Time–temperature–transformation (TTT) cure diagrams: Relationship between Tg and the temperature and time of cure for epoxy systems

A procedure is provided for estimating the time to full cure vs. isothermal cure temperature for vitrified epoxy systems. An equation relating the glass transition temperature of vitrified epoxy systems to the time and temperature of cure is developed.     

Time–temperature–transformation (TTT) cure diagrams: Relationship between Tg and the temperature and time of cure for a polyamic acid/polyimide system

Glass transition temperatures (T_g) were obtained vs. isothermal temperature (T_cure) and time of cure for a polyamic acid/polyimide system. A time–temperature–transformation (TTT) isothermal cure diagram was constructed to include the time to vitrification and iso-T_g curves. As for expoxies, the relationship between T_cure and the time to vitrification is S-shaped. Plots of T_g vs. T_cure show that solvent evaporation and chemical reaction are controlled by vitrification.     

Time-temperature-transformation (TTT) cure diagrams: Relationships between Tg,cure temperature,and time for DGEBA/DETA systems

Isothermal curing of a bisphenol A diglycidyl ether-based epoxy-resin-based, using an aliphatic polyamine, has been performed at temperatures between 20 and 60°C. Samples were cured isothermally at various intervals of time, and analyzed by differential scanning calorimetry (DSC). The glass transition temperature (T_g) and the conversion ratio cure determined by residual enthalpy analysis is used as an isothermal cure-controlled reaction. A time-temperature-transformation (TTT) isothermal cure diagram was carried out to include the time to vitrification and iso-T_g curves. © 1996 John Wiley & Sons, Inc.     

Competition between cure and thermal degradation in a high Tg epoxy system: Effect of time and temperature of isothermal cure on the glass transition temperature

The isothermal cure of a diglycidyl ether of bisphenol A with a tetrafunctional aromatic diamine has been studied in an attempt to achieve full cure (maximum glass transition temperature, T_g∞, ca. 170°C). Since high temperatures of cure are necessary for high T_g∞ systems (because of low reaction rates after vitrification), cure and thermal degradation reactions often compete. In this work T_g is used as a direct measure of conversion. An approach leading to a series of iso-T_g contours in a temperature vs. time transformation (TTT) diagram, which can be used to design time-temperature cure paths leading to particular values of T_g, is discussed.     

Time–temperature–transformation (TTT) cure diagram: Modeling the cure behavior of thermosets

The times to gelation and to vitrification for the isothermal cure of an amine-cured epoxy (Epon 828/PACM-20) have been measured on macroscopic and molecular levels by dynamic mechanical spectrometry (torsional braid analysis and Rheometrics dynamic spectrometer), infrared spectroscopy, and gel fraction experiments. The relationships between the extents of conversion at gelation and at vitrification and the isothermal cure temperature form the basis of a theoretical model of the time–temperature–transformation (TTT) cure diagram, in which the times to gelation and to vitrification during isothermal cure versus temperature are predicted. The model demonstrates that the “S” shape of the vitrification curve depends on the reaction kinetics, as well as on the physical parameters of the system, i.e., the glass transition temperatures of the uncured resin (T_g0), the fully cured resin (T_g∞), and the gel (_gelT_g). The bulk viscosity of a reactive system prior to gelation and/or vitrification is also described.     

Evolution of properties of an isocyanate/epoxy thermosetting system during cure: Continuous heating (CHT) and isothermal time—temperature—transformation (TTT) cure diagrams

The present article describes a methodology for examining the evolution of the properties vs. cure of a complex thermosetting isocyanate/epoxy reactive mixture which reacts through two consecutive but separable reaction regimes. The methodology is based on the use of the torsional braid analysis (TBA) technique and the continuous heating (CHT) and isothermal time—temperature—transformation (TTT) cure diagrams. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 15–25, 1997     

A methodology for characterizing reactive coatings: Time–temperature–transformation (TTT) analysis of the competition between cure,evaporation, and thermal degradation for an epoxy-phenolic system

A methodology, in terms of a macroscopic isothermal time–temperature–transformation (TTT) diagram, is presented for characterizing the changes that occur isothermally in a reactive thermosetting system in which evaporation, cure, and thermal degradation occur. Iso-weight loss contours show the progress of the loss of volatile material (mostly solvent). The gelation contour corresponds to the macroscopic viscosity rising to a definite level. The vitrification contour corresponds to the glass transition temperature (T_g) rising to the temperature of cure (T_cure). Iso-T_g contours show the progress of cure in terms of the easily measured T_g (rather than chemical conversion). The iso-T_g contours also show the influence of thermal degradation competing with cure. Degradation is responsible for difficulties in assigning the glass transition temperature of the fully cured material (i.e., T_g∞).     

