Crosslinking behaviour of diolmodified epoxies

Summary Diglycidyl ether of bisphenol A (BADGE) reacts with aliphatic alcohols to form different products, depending on the type of accelerator and the alcohol mole fraction. Using liquid state C-13 NMR different reactive groups as oxirane rings, primary and secondary hydroxyl groups were detected in dependence of the epoxide consumption. Crosslink and junction point resonances were identified by varying the cure state.     

Low-temperature thermal conductivity of diolmodified epoxies

Summary The thermal conductivity at low temperatures (between 0.5 K and 100 K) was measured for diolmodified epoxies. Diglycidyl ether of bisphenol A (DGEBA) was modified for this purpose by aliphatic diols with the structure HO-(-CH₂-)_n-OH in the presence of catalyst (either N,N-dimethyl benzylamine or magnesium perchlorate). Sample series with diols of n=4,8 and 12 were synthesized and measured. The results at T<20K shows a clear dependence of the thermal conductivity values on the chain length of the diols. The increasing amount of diol in the epoxies cause a larger change on these values in the same temperature range.     

Elution behaviour of diolmodified epoxides in size exclusion chromatography

The reaction of bisphenol A-diglycidyl ether (BADGE) with butane-1,4-diol (BD) in the presence of Mg(ClO₄)₂ leads to linear and branched oligomers. The formation ratio of these products depends on the reaction temperature. In experiments at 100°C, an epoxide consumption of up to 70% can be observed using HPLC. In this range all products show good solubility in THF, so that it is possible to follow the increasing molar mass by using SEC. A characteristic relation of the molar mass against the conversion rate is derived and SEC data of a branched product are discussed.     

Crosslinking studies in plasticized epoxies by means of dynamic measurements

A class of amine-cured epoxy resins containing various amounts of polysulfide plasticizer were subjected to dynamic testing during curing at high temperature. Both E modulus and loss factor were determined simultaneously. It was proved that the method allowed for rapid determination of the general pattern of the crosslinking procedure and the necessary curing time and, in general, that dynamic methods are most suitable for the mechanical characterization of polymers under curing at each stage of the curing cycle.     

Structural heterogeneity in epoxies

The effects of different cure procedures on the structure and properties of epoxy samples made from diglycidyl ether of bisphenol A (DGEBA) and mixtures of two linear aliphatic diamines were studied. The elastic modulus, fracture toughness, impact resistance, and glass transition temperature were determined for various cure schemes. The morphologies of the cured resins were characterized with small angle X-ray scattering. The results show that samples with the same average morphology (molecular network structure) have similar elastic moduli and glass transition temperatures. If some heterogeneity is introduced in the molecular network structure without changing the average structure, however, the experiments indicate that the toughness can be increased without significantly sacrificing other properties.     

Thermal properties of metal-filled epoxies

Thermal expansion coefficients and glass transition temperatures for metal–epoxy composites were determined experimentally. Results were in fair agreement with existing theories when certain fundamental assumptions were fulfilled. The effects of filler content and particle size as well as of adhesion between matrix and filler particles were investigated. The latter, in particular, was found to be of cardinal importance for the properties examined in the present work.     

Time-dependent properties of versamid cured epoxies

Versamid cured-epoxy specimens were loaded in tension, compression, and flexure at different strain rates and temperatures to determine the yield stress and strain, and tangent, secant, and relaxation moduli. A torsion pendulum was used to measure the dynamic properties as a function of temperature and frequency. The time-temperature superposition principle was used to reduce this data to master curves. It was concluded that the time-temperature shift factors for secant moduli up to the yield point, for stress relaxation and for dynamic moduli were identical and were independent of the mode of loading. It was also shown that the presence of fillers or reinforcing agents likewise had no effect on the shift factors.     

Indentation studies in aluminum-filled epoxies

A class of aluminum-filled epoxy composites were subjected to indentation tests over a wide temperature range. The tests were carried out under constant load and continuously varying temperature. The effect of aluminum content, applied load, and adhesion efficiency between matrix and aluminum particles on the indentation behavior was studied. Measured indentation values were found to lie within limits predicted theoretically.     

Solubility parameters of amine-crosslinked aromatic epoxies

For six epoxide–amine systems, based on mixtures of two different aromatic epoxides with four various aromatic amines, the solubility parameters δ were determined by calculation, by using several literature sources and molar additive laws, and experimentally from equilibrium concentrations of 25 solvents, by using bidimensional solubility maps. δ values ranging from 20 to 27 MPa^1/2 were found. Their variations with the epoxide and amine structure were discussed. The crosslink density was found to have a neglectable effect on the solvent absorption compared to interaction parameters.     

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.     

