Epoxy resins (DGEBA): The curing and physical aging process

Differential scanning calorimetry (DSC) and infrared spectroscopy (IR) were used to monitor the degree of cure of partially cured epoxy resin (Epon 828/MDA) samples. The extent of cure, as determined by residual heat of reaction, concurred with that determined by monitoring the infrared radiation absorbance of the epoxide group near 916 cm^?l. The fictive temperature T_{f, g} was found to increase with the degree of cure, increasing rapidly during cure until reaching a value near the cure temperature T_c of 130°C (approximately 80% cure) where the material vitrified. The greatly reduced reaction rate during the final 20% of cure was not only a consequence of vitrification but, as revealed by infrared spectroscopy, the result of the depletion in the number of reactive epoxide groups. The endothermic peak areas and peak temperatures evident during the DSC scans were used as a measure of the extent of “physical aging” which took place during the cure of this resin, and after, fully cured samples were aged 37°C below their ultimate glass temperature for various periods of time. The rate of physical aging slowed as the temperature increment (T_t,g ? T_c) increased. Although an endothermic peak was evident after only 1 h of cure (T_{f, g} = 138.3°C), such a peak did not appear until fully cured samples were aged for 16 h or more. Enthalpy data revealed that for partially cured material, the fictive temperature T_{f, a}, reflecting physical aging, increased with curing time. In contrast, the T_{f, a}, for fully cured samples decreased with sub-T_g aging time. The characteristic jump in the heat capacity ΔC_p which occurred at the T_{f, g} decreased as curing progressed. This decrease appears to be dependent upon the rotational and vibrational degrees of freedom of the glass. Finally, a graphical method of determining the fictive temperature T_{f, a}, of partially and fully cured epoxy material from measured endothermic peak areas was developed.     

Glass transition kinetics of some Se-Te-Ag chalcogenide glasses

Summary The present paper reports the Differential Scanning Calorimetric (DSC) study of some Ag doped Se-Te chalcogenide glasses. DSC runs were taken at different heating rates. Well-defined endothermic and exothermic peaks were obtained at glass transition and crystallization temperatures. The variation of glass transition temperature T_gwith Ag concentration has been studied. It has been found that T_gdecreases with increase in Ag concentration. The heating rate dependence of T_gis used to evaluate the activation energy of glass transition (DE_t). The value of<span style='font-size:10.0pt; font-family:"SymbolProp BT";mso-bidi-font-family:"SymbolProp BT"'>DE_thas been found to increase with increase in Ag concentration followed by nearly constant value at higher concentrations of Ag.     

Studies of the enthalpy relaxation and the “multiple melting” behavior of semicrystalline poly(arylene ether ether ketone) (PEEk)

We report the results of an investigation by differential scanning calorimetry (DSC) of two mobility controlled processes in the amorphous phas e of semicrystalline PEEK — enthalpy relaxation below the glass transition (T _g) and secondary crystallization aboveT _g. Both result in the observation of an endothermic peak just above the annealing temperature in the DSC scan of the polymer — the enthalpy recovery peak and the low temperature melting peak, respectively. There is a striking similarity in the time and temperature dependence of the endothermic peak for these two processes. These results are reminiscent of those obtained from small strain creep studies of physical aging of semicrystalline PEEK below and aboveT _g.We gratefully acknowledge support of this work by the National Science Foundation, Science and Technology Center for High Performance Polymeric Adhesives and Composites under DMR grant 91-2004 and by an NSF Young Investigator Award (DMR 93-57512).     