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     

Chitin derivatives. II. Time–temperature–transformation cure diagrams of the chitosan amidization process

The transformation of the salts of chitosan with acetic and propionic acid, chitosonium acetate and chitosonium propionate, into chitin or the respective homolog of amidized chitosan has been described on the basis of time–temperature–transformation (TTT) cure diagrams. The time to vitrification at various isothermal cure temperatures (T_c) was determined using dynamic mechanical thermal analysis. The time to full cure was derived using a T_g–T_c cure time relationship according to the method of Peng and Gillham, as well as by an extrapolation procedure. Consequently, TTT cure diagrams describing the temperature-driven regeneration process include full cure and vitrification curves. As in thermosets, this transformation displays an S-shaped vitrification curve, and the time to full cure increases with decreasing cure temperature. The time to full cure is very remote from the time to vitrification, and this is attributed to the tendency of vitrification to prevent full cure from being attained. The activation energies for vitrification of chitosonium acetate and chitosonium propionate derived from an Arrhenius equation are similar. This suggests that the same mechanism governs glass formation in the N-acetyl and N-propionyl-glucosamine derivatives. Additionally, the morphology of amidized chitosan and native chitin was examined using X-ray diffraction and FTIR analysis. X-ray diffraction results indicate that amidized chitosan is an amorphous material, whereas native chitin is crystalline. FTIR suggests the existence of hydrogen-bonded amide groups in native chitin but not in amidized chitosan. This difference in morphology between amidized chitosan and native chitin is accounted for in terms of the influence of glass formation in the former. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1879–1889, 1999     

Effect of time-temperature path of cure on the water absorption of high Tg epoxy resins

The effect of different time—temperature paths of cure on the water absorption of high T_g epoxy resins has been investigated. The resins were cured isothermally for different times, with the following results: as extent of cure increased, the glass transition temperature (T_g) increased, the room temperature (RT) modulus decreased, the RT density decreased, the RT diffusion coefficient appeared to decrease, and the RT water absorption increased. The decrease in RT density is related to an increase in free volume, which controls the amount of water absorbed. A qualitative model accounts for the increase in RT free volume with increasing cure. The model is based on a restricted decrease of free volume on cure due to the rigid molecular segments in the cured resin systems. The sorption isotherms can be characterized by the dual mode theory at low activities but at high activities the sorption is complicated by penetrant clustering. A thermodynamic approach, independent of the absorption model, can correlate sorption data at different temperatures. The diglycidyl resin was also cured for extended times at three temperatures, in an effort to achieve full cure at each temperature. For these, the higher the cure temperature, the lower the RT density, which could result from the lower initial density of materials cured at higher temperatures. The equilibrium water absorption increased with increasing cure temperature, consistent with the decrease in RT density. The systems studied were a diglycidyl ether of bisphenol A cured with an aromatic tetrafunctional diamine, trimethylene glycol di-p-aminobenzoate (T_g∞ = 156°C), and a triglycidyl ether of tris(hydroxyphenyl)methane cured with the same amine (T_g∞ = 268°C).     

Comparison of microwave and thermal cure of epoxy resins

Stoichiometric mixtures of DGEBA (diglycidyl ether of bisphenol A)/DDS (diaminodiphenyl sulfone) and DGEBA/mPDA (meta phenylene diamine) have been isothermally cured by electromagnetic radiation and conventional heating using thin film sample configurations. Fourier transform infrared spectroscopy (FTIR) was used to measure the extent of cure. Thermal mechanical analysis (TMA) was used to determine the glass transition temperatures directly from the cured thin film samples. Well-defined glass transitions were observed in the TMA thermograph for both thermal and microwave cured samples. Significant increases in the reaction rates have been observed in the microwave cured DGEBA/DDS samples. Only slight increases in the reaction rates have been observed in the microwave cured DGEBA/mPDA samples. Higher glass transition temperatures were obtained in microwave cured samples compared to those of thermally cured ones after gelation. The magnitude of increases of glass transition temperature is much larger for the DGEBA/DDS system than DGEBA/mPDA system. The microwave radiation effect was much more significant in DGEBA/DDS system than in DGEBA/mPDA system. DiBenedetto's model was used to fit the experimental T_g data of both thermal and microwave cured epoxy resins.     

