Cure monitoring of epoxy resins by fluorescence quenching

Summary The effect of curing on the fluorescence intensity of 1,6-diphenyl-1,3,5-hexatriene (DPH) and 9,10-dimethylanthracene (DMA) was studied using two epoxide/amine systems. In the system diglycidyl ether of Bisphenol A (DGEBA)/1,3-diaminopropane the fluorescence intensity of DMA, I_f, increases with increasing conversion of epoxy groups; this is explained by means of a dynamic model of fluorescence quenching by dissolved molecular oxygen. Contrariwise, in the other system under study, DGEBA/poly (oxypropylene) diamine (Jeffamine^R D-400), I_f of the DPH probe decreases, which is interpreted by using the model of static fluorescence quenching. Both effects are suggested for use in the cure monitoring of epoxy resins.     

Cure behavior of an interpenetrating diglycidyl ether of bisphenol A/poly(ethylene oxide) miscible system

Differential scanning calorimetry (DSC) was performed to investigate the cure behavior of epoxy networks of diglycidyl ether of bisphenol A/poly(ethylene oxide) (DGEBA/PEO) cured with 4,4'-diaminodiphenyl sulfone (DDS). An interesting miscibility has been recently reported for DGEBA/PEO networks of a semi-interpenetrating structure cured with aromatic amine. This study focused on the cure behavior and effects of miscible polymer diluents on cure kinetics. The physical miscible state between the polymer and epoxy was found to exert no alteration on the cure mechanism, which remained to be autocatalytic for DDS amine-curing of all DGEBA/PEO mixtures as well as the pure DGEBA. The PEO component, being in a miscible state with the epoxy/DDS throughout the cure, acted as a diluent for the reactive DGEBA epoxy and DDS components. The dilution effect could be partially compensated by raising the DDS/epoxy ratio in proportion to increased PEO fraction in DGEBA/PEO/DDS mixtures.     

Comparative cure behavior of DGEBA and DGEBP with 4-nitro-1,2-phenylenediamine

Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and advanced isoconversional kinetic analysis were used to study the curing reaction of diglycidyl ether of 4,4′-bisphenol A (DGEBA) epoxy monomer with an aromatic amine, 4-nitro-1,2-phenylenediamine (4-NPDA). The first DSC exothermic peak was assigned to the curing process of DGEBA with 4-NPDA. Kinetic analysis suggested that the effective activation energy for the cure process decreases from ≈120 to a practically constant value ≈60 kJ mol⁻¹. This system was compared with diglycidyl ether of 4,4′-bisphenol (DGEBP)/4-NPDA. DGEBA/4-NPDA system shows higher reaction temperature, lower reaction rate and lower glass transition temperature under the same cure condition. This can be explained by stereochemical structure of epoxy monomer and the effect of conjugation.     

Chemical interpretation of the relaxed permittivity during epoxy resin cure

The isothermal cure of a diglycidyl ether of Bisphenol-A (DGEBA) epoxy resin with diaminodiphenylsulfone has been characterized by microdielectrometry and differential scanning calorimetry. The cure temperatures ranged from 410 to 460K. The behavior of the relaxed (or static) dielectric permittivity vs. cure time and temperature was determined from the microdielectrometry data. The DSC data was fit to an autocatalyzed reaction kinetics model, which was then used to predict reactive group concentrations as a function of cure time and temperature. The temperature dependence of the relaxed permittivity at constant chemical conversion was examined in the context of the Onsager theory for the relaxed permittivity of a system of independent dipoles. This analysis indicated that the dipoles in the resin are not independent, as assumed by the Onsager theory, and that the behavior is similar to that observed in polyethers. An empirical modification to the Onsager theory was used in conjunction with the kinetic model to estimate dipole moments for the epoxide, primary amine, and reacted (secondary and tertiary) amine groups. The relative and absolute values of the dipole moments were in good agreement with estimates based on the structures, leading to the conclusion that the observed decrease of the relaxed permittivity during cure of this epoxy/amine system is due to the changing concentrations of polar reactive groups.     

