244, 2001     

Effect of atmosphere on the thermal decomposition of chlorinated natural rubber from latex

The kinetics of the thermal decompositions of chlorinated natural rubber (CNR) from latex under both air and nitrogen atmospheres were studied with thermogravimetric analysis (TGA). The thermooxidative decomposition of CNR had two weight-loss step changes in the TGA curves, which occurred at the two distinct temperature ranges of about 160–390 and 390–850°C, respectively. The gaseous products of the first step change were mainly HCl with a little CO₂, and the apparent reaction order (n) was 1.1. The reaction activation energy (E) increased linearly with the increment of heating rate (B), and the apparent activation energy (E₀), calculated by extrapolation back to zero B, was 101.7 kJ/mol. Bs ranging from 5 to 30°C/min were used. The initial temperature of weight loss (T₀) was 1.31B + 252°C, where B is in degrees Celsius per minute. The final temperature of weight loss (T_f) was 0.93B + 310°C, and the temperature of maximum weight-loss rate (T_p) was 1.03B + 287°C. The decomposition weight-loss percentage at T_p (C_p) and that at T_f (C_f) were not affected by B, and the average values were 38 and 60%, respectively. The second weight-loss step change was an oxidative decomposition of the molecular main chain. The value of n was 1.1. E increased linearly with the increment of B, and E₀ was 125.0 kJ/mol. C_f after the second step approached 100%, which indicated complete decomposition. The thermal decomposition of CNR in a N₂ atmosphere had only one weight-loss step change with an n of 1.1. E increased linearly with the increment of B, and E₀ was 98.6 kJ/mol. T₀ was 1.25B + 251°C, T_f was 0.91B + 315°C, and T_p was 1.09B + 286°C. C_p and C_f were not affected by B, and the average values were 37 and 68%, respectively. The weight percentage of more stable, nonthermal decomposed residue was about 30%. The thermal decompositions of CNR in both atmospheres were similar, mainly by dehydrochlorination, at the low temperature range (160–390°C) but were different at the high temperature range (390–850°C). © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2590–2598, 2001     

Study on hot air aging and thermooxidative degradation of peroxide prevulcanized natural rubber latex film

The air‐aging process at 120°C and the thermooxidative degradation of peroxide prevulcanized natural rubber latex (PPVL) film were studied with FTIR and thermal gravity (TG) and differential thermal gravity (DTG) analysis, respectively. The result of FTIR shows that the ? OH and ? COOH absorption of the rubber molecules at IR spectrum 3600–3200 cm^?1, the ? C?O absorption at 1708 cm^?1, and the ? C? OH absorption of alcohol at 1105 and 1060 cm^?1 increased continuously with extension of the aging time, but the ? CH₃ absorption of saturated hydrocarbon at 2966 and 2868 cm^?1, the ? CH₃ absorption at 1447 and 1378 cm^?1, and the C?C absorption at 835 cm^?1 decreased gradually. The result of TG‐DTG shows that the thermal degradation reaction of PPVL film in air atmosphere is a two‐stage reaction. The reaction order (n) of the first stage of thermooxidation reaction is 1.5; the activation energy of reaction (E) increases linearly with the increment of the heating rate, and the apparent activation energy (E₀) is 191.6 kJ mol^?1. The temperature at 5% weight loss (T_0.05), the temperature at maximum rate of weight loss (T_p), and the temperature at final weight loss (T_f) in the first stage of degradation reaction move toward the high temperature side as the heating rate quickened. The weight loss rate increases significantly with increment of heating rate; the correlation between the weight loss rate (α_p) of DTG peak and the heating rate is not obvious. The weight loss rate in the first stage (α_f1) rises as the heating rate increases. The final weight loss rate in second stage (α_f2) has no reference to heating rate; the weight loss rate of the rubber film is 99.9% at that time. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3196–3200, 2004     

