Moisture diffusion in epoxy systems

The moisture diffusion process of an epoxy system is studied as a function of epoxy‐amine stoichiometry and the resulting microstructure. Differences in diffusion behavior are related to the relative importance of diffusion through the low‐density and high‐density microstructural phases for different stoichiometries. Also, changes in saturation level with stoichiometry are explained by competing effects of free volume versus the content of the low‐density phase. Increasing the humidity level causes a corresponding increase in saturation level, while increasing the temperature causes more pronounced non‐Fickian behavior. The effects of absorbed moisture on the thermomechanical properties of the epoxies are also investigated. Reductions in the glass transition temperature, T_g, and moisture‐induced swelling strains are measured after exposure of samples to the three conditioning environments. Moisture‐induced swelling strains increase with increasing moisture content. The reductions in T_g range from 5 to 20°C and are generally larger for amine‐rich samples than for epoxy‐rich and stoichiometric samples. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 787–798, 1999     

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.     

A Study of the Interphase Region in Carbon Fibre/Epoxy Composites using Dynamic Mechanical Thermal Analysis

We have examined the effect of fibre addition on the glass transition temperature (T _g ) of two epoxy resin systems (an amine cured and an anhydride cured epoxy system) using dynamic mechanical thermal analysis (DMTA) and differential scanning calorimetry (DSC). The presence of fibres changes the glass transition temperature (T _g ) of an anhydride cured epoxy resin but does not affect that of an amine cured epoxy. The data suggest that two counteracting mechanisms are responsible for these changes: firstly, the presence of fibres causes a restriction of the molecular motion in the resin system, and secondly, the presence of carboxyi and keto-enol groups on the fibre surface inhibit curing of the resin close to the fibre, i.e. in the interphase region. The former increases the T _g and is a long range effect whereas the latter decreases the T _g and is a localised phenomenon. Changes in the dynamic properties of the interphase region are only detected when the samples are loaded in the longitudinal direction and not in the transverse direction where bulk matrix properties dominate. Sizing the fibres before their incorporation into the epoxy resin eliminates the variation in interfacial properties arising from differences in fibre surface chemistry.     

Mechanical,thermomechanical, and creep performance of CNT embedded epoxy at elevated temperatures: An emphasis on the role of carboxyl functionalization

In contrast to polymeric composites, the role of interface/interphase has been widely acknowledged to govern their overall properties and performance. Environmental temperature has substantial effects on the interfacial durability of polymer nanocomposites. In this regard, present investigation has been carried out to study the mechanical performance of pristine (UCNT) and carboxylic functionalized CNT (FCNT) embedded epoxy nanocomposites under different elevated temperatures. Higher flexural strength and modulus of FCNT‐EP nanocomposite were recorded over UCNT‐EP and neat epoxy at room temperature environment. Flexural testing at elevated temperatures revealed a higher rate of strength degradation in polymer nanocomposites over neat epoxy. Postfailure analysis of specimens has been conducted to understand the alteration in failure micro‐mechanisms upon UCNTs and FCNTs addition in epoxy. Variation in viscoelastic properties with temperature has been studied from dynamic mechanical thermal analysis and significant reduction in glass transition temperature (T_g) is observed for nanocomposites. In the studied temperature and stress combinations, FCNT‐EP nanocomposites exhibited better creep resistance over UCNT‐EP and neat epoxy. Room temperature strengthening, elevated temperature strength degradations, improved creep resistance and reduction in T_g in nanocomposites over neat polymer have been discussed in terms of dynamic nature and gradient structure of CNT/epoxy interphase. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44851.     

Curing of epoxy systems at sub‐glass transition temperature

Three epoxy‐amine thermoset systems were cured at a low ambient temperature. Evolution of the reaction kinetics and molecular structure during cure at the sub‐glass transition temperature was followed by DSC and chemorheology experiments. The effect of vitrification and the reaction exotherm on curing and final mechanical properties of the epoxy thermosets was determined. Thermomechanical properties of the low‐temperature cured systems depend on the reaction kinetics and volume of the reaction mixture. Curing of the fast‐reacting system in a large volume (12‐mm thick layer) resulted in the material with T_g exceeding the cure temperature by 70–80°C because of an exothermal temperature rise. However, the reaction in a too large volume (50‐mm layer) led to thermal degradation of the network. In contrast, thin layers (1.5 mm) were severely undercured. Well‐cured epoxy thermosets could be prepared at sub‐T_g temperatures by optimizing reaction conditions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3669–3676, 2006     

