Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “thermosets”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 181 records · Page 10

Tuning Epoxy Thermomechanics via Thermal Isomerization: A Route to Negative Coefficient of Thermal Expansion Materials

Fine control over the thermal expansion and contraction behavior of polymer materials is challenging. Most polymers have large coefficients of thermal expansion (CTEs), which preclude long performance lifetimes of composite materials. Herein, we report the design and synthesis of epoxy thermosets with low CTE values below their T g and large contraction behavior above T g by incorporating thermally contractile dibenzocyclooctane (DBCO) motifs within the thermoset network. This atypical thermomechanical behavior was rationalized in terms of a twist-boat to chair conformational equilibrium of the DBCO linkages. We anticipate these findings to be generally useful in the preparation of materials with designed CTE values.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dual C–H functionalization of polyolefins for covalent adaptable network formation via cooperative electrolysis

The increasing demand for carbon fibre-reinforced polymer composites with polyolefin thermoset matrices will lead to the generation of large volumes of low molecular weight waste oligomers during the fibre recovery process. To address this challenge, we present a cooperative electrolytic dual C–H bond functionalization strategy for the one-step installation of two key functional groups essential for dynamic linkages of these deconstructed oligomers. Through direct competition studies, we reveal the predominance of tertiary allylic C–H activation along the complex, branched oligomer backbone. The resulting difunctionalized oligomers form covalently adaptable networks with exceptional circularity. By establishing a sustainable pathway for upcycling deconstructed oligomers from carbon fibre-reinforced polymer fibre recovery, this strategy introduces thermoset materials derived directly from waste. Here, it advances sustainable manufacturing practices, contributing to a net-zero waste synthetic ecosystem, and highlights the prospects of mediated electrolysis in macromolecular transformations.

Electrocatalysis↗

Mechanically robust and reprocessable imine exchange networks from modular polyester pre-polymers

Covalent adaptable networks (CANs) containing reversible cross-links impart recyclability to thermoset materials without sacrificing their desirable properties (e.g. high tensile strength and solvent resistance). In addition to thermal recycling, the sustainability of these materials may be further improved by incorporating bio-sourced monomers or by enabling alternate end-of-life fates, such as biodegradation or recovery of starting materials. The alternating ring-opening copolymerisation of epoxides and cyclic anhydrides permits the modular synthesis of polyester pre-polymers that can then be cross-linked to form dynamic imine-linked networks. In this work, we report the synthesis and characterisation of five imine exchange polyester CANs with varied cross-linking densities and pre-polymer architectures. While the materials exhibit characteristic thermoset properties at service temperatures, differences in pre-polymer architecture produce distinct dynamic mechanical effects at elevated temperatures. The networks may be thermally reprocessed with full recovery of their tensile strengths and cross-linking densities, dissociated to pre-polymer, or hydrolytically degraded.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Catalytic conversion of high S-lignin to a sustainable tri-epoxide polymer precursor

More than 40 million tons of thermosetting plastics are produced annually and 70% of those are epoxy polymers. The synthesis of bio-based epoxide provides a pathway for making renewable thermoset plastics. We describe in this study the use of a genetically modified high-S poplar lignin to produce 4-propyl-2,6-dimethoxyphenol (DMPP), which is converted to the tri-functional compound propylpyrogallol (DMPPO) by a reaction catalysed by N 2 O 5 in the green solvent water. The resulting DMPPO can be converted to a novel tri-epoxide by reaction with epichlorohydrin. Native high-S lignin as well as several organosolv lignins extracted from this poplar biomass were investigated as feedstocks. Notably, direct reductive catalytic fractionation (RCF) of the high-S poplar wood over Pd–Zn/C catalyst with Pd : Zn ratio 1 : 10 at 225 °C under 35 bar H 2 in methanol gave the highest yield of biophenol monomers from the lignin present, the major product being DMPP. Under optimized conditions, conversion of DMPP to DMPPO over the Nb 2 O 5 was nearly quantitative (96% yield), and this conversion could be made without extensive prior purification of the DMPP. The Nb 2 O 5 catalyst could be recycled several times before significant deactivation. This sequence of two catalytic reactions demonstrates that the production of epoxides from lignin-derived DMPPO is a realistic strategy for making renewable polymer building blocks from biomass.

