Study of the physical aging of the epoxy system BADGE n = 0/m‐XDA/CaCO3

The physical aging of the epoxy network consisting of a diglycidyl ether of bisphenol A (BADGE n = 0), m‐xylylenediamine (m‐XDA), and calcium carbonate was studied by differential scanning calorimetry. The glass transition temperature and the variation of the specific heat capacities were calculated using the method based on the intersection of both enthalpy–temperature lines for glassy and liquid states. The apparent activation energy was calculated using a single method that involved separate temperature and excess enthalpy dependency. All calorimetric data were compared with those obtained for the epoxy network without filled calcium carbonate. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Activation energies for the epoxy system BADGE n = 0/m‐XDA obtained using data from thermogravimetric analysis

In this article we study the kinetics of thermal degradation of the epoxy system BADGE n = 0/m‐XDA using different kinetic methods with data from thermogravimetric analysis (TGA) in dynamic conditions. Activation energies obtained using different integral methods (Flynn‐Wall‐Ozawa and Coats‐Redfern Methods) are in good agreement with the value obtained using the Kissinger method (204.44 kJ/mol). The solid‐state decomposition mechanism followed by this epoxy system is a decelerated R_n type (phase boundary controlled reaction). We have also calculated activation energies using the Van Krevelen and the Horowitz‐Metzger methods. These last methods corroborate the decelerated behavior. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 776–782, 2001     

Lifetime predictions for the epoxy system BADGE n=0/m‐XDA using kinetic analysis of thermogravimetry curves

Lifetime of the epoxy system diglycidil ether of Bisphenol A (BADGE n=0)/ m‐xylylenediamine (m‐XDA) was calculated by thermogravimetric analysis. The Flynn‐Wall‐Ozawa method is used to determine the activation energy of the reaction. Experimental lifetimes in the range of 60–300°C vary from 1.41 10⁹ (2682 years) to 3.35 10^?4 min. This isoconversional method is not appropiate to calculate lifetime prediction because of high errors. Scaling factors were determined using the ratio of two reaction rates. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1692–1696, 2002     

Effects of diffusion on the kinetic study of the system BADGE n = 0/m‐xylylenediamine

The curing reactions of an epoxy system composed of a diglycidyl ether of bisphenol A (BADGE n=0) and m‐xylylenediamine (m‐XDA) were studied. Two models, the first based solely on chemical kinetics and the second accounting for diffusion, were used and compared to the experimental data. The epoxy resin was used as received in a first series of experiments. In a second series of experiments, the resin was purified in vacuo (180°C and 1 mmHg). 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 postvitrification stages. The investigation was made in the temperature range 50–110°C, which is considered optimum for the isothermal curing of the epoxy system studied. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2997–3005, 1999     

Kinetic analysis of relaxation process for the epoxy network diglycidyl ether of bisphenol A/m‐xylylenediamine

The relaxation kinetic of the epoxy network diglycidyl ether of bisphenol A (BADGE n = 0) and m‐xylylenediamine (m‐XDA) was analyzed from DSC experimental data, using different theoretical models. Based on a Petrie model, which involved separate contributions of temperature and structure, three characteristic parameters were calculated: a preexponential factor A, an apparent activation energy E_H, and a parameter C, which indicate the dependency of relaxation time on structure. This model allowed us to calculate the relaxation function at different ageing temperatures. Another method used to study a relaxation kinetic was the Kovacs–Hutchinson model, which takes into account the dependency of the relaxation time on temperature and structure. The last model used was a two‐parameter equation from Williams–Watts, where the relaxation time is independent of temperature. Using data of characteristic times a master curve for the relaxation function was obtained. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1591–1595, 2005     

Thermal degradation of the epoxy system BADGE n = 0/1,2‐DCH immersed in hydrochloric acid

The thermal degradation of an epoxy system consisting of diglycidyl ether of bisphenol‐A and 1,2‐diamine cyclohexane (BADGE n = 0/1,2‐DCH), immersed in hydrochloric acid for 30 days, was studied by thermogravimetric analysis, to determine the reaction mechanism of the degradation process. The results were compared with experimental data corresponding to the same epoxy system without exposure to the acid. It was found that the kinetic reaction mechanism changed with the immersion in HCl. The average activation energy of the solid‐state process was determined by using the Flynn‐Wall‐Ozawa method, resulting in 81 ± 2 kJ/mol. Different integral and differential methods and different reaction mechanisms reported in the literature were used and compared to this value. Analysis of experimental results suggests that in the conversion range studied, 5–20%, the reaction mechanism is somewhere between the different types of phase boundary controlled reaction and random nucleation with one nucleus on the individual particle. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 371–375, 2002     

