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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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At least 37 records · Page 2

3D Printing ofThermally Responsive Shape Memory LiquidCrystalline Epoxy Networks

Abstract A two-component liquid crystalline epoxy network (LCEN) with shape memory behavior was developed and evaluated as a candidate material for 3D printing. The cure kinetics of the uncured material and the shape memory properties of the cured LCEN were investigated by using parallel plate rheology and dynamic mechanical analysis, respectively. A commercially available fumed silica additive was introduced to the neat, uncured material to improve the rheological properties for 3D printing. The addition of fumed silica was found to increase the yield stress, shear-thinning behavior, and toughness of the uncured epoxy ink. Polarized light microscopy, differential scanning calorimetry, and wide-angle X-ray scattering measurements between the neat and additive-modified LCEN suggested a reduction in liquid crystalline alignment in the modified LCEN, owing to interactions between crystalline domains and fumed silica, which in turn influenced the mechanical behavior. Overall, the additive was found to be successful in preserving the shape memory properties of LCEN while improving its printability.

Chemistry↗

Characterization-curing-property studies of HBRF 55A resin formulations

Characterization curing property investigations on HBRF 55A resin formulations are reported. The initial studies on as received cured samples cut from a full-size FWC are reviewed. Inadequacies of as-received and aged samples are pointed out and additional electron microscopic evidence is offered. Characterization of as-received ingredients of HBRF 55A formulation is described. Specifically, Epon 826, Epon 828, EpiRez 5022, RD-2 and various amines, including Tonox and Tonox 60.40, were characterized. Cure kinetics of various formulations are investigated. Changes in physical/thermal properties (viscosity, specific heat, thermal conductivity and density) during cure are described.

Pearce, E. M.↗

Boron-10 Doped Polysiloxanes as Matrix Materials for Application in the Simultaneous Detection and Discrimination of Gamma Rays and Fast and Thermal Neutrons

Three boron-10 enriched aromatic molecules have been synthesized and incorporated into two different commercial polysiloxane resins, Shin Etsu KER-6000 and Wacker SilRes H62-C. Scintillating fluorophores, 9,9-dimethyl-2-phenylfluorene (PhF) and 2,5-diphenyloxazole (PPO), were tested in combination with each resin and boron-10 molecule for the simultaneous detection of gamma rays, fast neutrons, and thermal neutrons. Here, the H62-C resin was able to solubilize a large amount of PhF, in excess of 20 wt%. Cure kinetics were controlled through the addition of divinylbenzene and phenyl tris(dimethylsiloxy)silane cross-linker solution to the H62-C resin, with rheology experiments demonstrating a large reduction in time to gelation when 20 wt% cross-linker solution was added, from more than 4 hours to less than 1 hour. These polysiloxane resins can be cured in 3 hours under air, while common poly(vinyltoluene) scintillators require at least 4 days of heating and oxygen-free conditions. PhF-doped KER-6000 with tolyl boronate pinacol ester exhibited the best overall performance with a light yield of 62% relative to EJ-200 and thermal neutron capture at energies up to 103 keVee (84 keVee for EJ254B-5). Additionally, four samples exhibited light yields surpassing an industry-standard boron-doped plastic scintillator, Eljen’s EJ254B-5. Over the course of ten months, the KER-6000 samples showed precipitation of dopant molecules, which reduced their light yield by 15% on average, while H62-C proved to be more stable with only a 6% reduction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fully Recyclable CFRP Particles (CRADA 519)

The proposed resin-enhanced materials, which utilize fully recycled CFRP (carbon-fiber-reinforced polymer) particles, are enabled by PARC's proprietary Chemically Linked Particles Networks (13 granted patents and patent applications). PNNL and PARC have collaborated to develop manufacturing methods, such as vacuum-assisted wet compression molding and filament winding, for fabricating fiber-reinforced composites with the PARC matrix. PNNL has conducted various mechanical, physical, and thermal characterizations to compare their differences between the composites with baseline and PARC matrices. Those characterizations include density, void volume fraction, optical micrography, uniaxial tension, four-point bending/flexure, interlaminar shear, coefficient of thermal expansion, glass transition temperature, and curing kinetics.