09 BIOMASS FUELS↗

Tuneable phase behaviour and glass transition via polymerization-induced phase separation in crosslinked step-growth polymers

We report once limited to chain-growth polymerizations, fine control over polymerization-induced phase separation (PIPS) has recently been demonstrated in rubber-toughened thermoset materials formed through step-growth polymerizations. The domain length scales of these thermoset materials can be elegantly tuned by utilizing a binary mixture of curing agents (CAs) that individually yield disparate morphologies. Importantly, varying the composition of the binary mixture affects characteristics of the materials such as glass transition temperature and tensile behavior. Here, we establish a full phase diagram of PIPS in a rubber-toughened epoxy system tuned by a binary CA mixture to provide a robust framework of phase behaviour. X-Ray scattering in situ and post-PIPS is employed to elucidate the PIPS mechanism whereby an initial polymerization-induced compositional fluctuation causes nanoscale phase separation of rubber and epoxy components prior to local chain crosslinking and potential macrophase separation. We further demonstrate the universality of this approach by alternatively employing binary epoxy or binary rubber mixtures to achieve broad variations in morphology and glass transitions.

59 BASIC BIOLOGICAL SCIENCES↗

Tough and circular glass fiber composites via a tailored dynamic boronic ester interface

Glass fiber reinforced polymer (GFRP) composites are valued for their strength and cost-effectiveness. However, traditional GFRPs often face challenges for end-of-life recycling due to their non-depolymerizable thermoset matrices, and long-term performance due to inadequate interfacial adhesion, which can lead to fiber–matrix delamination. Here, in this work, we have designed dynamic fiber–matrix interfaces to allow tough and closed-loop recyclable GFRPs by utilizing a vitrimer, derived from upcycled polystyrene-b-poly(ethylene-co-butylene)-b-polystyrene (SEBS) with boronic ester (S-Bpin) and amine-based diol crosslinker. The boronic ester groups in S-Bpin form dynamic covalent bonds with the naturally present hydroxyl groups on the unsized GF surface, which eliminates the need for fiber sizing and enables facile closed-loop recyclability of both the fibers and the vitrimer matrix. The resulting strong fiber–matrix interface, depicted by the Raman mapping, leads to a 552% increase in-plane shear toughness (6.2 ± 0.3 MJ m -3 ) and 27% ultimate tensile strength (361 ± 89.2 MPa) compared to those of the conventional epoxy-based matrix (0.95 ± 0.05 MJ m -3 and 264 ± 59.7 MPa, respectively). The network rearrangement through dynamic boronic ester exchange enables fast thermoformability and repairability of micro-cracks at elevated temperatures. Additionally, both the matrix and composite demonstrate strong adhesion to various surfaces including steel and glasses exhibiting ≥6 MPa lap shear strength, which expands their suitability for diverse industrial applications. The readily created dynamic interface between boronic ester functionalized vitrimer and neat GFs presents a promising strategy for developing closed-loop recyclable, multifunctional structural materials, offering a sustainable alternative to non-recyclable thermoset GFRPs and contributes to a circular economy in composite materials.

36 MATERIALS SCIENCE↗

Revealing nanoscale dynamics during an epoxy curing reaction with x-ray photon correlation spectroscopy

In this work the evolution of nanoscale properties is measured during the thermally triggered curing of an industrial epoxy adhesive. We use x-ray photon correlation spectroscopy (XPCS) to track the progression of the curing reaction through the local dynamics of filler particles that reflect the formation of a thermoset network. Out-of-equilibrium dynamics are resolved through identification and analysis of the intensity– intensity autocorrelation functions obtained from XPCS. The characteristic time scale and local velocity of the filler is calculated as functions of time and temperature. We find that the dynamics speed up when approaching the curing temperature (T cure ), and decay rapidly once T cure is reached. We compare the results from XPCS to conventional macroscale characterization by differential scanning calorimetry (DSC). The demonstration and implementation of nanoscale characterization of curing reactions by XPCS proves useful for future development and optimization of epoxy thermoset materials and other industrial adhesive systems.

