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Impact properties of rubber-modified epoxy resin-graphite-fiber composites

To improve the impact resistance of graphite-fiber composites, a commercial and an experimental epoxy resin were modified with liquid reactive rubber and a brominated epoxy resin. The commercial epoxy was a tetrafunctional resin, and the experimental epoxy was a trifunctional resin. The reactive rubber was a carboxyl-terminated butadiene-acrylonitrile copolymer. The rubber content was varied from 0 to 25 percent (wt). The brominated epoxy resin was used at Br levels of 4, 19, and 35 percent of the resin. Composites were prepared with woven graphite cloth reinforcement. The composites were evaluated by using flexural strength in the dry state and an elevated temperature after saturation with water. The impact properties were determined by measuring shear strength after falling-ball impact and instrumented impact. The rubber-modified, trifunctional resin exhibited better properties, when tested in hot-wet conditions in a heated oven at 366 K (after boiling the material for 2 h in demineralized water), than the tetrafunctional resin. Improved impact resistance was observed with the addition of the reactive rubber to the epoxy resin. Further improvement was observed with the addition of the brominated epoxy resin.

Gilwee, W. J.

Flammability of Epoxy Resins Containing Phosphorus

As part of a program to develop fire-resistant exterior composite structures for future subsonic commercial and general aviation aircraft, flame-retardant epoxy resins are under investigation. Epoxies and their curing agents (aromatic diamines) containing phosphorus were synthesized and used to prepare epoxy formulations. Phosphorus was incorporated within the backbone of the epoxy resin and not used as an additive. The resulting cured neat epoxy formulations were characterized by thermogravimetric analysis, propane torch test, elemental analysis, microscale combustion calorimetry, and fire calorimetry. Several formulations showed excellent flame retardation with phosphorous contents as low as 1.5% by weight. The fracture toughness and compressive strength of several cured formulations showed no detrimental effect due to phosphorus content. The chemistry and properties of these new epoxy formulations are discussed.

Flammability studies

Reactive Modified Epoxy Resin and Its Miscible Blends Based on Recycled Oligomers from Solvolysis

Chemical depolymerization of fully cured epoxy resin with 20% reactive modifier was successfully performed via a solvent-assisted solvolysis process into low molecular weight recyclable oligomers (RO) at 240 °C in a pressure vessel at 650 psi for 4 h. The thermoset epoxy resin was depolymerized into transparent brown viscous fluid with a higher viscosity than the uncured epoxy resin with approximately 93% yield. Different concentrations of the RO were homogeneously mixed with the pure epoxy resin, and their curing kinetics, viscosity, FTIR, mechanical properties, DMA, and cross-link density were investigated. The curing kinetics of the pure reactive modified epoxy resin (baseline) and its mixtures with RO of different concentrations were investigated under both isothermal and nonisothermal conditions using small amplitude oscillatory shear flow. The elastic and viscous moduli (G′ and G″), complex viscosity (η*), and tan δ values were evaluated at different curing times and temperatures. The G′, G″, and η* increased dramatically, while tan δ decreased strongly by several orders of magnitude at the gel point. The zero-shear viscosity (η 0 ) was determined from the angular frequency dependent on η* based on the Cross model for different blend compositions in the liquid state before curing. The composition dependence of η 0 showed a positive deviation from the linear mixing rule and was well described by the Lecyar model. Here, the apparent activation energy of curing (E a ) was also evaluated according to the Arrhenius equation and was found to be 46 ± 2 kJ/mol regardless of the different contents of RO. For all blends up to 40 wt % RO, only one tan δ peak systematically shifting to lower temperatures with increasing content of RO was observed in the DMA measurements, indicating that the epoxy resin and the RO are miscible with up to 40 wt % RO.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Toughening mechanism in elastomer-modified epoxy resins, part 2

