Dynamic mechanical properties of nonstoichiometric,amine-cured epoxy resin

The dynamic mechanical properties of epoxy resins cured with nonstoichiometric amounts [37%–103% of stoichiometric composition (SC)] of diethylenetriamine at room temperature have been measured in the temperature range 85° to 300°K and correlated to structures of cured resins. The dynamic mechanical behavior changed above and below 62.5% of SC, at which network structures are formed. The intensities of γ- and β-peaks, ～150° and ～250°K, respectively, depend upon the concentration of DETA used. The processes of the γ- and β-peaks are discussed.     

Effect of physical annealing on the dynamic mechanical properties of a high-Tg amine-cured epoxy system

Physical annealing of a fully cured amine/epoxy system has been investigated using the freely oscillating TBA torsion pendulum technique. The material densifies spontaneously during annealing in an attempt to reach equilibrium, thereby changing material behavior. The dynamic mechanical behavior of a film specimen (T_g = 174°C, 0.3 Hz) and of a glass braid composite specimen (T_g = 182°C, 0.9 Hz) was monitored during isothermal annealing at sub-T_g temperatures (ranging to 230°C below T_g); after annealing, the behavior was measured vs. temperature and compared with that of the unannealed state. Isothermally, the storage modulus (G′) of the film specimen and the relative rigidity (1/P²) of the composite specimen increased almost linearly with log time, whereas the logarithmic decrement (Δ) decreased with time. The isothermal rates of annealing were determined from the rates of changes in G′ and in 1/P² for the film and composite specimens, respectively. In a wide temperature range between T_g and the secondary transition temperature, T_sec (≈ ?30°C, 2.3 Hz by TBA), the isothermal rates of annealing at the same annealing time appeared to be the same. Thermomechanical spectra of the isothermally annealed material revealed a maximum deviation in thermomechanical behavior from the unannealed material in the vicinity of the annealing temperature. The effects of physical aging were the same for the film and composite specimens. Effects of sequential annealing at two isothermal temperatures on the thermomechanical behavior were also investigated; when the second temperature was higher than the first, the effect of only the high-temperature annealing was evident, whereas the effect of annealing at both temperatures was revealed when the second temperature was lower than the first. Results suggest that physical annealing at different temperatures involves different length scales of chain segment relaxation and that the effects of isothermal aging can be eliminated by heating to below T_g.     

Structure-water absorption relationships for amine-cured epoxy resins

The equilibrium water absorption has been measured for 23 epoxide-amine networks of various structure including di, tri, and tetra functional epoxides, and diamines, which were mainly of the dianiline type (more or less sterically hindered in some cases). The comparative study of these systems shows clearly that the main hydrophilic loci are in the vicinity of tertiary amines, and that these latter groups play a concerted role with hydroxyl groups in the β position, in water bonding. Additive relationships between structure and equilibrium water absorption derived from these observations are proposed.     

Fracture and mechanical properties of epoxy resins and rubber-modified epoxy resins

Fracture and mechanical property data on a wide range of epoxy resin systems are presented. The extent to which toughening can be induced by heterophase rubber inclusions depends more on the curing agent used than on the resin component. The greatest improvements in toughness were obtained by rubber modification of epoxy resins cured with an anhydride. A preformed ABS polymer can be used to toughen many epoxy resin systems. With one major exception (where a large improvement was found) only small changes in tensile properties occur when small amounts of rubber are present.     

Correlations between dynamic mechanical properties and nodular morphology of cured epoxy resins

Various epoxy resin formulations, based on the diglycidyl ether of bisphenol A (DGEBA) and cured with diethylene triamine (DETA) were studied. Dynamic mechanical measurements were used to characterize changes in mechanical properties as a function of temperature. The morphology of the cured resins was investigated by transmission electron microscopy. Correlations between dynamic mechanical properties and morphology were described and discussed by applying the concept of inhomogeneous (nodular) thermoset morphology. The elastic storage modulus in the glassy state was determined primarily by the internodular matrix, whereas the glass transition of cured resins depended upon the intranodular crosslink density.     

Thermal expansion instability and creep in amine-cured epoxy resins

Similar thermal expansion instabilities, consisting of isothermal, time-dependent changes in thermal expansion after a rapid change in temperature, were observed in epoxy resins with different degrees of cross-linking. Creep experiments performed at different stages of expansion show decreases in tensile creep rate with decreased expansion. The role of changes in moisture content as a possible cause of the dimensional instability is examined for epoxy resins and a highly cross-linked polyurethane. Results indicate that the state of expansion is the primary cause of changes in creep rate rather than temperature or moisture content.     