Fatigue crack propagation of rubber-toughened epoxies

Epoxies containing epoxy-terminated butadiene acrylonitrile rubber (ETBN) or amino-terminated butadiene acrylonitrile rubber (ATBN) were prepared and studied in terms of fatigue crack propagation (FCP) resistance and toughening mechanisms. Rubber incorporation improves both impact and FCP resistance, but results in slightly lower Young's modulus and T_g As T_g increases, the degree of toughening decreases. Rubber-induced shear yielding of the epoxy matrix is believed to be the dominant toughening mechanism. Decreasing fatigue resistance with increasing cyclic frequency is observed for both neat and rubber-toughened epoxies. This result may be explained by the inability of these materials to undergo possible beneficial effects of hysteretic heating. FCP resistance is linearly proportional to M_c^1/2, where M_c is the apparent molecular weight between crosslinks determined on the rubber-toughened material. FCP resistance also increases with increasing static fracture toughness K_IC. ATBN-toughened epoxies demonstrated better fatigue resistance than ETBN-toughened systems.     

Structure-property relationships in rubber-toughened epoxies

Epoxies toughened with two reactive liquid rubbers, an epoxy-terminated butadiene acrylonitrile rubber (ETBN) and an amino-terminated butadiene acrylonitrile rubber (ATBN), were prepared and studied in terms of their structure property relationships. A two-phase structure was formed, consisting of spherical rubber particles dispersed in an epoxy matrix. A broad distribution of rubber particles was observed in all the materials with most of the particles ranging in size from 1 to 4 μm, but some particles exceeding 20 μm were also found. Impact strength, plane strain fracture toughness (K_IC), and fracture energy (G_IC) were increased, while Young's modulus and yield strength decreased slightly with increasing rubber content and volume fraction of the dispersed phase. Both G_IC and K_IC were found to increase with increasing apparent molecular weight between crosslinks and decreasing yield strength. The increased size of the plastic zone at the crack tip associated with decreasing yield strength could be the cause of the increased toughness. An ATBN-toughened system containing the greatest amount of epoxy sub-inclusion in the rubbery phase demonstrated the best fracture toughness in this series. In the present systems, rubber-enhanced shear deformation of the matrix is considered to be the major toughening mechanism. Curing conditions and the miscibility between the liquid rubber and the epoxy resin determine the phase morphology of the resulting two-phase systems. Kerner's equation successfully describes the modulus dependence on volume fraction for the two-phase epoxy materials.     

Toughening epoxies with halloysite nanotubes

An experimental attempt was made to characterize the fracture behaviour of epoxies modified by halloysite nanotubes and to investigate toughening mechanisms with nanoparticles other than carbon nanotubes (CNTs) and montmorillonite particles (MMTs). Halloysite-epoxy nanocomposites were prepared by mixing epoxy resin with halloysite particles (5 wt% and 10 wt%, respectively). It was found that halloysite nanoparticles, mainly nanotubes, are effective additives in increasing the fracture toughness of epoxy resins without sacrificing other properties such as strength, modulus and glass transition temperature. Indeed, there were also noticeable enhancements in strength and modulus for halloysite-epoxy nanocomposites because of the reinforcing effect of the halloysite nanotubes due to their large aspect ratios. Fracture toughness of the halloysite particle modified epoxies was markedly increased with the greatest improvement up to 50% in K_IC and 127% in G_IC. Increases in fracture toughness are mainly due to mechanisms such as crack bridging, crack deflection and plastic deformation of the epoxy around the halloysite particle clusters. Halloysite particle clusters can interact with cracks at the crack front, resisting the advance of the crack and resulting in an increase in fracture toughness.     

Interfacial studies in CTBN-modified epoxies

Rubber particle cavitation and concomitant shear deformation of the matrix is known to be a major source of toughening in rubber-modified epoxies. The role of the rubber-matrix interface in this toughening mechanism, however, is not well studied. It has been claimed by Chen and Jan [Polym. Eng. Sci., 31,577 (1991)] that introduction of a ductile interphase around the rubbery phase enhances plastic dilation of particles and thus contributes to fracture energy of modified blend. In spite of this promising development in rubber toughening, very few studies on the use of ductile interfaces to improve the fracture resistance of rubber-modified polymers have been initiated. The objective of this investigation is to examine the role of ductility of interface on the fracture toughness of rubber-modified epoxies. Both ductile and rigid interphases are incorporated around CTBN particles in a DGEBA epoxy matrix via end-capping of rubber with epoxy monomers different from that of the matrix. The results of this investigation suggest that introduction of a ductile interphase may indeed further improve the crack growth resistance of material under certain test conditions. In contrast, introduction of the rigid interphase, in the system studied, promoted interfacial debonding and plastic dilation but did not alter the mechanical performance of the rubber-modified blend. © 1995 John Wiley & Sons, Inc.     