The role of matrix ductility on the toughenability and toughening mechanism of elastomer-modified DGEBRA epoxies was investigated. Matrix ductility was varied by using epoxide resins of varying epoxide monomer molecular weights. These epoxide resins were cured using 4,4' diaminodiphenyl sulfone (DDS) and, in some cases, modified with 10% HYCAR(r)CTBN 1300X8. Fracture roughness values for the neat epoxies were found to be almost independent on the monomer molecular weight of the epoxide resin used. However, it was found that the fracture toughness of the elastomer-modified epoxies was very dependent upon the epoxide monomer molecular weight. Tensile dilatometry indicated that the toughening mechanism, when present, is similar to the mechanisms found for the piperidine cured epoxies in Part 1. SEM and OM corroborate this finding. Dynamic mechanical studies were conducted to shed light on the toughenability of the epoxies. The time-dependent small strain behavior of these epoxies were separated into their bulk and shear components. The bulk component is related to brittle fracture, whereas the shear component is related to yielding. It can be shown that the rates of shear and bulk strain energy buildup for a given stress are uniquely determined by the values of Poisson's ratio, nu. It was found that nu increases as the monomer molecular weight of the epoxide resin used increases. This increase in nu can be associated with the low temperature beta relaxation. The effect of increasing cross-link density is to shift the beta relaxation to higher temperatures and to decrease the magnitude of the beta relaxation. Thus, increasing cross-link density decreases nu and increases the tendency towards brittle fracture.

Yee, A. F.

Investigation of the effects of cobalt ions on epoxy properties

The effects of Co(acac)sub x complexes on MY-720 epoxy properties have been investigated. It appears that Co2(+) ions form antibonding or nonbonding orbitals which increase the free volume and also reduce the cohesiveness of the host epoxy. The effects of Co2(+) ions, on the other hand, seem to result in increased Cohesiveness of the epoxy. The experimental values of magnetic moments of both types of ions in MY-720 suggest that the orbital momentum contributions of the (3d) electrons are partially conserved, though the effect is more pronounced for Co2(+) ions. The coordination environment of the cobalt ions in the host epoxy does not appear to be uniquely defined. These results indicate that the effects of metal ions on resin properties cannot be easily predicted on the basis of ligand field theory argument alone. Complex interactions between metal ions and host epoxy molecular structure suggest the desirability of parallel experimental investigations of electronic, magnetic, and mechanical properties of metal ion-containing epoxy samples for comparison with theory.

Singh, J. J.

Poly(arylene ether-co-imidazole)s as toughness modifiers for epoxy resins

A toughened epoxy was prepared by reacting an epoxy resin with a poly(arylene ether-co-imidazole)s (PAEI). The epoxy resin comprises N,N,N',N'tetraglycidyl-4,4'- methylenebisbenzenamine and 4-aminophenyl sulfone. The PAEI was prepared by reacting an aromatic bisphenol, a bisphenol imidazole, and an activated aromatic dihalide or dinitro compound in the presence of potassium carbonate in a polar aprotic solvent at an elevated temperature. The epoxies which were modified with these particular PAEI's showed a significant increase in toughness with only a 10 weight percent loading of the PAEI into the epoxy. These toughened epoxies were used to prepare composites and molded parts.

Mcdaniel, Patricia D.

Exploratory Study on the Effects of Novel Diamine Curing Agents and Isocyanate Precursors on the Properties of New Epoxy and Urethane Adhesives

This report covers the results of investigations directed toward studying the effects of novel aromatic diamine structures on epoxy adhesive properties and includes work done under a modification to the original contract. Three aromatic diamines based on diphenylsulfone and benzophenone were studied as epoxy adhesive curing agents. Previously found differences in adhesive strengths for meta vs para orientation were not found in these series. The use of aluminum and alumina as fillers in a m,m'-methylene dianiline-cured epoxy adhesive was not found to be beneficial to adhesive strength. Alumina filled adhesives had much lower strength than unfilled adhesives. The unfilled m,m'-methylene dianiline-based epoxy adhesive had excellent resistance to moisture relative to a p,p'-methylene dianiline-based adhesive and maintained good strengths up to 250 F. A glass fiber composite based on a m,m'-methylene dianiline-cured epoxy appeared to be equivalent to the p,p'-methylene dianiline-cured epoxy as judged by short beam shear tests.