36 MATERIALS SCIENCE↗

Pultrusion and Vitrimer Composites: Emerging Pathways for Sustainable Structural Materials

Pultrusion is a manufacturing process used to produce fiber-reinforced polymer composites with excellent mechanical, thermal, and chemical properties. The resulting materials are lightweight, durable, and corrosion-resistant, making them valuable in aerospace, automotive, construction, and energy sectors. However, conventional thermoset composites remain difficult to recycle due to their infusible and insoluble cross-linked structure. This review explores integrating vitrimer technology a novel class of recyclable thermosets with dynamic covalent adaptive networks into the pultrusion process. As only limited studies have directly reported vitrimer pultrusion to date, this review provides a forward-looking perspective, highlighting fundamental principles, challenges, and opportunities that can guide future development of recyclable high-performance composites. Vitrimers combine the mechanical strength (tensile strength and modulus) of thermosets with the reprocessability and reshaping of thermoplastics through dynamic bond exchange mechanisms. These polymers offer high-temperature reprocessability, self-healing, and closed-loop recyclability, where recycling efficiency can be evaluated by the recovery yield retention of mechanical properties and reuse cycles meeting the demand for sustainable manufacturing. Key aspects discussed include resin formulation, fiber impregnation, curing cycles, and die design for vitrimer systems. The temperature-dependent bond exchange reactions present challenges in achieving optimal curing and strong fiber–matrix adhesion. Recent studies indicate that vitrimer-based composites can maintain structural integrity while enabling recycling and repair, with mechanical performance such as flexural and tensile strength comparable to conventional composites. Incorporating vitrimer materials into pultrusion could enable high-performance, lightweight products for a circular economy. The remaining challenges include optimizing curing kinetics, improving interfacial adhesion, and scaling production for widespread industrial adoption.

Fiber composites↗

Analysis of pultrusion processing for long fiber reinforced thermoplastic composite system

Pultrusion is one of the composite processing technology, commonly recognized as a simple and cost-effective means for the manufacturing of fiber-reinforced, resin matrix composite parts with different regular geometries. Previously, because the majority of the pultruded composite parts were made of thermosetting resin matrix, emphasis of the analysis on the process has been on the conservation of energy from various sources, such as heat conduction and the curing kinetics of the resin system. Analysis on the flow aspect of the process was almost absent in the literature for thermosetting process. With the increasing uses of thermoplastic materials, it is desirable to obtain the detailed velocity and pressure profiles inside the pultrusion die. Using a modified Darcy's law for flow through porous media, closed form analytical solutions for the velocity and pressure distributions inside the pultrusion die are obtained for the first time. This enables us to estimate the magnitude of viscous dissipation and it's effects on the pultruded parts. Pulling forces refined in the pultrusion processing are also analyzed. The analytical model derived in this study can be used to advance our knowledge and control of the pultrusion process for fiber reinforced thermoplastic composite parts.

Tso, W.↗

Resin transfer molding of textile preforms for aircraft structural applications

The NASA LaRC is conducting and supporting research to develop cost-effective fabrication methods that are applicable to primary composite aircraft structures. One of the most promising fabrication methods that has evolved is resin transfer molding (RTM) of dry textile material forms. RTM has been used for many years for secondary structures, but has received increased emphasis because it is an excellent method for applying resin to damage-tolerant textile preforms at low cost. Textile preforms based on processes such as weaving, braiding, knitting, stitching, and combinations of these have been shown to offer significant improvements in damage tolerance compared to laminated tape composites. The use of low-cost resins combined with textile preforms could provide a major breakthrough in achieving cost-effective composite aircraft structures. RTM uses resin in its lowest cost form, and storage and spoilage costs are minimal. Near net shape textile preforms are expected to be cost-effective because automated machines can be used to produce the preforms, post-cure operations such as machining and fastening are minimized, and material scrap rate may be reduced in comparison with traditional prepreg molding. The purpose of this paper is to discuss experimental and analytical techniques that are under development at NASA Langley to aid the engineer in developing RTM processes for airframe structural elements. Included are experimental techniques to characterize preform and resin behavior and analytical methods that were developed to predict resin flow and cure kinetics.

