Engineering topics

Lessard, Jacob J.

Publications and source records attributed to Lessard, Jacob J..

9 records

DOE OSTI2025

Videos of Chemically Activated Frontal Polymerization of Thermosets

Video recordings of the frontal ring-opening metathesis polymerization (FROMP) of thermoset polymer specimens in 10mm glass test tubes were collected in order to measure the front speed resulting from varied front initiation methods. Maximum front temperature was also measured. Polymerization resins comprised of dicyclopentadiene (DCPD) with 5 wt% 5-ethylidene-2-norbornene (ENB) added, grubbs’ second generation catalyst, and tributyl phosphite (TBP) inhibitor (8000:1:1 monomer:initiator:inhibitor ratio). Polymerization fronts were triggered using concentrated solutions of grubbs’ third generation catalyst in various solvents.

Cramblitt, Anna C.↗

DOE OSTI2024

Reactive extrusion of frontally polymerizing continuous carbon fiber reinforced polymer composites

The manufacturing of carbon fiber-reinforced polymer (CFRP) composites demands rapid and energy-efficient strategies. Frontal polymerization (FP) enables the manufacturing of CFRP using dicyclopentadiene (DCPD) thermoset polymer which meets these requirements. In this work, we introduce reactive extrusion of CFRP (RE-CFRP), where two rollers provide localized heat and pressure to sustain the curing reaction and the consolidation of a continuous carbon fiber tow pre-impregnated with DCPD. We study the effect of the extrusion speed, temperature, and compaction force on the properties of the produced CFRP. Mechanical testing confirms that the resulting fiber volume fraction and the elastic modulus are similar to bulk cured tows. A homogenized thermo-chemical model is developed to study the effect of the process parameters on the polymerization reaction. The process produces hollow woven composite tubes directly via extrusion and in situ curing. Overall, this process offers advantages in curing, tooling, speed, and energy.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Controlled patterning of crystalline domains by frontal polymerization

Materials with hierarchical architectures that combine soft and hard material domains with coalesced interfaces possess superior properties compared with their homogeneous counterparts. These architectures in synthetic materials have been achieved through deterministic manufacturing strategies such as 3D printing, which require an a priori design and active intervention throughout the process to achieve architectures spanning multiple length scales. Here we harness frontal polymerization spin mode dynamics to autonomously fabricate patterned crystalline domains in poly(cyclooctadiene) with multiscale organization. This rapid, dissipative processing method leads to the formation of amorphous and semi-crystalline domains emerging from the internal interfaces generated between the solid polymer and the propagating cure front. The size, spacing and arrangement of the domains are controlled by the interplay between the reaction kinetics, thermochemistry and boundary conditions. Small perturbations in the fabrication conditions reproducibly lead to remarkable changes in the patterned microstructure and the resulting strength, elastic modulus and toughness of the polymer. Furthermore, this ability to control mechanical properties and performance solely through the initial conditions and the mode of front propagation represents a marked advancement in the design and manufacturing of advanced multiscale materials. Drawing inspiration from biological systems in which structural complexity develops through dissipative reaction–diffusion processes, this study explores a transformative synthetic manufacturing strategy aimed at harnessing the principles underpinning morphogenic growth, unlocking new avenues for advanced materials design and fabrication. Synthetic coupled reaction-transport processes offer a versatile yet relatively underexplored method to manipulate the spatial attributes of synthetic materials10. Here we introduce an innovative manufacturing approach based on frontal ring-opening metathesis polymerization (FROMP) that draws parallels with morphogenic growth and development, enabling the formation of patterned microstructures within polymeric materials.

36 MATERIALS SCIENCE↗

DOE OSTI2024

A Mechanism-Based Reaction–Diffusion Model for Accelerated Discovery of Thermoset Resins Frontally Polymerized by Olefin Metathesis

Frontal ring-opening metathesis polymerization (FROMP) involves a self-perpetuating exothermic reaction, which enables the rapid and energy-efficient manufacturing of thermoset polymers and composites. Current state-of-the-art reaction–diffusion FROMP models rely on a phenomenological description of the olefin metathesis kinetics, limiting their ability to model the governing thermo-chemical FROMP processes. Furthermore, the existing models are unable to predict the variations in FROMP kinetics with changes in the resin composition and as a result are of limited utility toward accelerated discovery of new resin formulations. In this work, we formulate a chemically meaningful model grounded in the established mechanism of ring-opening metathesis polymerization (ROMP). Our study aims to validate the hypothesis that the ROMP mechanism, applicable to monomer-initiator solutions below 100 °C, remains valid under the nonideal conditions encountered in FROMP, including ambient to >200 °C temperatures, sharp temperature gradients, and neat monomer environments. Through extensive simulations, we demonstrate that our mechanism-based model accurately predicts the FROMP behavior across various resin compositions, including polymerization front velocities and thermal characteristics (e.g., T max ). Additionally, we introduce a semi-inverse workflow that predicts FROMP behavior from a single experimental data point. Notably, the physiochemical parameters utilized in our model can be obtained through DFT calculations and minimal experiments, highlighting the model’s potential for rapid screening of new FROMP chemistries in pursuit of thermoset polymers with superior thermo-chemo-mechanical properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Reactive Processing of Furan‐Based Monomers via Frontal Ring‐Opening Metathesis Polymerization for High Performance Materials