Study of epoxy and epoxy–cyanate networks thermal degradation to predict materials lifetime in use conditions

Composite materials are used more and more for aeronautical applications and they have to be as thermally stable as possible. The thermostability of carbon‐fiber/epoxy–cyanate composites elaborated with an autoadhesive and autoextinguish prepreg were tested. Dynamical and isothermal aging tests were carried out to evaluate the composite thermal stability. Thermal degradation products were identified by chromatography/mass spectrometry analysis and the results obtained were compared with data known on the material network structure. The physicochemical network structure evolutions and the thermal aging data are correlated with the interlaminar shear strength (ILSS) mechanical results. For epoxy–cyanate composites, cracking appears after a longer time of aging than for epoxy composites. This new epoxy–cyanate material isothermal stability seems to be good and particularly good if it was postcured after processing. The comparison of chemical, mechanical, and crack formation results obtained by accelerated aging tests allowed us to determine models to predict long‐term behavior. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3142–3153, 2000     

Reaction during cure of a blocked isocyanate–epoxy resin adhesive

Model compound reactions of isocyanate sources with alcohols and an epoxy resin indicated that the major reaction product from the phenol-blocked methylenebisphenylene diisocyanate and epoxy resin-based adhesive dip for poly(ethylene terephthalate) cord was a polyurethane. A significant portion of the hydroxyl groups required for the reaction were formed by ring opening of the epoxide groups of the resin. The reaction rate for the unblocking of the isocyanate source was inhibited in the presence of polyester yarn finishes containing sulfated esters of fatty acids. Also, compounds containing carboxylic acid groups and sulfonic acid groups inhibited the unblocking step. Amines and their salts catalyzed the unblocking step. A mechanism for the polyurethane adhesive–polyester bond based upon physical interaction is postulated. The presence of certain nonsulfated ester finishes permitted good wetting of the polyester surface and penetration of the adhesive into the polyester. By contrast, sulfated ester finishes result in poor wetting and penetration by the adhesive on the polyester. By contrast, sulfated ester finishes result in poor wetting and penetration by the adhesive on the polyester. The latter finishes resulted in a weak boundary layer between the adhesive and the cord.     

Thermokinetics and chemorheology of the cure reactions of the tetraglycidyl diamino diphenyl methane–diamino diphenyl sulfone epoxy systems

The cure behavior of commercial grade TGDDM–DDS mixtures of compositions ranging from 10 to 100 phr of hardener and the thermal polymerization of the epoxy component are analyzed by means of differential scanning calorimetry. The kinetic parameters and heats of reaction determined in isothermal and dynamic scans suggest that DDS primary amine addition and epoxide etherification dominate the cure reactions. The primary amine epoxide addition is characterized by overall heat of reaction (referred to the weight of the epoxy component) of 255 cal/g and by an activation energy of 16.6 kcal/mol. The corresponding values for the etherification reaction are, respectively, 170 cal/g and 41 kcal/mol. A method of derivation of the epoxide conversion from the heat evolved in DSC thermal scans of these systems is presented. The results are in good agreement with independent IR determinations. The steady shear and oscillatory viscosity measurements and the calorimetric analysis of the isothermal cure at 140°C, 160°C, and 180°C of a TGDDM–DDS mixture containing 35 phr of hardener indicate that gelation is principally governed by the primary amine addition. The gelation limits calculated in isothermal tests by combining the calorimetric analysis and the theory describing the nonlinear copolymerization of the tetrafunctional TGDDM with an essentially difunctional DDS were in good agreement with the values experimentally determined through rheological measurements.     

