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All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Product-specific kinetics reveal effect of epoxy crystallization on thermoset thermal degradation

Crystallization is a common problem for epoxy resins, which are ubiquitous in industrial and commercial use. Integration of crystallized epoxy monomers into cured thermosets has been shown to alter the thermosets’ final mechanical properties. However, no studies have investigated the impact of these crystals on the thermal stability of the thermoset. Here we investigate the degradation kinetics of a bisphenol F–based epoxy thermoset with and without crystallized monomers using Product-Specific Kinetic (PSK) analysis coupled with Evolved Gas Analysis-Mass Spectrometry (EGA-MS). PSK analysis revealed significant differences in evolved product ion kinetics, suggesting changes in the degradation kinetics between thermoset configurations. Further, it was concluded that early stages of degradation are influenced most by crystal presence due to the high concentration of unreacted epoxy monomers and lower cross-linking density of the cured network. After post-cure annealing, significant changes are observed in the degradation kinetics of thermosets without crystal inclusions. Conversely, post-cure annealing procedures of crystal integrated thermosets showed little change in the thermoset degradation kinetics across all conversion extents. These findings suggest that post-cure annealing of thermosets with crystals present at the onset does not alter the cross-linking density of the polymer network enough to significantly change the degradation kinetics. We hypothesize this is because the excess monomers from the melted crystals are unable to find suitable reaction sites for complete binding into the polymer network, which has direct implications for the material properties and final thermal stability of the thermoset.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Investigating the Crosslinking, Degradation, and Adhesion Behavior of Photovoltaic Encapsulants Under Thermal Accelerated Aging

Degradation of photovoltaic (PV) module encapsulant characteristics that lead to mechanical embrittlement and delamination remains a cause of failure in solar installations. A multiscale reliability model connecting the encapsulant mechanical and fracture properties to the degraded molecular structure and interfacial bonding to adjacent solar cell and glass substrates was previously published. The model, developed primarily for poly(ethylene-co-vinyl acetate) acetate (EVA) encapsulants, remains to be experimentally validated. Determining the degradation and crosslinking kinetics of alternative encapsulants, such as polyolefin elastomer (POE) and EVA/POE/EVA composites (EPE), can generalize the model. In this work, we subject fully cured EVA, POE, and EPE encapsulants to accelerated thermal aging to determine how high temperatures impact reaction kinetics. An increase in gel content (crosslinking) and decrease in crystallinity of the encapsulants under hot-aerobic (90 degrees C, 22% RH) and hot-anaerobic (90 degrees C, sealed in N 2 air) aging were observed, even in the absence of UV and crosslinking initiators. Fourier transform infrared spectroscopy (FTIR)-attenuated total reflectance analysis showed insignificant encapsulant degradation, demonstrating the critical role of UV and moisture in accelerating degradation. Adhesion testing performed on coupon-level specimens (cell/encapsulant/glass laminates) showed decreases in adhesion energy, Gc , from 5000 h of hot-dry (90 degrees C, ~1% RH) and hot-humid (90 degrees C, 60% RH) aging. POE coupons demonstrated the best stability, followed by EPE then EVA. For EVA and POE, hot-humid aged coupons experienced a larger decrease in Gc due to enhanced hydrolytic degradation. Hot-dry aging condition demonstrated that thermal degradation of the interface could be significant even if the encapsulant experiences negligible degradation in the absence of UV and elevated humidity.

accelerated aging↗
DOE OSTI2026

Suppressing proximity effects during rapid serial two-photon lithography through tuning of reaction–diffusion kinetics

The ability of two-photon lithography (TPL) to print deterministic nanoporous 3D structures is highly valuable for many applications. However, it is challenging to print such structures rapidly due to the proximity effects that cause closely spaced features to enlarge and merge. A key challenge is the limited understanding of the origins and spatiotemporal dynamics of the long-range proximity effects that extend beyond the optical focal spot. Here, we empirically investigate these proximity effects in serial TPL using custom-made acrylate-based photoresists. We demonstrate that the complex spatiotemporal dynamics of the proximity effects can be explained through the kinetics of the reaction–diffusion photopolymerization mechanisms that underlie the curing process. Specifically, we show that the proximity effects arise due to comparable timescales of reaction and diffusion of oxygen. Furthermore, we demonstrate that long-range proximity effects can be suppressed by introducing phenolic inhibitors, which reduce oxygen consumption through non-inhibiting side reactions and promote faster termination of curing reactions. These insights enabled improving the linewidths from >400 to 260 nm during printing of nanoporous 3D woodpiles at scanning speeds of 50 mm s −1 . Thus, the knowledge generated here can be applied to deterministically tune the proximity effects and enable rapid printing of high-resolution nanoporous 3D structures.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Solvent Impregnated Polymers Loaded with Liquid-Like Nanoparticle Organic Hybrid Materials for Enhanced Kinetics of Direct Air Capture and Point Source CO 2 Capture