Study of the epoxy system BADGE (n = 0)/1,2‐DCH/CaCO3 filler by DMA and DSC

The influence of an inorganic filler, CaCO₃, on the curing kinetics of an epoxy system composed of diglycidyl ether of bisphenol A [BADGE (n = 0)], 1,2‐diaminecyclohexane (1,2‐DCH), and CaCO₃ filler was studied by DMA and DSC. Different contents of filler in the range from 10 to 30%, referred to the total weight of the mixture, were tried. It was found that maximum reproducibility of the results and better performance correspond to a filler content of 20%. As usual, the T_g's obtained by DMA and DSC are different at 10–20°C. The results obtained from this study were compared with those corresponding to the system BADGE (n = 0)/1,2‐DCH without filler; the T_g for this last system is higher than that for the system with filler incorporated, whereas E′ and M_c (molecular weight between repetition units) are lower for the system without filler. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 366–370, 2002     

Influence of the filler CaCO3 on the cure kinetic of the epoxy network diglycidyl ether of bisphenol a (BADGE n = 0) with isophorone diamine

The influence of the presence of CaCO₃ on the cure reaction of the epoxy network diglycidyl ether of bisphenol A with isophorone diamine has been studied. The total enthalpy of reaction, the glass transition temperature and the partial enthalpies at different isothermal temperatures have been determined using differential scanning calorimetry (DSC) in dynamic and isothermal mode. A kinetic model accounting the influence of the diffusion of the reactive groups at high conversions was used. All the kinetic parameters have been compared with those of the system without filler (CaCO₃). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Curing kinetics of diglycidyl ether of bisphenol‐A (n = 0) using an iron‐containing porphyrin as cross‐linking agent

The curing reaction of a system consisting of a diglycidyl ether of bisphenol‐A (n = 0) and hemin (a protoporphyrin IX containing an iron ion and an additional chloride ligand) was studied with a differential scanning calorimeter. A maximum value of ?488.3 ± 8.4 J g^?1 was obtained for the enthalpy of the reaction. The kinetics of the process was studied by the isothermal method, observing that it obeys to Kamal's model, with an overall reaction order equal to 3. From the dependence of the kinetic constant with temperature, the activation energy, activation enthalpy, and activation entropy were determined. The ratio of the kinetic constants associated to the autocatalytic and nth order terms of the reaction rate, together with the thermodynamic activation parameters suggest a trend to the autocatalytic path mechanism with increasing temperatures. This study demonstrates that macrocycles can be used as cross‐linking agents for curing epoxy resins and that when metallomacrocycles are used, metal ions can be introduced into the network structure. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3972–3978, 2013     

Influence of an epoxy reactive diluent on the thermal degradation process of the system DGEBA n = 0/1,2 DCH

The thermal degradation of two epoxy systems diglycidyl ether of bisphenol A (DGEBA n = 0)/1,2‐diamine cyclohexane (DCH) containing different concentrations of an epoxy reactive diluent, vinylcyclohexene dioxide (VCHD), was studied by thermogravimetric analysis to determine the reaction mechanism of the degradation process for these two systems. Values of the activation energy, necessary for this study, were calculated by using various integral and differential methods. Values obtained by using the different methods were compared to the value obtained by Kissinger's method, which does not require a knowledge of the reaction mechanism. All the experimental results were compared to master curves in the range of Doyle's approximation (20–35% of conversion). Analysis of the results suggests that the two reaction mechanisms are R_n and F_n deceleratory type in contrast with the sigmoidal A₂ type of the system with filler and the sigmoidal A₄ type of the system without additives. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1199–1207, 2004     

Thermo‐reversible healing in a crosslinked polymer network containing covalent and thermo‐reversible bonds

The self‐healing behavior of a modified ureido‐amide based thermoplastic hybrid elastomer was investigated by increasing the concentration of non‐reversible (covalent) bonds compared to reversible (hydrogen) bonds. A crosslinked polymer network was synthesized using varying amounts of diglycidylether of bisphenol A and reacting with the ureido‐amide thermoplastic. Increasing epoxy content produced a more rigid and thermally stable hybrid network, which in turn decreased overall thermo‐reversible or healing behavior. Fracture toughness recoveries varied from 25% for the system containing the greatest number of covalent bonds to well over 200% for systems containing higher thermoplastic content. Substantial levels of healing, about 62% recovery, were still achieved despite the crosslinked network having a T_g above room temperature, 31°C as measured by differential scanning calorimetry (DSC). Dynamic mechanical thermal analysis was used to monitor thermo‐reversible behavior of the elastic moduli and thus probe molecular mobility within the glassy state. The extent and rate of recovery of the elastic modulus was dominated by the extent of thermal activation above the glass transition temperature. Fourier transform infrared spectroscopic and DSC studies confirmed that reacting the thermoplastic with an epoxy resin produced a covalently bonded crosslinked network and the epoxide groups were completely consumed. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Lifetime prediction of the epoxy system DGEBA (n = 0)/1,2‐DCH modified with an epoxy reactive diluent by thermogravimetric analysis