36 MATERIALS SCIENCE↗

Characterization of micro-sandwich structures via direct ink writing epoxy based cores

Sandwich structured (SS) composites demonstrate considerable flexural stiffness and high strength-to-weight ratios and can be tailored as functional materials. Historically they have been constrained to specific material types and geometry due to limitations in manufacturing methods. However, employing additive manufacturing (AM), specifically direct ink writing (DIW), can provide an alternative method for making SS composites with complex and controllable micro and mesostructures with multifunctionality targeted at desired mechanical, thermal, and electrical properties. DIW, an extrusion-based AM technique, uses a viscous and thixotropic ink with desired components that, once printed, is cured to obtain the final complex net shape parts. In this paper, a novel hybrid AM technique is employed to manufacture SS composite materials containing bisphenol A-based epoxy core and carbon fiber reinforced polymer (CFRP) face sheets that are fabricated via DIW and vacuum infusion process (VIP), respectfully. We demonstrate that the fabrication of these SS composites can be tailored from a thermosetting material, from which additives and/or various lattice structures can be manufactured to achieve enhanced and desirable mechanical integrity with functional properties. Surface topology and mechanical testing techniques are used to characterize the fabricated hybrid SS composites to study and assess mechanical stability. A rheo-kinetic cure model was developed for the core material to allow for additive manufacturing process requirements while ensuring complete cross-linking for the thermoset-based core material. Because of the ability to obtain relatively small core-thickness and controlled architecture, this method now allows for fabricating layered micro-sandwich structures for realizing further light-weighting in relevant applications.

36 MATERIALS SCIENCE↗

Processing Temperature Effect on Failure Behavior of Unidirectional Thermoplastic Polymer-fiber-reinforced Polymers (PFRPs)

This study aimed to examine the influence of processing temperature on the mechanical and morphological characteristics of unidirectional (UD) thermoplastic polymer-fiber-reinforced polymers (PFRPs), utilizing UHMWPE-polymer-fiber-reinforced HDPE composites as an example. To achieve this objective, UD thermoplastic PFRPs were produced through filament winding and hot pressing techniques, employing five distinct processing temperatures within the range spanning from the melting onset temperature of the polymer matrix to the melting peak temperature of the reinforcing polymer fiber. By conducting the uni-axial tensile tests on the UD UHMWPE-polymer-fiber-reinforced HDPE composites fabricated at different processing temperatures, it was shown that the optimal longitudinal tensile properties of the composites, comparable with glass-fiber-reinforced thermoset or thermoplastic polymers (GFRPs or GFRTPs) can be achieved when the processing temperature does not significantly exceeds the melting onset temperature of the reinforcing polymer fiber. However, when the processing temperature exceeds this threshold, the mechanical properties of the composites are significantly reduced, as evidenced by the transition in the failure morphology from the presence of significant splitting cracks to the occurrence of plastic necking due to the complete melting of the reinforcing polymer fibers in a composite. Particularly, the ductile behavior of the optimal thermoplastic PFRPs investigated in this study is superior than that of carbon-fiber-reinforced thermoset or thermoplastic polymers (CFRPs or CFRTPs) and even GFRPs and GFRTPs. This study not only provides valuable insights into the proper fabrication of high-performance thermoplastic PFRPs but also offers useful experimental data that can aid in the validation and development of computational models, particularly those related to processing modeling.

Qiao, Yao↗

Fully Recyclable Advanced Composites with Reduced Cure Times for Improved Manufacturing Efficiency

At Cyclotron Road, the participant team from Mallinda focused its research efforts on developing its Polyimine chemistry for commercial applications. The value-differentiating characteristics of the technology are predicated on the chemical reversibility of the system which opens the door for a number of industrial applications. In short, the company’s technology is a highly crosslinked thermoset polymer network that can exchange covalent bonds within the polymer matrix when the polymer is heated to the glass transition temperature of the material. This leads to a resin system that can alternate between rigid and semi-rigid states; allowing for compression molding, and surface welding of thermosetting composite materials made with polyimine polymers. This research project worked towards improving the thermal properties of its resin from 80 °C to over 260 °C. The improved properties of Mallinda’s resin unlocks development potential within the automotive and aerospace markets where advance composite materials require stringent performance requirements and elevated operating temperatures.