Glasgow, D. Gerald

Flame Retardant Epoxy Resins

As part of a program to develop fire resistant exterior composite structures for future subsonic commercial aircraft, flame retardant epoxy resins are under investigation. Epoxies and their curing agents (aromatic diamines) containing phosphorus were synthesized and used to prepare epoxy formulations. Phosphorus was incorporated within the backbone of the epoxy resin and not used as an additive. The resulting cured epoxies were characterized by thermogravimetric analysis, propane torch test, elemental analysis and microscale combustion calorimetry. Several formulations showed excellent flame retardation with phosphorous contents as low as 1.5% by weight. The fracture toughness of plaques of several cured formulations was determined on single-edge notched bend specimens. The chemistry and properties of these new epoxy formulations are discussed.

Thompson, C. M.

Epoxy Adhesives for Stator Magnet Assembly in Stirling Radioisotope Generators (SRG)

As NASA seeks to fulfill its goals of exploration and understanding through missions planned to visit the moons of Saturn and beyond, a number of challenges arise from the idea of deep space flight. One of the first problems associated with deep space travel is electrical power production for systems on the spacecraft. Conventional methods such as solar power are not practical because efficiency decreases substantially as the craft moves away from the Sun. The criterion for power generation during deep space missions are very specific, the main points requiring high reliability, low mass, minimal vibration and a long lifespan. A Stirling generator, although fairly old in concept, is considered to be a potential solution for electrical power generation for deep space flight. A Stirling generator works on the same electromagnetic principles of a standard generator, using the linear motion of the alternator through the stationary stator which produces electric induction. The motion of the alternator, however, is produced by the heating and cooling dynamics of pressurized gases. Essentially heating one end and cooling another of a contained gas will cause a periodic expansion and compression of the gas from one side to the other, which a displacer translates into linear mechanical motion. NASA needs to confirm that the materials used in the generator will be able to withstand the rigors of space and the life expectancy of the mission. I am working on the verification of the epoxy adhesives used to bond magnets to the steel lamination stack to complete the stator; in terms of in-service performance and durability under various space environments. Understanding the proper curing conditions, high temperature properties, and degassing problems as well as production difficulties are crucial to the long term success of the generator. system and steel substrate used in the stator. To optimize the curing conditions of the epoxies, modulated differential scanning calorimetry analysis was done as a function of cure time and temperatures. Adhesion bond strength was tested at various temperatures with lap shear samples using Hiperco 50 substrate to ensure that the proper adhesive is being used. To try and solve the problem of bondline thickness, micro glass beads of 0.0017" in diameter were investigated to see if any other physical properties of the epoxy were affected. Efforts will be made to develop a standard, optimized, fabrication process/procedure of sub-scale magnet-stator assemblies for various adhesive performance evaluation studies under simulated generator conditions. Also, accelerated aging testing will be done in a pressurized canister with stator assembly samples for three years to verify if any degassing or thermal degradation of the epoxy occurs. The necessity of verifying the correct epoxy adhesive system for the stator magnet in the SRG is crucial because failure of the stator assembly would jeopardize the electrical system, and thereby the entire mission itself. My work involves specimen fabrications, testing, and data analyses of the epoxy adhesive system for the stator magnet in the SRG is crucial because failure of the stator assembly would jeopardize the electrical system, and thereby the entire mission itself.

Cater, George M.

Process for Preparing Epoxy-Reinforced Silica Aerogels

One-pot reaction process for preparing epoxy-reinforced monolithic silica aerogels comprising the reaction of at least one silicon compound selected from the group consisting of alkoxysilanes, orthosilicates and combination thereof in any ratio with effective amounts of an epoxy monomer and an aminoalkoxy silane to obtain an epoxy monomer-silica sol in solution, subsequently preparing an epoxy-monomer silica gel from said silica sol solution followed by initiating polymerization of the epoxy monomer to obtain the epoxy-reinforced monolithic silica aerogel.

