P. Cortés

Addition of a reactive diluent to a catalyzed epoxy-anhydride system. I. Influence on the cure kinetics

The effect of a reactive diluent (RD) on the kinetics of the curing of an epoxy resin, based on diglycidyl ether of bisphenol A (DGEBA), with a carboxylic anhvdride derived from methyl-tetrahydrophthalic anhydride (MTHPA) catalyzed by a tertiary amine has been studied. The reactive diluent was a low-viscosity aliphatic diglycidyl ether, and the compositions per 100 parts by weight (pbw) of DGEBA were 10, 30, and 50 pbw of RD with the stoichiometric quantity of MTHPA and 1 pbw of catalyst. The curing kinetics was monitored by differential scanning calorimetry (DSC), and the kinetic parameters were determined from the nonisothermal DSC curves by the method described by Malek. The kinetic analysis suggests that the two-parameter autocatalytic model is the more appropriate to describe the kinetics of the curing reaction of this epoxy-anhydride system. The kinetic parameters thus derived satisfactorily simulate both the nonisothermal DSC curves and the isothermal conversion-time plots. Increasing the RD content leads to a small increase in both the nonisothermal and the isothermal heats of curing and has a slight effect on the kinetic parameters E, ln A, m, and n, and, consequently, on the overall reactivity of the system. On the other hand, the increase of the RD content significantly affects the structure of the crosslinked epoxy. It is confirmed that the introduction of aliphatic chains in the structure of the epoxy increases the mobility of the segmental chains in the glass transition region. The consequence of this chemical modification is a decrease of the glass transition temperature, Tg.

Enthalpy relaxation in a partially cured epoxy resin

The enthalpy relaxation of a partially cured (70%) epoxy resin, derived from diglycidyl ether of bisphenol-A cured by methyl-tetrahydrophthalic anhydride with accelerator, has been investigated. The key parameters of the structural relaxation (the apparent activation energy Δh*, the nonlinearity parameter x, and the nonexponentiality parameter β) are compared with those of the fully cured epoxy resin. The aging rates, characterized by the dependences of the enthalpy loss and peak temperature on log(annealing time), are greater in the partially cured epoxy than they are in the fully cured resin at an equivalent aging temperature (Ta = Tg − 20°C). There is a significant reduction in Δh*, from 1100 kJ mol−1 for the fully cured system to 615 kJ mol−1, as the degree of cure is reduced. The parameter x determined by the peak-shift method appears essentially independent of the degree of cure (x = 0.41 ± 0.03 for the partially cured resin compared with 0.42 ± 0.03 obtained previously for the fully cured resin), and does not follow the usually observed correlation of increasing x as Δh* decreases. This invariability of the parameter x seems to indicate that it is determined essentially by the local chemical structure of the backbone chain, and rather little by the supramolecular structure. On the other hand, the estimated nonexponentiality parameter β lies between 0.3 and 0.456, which is significantly lower than in the fully cured epoxy (β ≅ 0.5), indicative of a broadening of the distribution of relaxation times as the degree of cross-linking is reduced. Like the parameter x, this also does not follow the usual correlation with Δh*. These results are discussed in the framework of strong and fragile behavior of glass-forming systems, but it is difficult to reconcile these results in any simple way with the concept of strength and fragility.

Enthalpy relaxation in GexSe1−x chalcogenide glasses

Abstract Enthalpy relaxation in selenium samples and Ge x Se 1− x alloys with x =0.08 and 0.12 has been investigated by differential scanning calorimetry. All the samples have been submitted to comparable aging temperatures 10°C below the glass transition temperature for a period from 0.5 to 800 h. The apparent activation energy and the Narayanaswamy parameter, X , were calculated and the non-exponentiality parameter, β , was estimated for the samples. The introduction of the germanium atoms in the selenium chain changes the distribution of relaxation times, increases the relaxation rate per decade and decreases the apparent activation energy. No differences were observed in the Ge x Se 1− x alloys in the evaluation of these parameters.