Curing of diepoxides with tertiary amines: Influence of temperature and initiator concentration on polymerization rate and glass transition temperature

The cure of an epoxy resin based on diglycidyl ether of bisphenol A (DGEBA), with benzyldimethylamine (BDMA), was investigated using differential scanning calorimetry. The kinetics showed a first-order behavior with respect to both epoxy and tertiary amine concentrations and a non-Arrhenius dependence on temperature. An activation energy could be defined only in the low-temperature range, i.e., from 80 to 120°C. Its value (E = 24.2 kJ/mol = 5.8 kcal/mol) indicates a very slight dependence on temperature. The glass transition temperature of epoxy networks decreased with an increase in both the tertiary amine concentration and the cure temperature. These effects are attributed to plastification by the free amine and to the decrease in the average length of polyether chains, which, in turn, increases the number of network defects.     

In-situ cure monitoring of diamine cured epoxy by fiberoptic fluorimetry using extrinsic reactive fluorophore

This paper describes the application of a molecular sensor for in-situ monitoring of epoxy-diamine cure via remote sensing fiberoptic probes. A custom-built, fiberoptic fluorimeter allows on-line recording of fluorescence spectra directly from the cure environment. Cure reactions in epoxy-diamine network, such as diglycidyl ether of bisphenol A-diaminodiphenyl sulfone (DGEBA-DDS) or diglycidyl ether of butanediol-diaminodiphenyl sulfone (DGEB-DDS), have been monitored by a reactive molecular sensor, diamino azobenzene (DAA). DAA exhibits sensitive changes in UV-visible and fluorescence spectra due to the conversion of its primary amine groups to secondary and tertiary amine groups. Fluorescence intensities are correlated with extent of reaction in epoxy network and processing parameters, such as cure temperatures and time. The use of an internal reference dye for normalization of fluorescence intensities is necessary for the quantitative correlation of spectral signals with the network structure. Variables affecting the fluorescence intensity such as excitation volume, probe location, excitation intensity fluctuation, temperature, and background intensities from optical fiber can be calibrated by normalizing the signal intensities against the internal reference. Sulforhodamine 101 was found to be a satisfactory reference dye which provides stable, readable signals over temperatures up to 200°C.     

Cure kinetics of several epoxy–amine systems at ambient and high temperatures

Epoxy-crosslinker curing reactions and the extent of the reactions are critical parameters that influence the performance of each epoxy system. The curing of an epoxy prepolymer with an amine functional group may be accompanied by side reactions such as etherification. Commercial epoxy prepolymers were cured with different commercial amines at ambient as well as at elevated temperatures. Singularly, only epoxy–amine reactions were observed with diglycidyl ether of bisphenol-A (DGEBA)-based epoxides in our research even upon post-curing at 200°C. Etherification side reaction was found to occur at a cure temperature of 200°C in epoxides possessing a tertiary amine moiety. A combined goal of our research was to understand the effect of tougheners on the cure of epoxy–amine blend. To discern the effect of tougheners on the cure, core–shell rubber (CSR) particles were incorporated into the epoxy–amine blend. It was observed that CSR particles did not restrict the system from proceeding to complete reaction of epoxy moieties. Besides, CSR particles were found to accelerate the epoxy-amine reaction at a lower level of epoxy conversion. The lower activation energy of epoxy–amine reaction of CSR incorporated system compared to control supported the catalytic effect of CSR particles on the epoxy-amine reaction of epoxy prepolymer and amine blends.     