Hasko, Gregory H.↗

Resin Film Infusion (RFI) Process Modeling for Large Transport Aircraft Wing Structures

This investigation completed the verification of a three-dimensional resin transfer molding/resin film infusion (RTM/RFI) process simulation model. The model incorporates resin flow through an anisotropic carbon fiber preform, cure kinetics of the resin, and heat transfer within the preform/tool assembly. The computer model can predict the flow front location, resin pressure distribution, and thermal profiles in the modeled part. The formulation for the flow model is given using the finite element/control volume (FE/CV) technique based on Darcy's Law of creeping flow through a porous media. The FE/CV technique is a numerically efficient method for finding the flow front location and the fluid pressure. The heat transfer model is based on the three-dimensional, transient heat conduction equation, including heat generation. Boundary conditions include specified temperature and convection. The code was designed with a modular approach so the flow and/or the thermal module may be turned on or off as desired. Both models are solved sequentially in a quasi-steady state fashion. A mesh refinement study was completed on a one-element thick model to determine the recommended size of elements that would result in a converged model for a typical RFI analysis. Guidelines are established for checking the convergence of a model, and the recommended element sizes are listed. Several experiments were conducted and computer simulations of the experiments were run to verify the simulation model. Isothermal, non-reacting flow in a T-stiffened section was simulated to verify the flow module. Predicted infiltration times were within 12-20% of measured times. The predicted pressures were approximately 50% of the measured pressures. A study was performed to attempt to explain the difference in pressures. Non-isothermal experiments with a reactive resin were modeled to verify the thermal module and the resin model. Two panels were manufactured using the RFI process. One was a stepped panel and the other was a panel with two 'T' stiffeners. The difference between the predicted infiltration times and the experimental times was 4% to 23%.

Loos, Alfred C.↗

VARTM Model Development and Verification

In this investigation, a comprehensive Vacuum Assisted Resin Transfer Molding (VARTM) process simulation model was developed and verified. The model incorporates resin flow through the preform, compaction and relaxation of the preform, and viscosity and cure kinetics of the resin. The computer model can be used to analyze the resin flow details, track the thickness change of the preform, predict the total infiltration time and final fiber volume fraction of the parts, and determine whether the resin could completely infiltrate and uniformly wet out the preform.

Cano, Roberto J.↗

Exploring the Functional Performance of a Commercial High-Temperature Photopolymer Resin for Vat Photopolymerized Injection Molding Tools

Additive manufacturing (AM) presents a promising approach for rapid tooling, offering significant reductions in production costs and lead times compared to that of conventional moldmaking processes. This work examines the fabrication of molds for injection molding through vat photopolymerization (VPP) AM, using a commercially available photopolymer resin intended for high temperature applications (High Temp V2 resin). The photorheological behavior of the resin is examined to evaluate its curing kinetics and mechanical development during polymerization, ensuring suitability for mold fabrication. The thermal and mechanical properties of the printed photopolymer resin are characterized, alongside assessments of dimensional accuracy and surface finish, which are critical factors influencing the performance and quality of injection molded parts. Additionally, specimens produced using VPP-fabricated molds are evaluated and benchmarked against those molded with traditional metal molds.

Jones, Haley W. [Savannah River National Laborator↗

Adhesive joint evaluation by ultrasonic interface and lamb waves

Some results on the application of interface and Lamb waves for the study of curing of thin adhesive layers were summarized. In the case of thick substrates (thickness much more than the wave length) the interface waves can be used. In this case the experimental data can be inverted and the shear modulus of the adhesive film may be explicitly found based on the measured interface wave velocity. It is shown that interface waves can be used for the study of curing of structural adhesives as a function of different temperatures and other experimental conditions. The kinetics of curing was studied. In the case of thin substrates the wave phenomena are much more complicated. It is shown that for successful measurements proper selection of experimental conditions is very important. This can be done based on theoretical estimations. For correctly selected experimental conditions the Lamb waves may be a sensitive probe of adhesive bond quality and may be used or cure monitoring.