Thermogravimetric analysis of chitosan

The thermal degradation of chitosan at different heating rates B in nitrogen was studied by thermogravimetric analysis. The results indicate that the thermal degradation of chitosan in nitrogen is a one‐step reaction. The degradation temperatures increase with B. Experimentally, the initial degradation temperature (T₀) is (1.049B + 326.8)°C; the temperature at the maximum degradation rate, that is, the peak temperature on a differential thermogravimetry curve (T_p), is (1.291B + 355.2)°C; and the final degradation temperature (T_f) is (1.505B + 369.7)°C. The degradation rates at T_p and T_f are not affected by B, and their average values are 50.17% and 72.16%, respectively, the maximum thermal degradation reaction rate, that is, the peak height on a differential thermogravimetry curve (R_p), increases with B. The relationship between B and R_p is R_p = (1.20B + 2.44)% min^?1. The thermal degradation kinetic parameters are calculated with the Ozawa–Flynn–Wall method. The reaction activation energy (E) and frequency factor (A) change with an increasing degree of decomposition, and the variable trends of the two kinetic parameters are similar. The values of E and A increase remarkably during the initial stage of the reaction, then keep relatively steady, and finally reach a peak during the last stage. The velocity constants of the thermal degradation vary with the degree of decomposition and increase with the reaction temperature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Thermal analyses of poly(3-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate), and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)

Thermal analyses of poly(3-hydroxybutyrate) (PHB), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(HB–HV)], and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) [P(HB–HHx)] were made with thermogravimetry and differential scanning calorimetry (DSC). In the thermal degradation of PHB, the onset of weight loss occurred at the temperature (°C) given by T_o = 0.75B + 311, where B represents the heating rate (°C/min). The temperature at which the weight-loss rate was at a maximum was T_p = 0.91B + 320, and the temperature at which degradation was completed was T_f = 1.00B + 325. In the thermal degradation of P(HB–HV) (70:30), T_o = 0.96B + 308, T_p = 0.99B + 320, and T_f = 1.09B + 325. In the thermal degradation of P(HB–HHx) (85:15), T_o = 1.11B + 305, T_p = 1.10B + 319, and T_f = 1.16B + 325. The derivative thermogravimetry curves of PHB, P(HB–HV), and P(HB–HHx) confirmed only one weight-loss step change. The incorporation of 30 mol % 3-hydroxyvalerate (HV) and 15 mol % 3-hydroxyhexanoate (HHx) components into the polyester increased the various thermal temperatures T_o, T_p, and T_f relative to those of PHB by 3–12°C (measured at B = 40°C/min). DSC measurements showed that the incorporation of HV and HHx decreased the melting temperature relative to that of PHB by 70°C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 90–98, 2001     

Thermal degradation of poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) as studied by TG,TG–FTIR,and Py–GC/MS

The thermal degradation kinetics of poly(3‐hydroxybutyrate) (PHB) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) [poly(HB–HV)] under nitrogen was studied by thermogravimetry (TG). The results show that the thermal degradation temperatures (T_o, T_p, and T_f) increased with an increasing heating rate (B). Poly(HB–HV) was thermally more stable than PHB because its thermal degradation temperatures, T_o(0), T_p(0), and T_f(0)—determined by extrapolation to B = 0°C/min—increased by 13°C–15°C over those of PHB. The thermal degradation mechanism of PHB and poly(HB–HV) under nitrogen were investigated with TG–FTIR and Py–GC/MS. The results show that the degradation products of PHB are mainly propene, 2‐butenoic acid, propenyl‐2‐butenoate and butyric‐2‐butenoate; whereas, those of poly(HB–HV) are mainly propene, 2‐butenoic acid, 2‐pentenoic acid, propenyl‐2‐butenoate, propenyl‐2‐pentenoate, butyric‐2‐butenoate, pentanoic‐2‐pentenoate, and CO₂. The degradation is probably initiated from the chain scission of the ester linkage. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1530–1536, 2003     

Microstructure evolution of ammonia‐catalyzed phenolic resin during thermooxidative aging