Chemical modification of epoxy resins by dialkyl(or aryl) phosphates: Evaluation of fire behavior and thermal stability

The improvement of flame-retardation of thermosetted epoxy–amine resins was attempted by chemically incorporating phosphorus-containing reagents. By reacting 4,4′-diglycidylether of bisphenol A (DGEBA) with dialkyl (or aryl) phosphate, it was possible to chemically modify the epoxy resin and then cure it in the presence of 4,4′-diaminodiphenylsulfone (DDS) to obtain epoxy-amine resin with good flame-retardant and thermal stability behaviors. The quantitative aspect of the addition of dialkyl (or aryl) phosphate onto glycidyle oxiranes was evaluated by elemental analysis of the modified epoxy-amine resins. Flammability and thermal behaviors of modified DGEBA/DDS resins depend on the nature of phosphate groups (the best flame-retardation was observed on resins bearing phenyl phosphate groups) and their concentration in the material. In relation to DGEBA/DDS samples containing additives of the same structure [trialkyl(or aryl) phosphate], cured resins incorporating chemically bonded phosphate groups show a better flame-retardation. On the contrary to the nonomodified DGEBA/DDS [with or without trialkyl (or aryl) phosphate as additive], combustion of modified DGEBA/DDS resins is accompanied by formation of intumescent char. Chemical modification of DGEBA by dialkyl (or aryl) phosphates can be carried out in situ during the curing of epoxy resins without change in the fire behavior. © 1996 John Wiley & Sons, Inc.     

Blends of epoxy resins and polyphenylene oxide as processing aids and toughening agents 2: Curing kinetics,rheology, structure and properties

The curing behaviour, chemorheology, morphology and dynamic mechanical properties of epoxy ? polyphenylene oxide (PPO) blends were investigated over a wide range of compositions. Two bisphenol A based di‐epoxides ? pure and oligomeric DGEBA ? were used and their cure with primary, tertiary and quaternary amines was studied. 4,4′‐methylenebis(3‐chloro‐2,6‐diethylaniline) (MCDEA) showed high levels of cure and gave the highest exotherm peak temperature, and so was chosen for blending studies. Similarly pure DGEBA was selected for blending due to its slower reaction rate because of the absence of accelerating hydroxyl groups. For the PPO:DGEBA340/MCDEA system, the reaction rate was reduced with increasing PPO content due to a dilution effect but the heat of reaction were not significantly affected. The rheological behaviour during cure indicated that phase separation occurred prior to gelation, followed by vitrification. The times for phase separation, gelation and vitrification increased with higher PPO levels due to a reduction in the rate of polymerization. Dynamic mechanical thermal analysis of PPO:DGEBA340/MCDEA clearly showed two glass transitions due to the presence of phase separated regions where the lower T_g corresponded to an epoxy‐rich phase and the higher T_g represented the PPO‐rich phase. SEM observations of the cured PPO:DGEBA340/MCDEA blends revealed PPO particles in an epoxy matrix for blends with 10 wt% PPO, co‐continuous morphology for the blend with 30 wt% PPO and epoxy‐rich particles dispersed in a PPO‐rich matrix for 40wt% and more PPO. © 2014 Society of Chemical Industry     

Crosslinking of mixtures of DGEBA with 1,6-dioxaspiro[4,4]nonan-2,7-dione initiated by tertiary amines. Part IV. Effect of hydroxyl groups on initiation and curing kinetics

The anionic homopolymerization of DGEBA epoxy resin and its anionic copolymerization with a bislactone was studied using two alternative tertiary amines, 1-methylimidazole (1MI) and dimethylaminopyridine (DMAP) as initiators. 1MI caused slower cure than DMAP in neat DGEBA and DGEBA-bislactone formulations. Studies of the influence of the hydroxyl concentration in the DGEBA oligomer on its homopolymerization explain descrepancies in the literature regarding the ability of these initiators to produce full cure of the epoxy groups. In contrast, in the copolymerization of DGEBA-bislactone formulations, full cure could be readily achieved with either 1MI or DMAP as initiators, irrespective of the hydroxyl content. FTIR and DSC experiments show that this behaviour is associated with the formation of the carboxylate anion which plays an important part on the curing kinetics and the completion of cure.     