36 MATERIALS SCIENCE↗

Alternative Damage Tolerant Materials for Wind Turbine Blades: An Overview

Current wind turbine blade materials may not be damage tolerant to the extent necessary to optimize the Levelized Cost of Energy (LCOE) of wind energy plants. Traditionally, wind turbine blades have been designed using a safe-life approach, but advances in inspection techniques and structural health monitoring solutions give rise to the opportunity to design wind turbine blades using a damage tolerant approach. Materials selection is a key element of da mage tolerant design, so the extent of the damage tolerance of alternative materials has been analyzed through a literature review and discussions with industry leaders. Fabrics and resin selection significantly affect the damage tolerance of composites. Changes to fabric architecture may include through-the-thickness (TTT) fibers, stretch-broken carbon fiber (SBCF) composites, and aligned discontinuous fiber reinforced composites (ADFRCs). Previous research has demonstrated that using TTT fibers in creases damage tolerance, but additional research is necessary to demonstrate the effectiveness of SBCFs and ADFRCs in mitigating damage. Several studies have demonstrated increased damage tolerance when toughened resin systems are used. In addition to toughened resin systems, thermoplastics have been shown to be tougher than thermosets. However, thermosets have been traditionally preferred in wind turbine blade manufacturing due to ease of manufacturing. Thermoplastic resin system s have been developed that can be used with conventional manufacturing methods but have yet to be studied for its damage tolerant capabilities. Furthermore, cost and stress analyses on where to effectively implement TTT fibers, SBCF composites, ADFRCs, and toughened resin systems must be executed prior to incorporating new materials into wind turbine blade manufacturing.

17 WIND ENERGY↗

Dynamic Polymer Networks for On Demand Degradable Adhesives, Scaffolds, and Templates (Full Technical Report)

This feasibility study was motivated by a need for alternative mandrel materials to meet the next generation of inertial confinement fusion (ICF) ablator capsules. In response, a new polymer material based on reversible covalent bonds was proposed, with the objective to design thermosets to withstand elevated temperatures (140-200 degrees Celsius) while also being thermally degradable on-demand via controlled decomposition at temperatures above 200 degrees Celsius. A series of cyclopentadiene (Cp) containing thermosets were designed and synthesized to evaluate curing, reversibility and degradability via controlled retro-Diels Alder reactions using Cp-cycloaddition adducts as crosslinks. Ultimately, the current iteration of materials and strategy pursued in this study was assessed as impractical for meeting the needs and objectives of Lawrence Livermore National Laboratory’s (LLNL) target fabrication program.

36 MATERIALS SCIENCE↗

Dynamic Networks for On Demand Degradable Adhesives, Scaffolds and Templates (Abbreviated Final Report)

This feasibility study was motivated by a need for alternative mandrel materials to meet the next generation of inertial confinement fusion (ICF) ablator capsules. In response, a new polymer material based on reversible covalent bonds was proposed, with the objective to design thermosets to withstand elevated temperatures (140-200 degrees Celsius) while also being thermally degradable on-demand via controlled decomposition at temperatures above 200 degrees Celsius. A series of cyclopentadiene (Cp) containing thermosets were designed and synthesized to evaluate curing, reversibility and degradability controlled via retro-Diels Alder reactions using Cp-cycloaddition adducts as crosslinks. Ultimately, the current iteration of materials and strategy pursued in this study was assessed as impractical for meeting the needs and objectives of Lawrence Livermore National Laboratory’s (LLNL) target fabrication program.

36 MATERIALS SCIENCE↗

Coal-based Bricks & Blocks (CBBs): Process Development to Prototype Fabrication Coupled with Techno-Economic Analysis and Market Survey