Phase separation behavior of rubber-modified epoxies

The compatibility and phase separation behavior of mixtures of the diglycidyl ether of bisphenol A and carboxyl-terminated butadiene-acrylonitrile copolymers were studied by means of light transmission, viscosity measurements, and optical microscopy. Cloud point measurements of the blends prior to curing showed a strong influence of acrylonitrile on the miscibility behavior, especially near the critical composition of the system. In addition, the cloud point curves showed a highly skewed shape which turned out to be particularly favorable to the formation of a rigid but tough two-phase structure. Blends subjected to isothermal cure at 120°C were found to begin phase separation at a progressively shorter time with increase in the copolymer content. Furthermore, while the phase domains tended to cease growing at the time of gelation, the composition within the sample continued to change well beyond the gel point.     

Structure-property relations of polyethertriamine-cured bisphenol-A-diglycidyl ether epoxies

The relations between the chemical and physical network structure, the deformation and failure processes and the tensile mechanical properties of polyethertriamine-cured bisphenol-A-diglycidyl ether epoxies are reported for a series of epoxy glasses prepared from a range of polyethertriamine concentrations. Near-infra-red spectroscopy indicates that these glasses form exclusively from epoxide-amine addition reactions. Their T_g exhibits a maximum and swell ratio a minimum at the highest crosslink density. Stress-birefringence studies reveal that these highly crosslinked glasses are ductile and undergo necking and plastic deformation. The plastic deformation initially occurs homogeneously but ultimately becomes inhomogeneous and shear bands develop. Tensile failure occurs in the high strain shear band region. The ultimate tensile strain of these epoxies attains a maximum of 15% for the highest crosslinked glass. Off stoichiometric networks fail at lower strains because such networks inherently contain more defects in the form of unreacted ends. The density, yield stress, tensile strength, and modulus of these glasses all decrease with increasing polyethertriamine concentration as a result of increasing free volume because of the poor packing ability of the amine molecule. A slight minimum is superimposed on this downtrend in density and modulus with increasing amine content at the highest crosslink density because of geometric constraints imposed on segmental packing by the network crosslinks. The ability of these crosslinked glasses to undergo deformation is discussed in terms of the free volume and the crosslinked network topography. Network failure is considered in terms of stress-induced chain scission which is determined by the concentration ad extensibility of the least extensible network segments.     

Analysis of gel formation in imidazole-catalyzed epoxies

The network formation processes for imidazole-cured epoxy resins were examined by relating the reaction chemistry and the physical properties during cure. Network formation models were developed based on kinetic studies and the laws of conditional probability. These models were used to predict the weight-average molecular weight, the gel point, and the sol fraction as a function of the resin composition and the processing conditions. Rheological and extraction experiments were conducted to confirm the model results and to develop criteria for identifying the gel point.     

Physical properties of barium titanate-filled rubber-modified epoxies

Rubber-modified epoxies (RME) filled with different levels of barium titanate (BaTiO₃) have been characterized by using DSC, TGA, and TMA. The presence of the filler does not affect the glass transition temperature or the activation energy of pyrolysis; however, it does change other thermal properties. The dielectric constant increases markedly, but the dissipation factor remains fairly constant with increasing BaTiO₃ loading. The polymers, in MEK, exhibit slightly different degrees of swelling and their sol fractions vary. Mechanical properties, such as stress-strain relation, friction, abrasion, scratch hardness, and scrape adhesion of the polymers, will be described.     

Synthesis of solvent-modified epoxies via Chemically Induced Phase Separation: A new approach towards void toughening of epoxies

Summary  The fracture toughness has been investigated with single edge notched bending specimens in solvent-modified epoxies, which were prepared via the Chemically Induced Phase Separation technique. The generation of a controlled morphology with liquid droplets in the micrometer range leads to a substantial increase in the fracture energy of nearly 400% compared to the non-modified epoxy network. The critical stress intensity factor of these highly crosslinked thermosets does not vary significantly. These results demonstrate the general potential of the Chemically Induced Phase Separation technique to prepare porous thermosets, thus combining increased toughness with lowered density.     

Cure kinetics of neat versus reinforced epoxies

An investigation was carried out into the cure kinetics of neat vs reinforced epoxy systems. The formulations were composed of tetraglycidyl 4,4′-diaminodiphenyl methane (TGDDM) epoxy resin and diaminodiphenyl sulfone (DDS). Glass was used as reinforcement. A series of isothermal differential scanning calorimetry (DSC) thermograms were run and analyzed by the proposed autocatalytic kinetic model. An increase in reaction rate was observed at higher temperature and higher DDS concentration in both neat and reinforced formulations. The presence of reinforcement had an effect on the cure kinetics. The observed effect, however, was not very pronounced. Slightly lower values of the reaction rate constant and longer times needed to reach the maximum reaction rate were recorded in reinforced systems. After reaching the peak value, the rate of reaction dropped off faster in reinforced formulations, resulting in lower average value of H_ult, the ultimate heat of reaction. It was suggested that the reinforcement imposes restrictions on the molecular mobility of reactive species.