Meador, Mary Ann B

Static and Dynamic Thermomechanical Properties of Phase-Separated Epoxy Networks with Tuned Microstructures

Here, polymerization-induced phase separation is a useful method for the construction of heterogeneous epoxy networks with properties exceeding their homogeneous counterparts. In this work, we examine the static and dynamic thermomechanical properties of phase-separated epoxy networks salient to their application as encapsulants. Three heterogeneous epoxy-amine networks with nano-, meso-, and macro-phase-separated morphologies comprised of hard and soft domains are compared to a rigid, unstructured network. The glass transition profiles of the heterogeneous networks are complex, spanning many decades in the frequency domain. The nanophase-separated morphology leads to higher coefficient of thermal expansion, yet surprisingly is characterized by reduced residual stress. Under both quasi-static and dynamic compression (strain rates of order 10 –3 and 10 3 s –1 , respectively), the nanophase-separated network also exhibits higher modulus and strength. In split-Hopkinson bar experiments, the energy dissipation characteristics of the epoxy networks were nearly identical. Curiously, however, the Hugoniot response of the macro-phase-separated network determined by ballistic shockwave analysis indicates a remarkable ability of this material to mitigate shockwave propagation in comparison to many homogeneous and heterogeneous polymer materials. Collectively, this work reveals several previously unreported phenomena with respect to structure–property relationships in phase-separated epoxy networks, illustrating the potential value of systematically tuned microstructures for optimization of application-specific physical properties.

36 MATERIALS SCIENCE

The Triple Catalytic Action of Tertiary Nitrogen Catalysts in Recyclable Epoxy-Anhydride Thermosets

The thermosetting polymer matrix in fiber reinforced composites is an important component for energy related applications, such as the lightweighting of vehicles or their use in wind and waterpower turbine blades, due to their ability to provide superior adhesion, stiffness, and applicability to a wide range of manufacturing processes. Despite these benefits, today's thermosets are widely considered to be unrecyclable; thus, there is a large interest in redesigning these materials to be inherently recyclable so that energy intensive production of fibers and monomers can be circumvented, bolstering composite manufacture supply chains. Polyester covalent adaptable networks (PECANs) are one such promising alternative to the incumbent, nonrecyclable epoxy-amine thermosets. PECANs can be formed from the ring-opening co-polymerization (ROCOP) of epoxy-anhydride monomer mixtures and subsequent curing at mild temperatures to exhibit similar performance to conventional epoxies while also possessing unique dynamic chemistries along the ester-hydroxyl backbone that are capable of transesterification and thus reprocessability. While significant advancements have been made in formulating these materials for improved mechanical properties or optimizing solvolysis and reprocessing strategies, less attention has been placed on the impact of the residing amine catalyst used to generate the polyester network. In this work, we evaluated the triple-catalytic efficacy of 12 tertiary amines that act as a curing (bulk ROCOP), a transesterification (internal bond exchange), and a deconstruction (methanolysis) catalyst for PECAN thermosets. Specifically, we first distinguish between chain-growth and step-growth polymerization mechanisms for epoxy-amine and epoxy-anhydride mechanisms. We also utilized density functional theory (DFT) to estimate the basicity (pKb) of each catalyst. Of the tested catalysts, the ROCOP of the studied PECAN network can be completed between 95 and 247 min (at 80 degrees C), with variable gelation phenomena. Additionally, the stress relaxation (transesterification metric) efficiency of the tested PECAN networks with alternative embedded catalysts ranged from 95% to 15% reduction in stress after 5 h at 200 degrees C, and the depolymerization efficacy ranged from 2.5% to 9.8% deconstruction after 36 h at 130 degrees C. Overall, the nitrogen-based moieties were demonstrated to influence polymerization kinetics, catalyze the dynamic transesterification exchange mechanism, and aid in the solvolysis of the thermosets at end-of-life.

36 MATERIALS SCIENCE

Performance of filament-wound vessels from an organic fiber in several epoxy matrices

A study was carried out to select a state-of-the-art epoxy for wet filament winding. Ten epoxy systems were used to filament wind pressure vessels with a high-modulus, high-strength organic fiber. Data are reported on vessel performance, fiber strand strengths, and shear strengths for the different systems. Using our criteria (processibility, neat resin properties, and vessel performance), we find that an epoxy system based on the rubber-modified bis-phenol-F resin, diluted with vinyl cyclohexane dioxide and cured with mixed aromatic amines, can easily replace bis-phenol-A epoxies diluted with bis-(2, 3-epoxycyclopentyl) ether (such as ERL 2256 epoxy of Union Carbide) with comparable overall performance.

