Engineering PapersSearch

SEARCH · Engineering Papers

Results for “crosslinking”

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 55 records · Page 3

Development of Tailored Hydrocarbon-Based Pentablock Copolymer Membranes for Sodium-Polysulfide Flow Batteries

Long-duration energy storage (LDES) technologies are pivotal for the adoption of renewables like wind and solar. Non-aqueous redox flow batteries (NARFBs) with a sodium-polysulfide hybrid system feature high energy density independent of power density, yet face challenges with polysulfide shuttling. This study investigates a hydrocarbon-based penta-block copolymer membrane, Nexar, to mitigate crossover effects by balancing TFSI conversion and their crosslink density. The membranes are annealed to induce crosslinking for reducing electrolyte uptake and enhancing mechanical stability while demonstrating excellent ionic conductivity. The hydrocarbon-based membranes address environmental concerns associated with perfluoroalkyl substances and improve the performance and durability of NARFBs. In conclusion, our findings suggest that annealed Nexar membranes with tailored TFSI functionality offer a scalable, cost-effective solution for enhancing the efficiency of high-capacity energy storage systems, pivotal for grid integration of renewable sources.

25 ENERGY STORAGE

Chemically Recyclable Polyester Thermosets from Activated Adipic Acid and Renewable Polyols

This study outlines a method for producing chemically recyclable crosslinked polyesters using renewable polyols-glycerol and sorbitol-combined with adipic acid (AA), which is transformed/activated into a polyanhydride mixture prior to use. A three-step procedure has been designed: 1) an acid-catalyzed reaction of AA with nontoxic isopropenyl acetate or acetic anhydride to form a crosslinking mixture (CLM) made of adipic-acetic mixed polyanhydrides; 2) a solvent- and additive-free process where glycerol or sorbitol, or a combination thereof, is reacted with the CLM to achieve a prepolymer, and 3) a casting/molding of the liquid viscous prepolymer to yield a thermoset as the end product. Different thermosets (eight examples) are prepared by changing the reagents ratio. These solids are thoroughly characterized by tensile tests, DMA, high-resolution magic angle spinning and solid-state NMR, thermal gravimetric analysis, DSC, and fourier transformed infra red (FT-IR) spectroscopy. The formation of cross-linked polyesters is confirmed in all cases, but mechanical properties varied significantly from one specimen to another. Interestingly, a tensile strength up to 18 MPa-approximately an order of magnitude higher than similar polymers-is achieved when sorbitol and the CLM are used in a 1:1 wt% ratio. The chemical recycle of the resulting polymers is achieved via methanolysis with quantitative recovery of the monomeric units.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Integrated structural model of the palladin–actin complex using XL ‐ MS , docking, NMR , and SAXS

Abstract Palladin is an actin‐binding protein that accelerates actin polymerization and is linked to the metastasis of several types of cancer. Previously, three lysine residues in an immunoglobulin‐like domain of palladin have been identified as essential for actin binding. However, it is still unknown where palladin binds to F‐actin. Evidence that palladin binds to the sides of actin filaments to facilitate branching is supported by our previous study showing that palladin was able to compensate for Arp2/3 in the formation of Listeria actin comet tails. Here, we used chemical crosslinking to covalently link palladin and F‐actin residues based on spatial proximity. Samples were then enzymatically digested, separated by liquid chromatography, and analyzed by tandem mass spectrometry. Peptides containing the crosslinks and specific residues involved were then identified for input to the HADDOCK docking server to model the most likely binding conformation. Small‐angle x‐ray scattering was used to provide further insight into palladin flexibility and the binding interface, and NMR spectra identified potential interactions between palladin's Ig domains. Our final structural model of the F‐actin:palladin complex revealed how palladin interacts with and stabilizes F‐actin at the interface between two actin monomers. Three actin residues that were identified in this study also appear commonly in the actin‐binding interface with other proteins such as myotilin, myosin, and tropomodulin. An accurate structural representation of the complex between palladin and actin extends our understanding of palladin's role in promoting cancer metastasis through the regulation of actin dynamics.