Simulation approach to decomposition kinetics and thermal hazards of hexamethylenetetramine

The thermal stability of HMT under dynamic, isothermal and adiabatic conditions was investigated using differential scanning calorimeter (DSC) and accelerating rate calorimeter (ARC), respectively. It is found from the dynamic DSC results that the exothermic decomposition reaction appears immediately after endothermic peak, a coupling phenomenon of heat absorption and generation, and the endothermic peak and exothermic peak were indentified at about 277–289 and 279–296 °C (T_peak) with the heating rates 1, 2, 4 and 8 °C min⁻¹. The ARC results reveal that the initial decomposition temperature of HMT is about 236.55 °C, and the total gas production in decomposition process is 6.9 mol kg⁻¹. Based on the isothermal DSC and ARC data, some kinetic parameters have been determined using thermal safety software. The simulation results show that the exothermic decomposition process of HMT can be expressed by an autocatalytic reaction mechanism. There is also a good agreement between the kinetic model and kinetic parameters simulated based on the isothermal DSC and ARC data. Thermal hazards of HMT can be evaluated by carrying out thermal explosion simulations, which were based on kinetic models (Isothermal DSC and ARC) to predict several thermal hazard indicators, such as T_D24, T_D8, TCL, SADT, ET and CT so that we can optimize the conditions of transportation and storage for chemical, also minimizing industrial disasters.

     

Annealing effects on the solid state properties of transition-metal coordination complexes and networks based on diene polymers with palladium chloride

This study focuses on the thermal and mechanical properties of 1,2-polybutadiene and 3,4-polyisoprene with an inorganic salt, bis(acetonitrile)dichloropalladium (II). Upon mixing in THF, effective crosslinks are formed because the acetonitrile ligands of the palladium salt are displaced by olefinic pendant groups of the polymers. Using a simple nth-order irreversible kinetic rate model, the palladium-catalyzed Heck-like exothermic reaction in solid films was characterized via isothermal and nonisothermal DSC. Thermal energy and mass balances appropriate to a batch reactor are developed from first principles and applied to the isothermal DSC output curve to calculate the time dependence of reactant conversion. Relevant kinetic parameters, such as the order of the reaction, the characteristic time constant for the chemical reaction, and the activation energy, have been determined. The kinetic data suggest that the palladium-catalyzed crosslinking reactions are diffusion controlled in the solid state because the reaction order is very close to unity. Higher glass transition temperatures (T_g) are measured by dynamic mechanical thermal analysis (DMTA) and differential scanning calorimetry (DSC) when (i) palladium concentration, (ii) annealing (heat treatment) time, and (iii) annealing temperature increase. After 2 h of annealing at 80°C, which corresponds to a temperature below the first exothermic crosslinking reaction (≅ 115°C) during nonisothermal DSC kinetic studies, rubbery materials containing very low concentrations of PdCl₂ (i.e., 0.5 mol %) exhibit reinforced ductile stress-strain response. When annealing is performed at the peak temperature of the first exothermic event, the rubbery materials are transformed into glasses. Transition-metal compatibilization of atactic 1,2-polybutadiene and 3,4-polyisoprene via PdCl₂ is demonstrated by monitoring the glass transition obtained from dynamic mechanical tan δ profiles. The effect of annealing this ternary reactive “blend” produces a glassy material exhibiting an elevated T_g and synergistic mechanical properties. © 1996 John Wiley & Sons, Inc.     

Thermal behavior of ferroelectric Polyamide 11 in relation to pyroelectric properties

The pyroelectric properties of oriented thin films of ferroelectric Polyamide 11 have been studied in the temperature range of −100°C up to +140°C. The temperature dependence of the experimental pyroelectric coefficient has been analyzed. Three changes of slope of the pyroelectric coefficient are observed at −20, +50, and +100°C. The origin of the lower temperature event has not yet been defined. The upper transition is attributed to chain movements in crystalline regions, and more precisely, to a crystalline phase transition. The intermediate event is close to the glass transition temperature T_g observed by DSC. It is attributed to the manifestation of the glass transition. Below T_g, the variations of the pyroelectric coefficient are very small. For higher temperatures, it increases rapidly, attesting to a major contribution of secondary pyroelectricity and dimensional effects above T_g. The breaking of hydrogen bonds occurring at the glass transition temperature observed on DSC thermograms does not affect pyroelectric properties. Pyroelectric properties are mildly reduced after annealing at temperatures up to +140°C. A comparative study of oriented ferroelectric films prepared by quenching from the melt and nonoriented slowly cooled samples has been carried out by means of DSC. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 715–723, 1999     