The decline of coal use for energy production provides an abundance of local feedstock for new innovative uses and value-added products. Expanding the U.S. coal-value chain to manufacture high-value carbon products can strengthen the nation’s energy and mineral security, enhance the U.S. national defense security, increase the United States’ economic prosperity, while achieving U.S. environmental objectives. The primary project goal is a relatively light-weight composite product with superior (or comparable) compressive strength. Both virgin and, where available, post-consumer recycled thermoplastic versions are tested for each thermoplastic species. A useful attribute of thermoplastics as binders is that they can be heated to their melting point, cooled, and reheated again without significant degradation. A key advantage of thermoset CBBs is that they require only mixing and molding. CBB advantages include low cost, availability, binding ability and processability. Coal-based bricks and blocks (CBBs) weigh about 50% less than clay bricks and can be manufactured with an interlocking design to promote ease of use for the novice builder. CBB formulation is evaluated according to a design-of-experiments (DoE) approach. DoE variables are a) relative weight fractions of binder, b) relative proportions of large versus small (milled) anthracite size fractions, and c) additive percentage. Fabrication methods include hot-press molding and extrusion, the later being the most commercially viable. CBBs are tested for compressive strength, modulus of rupture (by flexure test) and water absorption per ASTM C67, with density determined by the Archimedes drainage method. Fractured interfaces are examined by SEM (Scanning Electron Microscopy) to resolve fracture dynamics and interior microstructure uniformity. Differential scanning calorimetry (DSC) is used to compare plastic transition temperatures i.e., glass and melting temperatures to contrast virgin with post-consumer recycled thermoplastics and optimize their usage. These results are used in the DoE analysis to identify the binder and relative weight percentages for optimum strength, density, and porosity. Overall, CBBs possess strength comparable to clay-based bricks but are non-permeable and hydrophobic, and hence resistant to degradation by freeze-fracturing, corrosion, and efflorescence. The strongest composites have been made with the following thermoplastic binders (in order of strength): thermoset, high-density polyethylene crosslink resin, high-density polyethylene, nylon 6/6, and polypropylene. Results from a techno-economic analysis TEA show economy of scale for CBBs by modularization and reveal the binder as the cost driver for material costs. Ideally, the incorporation of post-consumer recycled thermoplastic will decrease material acquisition costs and increase product sustainability. Notably, CBBs do not require the high temperature calcination needed to produce cement, nor do they require firing in the 1600-2400 °F range for three days using natural gas, as do clay brick equivalents. Instead, CBBs are heated to a modest <600 °F according to the melt flow index of the thermoplastic binder. Existing anthracite mines can be expanded to produce CBBs to reduce aggregate transportation costs and emissions that exist for clay bricks. TEA reflects this reduced energy cost while a comparative CO2 emission analysis quantifies the reduced environmental footprint. The market survey identifies several commercialization opportunities, dependent upon the brick classification.

01 COAL, LIGNITE, AND PEAT↗

SPERLU Selective Process for Efficient Removal of Lignin and Upgrading (Final Technical Report)

To meet the growing demand for bio-based chemicals and improve the profitability and efficiency of the emerging biorefinery industry, lignin is an abundant and attractive feedstock. Spero Renewables has developed a proprietary and patent-pending technology, the Selective Process for Efficient Removal of Lignin and Upgrading (SPERLU). The technology is a catalytic deconstruction and upgrading of lignin in lignocellulosic biomass or commercially available technical lignin to produce multi-functional phenol (MFP) products. The SPERLU process has been demonstrated and vetted on a lab scale to convert commercially available technical lignin to MFPs in yields of 60-90% (based on lignin). The MFP products can be separated and further upgraded through catalytic or biological means. Spero performed a detailed kinetic study of the SPERLU process and used the resulting kinetic data to design and construct a mini-pilot-scale reactor for routine production of hundreds of grams of MFP products. Spero’s lignin-based MFPs have been demonstrated for use as a drop-in replacement for bisphenol A (BPA) in the synthesis of thermoset polymers. Spero’s lignin-based thermoset polymers exhibit excellent mechanical properties and can be used in many applications. Additionally, a collaboration with the National Renewable Energy Lab (NREL) was used to evaluate the feasibility of upgrading SPERLU products through biological means into valuable chemicals. A comprehensive technoeconomic analysis (TEA) and Life-cycle analysis (LCA) have been completed and support the case for commercialization of the SPERLU technology. Through this project Spero has significantly de-risked the SPERLU technology and is actively planning larger scale pilot projects.