High‐Tg,heat resistant epoxy–silica hybrids with a low content of silica generated by nonaqueous sol–gel process

The epoxy‐silica hybrids showing high T_g and thermal stability are prepared by the non‐aqueous sol–gel process initiated with borontriflouride monoethylamine. Tetramethoxysilane (TMOS) is used as a precursor of silica and 3‐glycidyloxypropyl trimethoxysilane as a coupling agent to strengthen the interphase interaction with an epoxy matrix. The basic factors governing the nonaqueous sol–gel process are studied in order to reveal the formation–structure–properties relationships and to optimize the hybrid composition as well as conditions of the nonaqueous synthesis. The formation of the hybrid, its structure, thermomechanical properties and thermal stability are followed by chemorheology experiments, NMR, DMA and TGA. The most efficient reinforcement of the epoxy network is achieved by the combination of both alkoxysilanes, showing synergy effects. The hybrids with a low content (～10 wt %) of the in situ generated silica exhibit dramatic increase in T_g and the high modulus, 335 MPa, up to the temperature 300°C. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40899.     

Rheological characterization of 4,4′-bis(diethylamino)benzophenone-functionalized polybutadienes with low and medium vinyl content

An experimental study was undertaken to investigate the thermomechanical properties of a certain epoxy/amine configuration. The basic structure of all the epoxies was the same—DGEBA—and the curing agent used was PACM 20. By varying the epoxy prepolymer molecular weight and the stoichiometry between epoxy and amine, a range of different epoxy networks were produced. Glass transition temperatures were evaluated by using differentil scanning calorimetry (DSC). Modulus values as well as an alternative T_g determination were provided by dynamic mechanical analysis (DMA). Coefficients of thermal expansion were obtained from thermomechanical analysis (TMA). The tensile tests conducted at room and elevated temperatures provided additional modulus data along with the yield point, tensile strength, and elongation at break data. Property vs. stoichiometry curves exhibited a maximum for the glass transition temperature and the over the T_g modulus at the stoichiometric point. On the other hand, the under T_g modulus showed a minimum at the stoichiometric point. The results of the yield strength show remarkable similarity with the results of the modulus. Strength and elongation at break do not show clear trends, but a much different behavior is exhibited between room and elevated temperatures. © 1996 John Wiley & Sons, Inc.     

Free‐volume effects on the thermomechanical performance of epoxy–SiO2 nanocomposites

In this study, free‐volume effects on the thermal and mechanical properties of epoxy–SiO₂ nanocomposites were investigated. SiO₂ particles ranging from 15 nm to 2 µm were used, and the nature of the matrix–filler interphase was modified by surface grafting. Nanoparticles 15 nm in diameter yielded an increase in the glass‐transition temperature (T_g) of the composites up to 5 °C; at the same time, they increased the storage modulus (E′) from 2340 to 2725 MPa. Conversely, large particles markedly decreased both T_g and E′; this suggested the pivotal role of nanoparticle size on the final properties of the nanocomposite. The functionalization of SiO₂ nanoparticles markedly improved their dispersion within the epoxy matrix. The positron annihilation lifetime spectroscopy results indicate that the free volume strongly depended on the interphase. These experimental findings obtained here could be extrapolated to industrially relevant nanocomposites and could provide a rationale for the comprehension of free‐volume effects on the thermal and mechanical properties of nanocomposite materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45216.     

Transparent Surfactant/Epoxy Composite Coatings with Self‐Healing and Superhydrophilic Properties

In this paper, highly transparent, robust, and superhydrophilic polyethylene glycol tert‐octylphenyl ether nonionic surfactant/epoxy (Triton X‐100/epoxy, TXE) composite coatings are successfully prepared with a facile, one‐step drop‐casting method by mixing Triton X‐100 with an epoxy resin and an amine curing agent. The hydrogen bond reaction between the hydroxyl group of Triton X‐100 and the ether group of the epoxy resin improves the compatibility and reduces the glass transition temperature (T_g) of the TXE composite coatings. The free Triton X‐100 surfactant easily accumulates on the surface of the TXE composite coatings, which improves the hydrophilicity of the TXE composite coatings. The TXE composite coatings are self‐healable because of their low T_g and the migration of Triton X‐100 small molecule surfactant. Any damage arising from denting, cutting, or wiping by tetrahydrofuran can be healed, and the composite coating can regain its superhydrophilic properties through a heating process. The TXE composite coatings demonstrate excellent acid, alkali, salt, high temperature, and ultrasonic‐resistant properties. This facile preparation technique has the potential to be applied in the scalable fabrication of multifunctional coatings in anti‐fogging, oil–water separation, and optical–electric devices.     