The effect of steric hindrance on physical properties in an amine-cured epoxy

A pair of aliphatic amines were synthesized in order to study the effect steric hindrance has on the physical properties of an amine-cured epoxy resin. The hindered amine (TMSiDA) has NH₂ groups that are obstructed by the presence of adjacent methyl groups while the unhindered amine (SiDA) does not contain any NH₂ steric hindrance. DGEBA cured with TMSiDA is less dense, absorbs less moisture, and has a higher T_g than does SiDA/DGEBA. Torsional pendulum results show that TMSiDA/DGEBA has a slightly higher rubbery modulus and a secondary transition at a lower temperature than DGEBA cured with SiDA. Activation energies for the secondary transition were determined for TMSiDA/DGEBA and SiDA/DGEBA and are 19 and 14 kcal/mol, respectively.     

Influence of molecular interactions on spherulite morphology in miscible poly(ethylene oxide)/epoxy network versus poly(ethylene oxide)/poly(4‐vinyl phenol) blend

Relationships between the spherulite morphology and changes in hydrogen‐bonding interactions between the linear poly(ethylene oxide) (PEO) polymer and a crosslinking epoxy system (diglycidylether of bisphenol‐A resin with 4,4′‐diaminodiphenylsulfone) (DGEBA/DDS) before and after cure have been explored The hydrogen‐bonding interaction is more significant before cure because of the interactions between the ether group of PEO and the amine group of DDS. The interaction between PEO and epoxy/DDS becomes less in the cured network. The morphology of the PEO crystals is, in turn, affected by the contents and chemical structures (functional groups, molecular weights, crosslinks, etc) of crosslinking epoxy/DDS. PEO/poly(4‐vinyl phenol) (PVPh), a thermoplastic non‐curing miscible system with the hydrogen bonding between the ether group of PEO and the ? OH group of PVPh, is also compared. In comparison with the PEO/epoxy/DDS system, the spherulite morphology of PEO/PVPh becomes more extensively spread out, with the extents increasing with the PVPh contents in the PEO/PVPh blend. © 2001 Society of Chemical Industry     

Fourier transform infrared analysis of polycarbonate/epoxy mixtures cured with an aromatic amine

In our previous article, we established that polycarbonate (PC) can react with the diglycidyl ether of bisphenol-A (DGEBA) at 200°C through transesterification and addition reactions, resulting in degraded PC chains with phenolic end groups and also in PC/DGEBA copolymers. However, these reactions can be minimized or eliminated at lower temperatures, below 160°C. In this article, Fourier transform infrared analysis (FTIR) was used to study the curing kinetics of epoxies in the presence of PC. The curing agent was an aromatic amine, diaminodiphenyl methane (DDM). FTIR results showed that the presence of a small amount of PC promoted the amine–epoxide reactions, probably due to the catalytic effect of the phenolic end groups in the PC chains. However, the PC did not alter the epoxy cure reaction mechanism. Two different blending processes were used to premix the PC and DGEBA, namely, solution-blending and melt-blending processes, in order to give different extents of prereactions. If a solution-blending process was used, PC tended to undergo crystallization during an early stage of cure. When a melt-blending process was used, no melting peak was observed in the thermograms of the differential scanning calorimeter (DSC) for the modified epoxies; PC chains bonded to DGEBA during prereaction at 200°C, thus inhibiting the crystallization of PC during cure. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2395–2407, 1998     

Epoxy matrices for filament-wound carbon fiber composites

Epoxies suitable for filament-winding fibrous composites must be processible at ambient temperatures, nontoxic, chemically simple, undergo full cure at ≤ 100°C and, also, be tough and exhibit a T_g > 120°C. In this paper, we report the cure characteristics, processibility, toxicity, and mechnical and physical properties of a number of amine-cured diglycidyl ether of bisphenol-A (DGEBA) epoxide candidate systems suitable for filament-wound carbon fiber composites. 2,5-Dimethyl-2,5-hexane diamine (DMHDA)-cured DGEBA epoxy was found to be the most promising candidate. The good processibility and thermal properties, together with the low cure characteristics of the DGEBA–DMHDA epoxy system, are discussed in terms of molecular structure of the amine molecule. The network structural parameters that control epoxy toughness and subsequent embrittlement upon plastic flow are discussed. Evidence is presented for plastic flow-induced thermal and mechanical property deterioration of epoxies as a result of network chain scission.     