Rokhlin, S. I.↗

Investigating Fast Scanning Calorimetry and Differential Scanning Calorimetry as Screening Tools for Thermoset Polymer Material Compatibility with Laser-Based Powder Bed Fusion

As additive manufacturing (AM) technology has developed and progressed, a constant topic of research in the area is expanding the library of materials to be used with these techniques. Among AM methods that utilize polymers, laser-based powder bed fusion (PBF-LB) has preferentially used thermoplastic polymers as its starting materials, but the deposition and material joining method employed in PBF-LB may also be compatible with powdered thermoset polymer precursors as feedstocks. To assess the compatibility of candidate thermosetting polymers and PBF-LB, characterization techniques and protocols that link fundamental material behavior to material behavior in the processing environment are needed. Therefore, the objectives of this work are to compare the curing behavior measured with two different calorimetry techniques that can operate in different heating rate regimes, differential scanning calorimetry (DSC) and fast scanning calorimetry (FSC), and to assess the capabilities of these techniques to act as materials screening tools for PBF-LB. A commercial polyester powder coating is used as a model material to evaluate the potential of obtaining complimentary information for material screening through a combination of calorimetry methods, and its non-isothermal curing behavior is measured at heating rates between 5 °C/min and 7500 °C/min. Curing exotherms are observed with both calorimetry techniques, and comparing the enthalpy associated with curing shows that incomplete curing occurs at higher heating rates, with relative conversion values of approximately 30%. The curing data are fit with two isoconversional models, Friedman and Starink, which show a reduced activation energy at higher heating rates as well, signifying a lower barrier to curing at the conditions used in the FSC experiments. Overall, the results of this work indicate that using these two calorimetry techniques as tiered screening tools can provide valuable information about how curing may proceed in PBF-LB and inform materials selection and design activities for additive manufacturing.

36 MATERIALS SCIENCE↗

Material Needs and Measurement Challenges for Advanced Semiconductor Packaging: Understanding the Soft Side of Science

This Perspective builds upon insights from the National Institute of Standards and Technology (NIST)-organized workshop, “Materials and Metrology Needs for Advanced Semiconductor Packaging Strategies,” held at the 35th annual Electronics Packaging Symposium in Binghamton, NY, on September 5, 2024. It outlines critical challenges and opportunities related to polymer-based “soft” materials in advanced semiconductor packaging, with emphasis on polymer science, measurement science (metrology), and the strategic development of Research-Grade Test Materials (RGTMs). These efforts, led by the NIST CHIPS team, aim to advance the fundamental understanding of structure-property-processing relationships, promote standardized guidelines and innovative methods for material characterization, and accelerate the development, qualification, and adoption of next-generation packaging materials. The Perspective also distills key insights from the panel discussion with industry experts, emphasizing the need for close collaboration among materials scientists, process engineers, and metrology experts to enable a holistic strategy, further highlighting the importance of cross-sector partnerships among industry, academia, and government to address pressing challenges in packaging materials and processes.

97 MATHEMATICS AND COMPUTING↗

Impact of DMP-30 catalyst concentration on the degradation and kinetics of bisphenol A epoxy thermosets cured with linear amine hardener

Epoxy thermosets are a crucial component in carbon-fiber composites, serving as the organic binding matrix. Catalysts are commonly used in prepolymer formulations to accelerate curing of the thermosets. However, the impact of catalysts on the thermal stability, degradation pathways, and kinetics of the final thermoset is poorly understood. Here, in this work, Product-Specific Kinetics (PSK) analysis was utilized with isoconversional kinetics to provide a first look into the degradation kinetics of major pyrolysis pathways in bisphenol A (BPA) epoxy resins and determine the impact of altering catalysis concentrations on these kinetic pathways. Results revealed new insights into previously identified degradation pathways, provided evidence of multiple degradation pathways for some products, and showed that use of excess catalyst results in polymer network alterations and reduced thermal stability of the thermosets.