Synthesis and characterization of bisimide amines and bisimide amine-cured epoxy resins

A series of novel bisimide amines were synthesized and characterized and then utilized as curing agents with a standard epoxy resin, N,N′- tetraglycidyl-methylenedianiline (TGMDA), known commercially as MY720. The bisimide amines (BIA's) were synthesized by reaction of 4,4′-hexa-ffuoroisopropylidine (biphthalic acid dianhydride) (6F anhydride) with aromatic and aliphatic diamines in dimethyl formamide at reflux temperatures in yields ranging 24 to 99 percent. The diamines used were 3,3′-diaminodiphenylsulfone (3,3′-DDS), 4,4′-diaminodiphenylsulfone (4,4′-DDS), 1,12-dodecanediamine (1,12-DDA), alone and as mixtures to produce the BIA's 6F-3,3′- DDS, 6F-4,4′-DDS, 6F-3,3′-DDS-4,4′-DDS, 6F-3,3′-DDS-1, 12-DDA with various compositions, depending on the mode of addition and stoichiometry. The BIA's are isolated as mixtures containing monomer, oligomer, and polymeric species. They were characterized by elemental analysis, and high pressure liquid chromatography (HPLC). Epoxy resin specimens were fabricated by reaction of the standard epoxy (MY720) with the BIA and in some cases, mixtures of BIA and aromatic diamine, such as 3,3′-DDS. The bisimide amine cured epoxies (IME's) were characterized for moisture absorption, thermal properties, physical and mechanical properties. The bisimide amine epoxy (IME) resins were also characterized as matrices in Celion 6000/bisimide amine cured epoxy (IME) composites. The relative toughness characteristics of each IME formulation was measured by the 10° offaxis tensile test by measuring the uniaxial tensile, shear strengths and shear-strain-to-failure of the composite systems.     

Network mechanical properties of amine-cured epoxies

The technique of Impulse Viscoelasticity was used to characterize the network mechanical properties of amine-cured epoxies during cure. The effects of amine molecular weight, functionality and stoichiometry were investigated. Among the properties which were obtained were the equilibrium tensile modulus, gelation time, cure and thermal stresses, volumetric changes during cure, glass transition temperature, thermal expansion coefficient, and molecular weight between cress-links. It was found that these networks cured elastically and agreed closely with the predictions of rubber elasticity theory over a wide range of crosslink densities.     

Effects of chemical structure changes on thermal,mechanical, and crystalline properties of rigid rod epoxy resins

Effects of chemical structure changes on the thermal, mechanical, and crystalline properties of rigid rod epoxy resins have been studied for azomethine epoxy, biphenol epoxy, and tetramethyl biphenol epoxy. Rigid rod epoxies have exhibited better properties than those of the flexible bisphenol A epoxy. The chemical structures of both rigid rod epoxy and curing agent control the properties of cured rigid rod epoxies. When a flexible curing agent (methyl cyclohexane 1,2‐dicarboxylic anhydride) was used, the chemical structure of rigid rod epoxy has dominated effects on the properties. Thus, the azomethine epoxy has shown the best thermal and mechanical properties among three rigid rod epoxies. While a rigid curing agent (sulfanilamide) was used, the physical properties of cured epoxies are not only dependent on the chemical structures of epoxies but also on the ease of formation of ordered network. Among the cured rigid rod epoxies, only the biphenol epoxy cured by sulfanilamide exhibits a liquid crystalline network. It has the highest glass transition temperature (219°C) and the lowest coefficient of thermal expansion (20.8 μm/m°C). However, the most thermal stable system is azomethine epoxy cured with sulfanilamide. It has a weight loss (39%) at 450°C. Their excellent thermal and mechanical properties of rigid rod epoxies are useful in composites, printed wiring boards, integrated circuit encapsulations, etc. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 446–451, 2000     