Sargent, Rachel [Department of Chemistry and Bioch

Backbone Stiffness‐Dependent Photoluminescence of Pendant Fluorophores in Organic Nanoparticles

Fluorescent organic nanoparticles (FoNPs) with backbone stiffness‐dependent photoluminescence were synthesized via microemulsion atom transfer radical polymerization (ATRP) of 2‐(2‐bromoisobutyryloxy)ethyl methacrylate (BiBEM), ethylene glycol dimethacrylate (EGDMA), and methacrylate monomers bearing pendant fluorophores, 1‐pyrenemethyl methacrylate (PyMMA), or 4‐(1,2,2‐triphenylethenyl)benzenemethyl methacrylate (TPEMMA). The crosslinking density precisely tuned the intraparticle rigidity, enabling systematic control over emission mechanisms. Pyrene‐containing FoNPs exhibited a rigidity‐dependent transition from excimer‐dominated to monomer‐dominated fluorescence, whereas TPE‐based FoNPs displayed aggregation‐induced emission (AIE) enhancement as intramolecular motion was restricted. Solvent‐dependent studies revealed that increased polarity and viscosity, particularly in benzyl alcohol and DMSO, promoted cooperative rigidification and enhanced emission intensity through specific polymer–solvent interactions. Furthermore, the retained alkyl bromide chain ends on FoNPs enabled dual roles as initiators and crosslinkers in UV‐induced polymerization of poly(ethylene glycol) acrylates, forming luminescent FoNP–OEG hybrid gels with improved mechanical robustness. This work establishes a versatile platform for integrating tunable optical and mechanical properties into a single polymeric nanoparticle framework, offering new design principles for multifunctional soft materials and providing a platform for future sensing, imaging, and photonic applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Growth-induced Donnan exclusion influences swelling kinetics in highly charged dynamic polymerization hydrogels

Polymeric gels crosslinked by DNA sequences can exploit DNA strand-displacement reactions to promote swelling through dynamic polymerization. The degree of swelling and the rate of swelling must be directly tunable to achieve the promise of programmable soft matter. Though the kinetics of the strand-displacement reaction provide insertion rates up to 10 4 /Molar/second as measured in bulk solution, DNA hydrogel swelling can take upwards of 30 h to complete. Computational modeling of the reaction-induced swelling of these gels with our recently-developed reactive electrochemomechanical theory (Zimmerman et al., 2024) suggests that their extraordinarily slow swelling is partly due to a scaling mismatch between the addition of charge and the addition of fluid volume, leading to a large transient increase in the fixed charge density. The significant increase in the gel’s fixed charge density, due to the binding of negatively charged DNA, sharply restricts the concentration of mobile hairpins through the phenomenon of Donnan charge exclusion, an effect commonly exploited in nanofiltration applications using polymeric membranes. The scaling problem is overcome when the mean additional swelling provided to the hydrogel by addition of a crosslink is above a critical value, thus the swelling outpaces the charge accumulation, leading the fixed charge density to drop and significantly accelerating the swelling process. This study shows that Donnan exclusion can explain the kinetics of DNA hydrogel swelling, and studies ways to modulate the reaction speed by either modifying the salt concentration or increasing or decreasing the number of base pairs in each DNA sequence.

42 ENGINEERING

Structure-performance relationships in lignin-based transesterification vitrimers: The role of lignin structural features