Frontal ring-opening metathesis polymerization (FROMP) presents an energy-efficient approach to produce high-performance polymers, typically utilizing norbornene derivatives from Diels–Alder reactions. This study broadens the monomer repertoire for FROMP, incorporating the cycloaddition product of biosourced furan compounds and benzyne, namely 1,4-dihydro-1,4-epoxynaphthalene (HEN) derivatives. A computational screening of Diels–Alder products is conducted, selecting products with resistance to retro-Diels–Alder but also sufficient ring strain to facilitate FROMP. The experiments reveal that varying substituents both modulate the FROMP kinetics and enable the creation of thermoplastic materials characterized by different thermomechanical properties. Moreover, HEN-based crosslinkers are designed to enhance the resulting thermomechanical properties at high temperatures (>200 °C). The versatility of such materials is demonstrated through direct ink writing (DIW) to rapidly produce 3D structures without the need for printed supports. This research significantly extends the range of monomers suitable for FROMP, furthering efficient production of high-performance polymeric materials.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Using Data Science Tools to Reveal and Understand Subtle Relationships of Inhibitor Structure in Frontal Ring-Opening Metathesis Polymerization

The rate of frontal ring-opening metathesis polymerization (FROMP) using the Grubbs generation II catalyst is impacted by both the concentration and choice of monomers and inhibitors, usually organophosphorus derivatives. Herein we report a data-science-driven workflow to evaluate how these factors impact both the rate of FROMP and how long the formulation of the mixture is stable (pot life). Using this workflow, we built a classification model using a single-node decision tree to determine how a simple phosphine structural descriptor (V bur-near ) can bin long versus short pot life. Additionally, we applied a nonlinear kernel ridge regression model to predict how the inhibitor and selection/concentration of comonomers impact the FROMP rate. Furthermore, the analysis provides selection criteria for material network structures that span from highly cross-linked thermosets to non-cross-linked thermoplastics as well as degradable and nondegradable materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Unraveling Reactivity Differences: Room-Temperature Ring-Opening Metathesis Polymerization (ROMP) versus Frontal ROMP

Here, in this study, we explore the distinct reactivity patterns between frontal ring-opening metathesis polymerization (FROMP) and room-temperature solventless ring-opening metathesis polymerization (ROMP). Despite their shared mechanism, we find that FROMP is less sensitive to inhibitor concentration than room-temperature ROMP. By increasing the initiator-to-monomer ratio for a fixed inhibitor/initiator quantity, we find reduction in the ROMP background reactivity at room temperature (i.e., increased resin pot life). At elevated temperatures where inhibitor dissociation prevails, accelerated frontal polymerization rates are observed because of the concentrated presence of the initiator. Surprisingly, the strategy of employing higher initiator loading enhances both pot life and front speeds, which leads to FROMP rates exceeding prior reported values by over 5 times. This counterintuitive behavior is attributed to an increase in the proximity of the inhibitor to the initiator within the bulk resin and to whether the temperature favors coordination or dissociation of the inhibitor. A rapid method was developed for assessing resin pot life, and a straightforward model for active initiator behavior was established. Modified resin systems enabled direct ink writing of robust thermoset structures at rates much faster than previously possible.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Frontal Polymerization of Stereoisomers: Distinct Microstructures and Properties in Endo- and Exo- Dicyclopentadiene Thermosets

This study explores the relationship between monomer stereochemistry and the materials properties of thermosets generated by frontal ring-opening metathesis polymerization (FROMP). The exo- and endo-stereoisomers of dicyclopentadiene (DCPD) undergo rapid FROMP to fabricate robust thermosets within seconds. The exo-isomer provides significant benefits compared to the commonplace endo-DCPD resins; exo-DCPD supports faster fronts (≈3 times faster) than the endo-analogue and is an easier-to-handle liquid at room temperature. This work is among the first to explore the materials properties of p(exo-DCPD) thermosets. Here, we demonstrate a significant decrease in T g for products derived from exo-DCPD, despite having a similar rubbery plateau compared to p(endo-DCPD). Soluble oligomers were synthesized as models to probe the microstructural features affected by the monomer stereochemistry. Interestingly, hydrogenated oligomers of endo-DCPD exhibit slight differences in stereoregularity compared to their exo-counterparts. Finally, we incorporated a bisnorbornenyl cross-linker in exo-DCPD resins to boost the polymer T g , while also maintaining fronts that propagate faster than endo-DCPD.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Frontal Polymerization of Dihydrofuran Comonomer Facilitates Thermoset Deconstruction

Frontal ring-opening metathesis polymerization (FROMP) is a rapid, low-energy manufacturing reaction that is useful for curing thermosetting materials. FROMP of dicyclopentadiene (DCPD) results in poly(dicyclopentadiene) (p(DCPD)), a tough thermoset with excellent mechanical performance and chemical stability. Like most thermosets, p(DCPD) cannot be reprocessed and is therefore difficult to recycle. Previous work demonstrated that the incorporation of a small quantity of cleavable units in the strand segments of p(DCPD) networks enables their deconstruction. Here, we report that a commercially available multifunctional comonomer, 2,3-dihydrofuran (DHF), both acts as a potent Grubbs catalyst inhibitor during FROMP and introduces acid cleavable units. The resulting materials retain high performance characteristics, including glass-transition temperatures ranging from 115 to 165 °C and ultimate strength ranging from 35 to 40 MPa. The addition of DHF above critical loading levels enables deconstructable thermosets. Here, we further demonstrate freeform three-dimensional (3D) printing of deconstructable thermosets via frontal polymerization.

36 MATERIALS SCIENCE↗