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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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

An attempt is made to develop tough, moisture resistant, high char yield epoxy resins by means of novel bisimide amine (BIA) hardener curing agents and a state-of-the-art epoxy resin system. The BIAs are isolated as mixtures containing monomer, oligomer, and polymeric species, and then characterized by elemental analysis and high pressure liquid chromatography. The bisimide amine-cured epoxies (IMEs) were characterized with respect to moisture absorption, thermal properties, and physical and mechanical properties, as well as in the role of matrices in Celion 6000/IME composites. The relative toughness characteristics of each IME formulation was measured by the 10 deg off-axis tensile test, measuring the uniaxial tensile strength, shear strength, and shear-strain-to-failure of the composite systems.

Scola, D. A.↗

Neutralizing Amine-Cured Epoxy Surfaces

New surface treatment is a rapid, convenient, and effective method for converting unused amines and amine functional groups into neutral, noncorrosive substituted urea. Reaction proceeds at room temperature, takes only a few minutes, and leaves no corrosive residue. Surface should first be washed with alcohol to remove as much as possible of unreacted amine. Then it should be dried, since residual moisture or alcohol may consume some of treatment reagent and neutralization may then be incomplete.

Lee, S. Y.↗

Method of neutralizing the corrosive surface of amine-cured epoxy resins

The corrosive alkaline surface layer of an epoxy resin product formed by the curing of the epoxy with an aliphatic amine is eliminated by first applying a non-solvent to remove most or all of the free unreacted amine and then applying a layer of a chemical reagent to neutralize the unused amine or amine functional groups by forming a substituted urea. The surface then may be rinsed with acetone and then with alcohol. The non-solvent may be an alcohol. The neutralizing chemical reagent is a mono-isocyanate or a mono-isothiocyanate. Preferred is an aromatic mono-isocyanate such as phenyl isocyanate, nitrophenyl isocyanate and naplthyl isocyanate.

Lee, S. Y.↗

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

A study has been conducted with the objective of developing tough, moisture resistant, high char yield epoxy resins using novel bisimide amine (BIA) hardeners as curing agents with MY-720, a commercial state-of-the-art epoxy resin system. BIA cured epoxies are shown to have lower moisture absorption than MY-720 and other state-of-the-art epoxy resins; the tensile strengths and strain-to-failures of several of the bisimide epoxy resins (IME's) are higher than those of the state-of-the-art epoxies. Most IME's have compression properties equivalent to those of state-of-the-art epoxies. Two resin systems, IME-10 and IME-12-3, have better overall properties than other resin systems investigated.

Scola, D. A.↗

Aging Effects of Environmentally-Friendly Cleaners on Adhesive Bond Integrity

Because of the 1990 Clean Air Act Amendment many chlorinated solvents are being phased out of use in manufacturing industries. Replacement of the ODC (ozone- depleting chemicals) with less volatile, non-ozone depleting cleaners has been extensively studied over the past nine years at Thiokol Propulsion, Cordant Technologies. Many of the non-ODC cleaners contain compounds that can potentially degrade over time under conditions of high temperature, humidity and exposure to light. The chemical composition of environmentally conditioned cleaners and the subsequent effect on aluminum/amine-cured epoxy bond integrity as measured by Tapered Double Cantilever Beam were evaluated. From this study it is observed that moisture content increases for those cleaners containing polar compounds. Non-volatile residue content increases as stabilizers are depleted and the chemical compound limonene is oxidized. A change in aluminum/ amine-cured epoxy bond fracture toughness is observed as some of these cleaners age with increases in moisture and NVR content.

Biegert, L. L.↗

Mild chemical recycling of carbon fiber-reinforced epoxy composites in aqueous buffers and development of hydrothermally recyclable vitrimer composites from recyclates

Carbon fiber-reinforced polymer (CFRP) composites have gained widespread adoption across diverse industries. However, their inherent stability, stemming from the crosslinked structure of the matrix resin, poses a significant challenge in managing the growing volume of CFRP waste. Consequently, there is a pressing need for an eco-friendly upcycling method that effectively recovers and reuses both the valuable carbon fibers and the polymer matrix from CFRP waste. This study presents a novel approach for upcycling CFRP waste under environmentally friendly conditions. Firstly, CFRP waste with an amine-cured epoxy matrix was completely decomposed in aqueous buffer solutions under mild conditions (≤ 220 °C, pH = 4.8). Further, decomposed matrix polymer (DMP) was employed to transform conventional epoxy resins into recyclable vitrimers. Lastly, new composites that can be hydrothermally recycled were fabricated using both DMP and recovered carbon fibers. As a result, this work proposes a novel strategy for achieving a circular economy within the CFRP industry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of Amine and Anhydride Curing Agents on the VARTM Matrix Processing Properties