Hybrid CO 2 capture materials, solvent impregnated polymers (SIPs), are developed based on a simple and scalable encapsulation technique to enhance CO 2 capture kinetics of water-lean solvents with high viscosity. Liquid-like nanoparticle organic hybrid materials functionalized with polyethylenimine (NOHM-I-PEI) are incorporated into a shell material and UV-cured to produce gas-permeable solid sorbents with uniform NOHMs loading (NPEI-SIPs). The CO 2 capture kinetics of NPEI-SIPs show a remarkable 50-fold increase compared to that of neat NOHM-I-PEI due to a large increase in the NOHMs-CO 2 interfacial surface area provided by the SIP design. The optimum NOHM-I-PEI loading and sorption temperature are found to be ≈49 wt% and 50 °C, respectively, and NPEI-SIPs exhibit great thermal stability over 20 CO 2 capture/sorbent regeneration temperature swing cycles. The pseudoequilibrium CO 2 loadings of NPEI-SIPs under humid conditions are as high as 3.1 mmol CO 2 g -1 NPEI - SIPs for 15 vol% CO 2 (postcombustion capture) and 1.7 mmol CO 2 g -1 NPEI - SIPs for 400 ppm (direct air capture). Overall, these findings suggest that NPEI-SIPs can effectively capture CO 2 from a wide range of CO 2 concentrations including direct air capture while allowing the flexible design of CO 2 capture reactors by combining the benefits of liquid solvents and solid sorbents.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Mechanisms of internal curing water release from retentive and non-retentive superabsorbent polymers in cement paste

This paper examines the mechanisms of desorption within cement pastes for superabsorbent polymers (SAP) with different sorption kinetics: retentive and non-retentive (self-releasing). Despite the different behavior in solution, both SAP types mitigated the autogenous shrinkage of cement pastes. {sup 1}H NMR and X-ray tomography showed that the cavities formed by both SAP types were saturated until 9–11 h after mixing, while the entrained water in the cavities redistributed to the cement matrix afterwards. In particular, the non-retentive SAP might have rapidly released the absorbed water, but the released water stayed in the original cavities. Therefore, the behavior of the SAP in the pore solution may not completely determine their internal curing performance in cement pastes. In particular, the initial absorption that forms the solution-filled cavities might be more important than whether the SAP are able to retain the solution for extended periods of time or not.

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

Determining the Crosslinking and Degradation Reaction Kinetics in Photovoltaic Encapsulants Using Accelerated Aging: Preprint

Degradation of photovoltaic (PV) module encapsulant mechanical characteristics that lead to embrittlement and delamination remains a cause of failure in solar installations. A multiscale reliability model based on detailed molecular degradation reaction kinetics was previously published, connecting the encapsulant mechanical properties (elastic modulus, yield strength, and adhesion energy) to the degraded molecular structure and interfacial bond density to adjacent solar cell and glass substrates. The model, developed primarily for poly(ethylene-co-vinyl acetate) (EVA) encapsulants, remains to be experimentally validated. Determining the degradation and crosslinking kinetics of alternative encapsulants, such as polyolefin elastomer (POE) and EVA/POE/EVA composites (EPE), can further generalize the model. Importantly, the activation energy for crosslinking of fully cured PV encapsulant products from temperature or UV is presently unknown or unavailable. In this work, we subject EVA, POE, and EPE encapsulants to a set of accelerated aging conditions, varying the temperature, UV intensity, and relative humidity. We use DSC, FTIR, and Soxhlet extraction (gel content) to characterize the encapsulants' changing molecular structure. This allows for determination of the photochemical degradation and crosslinking kinetics of the encapsulants. Preliminary results show an increase in gel content (crosslinking) and a decrease in crystallinity of EVA, POE, and EPE encapsulants under hot-aerobic (90 deg C, 22% RH) and hot-anaerobic (90oC, sealed in N2 air) accelerated aging, even in the absence of UV and crosslinking initiating agents. For a least squares regression with an assumed first-order crosslinking kinetics, the crosslinking rate parameters were computed for the three encapsulants under hot-aerobic and hot-anaerobic aging conditions. FTIR analysis showed insignificant encapsulant degradation for hot-aerobic and hot-anaerobic aging, demonstrating the critical role of UV and moisture in accelerating degradation. Aging conditions with UV exposure and elevated humidity are presently in progress.