The thermooxidative aging of ammonia‐catalyzed phenolic resin for 30 days at 60–170°C was investigated in this article. The aging mechanism and thermal properties of the phenolic resin during thermooxidative aging were described by thermogravimetry (TG)–Fourier transform infrared (FTIR) spectroscopy, attenuated total reflectance (ATR)–FTIR spectroscopy, and dynamic mechanical thermal analysis. The results show that the C? N bond decomposed into ammonia and the dehydration condensation between the residual hydroxyl groups occurred during the thermooxidative aging. Because of the presence of oxygen, the methylene bridges were oxidized into carbonyl groups. After aging for 30 days, the mass loss ratio reached 4.50%. The results of weight change at high temperatures coincided with the results of TG–FTIR spectroscopy and ATR–FTIR spectroscopy. The glass‐transition temperature (T_g) increased from 240 to 312°C after thermooxidative aging for 30 days, which revealed the postcuring of phenolic resins. In addition, an empirical equation between the weight change ratio and T_g was obtained. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Mechanisms and kinetics of thermal degradation of poly(butylene succinate‐co‐propylene succinate)s

Poly(butylene succinate) (PBSu) and two PBSu‐rich poly(butylene succinate‐co‐propylene succinate)s were studied. Copolyesters were characterized as random copolymers, based on ¹³C‐NMR spectra. TGA‐FTIR was used to monitor the degradation products at a heating rate of 5°C/min under N₂. FTIR spectra revealed that the major products were anhydrides, which were formed following two cyclic intramolecular degradation mechanisms by the breaking of the weak O‐CH₂ bonds around succinate groups. Thermal stability at heating rates of 1, 3, 5, and 10°C/min under N₂ was investigated using TGA. The model‐free methods of the Friedman and Ozawa equations are useful for studying the activation energy of degradation in each period of mass loss. The results reveal that the random incorporation of minor propylene succinate units into PBSu did not markedly affect their thermal resistance. Two model‐fitting mechanisms were used to determine the mass loss function f(α), the activation energy and the associated mechanism. The mechanism of autocatalysis nth‐order, with f(α) = α^m(1 ? α)ⁿ, fitted the experimental data much more closely than did the nth‐order mechanism given by f(α) = (1 ? α)ⁿ. The obtained activation energy was used to estimate the failure temperature (T_f). The values of T_f for a mass loss of 5% and an endurance time of 60,000 h are 160.7, 155.5, and 159.3°C for PBSu and two the copolyesters, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermal degradations of chlorinated natural rubber from latex and chlorinated natural rubber from solution

The thermal degradations of chlorinated natural rubbers from latex (CNR‐L) and from solution (CNR‐S) under nitrogen atmosphere were studied with thermogravimetric analysis (TGA). The thermal degradations of CNR‐L and CNR‐S are one‐step reaction. The shapes of the thermogravimetric and derivative thermogravimetric curves are similar. The degradation temperatures of CNR‐L and CNR‐S increase linearly with the increment of heating rates. The heating rate hardly affects the thermal degradation rates of CNR‐L and CNR‐S at the various degradation stages. The thermal degradations of CNR‐S and CNR‐L are dehydrochlonation reactions. The reaction activation energy (E) of CNR, at the first stage, is around 100 kJ/mol. After that, E remains relatively steady (80–140 kJ/mol). At the last stage, E rises rapidly (130–270 kJ/mol). The variation tendency of frequency factor (A) is similar to that of E. As the initial degradation temperature T₀ of CNR‐L is 10.9°C lower than that of CNR‐S, the thermal stability of CNR‐S is better than that of CNR‐L, which may be caused by the difference of molecular structure between CNR‐L and CNR‐S, as FTIR results indicate that there are more ? OH, ? C?O and ? COO? groups in the CNR‐L molecular chains. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Study of Thermal Degradation Kinetics of Elastomeric Powder (Ground Tire Rubber)

This paper investigates the use of thermogravimetric analysis to study the kinetics of thermal degradation of ground tire rubber (GTR) obtained from reclaimed tires. We analyzed the composition of GTR and determined the content percentage of its components (volatile compounds, rubber, and ash) using thermogravimetric analysis (TGA). T ₁ and T ₂ temperature peaks corresponding to the maximum normalized weight loss rate (NWLR) of the two main rubber components of tires NR (natural rubber) and a BR/SBR (butadiene/styrene-butadiene rubber blend) using the Gaussian deconvolution method has been determined. The influence of GTR particle size and heating rate on reaction rates (dx/dt) and on degradation time during the degradation process has been analyzed.     