Glass Transition Study of Nile Tilapia Myofibrillar Protein Films Plasticized by Glycerin and Water

Studies on glass transition of myofibrillar proteins based edible films are scarce. This work aimed to determine the T _g of edible films from Nile Tilapia myofibrillar proteins as a function of water content. Films with 30 or 70 g of glycerol/100 g of protein and several water content, were analyzed with a DSC TA 2010. Samples conditioned at water activity between 0.11 and 0.75, clearly showed one glass transition at low temperatures (<223 K), and another transition, less visible, above 273 K. DSC curves of samples conditioned ata _w=0.84, also showed an endothermic peak below 273 K. These results rendered evidence of phase separation within edible films. This revised version was published online in July 2006 with corrections to the Cover Date.     

Latent energy of deformation of bisphenol A polycarbonate

The thermodynamic behavior of poly(bisphenol A carbonate) (PC) during uniaxial cold drawing and the properties of the drawn polymer were examined. Isothermal deformation calorimetric measurements were made during the drawing process. The deformation calorimeter measures heat, work, and internal energy changes for deformation. It was found that PC exhibited nonideal plasticity with approximately 50–80% of the work of deformation dissipated as heat. The remainder of the work of deformation was stored as a latent internal energy change. The value of the internal energy change was dependent on strain rate at 20°C but was not strongly dependent on temperature in the range 20–65°C. Thermomechanical measurements on cold-drawn PC samples demonstrated striking behavior at temperatures far below the glass transition temperature T_g. Stress-temperature experiments showed that the stress increased for uniaxially constrained samples, and this stress increase began at temperatures just above the deformation temperature. Additional experiments indicated that the changes which took place during cold drawing were physical in nature and were thermoreversible. These changes in physical properties are related to those which occur due to physical aging below T_g.     

Changes of mechanical properties in cold-crystallized syndiotactic polypropylene during aging

Many semicrystalline polymers undergo a process of aging when they are stored at temperatures higher than their glass-transition temperature (T _g). Syndiotactic polypropylene was quenched from the melt to −40 °C, crystallized from the glassy state at 20 or 40 °C and stored at the respective temperature for different aging times up to 7200 h. A significant increase in the tensile modulus and stress at yield and a decrease in strain at yield were observed for both aging temperatures. Differential scanning calorimetry (DSC) scans of aged material showed an endothermic annealing peak 15–30 °C above the previous aging temperature, the maximum temperature and enthalpic content of which increased with aging time. The position and the shape of the melting peak were not affected by aging. Scans of the storage modulus obtained from dynamic mechanical analyser measurements indicated a softening process starting at about 20 °C above the aging temperature and correlating with the annealing peak detected by DSC. Density measurements and wide-angle X-ray scattering investigations revealed that neither the crystallinity increased significantly nor did the crystal structure change. So the observed property changes induced by aging are attributed to microstructural changes within the amorphous phase. Furthermore, it could be shown by annealing experiments carried out at 60 °C, that aging above T _g is, analogous to aging below T _g (physical aging), a thermoreversible process. Received: 18 September 2000 Accepted: 2 January 2001     

Physical aging of polycarbonate investigated by dynamic viscoelasticity

The physical aging of polycarbonate was investigated with dynamic viscoelastic measurements. Physical aging was observed for samples aged at 110 °C (QA) and room temperature (QP) after being quenched from the molten state. The shapes of the temperature dispersion curves of the dynamic viscoelastic functions (E′, E″, and tan δ) of the QA and QP samples changed with aging time in a temperature range below the glass‐transition temperature (T_g). However, at temperatures close to but below T_g, the curves for the aged samples merged into the curve of the quenched sample at a temperature denoted T_H. T_H increased with aging time. The experimental results suggest that the aged sample has a memory of having been quenched and that as the sample approaches the equilibrium state, this memory is lost. Differential scanning calorimetry thermograms showed an endothermic peak below T_g for the QA samples. The peak temperature (T_p) also increased with aging time. T_H and T_p of the QA samples were approximately the same. The increase of both T_H and T_p with aging time indicates that the structure of the polymeric chain in the glassy state relaxes over larger segment scale lengths because the scale of the movable segments is related to temperature. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 337–341, 2001     