Thermogravimetric analysis was used to predict the lifetime of two three‐component systems of diglycidyl ether of bisphenol A (n = 0)/1,2‐diamine cyclohexane [DGEBA (n = 0)/1,2‐DCH] modified with different concentrations of an epoxy reactive diluent, vinylcyclohexene dioxide (VCHD). Experimental results were treated using two methods. The first method was independent of the degradation mechanism, and the second was based on the thermodegradation kinetic mechanism. The activation energies of the reaction were determined using the Flynn–Wall–Ozawa method. These values were compared with those obtained using Kissinger's method. From experimental results it was found that the optimum temperature of service for these materials were different, so one or the other must be selected, depending on the application temperature considered. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3835–3839, 2003     

Adjustable amine–epoxy composition in a stratified thin film with a spin‐coating process: A useful tool for establishing relationships between the local glass‐transition temperature at the interface and the network structure

An easy method for preparing supported homogeneous epoxy–amine thin films on a silica surface consisting of two distinct layers was developed via spin coating from epoxy–amine solutions. Because of these two layers had the controlled properties of the upper layer, we showed that it was possible to precisely control the epoxy–amine stoichiometry in the sublayer through the initial epoxy–amine ratio, the spin‐cast process, and the overall film thickness. First, in the thin films, the primary amine–epoxy conversion was constant, whatever the thickness and initial epoxy–amine stoichiometry for a given curing schedule. As the primary amine conversion can be independently tuned in thin films, it thus provided a rather unique and easy method for better understanding the relationship between the network structure curing at the interface and the resulting properties, such as the glass‐transition temperature (T_g) and elastic modulus. Here, we also showed that we could access the local T_g; this implied a potential application of these experimental data in predictive composite material properties. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42078.     

Relationships between thermally induced residual stresses and architecture of epoxy‐amine model networks

The capability of epoxy‐amine resins to develop residual stresses was studied as a function of temperature and network architecture. These residual stresses were induced while cooling epoxy‐glass bilayers from temperatures higher than the network glass transition temperature, T_g. This behavior was the result of the marked differences (α_r − α_g), in linear thermal expansion coefficient of the two components, as evidenced by the measurement of α_r for the epoxy networks under study. Various network architectures were selected, resulting from variation of (1) the chemical nature of both epoxide and curing agent, (2) the nature and relative amount of the chain‐extensor agent, and (3) the stoichiometric ratio. Three ranges of cooling temperature were observed systematically: first, the range of temperatures above T_g, where no stress has been detected, then an intermediate temperature range (from T_g to T*), where stresses develop quite slowly, and finally, the low temperature range (T < T*), where a linear increase in stress accompanies the decrease of temperature. The two latter regimes were quantitatively characterized by the extent, T_g − T*, of the first one and by the slope, SDR, of the second one. T_g − T* values were shown to be governed by the T_g of the network: the higher the T_g, the larger the gap between T_g and T*. This result was interpreted by accounting for the variation of relaxation rate at T_g from one network to the other. It was also shown that a semiempirical relationship holds between SDR and T_g: SDR decreases monotonically as T_g increases. By inspecting the effects of network architecture in more details, it turned out that SDR is governed by the Young's moduli, E_r(T − T_g), of the epoxy resins in the glassy state: the lower E_r(T − T_g), the lower SDR in a series of homologous networks. As E_r(T − T_g) values are known to be related to the characteristics of the secondary relaxation β, which depends, in turn, on crosslink density, SDR values were finally connected to the amplitude of the β relaxation processes. This finding was corroborated by the measurements on an antiplasticized dense network. Finally, data relative to thermoplastic‐filled networks showed that the addition of thermoplastic reduces the development of residual stresses, whatever the system, is homogeneous or biphasic. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 638–650, 2000     

Modification of a two‐component system by introducing an epoxy‐reactive diluent: Construction of a time–temperature–transformation (TTT) diagram

Curing reactions of a three‐component system consisting of an epoxy resin diglycidyl ether of bisphenol A (DGEBA n = 0), 1,2‐diaminecyclohexane as curing agent, and vinylcyclohexene dioxide as a reactive diluent were studied to calculate a time–temperature–transformation isothermal cure diagram for this system. Differential scanning calorimetry (DSC) was used to calculate the vitrification times. DSC data show a one‐to‐one relationship between T_g and fractional conversion α, independent of cure temperature. As a consequence, T_g can be used as a measure of conversion. The activation energy for the polymerization overall reaction was calculated from the gel times obtained using the solubility test (58.5 ± 1.3 kJ/mol). This value was similar to the results obtained for other similar epoxy systems. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1190–1198, 2004     