Addition of a reactive diluent to a catalyzed epoxy‐anhydride system. II. effect on enthalpy relaxation

Enthalpy relaxation in an epoxy resin based on diglycidyl ether of bisphenol A (DGEBA) with a reactive diluent cured with methyl-tetrahydrophthalic anhydride (MTHPA) with an accelerator was investigated by differential scanning calorimetry. The reactive diluent (RD) added was an aliphatic diglycidyl ether which was mixed in a proportion of 50 parts by weight (pbw) per 100 parts of DGEBA, with the stoichiometric quantity of MTHPA. The key parameters of the enthalpy relaxation investigated were the nonlinearity parameter, x, the apparent activation energy,Δh*, and the nonexponentiality parameter, β. The results were compared with other data obtained previously in similar epoxy-anhydride systems without an RD but with different degrees of conversion in order to analyze the effects of (a) the introduction of aliphatic chains of the RD in the epoxy structure and (b) a reduction in the crosslink density of the resin.

Effect of crosslink length on the enthalpy relaxation of fully cured epoxy–diamine resins

Enthalpy relaxation of epoxy–diamine thermosets of different crosslink lengths (CLL) has been studied by DSC. The epoxy resins based on diglycidyl ether of bisphenol A were cured with ethylenediamine (FEDA), and diamines of polyoxypropylene of 2.6 and 5.6 oxypropylene units, named FJ230 and FJ400, respectively. As was expected, increasing the CLL decreases the glass transition temperature Tg from 121°C (FEDA) to 47°C (FJ400). Aging experiments at Tg − 20 K for each resin permit the determination of the enthalpy loss, the relaxation rate per decade (βH), and the nonlinearity parameter, x. The apparent activation energy, Δh*, and the nonexponentiality parameter β are found for each resin from intrinsic cycles in which the sample is heated at 10 K min−1 following cooling at various rates through the glass transition region. An increase of CLL is related to an increase of βH, and of the nonlinearity parameter. In agreement with the general trend for thermoplastic polymers, the increase of the parameter x is correlated with a decrease of Δh* and with an increase in the nonexponentiality parameter. Application of the Adam–Gibbs (AG) theory reveals that the parameters B and Tf/T2 increase with CLL, corresponding to a decrease of the nonlinear behavior of the glassy epoxies. However, the T2 values calculated in this way appear unrealistic, and the alternative assumption that T2 = Tg −51.6 K, making use of the “universal” WLF constant, leads to a much smaller variation of B, which nevertheless still increases with CLL. From a consideration of the minimum number of configurations required for a cooperative rearrangement, it is argued that the elementary activation energy Δμ increases, and the minimum size of the cooperatively rearranging region decreases as CLL increases. This is consistent with the relaxation process becoming more cooperative as the CLL decreases, as is suggested by the decrease in the value of β.

Structural relaxation in fully cured epoxy resins

Enthalpy relaxation in a fully cured epoxy resin at 80°C has been investigated in two different laboratories, the Universitat Politecnica de Catalunya and Aberdeen University, and using two different instruments (Mettler and Perkin-Elmer, respectively) for differential scanning calorimetry. The same values of activation energy (1100 kJ mol−1) and ΔCp (0.34 J g−1 K−1) were obtained in each laboratory. However, the peak-shift method for the evaluation of the Narayanaswamy parameter, x, yields different values (0.45 from Catalunya and 0.39 from Aberdeen); similar differences are found for the non-exponentiality parameters β (0.3 < β < 0.456 from Catalunya and 0.456 < β < 0.6 from Aberdeen). These discrepancies are tentatively attributed to differing thermal gradients in the two calorimeters. Nevertheless, the values of x appear high when compared with other glasses with similar activation energies. It is suggested that this results from a ‘strengthening’ due to the cross-linked epoxy network structure.