An additive for increasing the strength and modulus of amine-cured epoxy resins

The reaction product of 4-hydroxyacetanilide and 1,2-epoxy-3-phenoxypropane, when added at 19 wt% to a conventional epoxy-resin-curing agent mixture, increases the tensile strength of the cured system from 82 MPa to 123 MPa and increases the shear modulus (20°C, 1 Hz) from 970 MPa to 1560 MPa. As well as showing increased strength, the tensile-test specimens also fail in a ductile fashion, i.e., the slope of the stress–strain curve is negative at failure, with appreciable localized deformation occurring during fracture. For notched samples (compact tension specimens), the fracture properties are strongly strain-rate-dependent. At low strain rates the additive-containing sample has a fracture energy (??, critical strain energy release rate) about twice that of the additive-free control, but at higher strain rates ?? falls to about 65° of the control value. The critical stress for crack propagation is also strain-rate-dependent and is about 50% higher than the control at low strain rates and about 10% less than the control at higher strain rates. Dynamic mechanical analysis and dielectric loss measurements indicate that the additive causes a decrease in the T_g and a suppression of the β-relaxation. Chemically, the additive accelerates the cure process but does not significantly alter the final extent of reaction of the epoxy resin. After curing, the additive is almost totally extractable by solvent indicating that it is not chemicaly bound to the polymer. These observations are discussed in terms of the concept of antiplasticization.     

Effects of chemical structure of hardener on curing evolution and on the dynamic mechanical behavior of epoxy resins

A diglycidyl ether of bisphenol-A-type difunctional epoxy resin was cured with different amine-type curing agents at stoichiometric ratios. The crosslink process was followed by viscosimetry and differential scanning calorimetry. The gelation time and the apparent activation energy were found to be strongly dependent on the structure of the hardener. The heat of reaction did not vary significantly when the hardener was changed. An interpretation based on structural aspects such as amine reactivity, steric hindrance, and chain rigidity is proposed for the variations corresponding to the curing process. Master viscosity curves have been built up for all mixtures. The effect of the hardener on the glass transition temperatures of the different mixtures has been analyzed taking into account the crosslink density, measured by the rubber modulus obtained by dynamic mechanical studies, and the chemical structure of the hardener chains. © 1995 John Wiley & Sons, Inc.     

Amine/epoxy stoichiometric ratio dependence of crosslinked structure and ductility in amine-cured epoxy thermosetting resins

Epoxy-amine thermosetting resins undergo different reactions depending on the amine/epoxy stoichiometric ratio (r). Although many desirable properties can be achieved by varying the stoichiometric ratio, the effects of the variation on the crosslinked structure and mechanical properties and the contribution of these factors to the ductility of materials have not been fully elucidated. This study investigates the brittle-ductile behavior of epoxies with various stoichiometric ratios and performs curing simulations using molecular dynamics (MD) to evaluate the crosslinked structures. The molecular structure is predominantly branched in low-stoichiometric ratio samples, whereas the chain extension type structure dominates the high-stoichiometric ratio samples. As a result, the higher-stoichiometric ratio samples enhances the ductility of materials and the elongation at break increases form 1.4% (r = 0.6) to 11.4% (r = 1.4). Additionally, the tensile strength (105.4 MPa) and strain energy (7.96 J/cm³) are maximum at r = 0.8 and 1.2, respectively. On the other hand, the Young's modulus is negatively impacted and it decreased from 4.2 to 2.7 GPa with increasing stoichiometric ratio.     

Relationship between structure and mechanical properties in rubber-toughened epoxy resins

Toughened polymers were prepared by adding CTBN rubbers to DGEBA-type epoxy resins. Structure was varied by altering the type and concentration of hardener, the initial molecular weight of the resin, the amount of Bisphenol A added, and the conditions of cure. Electron microscopy showed that these factors affected both particle size and degree of phase separation: rapid curing inhibited phase separation, and produced small particles. Increasing the molecular weight of the resin, either directly or by reaction with Bisphenol A, improved phase separation. Dynamic mechanical measurements of rubber phase volume proved possible, although T_g of the CTBN rubber coincided with a β process in the epoxy resin. Fracture resistance, measured by G_IC, increased linearly with rubber phase volume. Creep and yield behaviour were also affected by the degree of phase separation.     

A dynamic mechanical study of the curing reaction of two epoxy resins

The curing behavior of two commercially formulated epoxy resins composed of the tetrafunctional amine dicyandiamide and with differing epoxy components, 4,4′-bisglycidylphenyl-2,2′-propane and the tetraglycidyl ether of methylene dianiline, is characterized by dynamic spring analysis. This supported viscoelastic technique is well suited to the determination of the onset of gelation under isothermal conditions but the method is not useful for monitoring later stages of reaction when the resins become more rigid. The activation energy for the curing of the two resins is about 87 kJ/mole (20.7 kcal/mole). Rate constants for the first order curing reaction are given. Additional studies of films cured below the ultimate T_g show that two relaxations can be observed upon heating. The first relaxation occurs near the original isothermal cure temperature with a low activation energy, about 250 kJ/mole, whereas the second relaxation occurs near the ultimate T_g, under the conditions used here, with an activation energy of 500–650 kJ/mole. It is believed that these activation energies provide a unique method of characterizing the molecular mobility of epoxy resins at various states of cure.     