Lignin has been hailed as an ideal renewable alternative for petrochemical-based prepolymers in material synthesis for a sustainable and circular economy, due to its abundant aromatic network and high carbon content. However, the properties and performance of lignin-derived macromolecules are strongly influenced by the lignin itself. While numerous studies have explored the impact of lignin content on the thermomechanical performance of lignin-based vitrimers, literature on how the inherent structural features of lignin affect these properties is scanty. In this study, hardwood organosolv lignin was fractionated in ethyl acetate, ethanol, and acetone to obtain lignin fractions with varying structural characteristics. These fractions were then modified through carboxylation and crosslinked with epoxidized soybean oil (ESO) at a hydroxyl to epoxy group ratio of 1:1 to produce lignin-based transesterification vitrimers (LVs). The thermal properties (i.e. glass transition temperature and thermal stability), tensile strength, storage modulus, and stress relaxation behavior of the LVs were studied and carefully related to the structural features of lignin. The results revealed a positive relationship between strong hydroxyl content in modified lignin and the tensile strength (5.10–9.71 MPa), storage modulus (1099.4 – 1372.8 MPa), crosslinking density, and stress relaxation of the LVs. Additionally, both the storage modulus and tensile strength exhibited a positive relationship with the ratio of rigid linkages in modified lignin, while lignin molecular weight was found to significantly impact the thermal properties of LVs (i.e Tg and thermal stability). This study not only highlights the valorization of lignin in vitrimer synthesis but also provide insights for designing lignin-based materials with tailored properties for specific applications.

Bio-based polymer

Ammonium-coordinated exchanger (ACE) functionalized silica sorbents for recovering/removing aqueous anionic contaminants

There are limited studies of functionalized silica anion exchange sorbents used for critical/heavy metal recovery/removal relative to polymeric and other inorganic materials. This work features ammonium-coordinated exchanger (ACE) anion exchange particle sorbents prepared by either acid-washing epoxy-crosslinked polyethylenimine (PEI) hydrogen bonded within/to a silica particle sorbent (two-step method) or reacting a di-chlorinated crosslinker, α,α-dichloro-p-xylene (DPX), with PEI within silica (single-step method). Energy dispersive X-ray spectroscopy (EDS) and infrared spectroscopy confirmed the presence of -NH 2 + ···Cl - and -NH 3 + ···Cl - groups, which removed oxyanionic species –arsenate, selenate, chromate, sulfate, phosphate, and nitrate– plus bromide from ideal solutions, authentic acid mine drainage (AMD), and authentic flue gas desulfurization (FGD) wastewater. Affinity of the anions for ACE varied across single- and mixed-element solutions. However, affinity for CrO 4 2- was among the highest in both cases. Total anion uptake by the optimized ACE, PEI-E3-HCl_1.1, reached 1.2 mmol anion/g-sorb. (0.56 mmol CrO 4 2- /g), or ∼2.3 mmol negative charge/g-sorb. This was close to the 0.52 mmol CrO 4 2- /g of a commercial anion exchange resin. Near-consistent removal of 20–80 % of each anion from FGD during an eight-cycle adsorption-desorption (1 M NaCl) test predicted good ACE viability for testing under practical conditions at larger scale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Non-equilibrium simulations of hydraulic permeation: Role of mechanical boundary conditions in dense membranes

Understanding the mechanisms of water transport in reverse osmosis membranes is critical for improving membrane performance and guiding material design. While classical models describe transport as either solution-diffusion (SD)—involving concentration-driven diffusion through a homogeneous medium—or pore-flow (PF)—involving pressure-driven convection through percolated water channels—their applicability to crosslinked polyamide membranes remains debated. Here, using non-equilibrium molecular dynamics simulations, we investigate the impact of mechanical support conditions on pressure-driven water transport in polyamide membranes across varying crosslink densities and pressure differentials (1000–5000 bar). Two support conditions are considered: graphene-restrained, representing experimentally relevant supported membranes, and freeze-restrained, mimicking a self-supported structure. In graphene-restrained systems, water concentration gradients and constant pressure profiles emerge, consistent with SD theory and incompatible with PF assumptions due to the absence of percolated pores and sub-nanometer voids. In contrast, freeze-restrained systems display uniform water concentration and linearly decreasing pressure at 1000 bar, and exhibit compressibility-induced water gradients and partial percolation at 5000 bar, resembling PF-like behavior. However, the underlying assumptions of PF theory—continuous solvent pathways and pressure transmission through water-filled pores—are not met under most conditions. Our results demonstrate that accurate modeling of reverse osmosis membranes must incorporate realistic mechanical boundary conditions to distinguish between transport mechanisms. For dense polyamide membranes supported by porous substrates, graphene-restrained simulations best reflect experimental setups and support the SD model as the dominant mechanism of water permeation.