Physical aging studies of amorphous linear polyesters. Part II. Dependence of structural relaxation parameters on the chemical structure

The enthalpy relaxation of a series of linear amorphous polyesters (poly(propylene isophthalate)(PPIP), poly(propylene terephthalate) (PPTP), poly(ethylene terephthalate) (PETP), and poly(dipropylene terephthalate) (PDPT)) has been investigated by differential scanning calorimetry (DSC). These polyesters have been annealed at equal undercooling below their respective glass transition temperatures, T g , (T g - 27°C, T g - 15°C, and Tg - 9°C) for periods of time from 15 min to 480 h. The key parameters of structural relaxation, namely the apparent activation energy (Δh*), the nonlinearity parameter (x) and the nonexponentiality parameter (β), have been determined for each polyester and related to an effective relaxation rate (1/τ eff ) and to the chemical structure. We observe that the variation of the structural relaxation parameters shows a trend that is common to other polymeric systems, whereby an increase of x and β corresponds a decrease in Δh*. The comparison of these parameters in PETP and in PPTP gives information about the effect of the introduction of a methyl group pendant from the main chain; the x parameter increases (i.e., a reduced contribution of the structure to the relaxation times), β increases (i.e., a narrow distribution of relaxation times), and Δh* decreases. Additionally, enthalpy relaxation experiments show that a decrease of Δh* correlates with an increase of 1/τ eff , when they are measured at a fixed value of the excess enthalpy, δ H . The introduction of an isopropyl ether group in PDPT with respect to PPTP decreases both x and β, but increases Δh*, which the rate of relaxation decreases. The ring substitution in PPTP and PPIP originates less significant changes in the structural parameters.

A New Epoxy-Based Layered Silicate Nanocomposite Using a Hyperbranched Polymer: Study of the Curing Reaction and Nanostructure Development

Polymer layered silicate (PLS) nanocomposites have been prepared with diglycidyl ether of bisphenol-A (DGEBA) epoxy resin as the matrix and organically modified montmorillonite (MMT) as the clay nanofiller. Resin-clay mixtures with different clay contents (zero, two, five and 10 wt%) were cured, both isothermally andnon-isothermally, using a poly(ethyleneimine) hyperbranched polymer (HBP), the cure kinetics being monitored by differential scanning calorimetry (DSC). The nanostructure of the cured nanocomposites was characterized by small angle X-ray scattering (SAXS) and transmission electron microscopy (TEM), and their mechanical properties were determined by dynamic mechanical analysis (DMA) and impact testing. The results are compared with an earlier study of the structure and properties of the same DGEBA-MMT system cured with a polyoxypropylene diamine, Jeffamine. There are very few examples of the use of HBP as a curing agent in epoxy PLS nanocomposites; here, it is found to enhance significantly the degree of exfoliation of these nanocomposites compared with those cured with Jeffamine, with a corresponding enhancement in the impact energy for nanocomposites with the low clay content of 2 wt%. These changes are attributed to the different cure kinetics with the HBP, in which the intra-gallery homopolymerization reaction is accelerated, such that it occurs before the bulk cross-linking reaction.

Enthalpy relaxation in polymethyl(α-n-alkyl)acrylates : Effect of length of alkyl chain

In this work, we have investigated by DSC the structural relaxation of amorphous polymethyl(α-n-alkyl)acrylates in which it is possible to change the length of the alkyl chain. We have evaluated the Narayanaswamy parameter, x, which controls the relative contribution of temperature and of structure to the relaxation time, the apparent activation energy, Δh * , and the nonexponentiality parameter, β, of the stretched exponential response function. The results suggest that x increases while Δh * decreases and β remains constant as the length of the side chain increases. This allows us to comment on the effect of chemical modification on the relaxation kinetics.

The use of DSC to characterize structural relaxation in thermosetting polymers

Structural relaxation in different epoxy-anhydride and epoxy-diamine resins has been investigated by differential scanning calorimetry using annealing and cooling rate experiments. The annealing experiments lead to the determination of enthalpy loss,δH, at an equivalent annealing temperatureTa=Tg-20, and for periods of annealing time, ta, between 1 h and 4 months. The variation ofδH with logta, defines a relaxation rate per decade,rrpd, which is very sensitive to changes of the epoxy network. The cooling rate experiments allow the determination of the apparent activation energy,δh*. The effect of the degree of crosslinking, the addition of a reactive diluent, which acts as flexibilizer, and the length of cross-link onrrpd and δh* was studied.