Effects of diffusion on the kinetic study and TTT cure diagram for an epoxy/diamine system

The curing reactions of an epoxy system consisting of a diglycidyl ether of bisphenol A (BADGE n = 0) and 1,2-diamine cyclohexane (DCH) were studied to determine a time–temperature–transformation (TTT) isothermal cure diagram for this system. Differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and a solubility test were used to obtain the different experimental data reported. Two models, one based solely on chemical kinetics and the other accounting for diffusion, were used and compared to the experimental data. The inclusion of a diffusion factor in the second model allowed for the cure kinetics to be predicted over the whole range of conversion covering both pre- and post-vitrification stages. The investigation was made in the temperature range 60–100°C, which is considered optimum for the isothermal curing of the epoxy system studied. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1931–1938, 1998     

TTT isothermal cure diagram of a dyglicidyl ether of bisphenol A/1,3-bisaminomethylcyclohexane (DGEBA/1,3-BAC) epoxy resin system

The isothermal cure of an epoxy-cycloaliphatic amine system has been studied following the evolution of both glass transition temperature and conversion. A functional relationship between T_g and conversion is established. The cure reaction is satisfactorily described by a phenomenological model with parameters determined from DSC experiments. By applying the kinetic model, gelation and vitrification curves are calculated and compared with experimental times to gelation and times to vitrification determined at temperatures between 50 and 100°C. The isothermal time-temperature-transformation (TTT) curing diagram including iso-T_g contours has been established. © 1996 John Wiley & Sons, Inc.     

Temperature–frequency transformation in dielectric thermal analysis (DETA) of wood relaxation properties

A direct method for the transformation of temperature dependences of dielectric loss factor (ε″) obtained at any frequency, into frequency dependences at any temperature was worked out. The method was tested and the accuracy of the analysis was verified for the case of local processes of dielectric relaxation in wood in the directions parallel and perpendicular to the fibers. The obtained solutions proved that a common representative of all considered dielectric absorption spectra is the distribution of dielectric absorption intensity vs. free energy of activation of an adequate individual relaxation process. The origin of the difference in the peak intensity of dielectric relaxation spectra, obtained at various experimental temperatures, was explained as a consequence of simple proportionality between the free energy of activation of relaxation and the energy of activation of rotators generation. A recently developed method of transformation is believed to give a new universal approach to the dielectric and dynamic mechanical thermal analysis of polymer systems. © 1996 John Wiley & Sons, Inc.     

A structure–property rationalization of some poly(carboxyl–epoxy) thermosets

The glass transition temperatures, T_g, and strength properties have been determined for an acrylic-based prepolymer containing 25 mole-% carboxyl functionality crosslinked with five different diepoxides. The T_g values vary from 100° to 200°C, and ultimate elongations of 2% to 7% at 25°C are observed with the different crosslinking agents. These variations are rationalized in terms of the structural elements present in the diepoxides. Thermosets possessing rigid structural units at the crosslink points connected by flexible segments have the best all-around combination of T_g and tensile properties. A decline in these properties was noted when the epoxide/carboxyl ratio exceeded unity owing to the formation of mixed networks and free chain ends.     

Study of the thermal degradation of poly(N-vinyl-2-pyrrolidone) by thermogravimetry–FTIR

The thermal degradation of poly(N-vinyl-2-pyrrolidone) (PVP) was studied by dynamic thermogravimetric analysis (TGA) in the range 200–600°C under nitrogen and oxygen atmospheres at various heating rates. The apparent activation energy of the degradative process was determined by the application of kinetic treatments, giving an average value of 242 kj/mol in N₂, whereas in the presence of oxygen, two trends may be considered: At relatively low temperatures (200–400°C) and degrees of conversion, α, lower than 0.5, we obtained an average value of 199 kj/mol, whereas in the temperature interval 400–600°C with degrees of conversion higher than 0.5, the value of E_a was 306 kj/mol. Isothermal experiments carried out in N₂ in the interval 350–400°C gave an average value of E_a = 231 kj/mol, in good agreement with that obtained from dynamic treatments. The FTIR spectra of the volatile compounds evolved in degradation experiments carried out in N₂ as well as in the presence of oxygen suggest that PVP is thermally degraded, predominantly, by the release of the pyrrolidone side group and the subsequent decomposition of polyenic sequences. © 1993 John Wiley & Sons, Inc.