molecular dynamics

Self-Assembly Driven Microlithography via Near-Infrared Light Activation

Current vat photopolymerization (VP) relies on UV or visible light to start the rapid crosslinking of liquid photocurable resins into 3D-printed structures. Here, we develop a self-assembly-driven photopatterning approach to photothermally generate polymeric solids by combining thermoplasmonic nanoparticles and thermoresponsive polymers, in which near-infrared (NIR) light activates thermoplasmonic heating of nanoparticles, triggering the irreversible self-assembly of thermoresponsive polymers into insoluble mesoglobules. A small amount of thermal initiator and crosslinker leads to irreversible self-assembly of polymer nanocomposites. NIR light offers deeper penetration and reduced scattering compared to UV, enabling more uniform curing of thicker or filled materials and expanded process control for composites or opaque systems. Thermoplasmonic heat generation is achieved using surface-modified gold nanorods (AuNRs) with a longitudinal localized surface plasmon resonance peak in the NIR region. Key variables such as polymer composition, molecular weight, physical interactions at the nanoparticle–polymer interface, which can be tuned by surface functionalization, AuNR concentration, and pH can be used to tailor the assembly behavior of these systems, including photothermal effect, flocculation, and cloud point temperature, and the mechanical properties of the final structures. Collectively, these results highlight a platform for photothermally-driven microlithography of polymer solids with diverse, tunable macroscopic properties, enabled by low-energy NIR light-activated self-assembly.

36 MATERIALS SCIENCE

Epoxy-based vitrimeric semi-interpenetrating network/MXene nanocomposites for hydrogen gas barrier applications

Herein, we report MXene-filled epoxy-based vitrimeric nanocomposites featuring a semi-interpenetrating network (S-IPN) to develop a hydrogen gas (H 2 ) barrier coating with self-healing characteristics for compressed H 2 storage applications. The reversible epoxy network was formed by synthesizing linear epoxy chains with pendent bis-hydroxyl groups using amino diol, which were then crosslinked with 1,4-benzenediboronic acid to generate dynamic boronic ester linkages. To achieve the S-IPN-type molecular arrangement, the epoxy chains were in situ crosslinked in the presence of poly(ethylene-co-vinyl alcohol) (EVOH), giving rise to a self-healing network (EEP) with a healing efficiency of 87%. Into the S-IPN vitrimer (EEP), a 2D platelet-type nanofiller MXene was incorporated to introduce a tortuous path for H 2 gas diffusion along with improved mechanical properties. The nanocomposite coating was applied to nylon 6 liner material, which is conventionally used in all-composite H 2 storage vessels. Further, the application of a 2 wt% MXene/EEP nanocomposite coating showed a permeability coefficient of 0.062 cm 3 mm m -2 d -1 atm -1 exhibiting ~96% reduction in gas permeability compared to uncoated nylon 6. The same nanocomposite exhibited a healing efficiency of 79%. Increasing the MXene loading to 10 wt% further reduced the permeability coefficient to 0.002 cm 3 mm m -2 d -1 atm -1 ; however, the healing efficiency decreased due to restricted chain mobility. In essence, the current work highlights the potential of vitrimeric S-IPN nanocomposite coatings for H 2 gas-barrier applications, enhancing safety and performance.