To ensure successful application of composite structure for aerospace vehicles, it is necessary to develop material systems that meet a variety of requirements. The industry has recently developed a number of low-viscosity epoxy resins to meet the processing requirements associated with vacuum assisted resin transfer molding (VARTM) of aerospace components. The curing kinetics and viscosity of two of these resins, an amine-cured epoxy system, Applied Poleramic, Inc. VR-56-4 1, and an anhydride-cured epoxy system, A.T.A.R.D. Laboratories SI-ZG-5A, have been characterized for application in the VARTM process. Simulations were carried out using the process model, COMPRO, to examine heat transfer, curing kinetics and viscosity for different panel thicknesses and cure cycles. Results of these simulations indicate that the two resins have significantly different curing behaviors and flow characteristics.

Brian W Grimsley↗

Latent Hardeners for the Assembly of Epoxy Composites

Large-scale composite structures are commonly joined by secondary bonding of molded-and-cured thermoset components. This approach may result in unpredictable joint strengths. In contrast, assemblies made by co-curing, although limited in size by the mold, result in stable structures, and are certifiable for commercial aviation because of structural continuity through the joints. Multifunctional epoxy resins were prepared that should produce fully-cured subcomponents with uncured joining surfaces, enabling them to be assembled by co-curing in a subsequent out-of-autoclave process. Aromatic diamines were protected by condensation with a ketone or aldehyde to form imines. Properties of the amine-cured epoxy were compared with those of commercially available thermosetting epoxy resins and rheology and thermal analysis were used to demonstrate the efficacy of imine protection. Optimum conditions to reverse the protecting chemistry in the solid state using moisture and acid catalysis were determined. Alternative chemistries were also investigated. For example, chain reaction depolymerization and photoinitiated catalysts would be expected to minimize liberation of volatile organic content upon deprotection and avoid residual reactive species that could damage the resin. Results from the analysis of protected and deprotected resins will be presented.

Palmieri, Frank↗

New diamine hardeners for epoxies

Stronger amine-cured polyepoxides can be obtained by using those diaminobenzophenones and diaminodiphenylmethanes that have amine groups located at ortho or meta positions to carbonyl or methylene groups joining two benzene rings.

Bell, V. L.↗

The Effect of Water on the Work of Adhesion at Epoxy Interfaces by Molecular Dynamics Simulation

Molecular dynamics simulation can be used to explore the detailed effects of chemistry on properties of materials. In this paper, two different epoxies found in aerospace resins are modeled using molecular dynamics. The first material, an amine-cured tetrafunctional epoxy, represents a composite matrix resin, while the second represents a 177 C-cured adhesive. Surface energies are derived for both epoxies and the work of adhesion values calculated for the epoxy/epoxy interfaces agree with experiment. Adding water -- to simulate the effect of moisture exposure -- reduced the work of adhesion in one case, and increased it in the other. To explore the difference, the various energy terms that make up the net work of adhesion were compared and the location of the added water was examined.

Hinkley, J.A.↗

Evolved Gas Analysis–Mass Spectrometry Exposes Polymer Network Structures

Polymer network structures in epoxy thermosets play an important role in the final thermoset material properties. However, analytical characterization of these network structures is difficult due to their amorphous nature. In this work, the application of evolved gas analysis–mass spectrometry (EGA-MS) to characterize the polymer network structures of bisphenol A (BPA)-based thermosets is demonstrated. Analytical characterization of the polymer network structures is accomplished by monitoring the Product-Specific Kinetics (PSK) of BPA monomer formation during thermal degradation investigations. We relate observed differences in the activation energy (E a ) of BPA monomer formation to the local packing environment around the BPA monomer units within the polymer network. Variations in the local environment related to the polymer networks manifest qualitatively as broadening in the thermal profile of the BPA monomer evolution and quantitatively as changes in the activation energy (E a ). Three BPA thermoset formulations were investigated; two amine-cured thermoset with 4,4′-diaminodiphenylmethane (DDM) or poly(propylene glycol) bis(2-amino-propyl ether) (PPG400) and a homopolymerized thermoset via curing with Epikure 3253 catalyst (3253). Results revealed that the 3253 thermoset contained two distinct packing densities in the polymer network, while DDM and PPG400 thermosets had uniform distributions of packing densities. Results from the DDM thermoset revealed a gradually decreasing E a , while the apparent E a of PPG400 was consistent over the entire degradation. Furthermore, these differences in E a were concluded to stem from the flexibility of the corresponding polymer networks and the ability of the network components to rearrange and occupy formed voids. Due to the minimal sample required for analysis (100–200 μg), this EGA-MS technique has great potential for postproduction evaluation of composite parts to identify changes in the polymer networks from use and aging, which could signal compromised performance.

Degradation↗