Reaction kinetics modeling and thermal properties of epoxy–amines as measured by modulated‐temperature DSC. I. Linear step‐growth polymerization of DGEBA + aniline

A mechanistic approach including both reactive and nonreactive complexes can successfully simulate both nonreversing (NR) heat flow and heat capacity (C_p) signals from modulated‐temperature DSC in isothermal and nonisothermal reaction conditions for different mixtures of diglycidyl ether of bisphenol A + aniline. The reaction of the primary amine with an epoxy–amine complex initiates cure (E_1A1 = 80 kJ mol^?1), whereas the reactions of the primary amine (E_1OH = 48 kJ mol^?1) and secondary amine (E_2OH = 48 kJ mol^?1) with an epoxy–hydroxyl complex are rate determining from about 2% epoxy conversion on. The reliability of the proposed mechanistic model was verified by experimental concentration profiles from Raman spectroscopy. When cure temperatures are chosen inside or below the full cure glass‐transition region, vitrification takes place partially or completely, respectively, as can be concluded from the magnitude of the stepwise decrease in C_p. The effect of the epoxy conversion (x) and mixture composition on thermal properties such as the glass‐transition temperature (T_g), the change in heat capacity at T_g [ΔC_p(T_g)], and the width of the glass transition region (ΔT_g) are considered. The Couchman relationship, in which only T_g and ΔC_p(T_g) of both the unreacted and the fully reacted systems are needed, was evaluated to predict the T_g– x relation by using simulated concentration profiles. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91:2798–2813, 2004     

Characterization of epoxy foams

Epoxy foams were prepared from the commercial system (LY 5054 epoxy resin, HY 5054 amine as curing agent, and DY 5054 siloxane as foaming agent) supplied by Ciba‐Geigy. From the differential scanning calorimeter results the optimal epoxy–amine ratio was determined. A maximum T_g∞ value of 85°C was found for an epoxy–amine ratio of 100:35 by weight. In this system, the siloxane reacts with the amine releasing hydrogen that acts as the real foaming agent. The density decreased from 490 to 215 kg/m³ as the epoxy:blowing agent ratio increased from 100:1 to 100:3 by weight of the reactive mixture. Under the synthesizing conditions, the glass transition temperature (T_g∞) of the foam did not vary significantly as the blowing agent increased. The modulus and compressive strength of the foam exhibited a power‐law dependence with respect to density of the form: E∝(ρ)ⁿ, where n=1.8. Scanning electron microscopy analysis verified that the foam have a closed cell structure. The relation between composition, final morphology, density, and properties of the foam was analyzed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2992–2996, 2003     

Torsional braid analysis of the aromatic amine cure of epoxy resins

The cure behavior of diglycidyl ether of bisphenol A (DGEBA) type of epoxy resins with three aromatic diamines, 4,4′-diaminodiphenyl methane (DDM), 4,4′-diaminodiphenyl sulfone (44DDS), and 3,3′-diaminodiphenyl sulfone (33DDS) was studied by torsional braid analysis. For each curing agent the stoichiometry of the resin mixtures was varied from a two to one excess of amino hydrogens per epoxy group to a two to one excess of epoxy groups per amino hydrogen. Isothermal cures of the resin mixtures were carried out from 70 to 210°C (range depending on epoxy—amine mixture), followed by a temperature scan to determine the glass transition temperature (T_g). The times to the isothermal liquid-to-rubber transition were shortest for the DDM mixtures and longest for the 44DDS mixtures. The liquid-to-rubber transition times were also shortest for the amine excess mixtures when stoichiometry was varied. A relatively rapid reaction to the liquid-to-rubber transition was observed for the epoxy excess mixtures, followed by an exceedingly slow reaction process at cure temperatures well above the T_g. This slow process was only observed for epoxy excess mixtures and eventually led to significant increases in T_g. Using time—temperature shifts of the glass transition temperature vs. logarithm of time, activation energies approximately 50% higher were derived for this process compared to those derived from the liquid-to-rubber transition. The rate of this reaction was virtually independent of curing agent and was attributed to etherification taking place in the epoxy excess mixtures. © 1994 John Wiley & Sons, Inc.     