42 ENGINEERING

An enzyme-based approach for highly efficient self-replication of DNA origami dimers

Self-replication and exponential growth are essential to all living things, the driving force for Darwinian evolution, and potentially useful in nanotechnology for large-scale production of nanoscopic materials. An artificial (nonliving) self-replication system has been shown to exhibit exponential growth and selection using DNA monomer origami tiles templated on a dimer seed. That system purposefully avoided the use of enzymes to get a hint of how self-replication might have evolved in a prebiotic world by using CNV K and UV light to crosslink complementary DNA single strands. For further investigations into competition and extinction and for potential applications involving biocompatibility, we wanted to investigate enzymatic ligation to replace the chemical photo crosslinking step. Here, we present a system which uses thermotolerant T4 DNA ligase and no UV. This system has several additional advantages including a much faster cycling time, yielding 2,000,000 amplifications in 12 h. We also introduce competition to study the possibility of Darwinian-like evolution. Two pairs of DNA origami tiles compete for the same connection strands and show different growth rates under different connection strand concentrations. This system has the potential to combine with other enzymes, such as RNA polymerase to support feedback, allowing us to fine-tune replication dynamics and achieve sophisticated, life-like behaviors. The highly efficient self-replication and exponential growth of DNA origami dimers demonstrated in this work not only enhances our understanding of Darwinian evolution in nature but also opens the door to applications ranging from synthetic biology to smart materials.

Science & Technology - Other Topics

Alginate–Amorphous Calcium Carbonate Hydrogels for Controlled Therapeutic Release

Alginate hydrogels are widely explored as biocompatible matrices for transdermal delivery of therapeutic compounds but burst release and mechanical stability remain persistent challenges in drug delivery systems. This experimental study investigated alginate–amorphous calcium carbonate (ACC) hydrogel composites designed to regulate release of model anti-inflammatory compound, ibuprofen. Hydrogels containing 1.6–2.0 wt% sodium alginate were crosslinked with CaCl₂ and combined with ACC through two incorporation pathways: (i) separate addition of ACC and ibuprofen or (ii) co-precipitation of ACC onto ibuprofen prior to hydrogel incorporation. Hydrogels without ACC served as Control. Biocomposite structure and properties were characterized and release profiles quantified using Korsmeyer–Peppas (KP) model.Burst release was curbed as crosslinking time increased, highlighting importance of network density in diffusion control. Co-precipitating ACC with ibuprofen prior to incorporating into the hydrogel suppressed burst release and sustained release for > ~72 h. Rheological measurements indicate ACC reinforces hydrogel network, increasing storage modulus while maintaining hydration and flexibility. KP model indicates release is diffusion-controlled, with deviations reflecting contributions from diffusion barriers and morphologic/structural changes near the ACC coated ibuprofen. ACC within alginate hydrogels provides a strategy for tuning drug release while preserving mechanical properties relevant to transdermal applications.

36 MATERIALS SCIENCE

Evaluating Polymer Properties with Different Additives for Carbon Capture and Other Applications

Anthropogenic climate change is one of this generation’s most pressing concerns, with the potential to completely alter the delicate balance we’ve struck with nature. Already, global temperatures have risen 1.29°C, leading to disrupted weather systems, extinctions, increased risks of wildfires, and sea level rise, to name a few effects. Carbon dioxide emission from the combustion of fossil fuels and other industrial activity is a large driver of this phenomenon, as it absorbs heat before it can be radiated away from Earth, trapping it. Carbon dioxide has reached unprecedented levels in our atmosphere, showing a 50% increase from preindustrial averages to a whopping 430 ppm. Thus, reducing the amount of carbon dioxide via carbon capture technology is an important endeavor that serves to benefit everyone. The Microencapsulated CO 2 Sorbent (MECS) team at Lawrence Livermore National Laboratory (LLNL) has turned to microencapsulation to approach this endeavor. Microcapsules provide an attractive approach to carbon capture, combining large surface areas for more efficient mass transfer, regenerative abilities, reduced solvent loss, and improved handling. Additionally, while existing carbon capture technology relies on industrial plants, capsules could present a modular approach to carbon capture, reducing the need for extensive physical infrastructure. The MECS team’s design consists of a polymer membrane that contains a liquid carbon sequestering sorbent, aqueous sodium carbonate. The carbon capturing reaction occurs in three distinct steps, the first of which is the dissolution of carbon dioxide into the sorbent solution and its conversion into carbonic acid (H 2 CO 3 ), shown in equations 1 and 2 respectively. Because this step hinges upon the ability of carbon dioxide to reach the solution inside the capsule, it is necessary that the microcapsule shell is permeable to carbon dioxide gas. The MECS team produces these microcapsules using the in-air droplet encapsulation apparatus (IDEA) shown in figure 1, which can produce uniform micron-scale droplets at speeds much faster than traditional single-dispersal microfluidic-based techniques. The IDEA Is 100 times faster than these current techniques and can reach up to 1000 times their speed when incorporating a multi-nozzle design. Additionally, because droplets are produced in-air via vibration, IDEA can decrease post-processing times and material waste by 99% and can fabricate microgels that are 10 to 100 times more viscous than can be produced via traditional microfluidics. While this design represents a breakthrough in the throughput, efficiency, and tunability of microcapsule production, it imposes a major constraint on the microcapsule curing process. Because microcapsule shells are crosslinked with UV light while falling 30 cm through the air, this gives them a reaction window of approximately 0.2 seconds. Thus, the system and shell formulations must be optimized such that the shells can be fully crosslinked within this very narrow window, prompting investigations into curing behavior.