Chiao, T. T.

Exploratory study on the effects of novel diamine curing agents and isocyanate precursors on the properties on new epoxy and urethane adhesives

Aromatic diamines based on diphenyl sulfone and benzophenone were studied as epoxy adhesive curing agents. Previously found differences in adhesive strengths for meta vs para orientation were not found in these series. The use of aluminum and alumina as fillers in a m,m prime-methylene dianiline-cured epoxy adhesive was not found to be beneficial to adhesive strength. Alumina filled adhesives had much lower strength than unfilled adhesives. The unfilled m,m prime-methylene dianiline-based epoxy adhesive had excellent resistance to moisture relative to a p,p prime-methylene dianiline-based adhesive and maintained good strengths up to 250 F. A glass fiber composite based on a m,m prime-methylene dianiline-cured epoxy appeared to be equivalent to the p,p prime-methylene dianiline-cured epoxy as judged by short beam shear tests.

Glasgow, D. G.

Physical aging of linear and network epoxy resins

Network and linear epoxy resins principally based on the diglycidyl ether of bisphenol-A and its oligomers are prepared and studied using diamine and anhydride crosslinking agents. Rubber modified epoxies and a carbon fiber reinforced composite are also investigated. All materials display time-dependent changes when stored at temperatures below the glass transition temperature after quenching (sub-T/g/ annealing). Solvent sorption experiments initiated after different sub-T(g) annealing times demonstrate that the rate of solvent uptake can be indirectly related to the free volume of the epoxy resins. Residual thermal stresses and water are found to have little effect on the physical aging process, which affects the sub-T(g) properties of uniaxial carbon fiber reinforced epoxy material. Finally, the importance of the recovery phenomenon which affects the durability of epoxy glasses is considered.

Kong, E. S.-W.

Cobalt ion-containing epoxies

Varying concentrations of an organometallic cobalt complex were added to an epoxy system currently used by the aerospace industry as a composite matrix resin. Methods for combining cobalt (III) acetylacetonate with a tetraglycidyl 4,4 prime - diaminodiphenylmethane-based epoxy were investigated. The effects of increasing cobalt ion concentration on the epoxy cure were demonstrated by epoxy gel times and differential scanning calorimetry cure exotherms. Analysis on cured cobalt-containing epoxy castings included determination of glass transition temperatures by thermomechanical analysis, thermooxidative stabilities by thermogravimetric analysis, and densities in a density gradient column. Flexural strength and stiffness were also measured on the neat resin castings.

Stoakley, D. M.

Regeneration efficiency, shuttle heat loss and thermal conductivity in epoxy-composite annualr gap regenerators from 4K to 80K

A test apparatus designed to simulate a section of a Stirling cycle cryocooler was built. Measurements of regeneration efficiency, shuttle heat loss and thermal conductivity reported for several regenerator test sections. The test composites were epoxy glass, epoxy glass with lead particles, epoxy glass with activated charcoal and epoxy graphite. Losses measured for these materials were approximately the same. Losses are in good agreement with those calculated theoretically for an epoxy glass (C-10) composite. The implications of these results on cryocooler design are discussed.

Myrtle, K.

Modified Epoxy Composites

The properties of a rubber-modified experimental epoxy resin and a standard epoxy as composite matrices were studied. In addition, a brominated epoxy resin was used in varying quantities to improve the fire resistance of the composite. The experimental resin was tris-(hydroxyphenyl)methane triglycidyl ether, known as tris epoxy novolac (TEN). The standard epoxy resin used was tetraglycidyl 4,4'-diaminodiphenyl methane (TGDDM). The above resins were modified with carboxyl-terminated butadiene acrylonitrile (CTBN) rubber. It is concluded that: (1) modification of TEN resin with bromine gives better impact resistance than rubber modification alone; (2) 25% rubber addition is necessary to obtain significant improvement in impact resistance; (3) impact resistance increases with bromine content; (4) impact velocity does not significantly affect the energy absorbed by the test sample; (5) Tg did not decline with rubber modification; and (6) TEN resin had better hot/wet properties than TGDDM resin.

Gilwee, W. J.