Thermal analysis of the double-melting behavior of poly(L-lactic acid)

The melting and crystallization behavior of poly(L -lactic acid) (PLLA; weight-average molecular weight = 3 × 10⁵) was studied with differential scanning calorimetry (DSC). DSC curves for PLLA samples were obtained at various cooling rates (CRs) from the melt (210 °C). The peak crystallization temperature and the exothermic heat of crystallization determined from the DSC curve decreased almost linearly with increasing log(CR). DSC melting curves for the melt-crystallized samples were obtained at various heating rates (HRs). The double-melting behavior was confirmed by the double endothermic peaks, a high-temperature peak (H) and a low-temperature peak (L), that appeared in the DSC curves at slow HRs for the samples prepared with a slow CR. Peak L increased with increasing HR, whereas peak H decreased. The peak melting temperatures of L and H [T_m(L) and T_m(H)] decreased linearly with log(HR). The appearance region of the double-melting peaks (L and H) was illustrated in a CR–HR map. Peak L decreased with increasing CR, whereas peak H increased. T_m(L) and T_m(H) decreased almost linearly with log(CR). The characteristics of the crystallization and double-melting behavior were explained by the slow rates of crystallization and recrystallization, respectively. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 25–32, 2004     

Synergism and multiple mechanical relaxations observed in ternary systems based on benzoxazine,epoxy, and phenolic resins

The synergism in the glass‐transition temperature (T_g) of ternary systems based on benzoxazine (B), epoxy (E), and phenolic (P) resins is reported. The systems show the maximum T_g up to about 180 °C in BEP541 (B/E/P = 5/4/1). Adding a small fraction of phenolic resin enhances the crosslink density and, therefore, the T_g in the copolymers of benzoxazine and epoxy resins. To obtain the ultimate T_g in the ternary systems, 6–10 wt % phenolic resin is needed. The molecular rigidity from benzoxazine and the improved crosslink density from epoxy contribute to the synergistic behavior. The mechanical relaxation spectra of the fully cured ternary systems in a temperature range of −140 to 350 °C show four types of relaxation transitions: γ transition at −80 to −60 °C, β transition at 60–80 °C, α₁ transition at 135–190 °C, and α₂ transition at 290–300 °C. The partially cured specimens show an additional loss peak that is frequency‐independent as a result of the further curing process of the materials. The ternary systems have a potential use as electronic packaging molding compounds as well as other highly filled systems. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1687–1698, 2000     

Thermal transitions of gelatin evaluated using DSC sample pans of various seal integrities

Differential scanning calorimetry (DSC) has become a popular tool to investigate thermal transitions in food ingredients such as gelatin. Upon heating commercial gelatin samples beyond glass transition (T _g) and melting (T _m) temperatures, a relatively large endothermic transition (T _i) can be observed. We have observed that both the peak temperature and the enthalpy of the T _i transition are influenced by the integrity of the seal of the DSC pans used for the analysis. This study shows that escape of moisture from the DSC pan appears to be responsible for this effect. The effect of different types of DSC pans, as well as technique of sealing them on the T _i transition were evaluated using DSC, SDT, and TG–MS.     