Bisphenol A↗

Aluminum Based Solvent-Free Organic–Inorganic Hybrid Materials

In emerging materials, molecular hybrids are especially promising, as they have molecular level mixing of the organic and inorganic components, producing homogeneous materials without interfaces that can deteriorate properties. However, the current methods of manufacturing molecular hybrids are based on solution processing, which is impractical for bulk materials such as may be used for optically clear radiation and electromagnetic shielding components or photonics. Here we examine molecular hybrids composed of aluminum isopropoxide (AIP) and epoxy resins aiming to understand the molecular scale chemistry and manufacturability of these hybrid materials. DSCmonitored cure revealed the ideal cure temperature for these materials is 160−170 °C and demonstrated that an AIP concentration of 16.7 wt % maximizes the extent of reaction. Kinetic analysis of the curing reaction showed the Sestak−Berggren autocatalytic model is effective at temperatures over 140 °C but the reaction has diffusion limitations at a temperature of 120 °C. Mechanical testing with custom resin molds revealed a decrease in properties of the bulk samples with increasing AIP content due to an increase in defects but further testing with nanoindentation demonstrated comparable or improved mechanical properties of AIP-epoxy hybrids compared to epoxy resin with a standard hardener. Ultimately, this work lays the foundation for hardener-free epoxy-aluminum inorganic/organic hybrids and presents opportunities to expand on properties for specific applications such as thermal conductivity, optical clarity, and dielectric constant.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamic mechanical characterization of cure of a polyimide-graphite fiber composite (PMR 15/Celion 6000)

Dynamic mechanical studies of thermosetting PMR 15 polyimide/Celion 6000 composites were used to characterize cure behavior. Variation in composite shear modulus with cure time for laminates partially cured under 3.45 MPa pressure was compared with that of laminates fully cured under pressure to select a partially cured system whose behavior corresponded with that of the pressure-cured composites. An empirical kinetic model was developed that relates relative composite shear moduli to cure time and temperature. This model, coupled with standard statistical techniques, was used in the determination of an overall activation energy, E = 145 kj/mole (35 kcal/mole) and order of reaction, n, for the cure reaction(s). The empirical relationship defining dynamic modulus as a function of time and temperature remained linear well into the glassy region. Changes in dynamic glass-transition temperature and in the breadth of the transition peaks with cure time are discussed. Shear modulus and damping were found to be more sensitive measures of relative extent of cure than Fourier transform infrared spectroscopy.

Hurwitz, F. I.↗

Tuning the Mechanical Properties of Crosslinked Copolymers via Sequence and Solvent‐Selective Swelling for Vat Photopolymerization

Block copolymers (BCPs) offer distinct advantages for vat photopolymerization by enabling mechanically programmable network structures through microphase-separated morphologies that can be kinetically trapped during curing, yielding properties unattainable in homogeneous resins. However, the respective roles of repeat-unit sequence and solvent environment, together with their interplay in directing network formation and mechanical performance, remain unclear. Here, we synthesize a series of CO 2 -based polycarbonate copolymers comprising a crosslinkable glassy poly(vinyl cyclohexene carbonate) (PVCHC, A block) and a non-crosslinkable soft poly(propylene carbonate) (PPC, B block). The polymer sequence is systematically varied (ABA, BAB, and statistical), and solvent choice controls block-selective swelling to jointly control gelation behavior, microphase morphology, and mechanical response through changes in the accessibility and local environment of photocrosslinkable vinyl groups during network formation, as revealed by photorheology and small angle x-ray scattering. By tuning polymer sequence and curing solvent, we transform nominally identical formulations from brittle to highly ductile materials, achieving a three-orders-of-magnitude range in toughness (0.003 to 9.1 MJ m −3 ). These results establish clear structure–processing–property relationships and identify polymer sequence and selective solvation as powerful strategies for programming both printability and performance of block copolymer resins for additive manufacturing.

additive manufacturing↗