36 MATERIALS SCIENCE

PET waste- and bio-derived imine vitrimers for shape-memory, intrinsic flame-retardant, and recyclable carbon fiber composites

Developing circular multifunctional vitrimers and carbon fiber–reinforced polymers (CFRPs) that are simultaneously recyclable, mechanically robust, and intrinsically flame retardant remains a major challenge. Here, in this study, we report multifunctional vitrimers and their carbon fiber–reinforced vitrimer (CFRV) composites, where the vitrimer design integrates closed-loop recyclability, enhanced interfacial adhesion, and intrinsic flame retardancy within a single materials platform. The vitrimer matrix is synthesized from post-consumer polyethylene terephthalate (PET) waste and a vanillin-derived phosphorus-containing crosslinker, forming an imine-based network. The resulting vitrimer resin exhibits high tensile strength, thermal healability, repeated reprocessability, programmable shape memory, and rapid chemical depolymerization under mild conditions. Amine-functionalized carbon fibers significantly improve fiber–matrix interfacial bonding, yielding CFRVs with tensile strengths up to 789 MPa and complete recovery of structurally intact fibers after chemical recycling. The phosphorus-rich aromatic network further imparts intrinsic flame retardancy, enabling self-extinguishing behavior without external additives. This work advances a materials design paradigm for next-generation multifunctional, sustainable vitrimers and CFRVs, while simultaneously addressing the recycling challenges associated with both plastic and CFRP waste.

Bio-derived crosslinker

Citric Acid Functionalized Natural Fibers to Enhance Thermal Stability and Moisture Resistance in Polylactic Acid Composites

Cellulosic fibers can impart many unique benefits into composite applications, such as reduced weight or structural reinforcement; however, these materials also increase hygroscopicity and decrease thermal stability, restricting broader applications. The present work adapted an experimental process for functionalizing the cellulose surface using citric acid (CA) for three fibers: a 100% cellulose bleached soft Kraft pulp (e.g., creafill) and two natural fibers with similar composition but different fiber morphology, flax fiber and banana fiber. The process uses CA with a sodium hypophosphite (SHP) catalyst to chemically functionalize fiber surfaces, and the reaction mechanism was investigated through Fourier Transform Infrared Spectroscopy (FTIR), which suggested a grafting mechanism rather than a surface-based crosslinking between neighboring sites. Functionalized fibers were compounded into polylactic acid (PLA) at 20 wt.% to better understand how this functionalization might impact critical performance properties like thermal stability, crystallization, thermal mechanical properties, and water uptake of these composites. The study demonstrated varying levels of efficacy for the functionalization of cellulosic fibers with CA/SHP and the fiber with the most open microstructure, e.g., banana fiber, exhibited the largest change in its properties with a 38% reduction in water uptake compared to untreated banana fiber composites. Parallel evaluation of the functionalization process for different fibers demonstrates the importance of fiber morphology on surface modification and can enable their use in composites by demonstrating the efficacy of this potentially low-cost, low-toxicity method for reducing hygroscopicity and improving thermal stability.