Structure–initiator activity dependence of aminimides as thermally latent initiators in the polymerization of glycidyl phenyl ether

Novel aliphatic aminimides were synthesized from the corresponding carboxylic acid esters, 1,1‐dimethylhydrazine, and epoxides in 54–95% yields. Bulk polymerization of glycidyl phenyl ether (GPE) with 3 mol % of the aminimides was evaluated by DSC as a model process for curing of epoxy resin. All the aminimides showed no exothermic DSC peak below 120 °C but showed sharp exothermic peaks above 137 °C, indicating good thermal latency. Good relationships were observed between the calculated bond length from the carbonyl carbon to the α‐carbon of the aliphatic group (R C), DSC onset temperatures, and the thermal dissociation temperatures (T_d 's) of the aminimides. The aminimide with a longer R C bond length showed lower T_d and DSC onset temperature, that is, higher activity. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3428–3433, 2000     

Thermally stimulated current and DSC studies of the broadened glass transition in liquid crystalline polymers

The high sensitivity of the thermally stimulated current, thermal sampling (TS) method is emphasized in a study of the breadth of the glass transition in several liquid-crystalline polymers (LCPs). Differential scanning calorimetry (DSC) was performed on all samples to further quantify the glass transition regions. For “random” copolyester LCPs with widely varying degrees of crystallinity, including highly amorphous samples, very broad glass tran-sition regions were observed. One semicrystalline alternating copolyester and a series of semicrystalline azomethine LCPs were studied as examples of structurally regular polymers. These exhibited relatively sharp glass transitions more comparable to ordinary isotropic amorphous or semicrystalline polymers. The broad glass transitions in the random copolyesters are attributed to structural heterogeneity of the chains. In one example of a moderate-crystallinity random copolyester LCP (Vectra), glass transitions ranging up to ca. 150°C in breadth were determined by the thermal sampling (TS) method and DSC. In other lower crystallinity copolyester LCPs, the main glass transition temperature as determined by DSC was comparable to that determined by TSC although cooperative relaxations of a minor fraction of the overall relaxing species were detected well below the main T_g, by the TS method and not by DSC. Rapid quenches from the isotropic melt to an isotropic glass were possible with one LCP. The anisotropic and isotropic glassy states for this LCP were found to have the same breadth of the glass transition as was determined by the TS method, although TSC and DSC show that T_g is shifted downward by ca. 15°C in the anisotropic glass as compared to the isotropic glass. © 1993 John Wiley & Sons, Inc.     

Thermal characterization of dental composites by TG/DTG and DSC

Dental composites can be improved by heat treatment, as a possible way to increase mechanical properties due to additional cure (post-cure). Direct dental composites are essentially similar to the indirect ones, supposing they have the same indication. Therefore, to establish a heat treatment protocol for direct composites, using as indirect (photoactivated by continuous and pulse-delay techniques), a characterization (TG/DTG and DSC) is necessary to determine parameters, such as mass loss by thermal decomposition, heat of reaction and glass transition temperature (T _g). By the results of this study, a heat treatment could be carried out above 160 °C (above T _g, and even higher than the endset exothermic event) and under 180 °C (temperature of significant initial mass loss).     

EFFECT OF PARTICLE SIZE ON THE FILMING PROCESS OF POLYSTYRENE LATEX STUDIED BY AFM

The film formation process of micro-PS particles (diameter 742 nm) and nano-PS particles (diameter 29 nm) wasstudied by atomic force microscopy and differential scanning calorimetry. During a step heating process, the particles wereannealed for 0.5 h at each selected temperature. It was found that the deformation and interdiffusion temperatures of themicro-PS particles are ca. 120-130℃ and 140-150℃, that of the nano-PS particles are 90℃ and 100-110℃ respectively.The DSC traces of nano-PS particles showed that there was an exothermic peak near T_g after annealing for 0.5 h at theselected temperatures below 90℃; otherwise, the exothermic peak disappeared after annealing at 100℃ or above. Comparedwith the micro-PS pedicles, the sintering process of nano-PS particles occurs at much lower temperature determined by theconfined state of polymer chains with higher conformational energy in nano-particles, and completes in a much narrowertemperature range driven mainly by the larger total surface energy.     