adhesion↗
DOE OSTI2021

A positivity-preserving and conservative intersection-distribution-based remapping algorithm for staggered ALE hydrodynamics on arbitrary meshes

In this study, we introduce new intersection-distribution-based remapping tools for indirect staggered arbitrary Lagrangian-Eulerian (ALE) simulations of multi-material shock hydrodynamics on arbitrary meshes. In addition to conserving momentum and total energy, the three-stage remapper proposed in this work preserves non-negativity of the internal energy. At the first stage, we construct slope-limited piecewise-linear reconstructions of all conserved quantities on zones of the source mesh and perform intersection-based remap to obtain bound-preserving zonal quantities on the target mesh. At the second stage, we define bound-preserving nodal quantities of the staggered ALE discretization as convex combinations of corner quantities. The nodal internal energy is corrected in a way which keeps it non-negative, while providing exact conservation of total energy. At the final stage, we distribute the non-negative nodal internal energy to corners, zones and materials using non-negative weights. Proofs of positivity preservation are provided for each stage. This work is a natural extension of our paper [14] in which a similar intersection-distribution-based remapping procedure was employed. The original version used a nodal kinetic energy fix which did not provably ensure positivity preservation for the zonal internal energy after the final distribution stage. The new algorithm cures this potential drawback by using ‘coordinated’ limiters for piecewise-linear reconstructions, remapping the internal energy to nodes and correcting it before redistribution. The effectiveness of the new nodal fix is illustrated by numerical examples.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2021

Applications of Kinetic Methods in Thermal Analysis: A Review

Determining kinetic parameters such as activation energy (Ea), pre-exponential factor (A), rate constants, and reaction order (n) via thermal analysis techniques is important to material synthesis and fabrication, industrial production, biomedicals, energy storage, catalysis, etc. Various kinetic methods based on the non-isothermal techniques have been developed to obtain the kinetic parameters. In this review, we focus on introducing various kinetic methods in non-isothermal analysis and their applications in different reactions, including thermal decomposition, solid-state phase transformation, crystallization, thermal ignition, curing process, etc.

Zhang, Xin↗
DOE OSTI2024

On the cogent formulation of an elastomeric silicone ink material for direct ink write ( DIW ) 3D printing

Abstract Adhesives and sealants show fine rheology with good physical and mechanical properties as viscous pastes, a possible starting point for developing direct ink writing (DIW) 3D printing ink. However, many commercial adhesives and sealants take days or weeks to cure fully. DIW 3D‐printed parts made directly from these sealants are not designed for a scalable manufacturing process and high‐volume production. Moreover, most of these adhesives and sealants have volume shrinkage during cure. A systematic understanding of formulation methods and design principles for an elastomeric silicone DIW ink can overcome these issues. This study presents the cogent formulation development of a 3D printable thermoset elastomer silicone that gels and cures isotropically in minutes, reducing cycle time for rapid ink development with no shrinkage during cure. More specifically, we outline the principles of raw material selection of a formulation to achieve excellent rheology, printability, synchronized working, and gel time fitting requirements closer to scalable manufacturing. The reaction kinetics and their corresponding 3D‐printed structural properties are also described. Interest in future work is toward a rational DIW 3D printing ink material development protocol and use of machine learning (ML). Highlights Formulation method flexibility and design principle of DIW ink. Raw material selection principle to achieve optimal rheology for DIW printing. Ink gel kinetics for large‐scale DIW manufacturing. Hydrosilylation conversion over time at different ambient temperatures. Structural properties of DIW 3D printed parts.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Towards ternary binders involving limestone additions — A review