Thermal degradation study of interpenetrating polymer network based on modified bismaleimide resin and cyanate ester

Interpenetrating polymer networks (IPNs) based on different ratios of a modified bismaleimide resin (BMI/DBA) and cyanate ester (b10) have been synthesized via prepolymerization followed by thermal curing. A systematic thermal degradation study of these new BMI/DBA‐CE IPN resin systems was conducted by thermogravimetric analysis at different heating rates both in N₂ (thermal stability) and in air (thermal‐oxidative stability). The cured BMI/DBA‐CE IPN resin systems show excellent thermal stability, which could be demonstrated by 5% weight loss temperature (T_5%) ranging between 409 and 423 °C, maximum decomposition rate temperature (T_max) ranging between 423 and 451 °C, and the char yields at 800 °C ranging from 37% to 41% in nitrogen at a heating rate of 10 °C min^?1. The apparent activation energy associated with the main degradation stage of the cured BMI/DBA‐CE IPN resin systems was determined using the Kissinger method. The obtained results provide useful information in drawing correlation between thermal properties and structure. © 2003 Society of Chemical Industry     

环氧化天然橡胶硫化胶在不同气氛下的热降解行为？

利用热重-微商热重（ TG-DTG-DSC）研究了在氮气、空气氛围中ENR硫化胶的热降解动力学,根据不同升温速率下得到的热重数据,通过Ozawa-Flynn-Wall模型求取热降解过程的活化能E、指前因子A等参数,得到ENR硫化胶在不同气氛下降解反应过程中动力学参数方面的差异。 ENR在氮气气氛中降解时为一步反应,在空气中为复杂多步反应。另外,空气气氛中的活化能E和指前因子A均大于氮气中。     

Comparison and evaluation of the thermooxidative stability of medical natural rubber latex products prepared with a sulfur vulcanization system and a peroxide vulcanization system

This article deals with our study of the thermooxidative degradation of medical natural rubber latex tubes prepared with sulfur‐prevulcanized latex (sample I) and peroxide‐prevulcanized latex (sample II) in a dynamic air atmosphere by the use of the thermogravimetry/differential thermogravimetry method as well as the evaluation of the thermooxidative stability of these two samples. The test results showed that an oxygen‐absorption mass‐gain process occurred after a slight mass loss; the mass‐gain rate decreased with an increase in the temperature rising rate (β), and this was more prominent in sample II than in sample I. The maximum mass‐gain rate of sample II was 1.43% when β was 5°C/min, which was 5.02 times that of sample I; the thermooxidative stability of sample II was also lower than that of sample I. Because the oxygen absorption of sample II clearly caused serious oxidation, the balanced initial temperature, the temperature of the balanced degradation peak, and the balanced final temperature of sample II in the first reaction stage were obviously lower than those of sample I. The apparent activation energy (E_o = 143.6 kJ/mol) of sample I was significantly higher than that of sample II, and the stability of sample I was also higher than that of sample II. The temperature of the balanced degradation peak of sample II in the second reaction stage was higher than that of sample I, and E_o (154.0 kJ/mol) of sample II was significantly higher than that of sample I; the stability of sample II was also higher. Thermogravimetry curves of the two samples at various β values intercrossed each other, and the temperature at the crosspoint and the degradation rate increased linearly as β increased. On the temperature segment from the initial temperature to the crosspoint, the degradation rate of sample II was higher than that of sample I when the temperature of the two samples was the same, but on the segment from the crosspoint to the final temperature, the degradation rate of sample II was lower than that of sample I when the temperature of the two samples was the same. The degradation rate of the samples at 600°C was 99.2–99.5%. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 591–597, 2005     

Thermal analysis of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) irradiated under vacuum

Poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) was irradiated by ⁶⁰Co γ‐rays (doses of 50, 100 and 200 kGy) under vacuum. The thermal analysis of control and irradiated PHBV, under vacuum was carried out by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The tensile properties of control and irradiated PHBV were examined by using an Instron tensile testing machine. In the thermal degradation of control and irradiated PHBV, a one‐step weight loss was observed. The derivative thermogravimetric curves of control and irradiated PHBV confirmed only one weight‐loss step change. The onset degradation temperature (T_o) and the temperature of maximum weight‐loss rate (T_p) of control and irradiated PHBV were in line with the heating rate (°C min^?1). T_o and T_P of PHBV decreased with increasing radiation dose at the same heating rate. The DSC results showed that ⁶⁰Co γ‐radiation significantly affected the thermal properties of PHBV. With increasing radiation dose, the melting temperature (T_m) of PHBV shifted to a lower value, due to the decrease in crystal size. The tensile strength and fracture strain of the irradiated PHBV decreased, hence indicating an increased brittleness. Copyright © 2004 Society of Chemical Industry     

Thermal degradation of polymethacrylic ester containing bisphenol-S

Thermal degradation of polymethacrylic ester containing bisphenol-S, poly(BPS-M), was investigated under nitrogen and air atmosphere at various heating rates. Ozawa's method was used to calculate the kinetic parameters, activation energy, preexponential factor and reaction order. Thermodegradation of the polymer occurs in one or two stages in nitrogen and air, respectively. The temperature at the start of intense degradation (T_start) and the temperature corresponding to a 50% mass loss (T_50%) were found to be 300 and 402°C, respectively, at a heating rate of 10°C min^?1 in nitrogen. Larger sample masses have a larger temperature interval (ΔT) and a greater mass loss (ΔW). The kinetic order of degradation is unity both in nitrogen and air. The direct pyrolysis mass spectrum of the polymer shows one degradation peak. The most important degradation process under inert atmosphere is the loss of carbon dioxide, phenol and sulphur dioxide. A possible mechanism for thermal decomposition of poly(BPS-M) is proposed based on the product analyses.     

The Curing Behavior and Adhesion Strength of the Epoxidized Natural Rubber Modified Epoxy/Dicyandiamide System

The curing properties and adhesive strengths of the epoxidized natural rubber (ENR, 25 mole percent epoxidation) modified epoxy systems are studied with differential thermal calorimetry (DSC), scanning electron microscopy (SEM), and lap shear strength (LSS) measurement. The results of DSC analyses indicate that the curing exotherm, the curing rate, the reaction order, and the glass transition temperature of the epoxy system are affected by the presence of reactive ENR. From SEM micrographs, it is obtained that a second spherical rubber phase is formed during cure and the particle size of the rubber phase is increased by increasing the curing temperature and the ENR content. The changes of the volume fraction of the rubber phase and the T_g of the cured systems indicate that the mutual dissolution between epoxy resin and ENR happens and which changes with the curing temperature and the ENR content. The LSS of adhesive joints prepared with the ENR modified adhesives are all lower than those of the unmodified epoxy system, and decrease with increasing the amount of ENR added because of the limited compatibility of the ENR with the epoxy matrix.     

Enthalpies of vaporization of oligomers of poly(hexamethylene sebacate) and esters of alkylcarboxylic acids

Enthalpies of vaporization for esters covering a molecular weight range of about 74–939 g/mol · [monocarboxylics; linear esters of sebacic series; branched esters of triglyceride series; and, oligomer esters of poly(hexamethylene sebacate)] and a temperature range of about 273.15–523.15 K have been empirically fitted to within about 5% to an equation of the following form: ΔHv(T,M) = S(T)f(M) + I₀(T), where S(T) = C Ln(T) + K₀, I₀(T) = aT + b₀, and f(M) = M/(1 + a₀M), M is the molecular weight (molar mass); T is in degrees Kelvin; and, C, K₀, a, b₀, and a₀ are constants. These results were used to determine the heat capacity difference, ΔC_p = C_p(l) − C_p(g), and compared to calculated values from functional relationships of C_p(l) and C_p(g), l is liquid g is gas. The heat capacity difference results in conjunction with C_p(l) were used to empirically calculate the heat capacity of the gas, C_p(g), over the molecular weight and temperature ranges investigated and compared to a group contribution method. The functional forms for ΔHv(T,M), ΔC_p(T,M), C_p(l), and C_p(g) were also found to be applicable for n-alkanes. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 731–746, 1998