09 BIOMASS FUELS↗

Additively Manufactured, Lightweight, Low-Cost Composite Vessels for Compressed Natural Gas Fuel Storage

This project will develop a process to combine AM via direct ink writing (DIW) technology for CFC printing and to use design optimization tools pioneered at LLNL, with advances in resin/composite formulation enabled by chemical and nano-material modification to produce lightweight low-cost CNG tanks. Our approach will yield sub-scale prototype composite pressure tanks equivalent to Type-5 CNG vessel designs that demonstrate a potential cost-benefit advantage. Central to our vision is using agile AM and design based on computationally informed DIW of both short and continuous CF, further coupled with high-performance thermoset polymer matrixes modified by emergent nanomaterials. Our single-stage, multi-material AM technology, combined with a decreased volume fraction of CF and an increased proportion of economically advantaged short fiber, all together drive the reduction in manufacturing time and overall cost. Importantly, reductions in continuous fiber and overall fiber volume fraction will be achieved without detriment to the mechanical strength of the composite vessel. This will be achieved by employing a single process using multi materials grading involving a thermoset resin “ink” modified with aligned nanoplatelets to leverage the efficient tortuous-path gas barrier effect, printed as an inner flexible gas barrier as the initial stage in our manufacturing process before compositionally grading the AM feedstock in real-time to transition to a rigid, structural CF-filled resin. The proposed hybrid construction is projected to achieve pressure ratings at a service range of 2,900–3,600 psi with a 3× burst safety factor comparable to conventional filament-wound composite tanks with an estimated 30–50% reduction in total manufacturing cost.

03 NATURAL GAS↗

Heterogeneous Polymer Dynamics Explored Using Static 1H NMR Spectra

NMR spectroscopy continues to provide important molecular level details of dynamics in different polymer materials, ranging from rubbers to highly crosslinked composites. It has been argued that thermoset polymers containing dynamic and chemical heterogeneities can be fully cured at temperatures well below the final glass transition temperature (Tg). In this paper, we described the use of static solid-state 1H NMR spectroscopy to measure the activation of different chain dynamics as a function of temperature. Near Tg, increasing polymer segmental chain fluctuations lead to dynamic averaging of the local homonuclear proton-proton (1H-1H) dipolar couplings, as reflected in the reduction of the NMR line shape second moment (M2) when motions are faster than the magnitude of the dipolar coupling. In general, for polymer systems, distributions in the dynamic correlation times are commonly expected. To help identify the limitations and pitfalls of M2 analyses, the impact of activation energy or, equivalently, correlation time distributions, on the analysis of 1H NMR M2 temperature variations is explored. It is shown by using normalized reference curves that the distributions in dynamic activation energies can be measured from the M2 temperature behavior. An example of the M2 analysis for a series of thermosetting polymers with systematically varied dynamic heterogeneity is presented and discussed.

36 MATERIALS SCIENCE↗

Recent Advances in the Application of Functionalized Lignin in Value-Added Polymeric Materials

The quest for converting lignin into high-value products has been continuously pursued in the past few decades. In its native form, lignin is a group of heterogeneous polymers comprised of phenylpropanoids. The major commercial lignin streams, including Kraft lignin, lignosulfonates, soda lignin and organosolv lignin, are produced from industrial processes including the paper and pulping industry and emerging lignocellulosic biorefineries. Although lignin has been viewed as a low-cost and renewable feedstock to replace petroleum-based materials, its utilization in polymeric materials has been suppressed due to the low reactivity and inherent physicochemical properties of lignin. Hence, various lignin modification strategies have been developed to overcome these problems. Herein, we review recent progress made in the utilization of functionalized lignins in commodity polymers including thermoset resins, blends/composites, grafted functionalized copolymers and carbon fiber precursors. In the synthesis of thermoset resins such as polyurethane, phenol-formaldehyde and epoxy, they are covalently incorporated into the polymer matrix, and the discussion is focused on chemical modifications improving the reactivity of technical lignins. In blends/composites, functionalization of technical lignins is based upon tuning the intermolecular forces between polymer components. In addition, grafted functional polymers have expanded the utilization of lignin-based copolymers to biomedical materials and value-added additives. Different modification approaches have also been applied to facilitate the application of lignin as carbon fiber precursors, heavy metal adsorbents and nanoparticles. These emerging fields will create new opportunities in cost-effectively integrating the lignin valorization into lignocellulosic biorefineries.

36 MATERIALS SCIENCE↗