The review summarises literature to examine the transition from portland limestone cement system to composite ternary binder systems involving limestone. Interest in limestone addition as an ideal component in multicomponent binder systems has surged as evident from the large volume of literature published in the recent past. A ternary blended system, with co-substitution of limestone, has the potential to complement the reaction of the supplementary cementitious materials (SCMs). The direct addition of limestone powder helps to attain higher substitution levels of portland cement clinker, improve early age properties, and supplement SCM's reactivity. However, the dilution of hydrates could hamper the long-term benefits. In this review, the interaction of fine limestone is classified and elaborated under two broad umbrellas: physical and chemical interactions. The physical interactions can manifest in three ways, namely, filler action, shearing action and improved packing, which alters reaction rate and extent at early ages. The chemical interactions also modify the reaction kinetics and phase assemblage due to nucleation of C-S-H on calcite surfaces, preservation of the ettringite phase and formation of carboaluminates. Two different forms of carboaluminate hydrates — hemicarboaluminate and mono-carboaluminate can be present in the hydrate matrix depending on the balance between carbonate ions and aluminates in the pore solution. Several factors such as replacement level, particle size, choice of SCM, its reactivity and reactive aluminates content, sulphate levels, curing temperature, and duration of curing can control the carboaluminate formation, reaction degree of SCMs and chemical interaction from limestone additions. A combination of physical and chemical effects makes fine limestone a potential material for co-substitution with aluminosilicate based SCMs, mainly fly ash, slag, and calcined clay. In this review, the factors affecting limestone-SCM composites are summarised based on a detailed literature survey. The effects of SCM-limestone cement composites on hydration kinetics, reaction chemistry, the reactivity of SCMs, the stability of hydrated phases, and contribution to the physical structure development and macroscopic properties by evaluating hydration and mechanical properties are discussed. The importance of AFm (Al{sub 2}O{sub 3}–Fe{sub 2}O{sub 3}-mono) phases in various deterioration mechanisms in concrete and their influence on performance characteristics in different exposure environment is critically appraised.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Topology-Informed Design Rules for Deconstructable Thermoset Copolymer Networks

Existing models of thermoset deconstruction facilitated by incorporating cleavable comonomers rely on a mean-field reverse gel point paradigm, which predicts network dissolution once cleavable bonds reach a critical stoichiometric threshold, but does not account for where those bonds reside within the network architecture. Using reactive coarse-grained molecular dynamics simulations coupled with graph-theoretic analysis, we extend this stoichiometric picture to show that deconstructability is governed by the curing-imprinted network topology rather than stoichiometry alone. This topological organization is hierarchical: at the local scale, the elastic effectiveness of cross-link junctions determines which cross-links constitute the load-bearing scaffold; at the mesoscale, the cross-linking rate kinetically templates that scaffold into topologically modular communities─densely cross-linked clusters connected by sparse bridging strands that sustain network connectivity. Using betweenness centrality to identify nodes that disproportionately lie on intercommunity shortest paths, we demonstrate that effective deconstruction of the network into macromolecular fragments requires cleavable comonomers to intercept these high-centrality bridging strands. We further find that under uniform, disassortative comonomer incorporation, this topological requirement provides a mechanistic basis for extending the reverse gel point to incorporate network topology. We also show that modularity imposes a fundamental limit on fragment uniformity that persists even when the centrality requirement is met. Finally, we demonstrate that chain stiffness provides a nearly independent lever to suppress mechanically redundant cross-links and raise the glass transition temperature without significantly altering the deconstruction outcome. Together, these findings reframe the thermoset design space around network topology and provide actionable guidelines for engineering thermoset copolymers with predictable deconstructability and targeted thermomechanical performance.

coarse-grained molecular dynamics↗
DOE OSTI2022

Plastic Scintillators via Rapid Photoinitiated Cationic Polymerization of Vinyltoluene

Cationic photopolymerization is applied for the rapid curing of a vinyltoluene and fluorophore solution into an efficient plastic scintillator. A hard solid is obtained via UV light-initiated polymerization of vinyltoluene, diaryliodonium salt, 9,9-dimethyl-2-phenylfluorene (PhF), and 9,9-dimethyl-2,7-distyrlfluorene (SFS) at ambient conditions with high conversion rates under a range of cationic photoinitiator concentrations, fluorophore concentrations, and light intensities. Insight into photopolymerization kinetics via photo differential scanning calorimetry (photoDSC) revealed photocuring time scales similar to those achieved in a commercial 3D printing resin. Furthermore, scintillator samples prepared cationically performed well compared to samples of equivalent compositions prepared by a lengthy thermally initiated radical polymerization.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Holistic Microstructure Control Strategies in Photopolymerization‐Induced Phase Separation of Acrylate Systems