Nonisothermal cure kinetics of DGEBA with novel aromatic diamine

The effect of the molar ratio of diglycidyl ether of a bisphenol‐A based epoxy (DGEBA) and synthesized 4‐phenyl‐2,6‐bis(4‐aminophenyl)pyridine (PAP) as curing agent during nonisothermal cure reaction by the Kissinger, Ozawa, and isoconversional equations was studied. The cure mechanism was studied by FTIR analysis. Kinetic analysis of the curing reaction of DGEBA at two different concentrations (42 and 32 phr) of the curing agent was studied by using DSC analysis. With an increasing PAP content, the pre‐exponential factor increased by increasing collision probability between epoxide and primary or secondary amine groups in noncataltyic or catalytic modes. The activation energy also increased because of the increasing content of crosslink density. The activation energies obtained from three equations were in good agreement. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3076–3083, 2007.     

Curing kinetics of epoxy cured by cardanol-based phenalkamines synthesized from different polyethylenepolyamines by Mannich reaction

Phenalkamines with different structures are expected to affect the curing reaction of epoxy, yet the exact mechanism remains to be elucidated. In this study, four cardanol-based phenalkamines (named PK1, PK2, PK3, and PK4, respectively), synthesized from ethylenediamine, diethylenetriamine, triethylenetetramine, and pentaethylenehexamine, were used as curing agents in diglycidyl ether of bisphenol A (DGEBA) epoxy system. The phenalkamines were characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance, and time-of-flight secondary ion mass spectrometry. The curing behaviors and kinetics were investigated by non-isothermal differential scanning calorimetry, and the activation energies of the reactions (E _α ) were determined using Kissinger–Akahira–Sunose (KAS) and Starink methods. The results indicate a similar curing mechanism for all four phenalkamines. All E _α values remain almost constant in the range of 0.05 ≤ α ≤ 0.6, and increase dramatically after α > 0.6 due to greater viscosity of the reaction systems. The diffusion of reactive groups plays an increasingly important role in determining the curing kinetics. In addition, DGEBA/PK1 and DGEBA/PK2 have lower initial E _α values than DGEBA/PK3 and DGEBA/PK4, because PK1 and PK2 have lower viscosity than PK3 and PK4. When α is high, DGEBA/PK1 and DGEBA/PK2 have higher E _α values than DGEBA/PK3 and DGEBA/PK4, because more tertiary amine groups can be formed in the reactions between the epoxy and secondary amine groups in the DGEBA/PK3 and DGEBA/PK4 systems, which catalyze the curing reaction and it thus lowers energetic barrier.     

Novel phosphorus-modified polysulfone as a combined flame retardant and toughness modifier for epoxy resins

A novel phosphorus-modified polysulfone (P-PSu) was employed as a combined toughness modifier and a source of flame retardancy for a DGEBA/DDS thermosetting system. In comparison to the results of a commercially available polysulfone (PSu), commonly used as a toughness modifier, the chemorheological changes during curing measured by means of temperature-modulated DSC revealed an earlier occurrence of mobility restrictions in the P-PSu-modified epoxy. A higher viscosity and secondary epoxy-modifier reactions induced a sooner vitrification of the reacting mixture; effects that effectively prevented any phase separation and morphology development in the resulting material during cure. Thus, only about a 20% increase in fracture toughness was observed in the epoxy modified with 20 wt.% of P-PSu, cured under standard conditions at 180 °C for 2 h. Blends of the phosphorus-modified and the standard polysulfone (PSu) were also prepared in various mixing ratios and were used to modify the same thermosetting system. Again, no evidence for phase separation of the P-PSu was found in the epoxy modified with the P-PSu/PSu blends cured under the selected experimental conditions. The particular microstructures formed upon curing these novel materials are attributed to a separation of PSu from a miscible P-PSu-epoxy mixture. Nevertheless, the blends of P-PSu/PSu were found to be effective toughness/flame retardancy enhancers owing to the simultaneous microstructure development and polymer interpenetration.     