Characterization of epoxies cured with bimodal blends of polyetheramines

DGEBA was cured with bimodal blends of polyetheramines as well as with single molecular weight amines while maintaining stoichiometry. Glass transition temperatures (T_gs) and moduli were measured using dynamic mechanical analysis (DMA). Fracture properties were measured using the compact tension geometry and testing was performed at both ambient and non‐ambient temperatures, investigating toughness changes as a function of temperature. For constant amine average molecular weights, the addition of high molecular weight amines caused increased glassy moduli at a constant T ? T_g and decreased densities while broadening the glass transition without changing the fracture toughness. The fracture behavior, specifically the slip‐stick to brittle transition, was affected by the broadened transitions. T_g, breadth of T_g, and total damping were found to be proportional to the volume fraction of amine in the system. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1621–1631, 2013     

Blends of epoxy resin with amine‐terminated polyoxypropylene elastomer: Morphology and properties

A liquid diglycidyl ether of bisphenol A (DGEBA) epoxy resin is blended in various proportions with amine‐terminated polyoxypropylene (POPTA) and cured using an aliphatic diamine hardener. The degree of crosslinking is varied by altering the ratio of diamine to epoxy molecules in the blend. The mixture undergoes almost complete phase separation during cure, forming spherical elastomer particles at POPTA concentrations up to 20 wt %, and a more co‐continuous morphology at 25 wt %. In particulate blends, the highest toughness is achieved with nonstoichiometric amine‐to‐epoxy ratios, which produce low degrees of crosslinking in the resin phase. In these blends, the correlation between G_IC and plateau modulus (above the resin T_g), over a wide range of amine‐to‐epoxy ratios, confirms the importance of resin ductility in determining the fracture resistance of rubber‐modified thermosets. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 427–434, 1999     

Thermosetting cure diagrams: Calculation and application

The time–temperature–transformation (TTT) isothermal cure diagram and the continuous-heating-transformation (CHT) cure diagram are calculated from a reaction model for a high-T_g epoxy/amine system that has been developed to describe both epoxy/amine and etherification reactions in kinetically and diffusion-controlled reaction regimes. The cure diagrams are applied to various processing operations. The optimization of processing and of material properties by exploiting gelation and/or vitrification during cure is discussed. © 1994 John Wiley & Sons, Inc.     

Thermal and mechanical properties of tetra‐functional mesogenic type epoxy resin cured with aromatic amine

A novel tetra‐functional epoxy monomer with mesogenic groups was synthesized and characterized by ¹H‐NMR and FTIR. The synthesized epoxy monomer was cured with aromatic amine to improve the thermal property of epoxy/amine cured system. The glass transition temperature (T_g) and coefficient of thermal expansion (CTE) of the cured system were investigated by dynamic mechanical analysis and thermal mechanical analysis. The properties of the cured system were compared with the conventional bisphenol‐A type epoxy and mesogenic type epoxy system. The storage modulus of the tetra‐functional mesogenic epoxy cured systems showed the value of 0.96 GPa at 250 °C, and T_g‐less behavior was clearly observed. The cured system also showed a low CTE at temperatures above 150 °C without incorporation of inorganic components. These phenomena were achieved by suppression of the thermal motion of network chains by introduction of both mesogenic groups and branched structure to increase the cross linking density. The temperature dependency of the tensile property and thermal conductivity of the cured system was also investigated. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46181.     

Kinetic studies of POSS–DGEBA precursors derived from monoamine functional POSS using dynamic dielectric sensing and nuclear magnetic resonance

Incorporation of pre‐reacted monofunctional polyhedral oligomeric silsesquioxane (POSS)–epoxy adducts dramatically improves dispersion of POSS in epoxy–amine networks. The relationship between reaction kinetics and mechanism for formation of POSS–epoxy adducts versus reaction temperature was investigated. Reactivities of epoxy–monoamine functional POSS molecules were determined using in situ reaction monitoring by dynamic dielectric sensing and ²⁹Si NMR spectroscopy. The amine‐functional POSS–epoxy isothermal reaction showed reduced reactivity due to reduced molecular mobility, that is, diffusion limitations. Kinetic parameters were determined by fitting ²⁹Si NMR data to the model of Kamal that was extended to include diffusion. Fitting of this model to experimental data showed very good agreement over the entire conversion range for pre‐reaction between amine‐functionalized POSS and epoxy. An autocatalytic mechanism, the same as that for the neat epoxy–amine systems, was indicated. Gel permeation chromatography, scanning electron microscopy and transmission electron microscopy were used to investigate molecular weight evolution and morphology of final networks cured by 4,4′ diaminodiphenyl sulfone using pre‐reacted POSS–epoxy adducts. POSS aggregate size decreased with increased pre‐reaction temperature; more homogenous POSS dispersion was observed with higher pre‐reaction temperature. Dynamic mechanical analysis demonstrated that T_g of composites decreased slightly compared to that of the neat matrix and there appeared to be little change in microstructural heterogeneity. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45994.     