Synthesis and network parameters of hydrophobic poly(N‐[3‐(dimethylaminopropyl)]methacrylamide‐co‐lauryl acrylate) hydrogels

Hydrophobic poly(N‐[3‐(dimethylaminopropyl)]methacrylamide‐co‐lauryl acrylate) [P(DMAPMA‐co‐LA)] hydrogels with different LA content were synthesized by free‐radical crosslinking copolymerization of corresponding monomers in water by using N,N‐methylenebis(acrylamide) as the crosslinker, ammonium persulfate as the initiator, and N,N,N′,N′‐tetramethylethylenediamine as the activator. The swelling equilibrium of the hydrogels was investigated as a function of temperature and hydrophobic comonomer content in pure water. An interesting feature of the swelling behavior of the P(DMAPMA‐co‐LA) hydrogels with low LA content was the reshrinking phase transition where the hydrogels swell once and collapse as temperature was varied in the range of 30–40°C. The average molecular mass between crosslinks (M?_c) and polymer–solvent interaction parameter (χ) of the hydrogels were calculated from equilibrium swelling values. The enthalpy (ΔH) and entropy (ΔS) changes appearing in the χ parameter for the hydrogels were determined by using the Flory–Rehner theory based on the phantom network model of swelling equilibrium. The positive values for ΔH and ΔS indicated that the hydrogels had a positive temperature‐sensitive property in water, that is, swelling at a higher temperature and shrinking at a lower temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4159–4166, 2006     

Effects of epoxy content on dynamic mechanical behaviour of PEI‐toughened dicyanate–novolac epoxy blends

By varying the cyanate/epoxy ratio, three polyetherimide(PEI)‐modified bisphenol A dicyanate–novolac epoxy resin blends with different epoxy contents were prepared. The effects of epoxy content on the dynamic mechanical behaviour of those blends were investigated by dynamic mechanical thermal analysis. The results showed that the glass transition temperature of the cyanate–epoxy network (T_g1) in the modified blend decreases with epoxy content. When the epoxy content increases, both the width of the glass transition of the cyanate–epoxy network and its peak density are depressed substantially. Although the tangent delta peak value of PEI is basically independent of epoxy content, the T_g of PEI (T_g2) decreases with epoxy content. T_g1 is independent of the PEI loading. When T_g1 is lower than T_g2, however, the T_g1 in the blend with revised phase structure is substantially lower than other blends. Copyright © 2004 Society of Chemical Industry     

Toughness response of vinylester/epoxy‐based thermosets of interpenetrating network structure as a function of the epoxy resin formulation: Effects of the cyclohexylene linkage

Vinylester/epoxy (VE/EP)‐based thermosets of interpenetrating network (IPN) structures were produced by using a VE resin (bismethacryloxy derivative of a bisphenol A–type EP resin) with aliphatic (Al‐EP) and cycloaliphatic (Cal‐EP) EP resins. Curing of the EP resins occurred either with an aliphatic (Al‐Am) or cycloaliphatic diamine compound (Cal‐Am). Dynamic mechanical thermal analysis (DMTA) and atomic force microscopy (AFM) suggested the presence of an interpenetrating network (IPN) in the resulting thermosets. Fracture toughness (K_c) and fracture energy (G_c) were used as the toughness characterization parameters of the linear elastic fracture mechanics. Unexpectedly high K_c and G_c data were found for the systems containing cyclohexylene units in the EP network, such as VE/Al‐EP+Cal‐Am and VE/Cal‐EP+Al‐Am. This was attributed to the beneficial effects of the conformational changes of the cyclohexylene linkages (chair/boat), which were closely analogous to those in some thermoplastic copolyesters. The failure mode of the VE/EP thermoset combinations was studied in scanning electron microscopy (SEM) and discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2124–2131, 2003     

High‐performance biobased epoxy derived from rosin

Great achievements have been made in the research of biobased thermoplastic polymers, but the progress concerning thermosetting resins has been minor. In particular, research on high‐performance thermosetting polymers from renewable feedstock has not been reported elsewhere. A novel biobased epoxy was synthesized from a rosin acid. Its chemical structure was confirmed using ¹H NMR, ¹³C NMR and Fourier transform infrared spectroscopy. The results indicated that the rosin‐based epoxy possessed high glass transition temperature (T_g = 153.8 °C), high storage modulus at room temperature (G′ = 2.4 GPa) and good thermal stability. A rosin‐based epoxy with excellent properties was achieved. The results suggest it is possible to develop high‐performance thermosetting resins from renewable resources. Copyright © 2010 Society of Chemical Industry