Studying on the curing kinetics of a DGEBA/EMI-2,4/nano-sized carborundum system with two curing kinetic methods

Curing kinetics of a bisphenol-A glycidol ether epoxy resin (DGEBA)/2-ethyl-4-methylimidazole (EMI-2,4)/nano-sized SiC(nano-SiC) system was investigated with two kinetic methods by means of differential scanning calorimetry (DSC). Methods I and II were deduced by assuming a constant E and a variable E, respectively. With method I, the cure reaction activation energy E, the frequency factor A and the overall order of reaction m+n are calculated to be 71.75 kJ mol⁻¹, e^20.55 and 2.20, respectively. These results were used to have a simple qualitative comparison with the DGEBA/EMI-2,4 system. With method II, E is proved to decrease initially, and then increase as the cure reaction proceeds. The value of E spans from 42.4 to 95.8 kJ mol⁻¹. Furthermore, the variations of E were also used to study the cure reaction mechanism, and the shrinking core model was used to study the resin-particle reaction. Methods I and II are effective as long as they are used in proper aspects. With these two methods used all together, we can have a comprehensive and in-depth understanding of the curing kinetics of the DGEBA/EMI-2,4/nano-SiC system and the effect of nano-SiC particles on the curing kinetics of the DGEBA/EMI-2,4 system.     

Influence of multi-walled carbon nanotubes on the cure behavior of epoxy-imidazole system

The effect of multi-walled carbon nanotubes (MWCNTs) on the cure behavior of diglycidyl ether of bisphenol-A glycidol ether epoxy resin/2-ethyl-4-methylimidazole (DGEBA/EMI-2,4) system during the cure process was studied with dynamic differential scanning calorimetry. The results showed that, at the initial curing stage, MWCNTs act as catalyst and facilitate the curing, moreover, this accelerating effect is already noticeable at the lowest content of MWCNTs investigated (1 wt%) with slightly further effect at higher contents, suggesting a saturation of catalyzing action at higher contents investigated (3.5 wt%). Then, at the later curing stage, MWCNTs prevent from the occurrence of vitrification. The cure acceleration effect caused by MWCNTs could bring positive effect on the processing of composite since it needs shorter pre-cure time or lower pre-temperature, however, the hindrance effect to vitrification phenomena would bring negative effect as it needs longer post-cure time or higher post-temperature. Furthermore, it was also found that the addition of MWCNTs does not change the autocatalytic cure reaction mechanism of the DGEBA/EMI-2,4 system, but decreases the overall degree of cure, as evidenced by lower total heat of reaction and lower glass transition temperatures of the cured composites compared to neat epoxy.     

Real-time monitoring of the cure reaction of a TGDDM/DDS epoxy resin using fiber optic FT-IR

The feasibility of using remote FT-IR spectroscopy to monitor the gelation reaction of an epoxy resin used in advanced composite materials has been studied. The commercial epoxy resins MY720 and MY721, consisting mostly of tetraglycidyl 4,4′-diaminodiphenyl methane (TGDDM) were cured with diaminodiphenylsulfone (DDS) in a microcapillary cell connected to an FT-IR spectrometer by single silica fiber optics. By operating in the near-IR, direct measurement of the consumption of epoxide and primary amine and growth in hydroxyl groups was possible. It was found that the primary amine band at 5067 cm^?1 was the most sensitive for rapid and accurate real-time monitoring of the cure reaction up to gelation. The temperature dependence of amine consumption from 135 to 180°C gave an activation energy of 70 kJ mol^?1 for the cure reaction in agreement with DSC. Several artefacts involved in using fiber optic FT-IR in this way have been identified.