Cure modeling and monitoring of epoxy/amine resin systems. II. Network formation and chemoviscosity modeling

The glass transition temperature (T_g) advancement and the chemoviscosity development under isothermal conditions have been investigated for four epoxy/amine systems, including commercial RTM6 and F934 resins. Differential scanning calorimetry (DSC) was the thermoanalytical technique used to determine the T_g advancement and rheometry the technique for the determination of the chemoviscosity profiles of these resin systems. The complex cure kinetics were correlated to the T_g advancement via an one‐to‐one relationship using Di Benedetto's formula. It was revealed that the three‐dimensional network formation follows a single activated mechanism independent of whether the cure kinetics follow a single or several activation mechanisms. The viscosity profiles showed the typical characteristics of epoxy/amine cure. A modified version of the Williams‐Landel‐Ferry equation (WLF) was adequate to model the viscosity profiles of all the resin systems, in the temperature range 130 to 170°C, with a very good degree of accuracy. The parameters of the WLF equation were found to vary in a systematic manner with cure temperature. Further correlation between T_g and viscosity showed that gelation, defined as the point where viscosity reaches 10⁴ Pas, occurs at a unique T_g value for each resin system, which is independent of the cure conditions. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2178–2188, 2000     

Microstructure evolution of SW/EPN composites during hot air aging

In this article, the hot air aging of high strength glass fiber fabric/epoxy novolac resin (SW/EPN) composites was investigated by the aid of the aging behavior of EPN, mainly focusing on the microstructure evolvement of SW/EPN composites. The aging mechanism and thermal mechanical properties of SW/EPN composites were analyzed by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, thermo‐gravimetric analyzer coupled with Fourier transform infrared spectrometry, and dynamic mechanical thermal analysis. The results showed that micro cracks initiated and propagated at the fiber–matrix interphase because of the heat and oxygen effect. After long‐time aging at elevated temperatures, delamination phenomenon was discovered in SW/EPN composites. The results of weight changes showed that the degradation of EPN played a major role in SW/EPN composites. Moreover, the degradation of EPN contained post‐curing, oxidation, and decomposition. The results also revealed that unaged EPN indicated two glass transition temperatures (T_g1 and T_g2). T_g1 increased for post curing while T_g2 decreased for oxidation with increasing of aging time and temperature. In the final period of aging at higher temperatures, only one T_g was observed because the formation of perfect crosslinked networks made EPN homogeneous. In addition, the relationship between T_g and chemical structure, as well as T_g and mass loss, confirmed that the variation of T_g depended on chemical changes. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40128.     

A comparative study between epoxy/Titania micro‐ and nanoparticulate composites thermal and mechanical behavior by means of particle–matrix interphase considerations

The aim of the present study is to examine and compare the thermal and mechanical properties of epoxy resin/TiO₂ particle microcomposites (0.2 μm) and nanocomposites (21 nm). Composite materials consisting of epoxy resin reinforced with different amounts of TiO₂ microparticles (1, 5, 10, 15, and 20% wt) and TiO₂ nanoparticles (0.5%, 1%, 3%wt) were prepared. The thermal and mechanical properties of the manufactured composites were investigated and compared through differential scanning calorimetry (DSC) and three‐point bending tests (3PB). Lipatov's Theory was then applied on the DSC results, thus leading to the calculation of the particle‐matrix interphase thickness which was correlated to experimental findings. The glass transition temperature (T_g) of the materials was obtained and the effect of the grain size on the measured T_g values was investigated. The data obtained from DSC tests for both micro‐ and nanoinclusions when normalized with respect to the specific surface area of the particles, resulted in a single continuous curve describing the normalized phase transition enthalpy variation with filler weight fraction. POLYM. ENG. SCI., 58:1146–1154, 2018. © 2017 Society of Plastics Engineers