Open porous materials, known for their large surface area and interconnected structures, are essential in various applications, including batteries, ion exchange, catalysis, filtration, and electronic waste recycling. A critical aspect of the functionality of porous membranes is the precise control of pore size and morphology. Photopolymerization-induced phase separation (photo-PIPS) offers a convenient and versatile methods for creating porous structures. However, controlling the porous morphology remains challenging due to the complex interplay between thermodynamics, polymerization kinetics, and monomer structures, which makes it difficult to establish the relationship between processing conditions and resulting morphology in photo-PIPS. Herein, a physics-based phase-field model capable of generating and characterizing the microstructures of porous materials based on both average and localized features is developed. Using the phase-field simulations as test bed, the effects of polarity, light intensity, and curing temperature, as well as the previously unexplored roles of chain transfer agents and substrates, on the morphology of the resulting porous microstructure are investigated. Experiments are performed to verify the results predicted by the simulations. This work lays out a comprehensive guide for designing PIPS-derived porous microstructures and offers practical engineering strategies for tailoring microstructure-level topology and size of pores for application-specific needs.

36 MATERIALS SCIENCE↗
DOE OSTI2020

The molecular basis of pyrazinamide activity on Mycobacterium tuberculosis PanD

Pyrazinamide has been a mainstay in the multidrug regimens used to treat tuberculosis. It is active against the persistent, non-replicating mycobacteria responsible for the protracted therapy required to cure tuberculosis. Pyrazinamide is a pro-drug that is converted into pyrazinoic acid (POA) by pyrazinamidase, however, the exact target of the drug has been difficult to determine. Here we show the enzyme PanD binds POA in its active site in a manner consistent with competitive inhibition. The active site is not directly accessible to the inhibitor, suggesting the protein must undergo a conformational change to bind the inhibitor. This is consistent with the slow binding kinetics we determined for POA. Drug-resistant mutations cluster near loops that lay on top of the active site. These resistant mutants show reduced affinity and residence time of POA consistent with a model where resistance occurs by destabilizing the closed conformation of the active site.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

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↗
DOE OSTI2023

Unexpected Thermomechanical Behavior of Off-Stoichiometry Epoxy/Amine Materials

Recent studies on off-stoichiometric thermosets reveal unique viscoelastic behavior derived from increased free volume and physical interactions between chain ends. To understand structural characteristics arising from cure and its effect on properties, we developed a Monte Carlo model based on step-growth polymerization. Our model accurately predicted structure–property trends for a two-component system of EPON 828 (EPON) and ethylenediamine. A second epoxy monomer, D.E.R. 732 (DER), was investigated to modulate T g . Binary mixtures of EPON and DER in off-stoichiometric, amine-rich formulations resulted in nonlinear evolution of thermomechanical properties with respect to initial formulation stoichiometry. Modifying our model with kinetic parameters allowing for differential epoxide/amine reaction kinetics only partially accounted for trends in T g , suggesting that spatiotemporal contributions-not captured by our model-were significant determinants of material properties compared to polymer architecture for three-component systems. Here these findings underpin the importance of spatial awareness in modeling to inform the development of dynamic thermosets.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Rapid curing dynamics of PEG-thiol-ene resins allow facile 3D bioprinting and in-air cell-laden microgel fabrication

Thiol-norbornene photoclick hydrogels are highly efficient in tissue engineering applications due to their fast gelation, cytocompatibility, and tunability. In this work, we utilized the advantageous features of polyethylene glycol (PEG)-thiol-ene resins to enable fabrication of complex and heterogeneous tissue scaffolds using 3D bioprinting and in-air drop encapsulation techniques. We demonstrated that photoclickable PEG-thiol-ene resins could be tuned by varying the ratio of PEG-dithiol to PEG norbornene to generate a wide range of mechanical stiffness (0.5–12 kPa) and swelling ratios. Importantly, all formulations maintained a constant, rapid gelation time (<0.5 s). We used this resin in biological projection microstereolithography (BioPµSL) to print complex structures with geometric fidelity and demonstrated biocompatibility by printing cell-laden microgrids. Moreover, the rapid gelling kinetics of this resin permitted high-throughput fabrication of tunable, cell-laden microgels in air using a biological in-air drop encapsulation apparatus (BioIDEA). We demonstrated that these microgels could support cell viability and be assembled into a gradient structure. This PEG-thiol-ene resin, along with BioPµSL and BioIDEA technology, will allow rapid fabrication of complex and heterogeneous tissues that mimic native tissues with cellular and mechanical gradients. The engineered tissue scaffolds with a controlled microscale porosity could be utilized in applications including gradient tissue engineering, biosensing, and in vitro tissue models.

36 MATERIALS SCIENCE↗