Heating effect on the DSC melting curve of flaxseed oil

Flaxseed oil is rich in the alpha-linolenic acid. The effect of heating on the thermal properties of flaxseed oil extracted from flax seeds has been investigated. The flaxseed oils were heated at a certain temperature (75, 105, and 135 °C, respectively) for 48 h. The melting curve (from ?75 to 100 °C) of flaxseed oil was determined by differential scanning calorimetry (DSC) at intervals of 4 h. Three DSC parameters of exothermic event and endothermic event, namely, peak temperature (T _peak), enthalpy, and temperature range were determined. The initial flaxseed oil exhibited an exothermic peak, two endothermic peaks, and two endothermic shoulders between ?68 and ?5 °C in the melting profile. Heating temperature had a significant influence on the oxidative deterioration of flaxseed oil. The melting curve and parameters of flaxseed oil were almost not changed when flaxseed oil was heated at 75 °C. However, the endothermic peaks of melting curve decreased dramatically with the increasing of heating time when heating temperature was above 105 °C. There is almost no change of melting heat flow of flaxseed oil when heating time exceeded 32 h at 135 °C. The preliminary results suggest that the DSC melting profile can be used as a fast and direct way to assess the deterioration degree of flaxseed oil.     

Metal‐free synthesis of novel biobased dihydroxyl‐terminated aliphatic polyesters as building blocks for thermoplastic polyurethanes

Using the organic compound 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD) as a catalyst for step‐growth polymerization, a series of well‐defined hydroxyl‐telechelic renewable aliphatic polyesters (including poly(1,3‐propylene adipate); poly(1,4‐butylene adipate); poly(1,12‐dodecylene sebacate); and poly(1,2‐dimethylethylene adipate), PDMEA) were synthesized and studied. PDMEA is a novel polyester, which has not been reported before. The results of ¹H NMR and Matrix‐assisted laser desorption ionization time‐of‐flight mass spectrometry indicate that the polymers are fully hydroxyl terminated. From differential scanning calorimetry (DSC) thermograms, we found that the glass transition temperatures (T_g) of these polyesters are below ?20 °C. Only a T_g but no melting peak is observed in the DSC curve of the novel PDMEA. This indicates that PDMEA, contrary to the other renewable polyesters, is totally amorphous. Furthermore, using hexamethylene diisocyanate and hexamethylene diamine, poly(ester urethane urea)s (PEUUs) based on PDMEA were successfully synthesized. The T_g of the prepared PEUUs is below 0 °C, and no melting behavior of the soft‐segment is observed. The PEUU, with a flow temperature of over 200 °C, thus behaves as an elastomer at room temperature. Its mechanical properties, such as a relatively low tensile E‐modulus (≈20 MPa) at room temperature and a sufficiently high strain at break (≈560%), make it suitable for use in, for example, biomedical applications. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Thermal analysis and microscopical characterization of cholesterol in gallstones

Summary Cholesterol constitutes the major component of most gallstones. It was identified and determined in gallstones by thermal analysis technique (DSC and TG-DTA), mainly by the use of the melting temperature (T_onset=145°C and T_max=149°C) and by DTG peak decomposition (T_max=364°C). Cholesterol anhydrous (ChA), which showed endothermic polymorphic peak, T_max=40°C, without mass loss, was differentiated from cholesterol monohydrate (ChH), which showed a broad endothermic peak, T_max=59°C, attributed to loss of water of crystallization (theoretical 4.45%). Morphological studies of gallstones were performed by optical microscopy and scanning electron microscopy (SEM). The stones consisted of a pigmented core with a variably-sized irregular central cavity, surrounded by a radially arranged deposits of plate-like ChH. The outer part of the stones showed ChA crystal arborescences. X-ray microanalysis gave a typical spectrum rich in C and O, and in some instances the presence of P, which was attributed to the presence of phospholipids. CaCO₃ was easily characterized by TG with the use of DTG decomposition peak at 674°C.