Effect of fibers treatment on dynamic mechanical and thermal properties of epoxy hybrid composites

Epoxy hybrid composites fabricated by reinforcing 2‐hydroxy ethyl acrylate (2‐HEA) treated oil palm empty fruit bunch (EFB) and jute fibers. It assume that chemical modification of jute and oil palm EFB fibers increased fiber/matrix interfacial bonding and it results in enhanced thermal properties of hybrid composites. Dynamic mechanical and thermal analysis of treated hybrid composites was carried out. Results indicated that chemical modification of oil palm EFB and jute fibers affect the dynamic mechanical and thermal properties of hybrid composites. The storage modulus values of hybrid composites increases with chemical treatment and loss modulus increased with fiber treatment in hybrid composites. Damping factor peak values of treated hybrid composites shifted toward the lower temperature compared to both untreated hybrid composites. Cole–Cole analysis was made to understand the phase behaviour of the hybrid composites. Thermogravimetric analysis indicated an increased in thermal stability of hybrid composite with the incorporation of chemically modified fibers. POLYM. COMPOS., 36:1669–1674, 2015. © 2014 Society of Plastics Engineers     

Morphology and mechanical properties of epoxy resins containing functionalized perfluoroether oligomers

Chain extended perfluoroether oligomers were found to be miscible with bisphenol epoxy resins at all concentrations. These were evaluated as modifiers for anhydride cured resin systems, taking advantage of the carboxylic acid functionality at the chain ends. By altering the mixing and curing procedure different two-phases morphologies could be obtained varying from fine co-continuous networks, which produced transparent castings, to opaque systems consisting of precipitated heterogeneous particles. While the T_g and flexural modulus were found to be slightly lower than the control cure resin, the addition of the fluoroligomer modifier produced large increases in flexural strength, ductility, and fracture toughness. Samples with an IPN type morphology were found to exhibit an increase in ductility after aging at 200°C for three weeks proportionally to the concentration of fluoroligomer used.     

Time-dependent changes in mechanical properties of neat and reinforced epoxy resins

Several neat and reinforced epoxy resin formulations were prepared and investigated. Solid glass microspheres, with and without coupling agent, were used as reinforcement. After completion of post-cure all samples were quenched into an ice-water bath. Upon removal from the ice-water bath, dynamic mechanical and fracture properties of all samples were evaluated as a function of time elapsed after quenching. Electron microscopic evidence was obtained for the existence of nodular morphology in all cured systems. The changes in dynamic mechanical and fracture parameters, induced by the sub-T_g annealing, were described in terms of the model of inhomogeneous thermoset morphology.     

Preparation and mechanical properties of modified epoxy resins with flexible diamines

Diglycidyl ether of bisphenol A (DGEBA) is one of the most widely used epoxy resins for many industrial applications, including cryogenic engineering. In this paper, diethyl toluene diamine (DETD) cured DGEBA epoxy resin has been modified by two flexible diamines (D-230 and D-400). The cryogenic mechanical behaviors of the modified epoxy resins are studied in terms of the tensile properties and Charpy impact strength at cryogenic temperature (77 K) and compared to their corresponding properties at room temperature (RT). The results show that the addition of flexible diamines generally improves the elongation at break and impact strength at both RT and 77 K. The exception is the impact strength at 77 K filled with 21 wt% and 49 wt% D-400. Further, two interesting observations are made: (a) the cryogenic tensile strength increases with increasing the flexible diamine content; and (b) the RT tensile strength can only be improved by adding a proper content of flexible diamines. It is concluded that the addition of a selected amount namely 21–78 wt% of D-230 can simultaneously strengthen and toughen DGEBA epoxy resins at both RT and 77 K. However, only the addition of 21 wt% D-400 can simultaneously enhance the strength and ductility/impact strength of DGEBA epoxy resins at RT. The impact fracture surfaces are examined using scanning electron microscopy (SEM) to explain the impact strength results. Finally, differential scanning calorimetry (DSC) analysis shows that the glass transition temperature (T_g) decreases with increasing the flexible diamine content. The presence of a single T_g reveals that the flexible diamine-modified epoxy resins have a homogeneous phase structure.     

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.