citric acid

Pillared Laminar Vermiculite Membranes with Tunable Monovalent and Multivalent Ion Selectivity

Effective membrane separation of Li + from Na + and Mg 2+ is crucial for lithium extraction from water yet challenging for conventional polymeric membranes. Two dimensional (2D) membranes with ordered laminar structures and tunable physicochemical properties offer distinctive ion-sieving capabilities promising for lithium extraction. Recently, phyllosilicates are introduced as abundant and cost-effective source materials for such membranes. However, their water instability and low inherent ion transport selectivity hinder practical applications. Herein, a new class of laminar membranes with excellent stability and tunable ion sieving is reported by incorporating inorganic alumina pillars into vermiculite interlayers. Crosslinking vermiculite flakes with alumina pillars significantly strengthens interlamellar interactions, resulting in robust water stability. Doping of Na + before the pillaring process reverses the membrane's surface charge, substantially boosting Li + separation from multivalent cations via electrostatic interactions. Lithium extraction is often complicated by the presence of co-existing monovalent cations (e.g., Na + ) at higher concentrations. Here, by introducing excess Na + into the membrane after the pillaring process, the separation of Li + from monovalent cations is enhanced through steric effects. This work realizes both monovalent/multivalent and monovalent/monovalent selective ion sieving with the same membrane platform. A separation mechanism is proposed based on Donnan exclusion and size exclusion, providing new insights for membrane design for resource recovery applications.

2D materials

Multi‐Material Gradient Printing Using Meniscus‐enabled Projection Stereolithography (MAPS)

Light‐based additive manufacturing methods are widely used to print high‐resolution 3D structures for applications in tissue engineering, soft robotics, photonics, and microfluidics, among others. Despite this progress, multi‐material printing with these methods remains challenging due to constraints associated with hardware modifications, control systems, cross‐contamination, waste, and resin properties. Here, a new printing platform coined Meniscus‐enabled Projection Stereolithography (MAPS) is reported, a vat‐free method that relies on generating and maintaining a resin meniscus between a crosslinked structure and bottom window to print lateral, vertical, discrete, or gradient multi‐material 3D structures with no waste and user‐defined mixing between layers. MAPS is compatible with a wide range of resins shown and can print complex multi‐material 3D structures without requiring specialized hardware, software, or complex washing protocols. MAPS's ability to print structures with microscale variations in mechanical stiffness, opacity, surface energy, cell densities, and magnetic properties provides a generic method to make advanced materials for a broad range of applications.

bioprinting

Hybrid Additive and Subtractive Manufacturing of Dual‐Wavelength Photopolymer Thermosets

Additive manufacturing (AM) techniques such as digital light processing (DLP) AM and stereolithography enable the production of highly complex structures with speed and ease as not previously possible. However, many traditional thermosetting photopolymers used in these processes result in a permanently crosslinked structure incapable of being broken down or modified without the use of energy-intensive processes such as mechanical machining or ablation. To overcome this limitation, this production is described of thiol-ene photopolymer thermosets with dual-wavelength photopolymerization and photodegradation reaction pathways. The dual wavelength selectivity of the polymerization (405 nm) and degradation (365 nm) processes, combined with dual-wavelength DLP AM technology, enables hybrid manufacturing with the ability to add and sequentially subtract material with excellent spatiotemporal control. 2D lithographs and complex 3D architectures with soft elastomeric properties are produced with resolutions as small as 50 µm. Furthermore, the ability to selectively subtract supports from 3D printed structures with deliberate and accurate control is demonstrated. In conclusion, the ability to correct or modify existing structures enables a new paradigm of adaptable materials for corrective manufacturing techniques and temporary structures.

3D Printing