Bio-based lactone acrylic plastics with performance and recyclability advantages
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36 MATERIALS SCIENCE↗
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Influence of fluorescent dopants on the vat photopolymerization of acrylate-based plastic scintillators for application in neutron/gamma pulse shape discrimination
Plastic scintillators, a class of solid-state materials used for radiation detection, were additively manufactured with vat photopolymerization. The photopolymer resins consisted of a primary dopant and a secondary dopant dissolved in a bisphenol A ethoxylate diacrylate-based matrix. The absorptive dopants significantly influence important print parameters, for example, secondary dopants decrease the light penetration depth by a factor > 12×. The primary dopant 2,5-diphenyloxazole had minimal impact on the printing process even when loaded at 25 % by mass of the resin. Working curve measurements, which relate energy dose to cure depth, were performed as a function of feature size to further assess the influence of dopants. Photopatterns smaller than 150 µm width had apparent increases in critical energy dose compared to larger photopatterns, while all resins maintained printed features in line gratings with 50 µm of separation. Printed scintillator monoliths were compared to scintillators cast by traditional molding, demonstrating that the layer-by-layer printing process does not decrease scintillation response. In conclusion, a maximum light output of 31 % of a benchmark plastic scintillator (EJ-200) and successful pulse shape discrimination were achieved with 20 % by mass 2,5-diphenyloxazole as the primary dopant and 0.1 % by mass 9,9-dimethyl-2,7-distyrylfluorene as the secondary dopant in printed scintillator samples.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Transition from Vogel-Fulcher-Tammann to Arrhenius Ion-Conducting Behavior in Poly(Ethyl Acrylate)-Based Solid Polymer Electrolytes via Succinonitrile Plasticizer Addition
Solid polymer electrolytes (SPEs) offer potential advantages over liquid electrolytes, including flexibility, safety, and processability. However, they suffer from low room-temperature ionic conductivity. Recently, it has been reported a poly(ethyl acrylate) based (polyEA) SPE, by incorporating 50 wt% of succinonitrile (SN) solid plasticizer, 30 wt% of lithium salt and 5 wt% of fluoroethylene carbonate additive, which achieves a high room-temperature ionic conductivity of 1.01 × 10 −3 S cm −1 (Nat. Nanotechnol, 2022, 17, 768-776). This novel SPE exhibits stability against Li 0 and anodic stability up to 4.9 V vs Li + /Li. However, the specific mechanism responsible for its high ionic conductivity remains elusive. In this work, by adjusting the weight ratio of SN in the SPE, a transition from Vogel-Fulcher-Tammann to Arrhenius ion-conducting behavior is observed. It is demonstrated that the addition of SN leads to the gradual decoupling of Li-ion from the polymer backbone and its coordination with SN, as revealed by 6 Li solid-state nuclear magnetic resonance spectroscopy. As a result, Li-ion migration primarily occurs through SN rather than the segmental motion of the polymer backbone. Performances of the SPE in Cu||Li, Li||Li and a LiFePO 4 ||Li pouch cells are shown to demonstrate the commercial viability of this SPE in Li 0 -anode solid-state batteries.
Electrochemistry↗
Hybrid epoxy–acrylate resins for wavelength-selective multimaterial 3D printing
Structures in nature have evolved to combine hard and soft materials in precise 3D arrangements, which imbues bulk properties and functionality that remain elusive to mimic synthetically. However, the potential for biomimetic analogs to seamlessly interface hard materials with soft surfaces for applications ranging from robotics and sealants to medical devices (e.g., prosthetics and wearable health monitors) has driven the demand for innovative chemistries and manufacturing approaches. Herein, we unveil a liquid resin for rapid, high resolution digital light processing (DLP) 3D printing of multimaterial objects with an unprecedented combination of strength, elasticity, and resistance to aging. Two enabling discoveries are the use of a covalently bound (hybrid) epoxy-acrylate monomer that precludes plasticization of soft domains and a wavelength-selective photosensitizer that accelerates cationic curing for hard domains. Using dual projection for multicolor DLP 3D printing (UV and violet light), several bioinspired metamaterial structures are fabricated, including one with hard springs embedded in a soft cylinder to adjust compressive behavior and a detailed knee joint featuring “bones” and “ligaments” for smooth motion. Lastly, the application of this system to facilitate selective stretching for electronic devices is demonstrated with a proof-of-concept device.
36 MATERIALS SCIENCE↗
Experimental Investigation on the Performance Loss of Cross-Linked Polymers During Photo-Oxidative Aging
Abstract Polymeric substances have seen an unprecedented integration in countless applications and fields of life, subjecting them to a broad range of environmental conditions, which can cause a form of damage to the structural and mechanical properties of these components known as aging. In this study we investigate the effects of the degradation of polymeric materials due to the extended exposure to sunlight, which can be simulated through controlled photo-oxidative aging using ultraviolet (UV) radiation as the main catalyst of this phenomenon. The effects on mechanical behavior and chemical properties of four polymeric materials with different mechanical characteristics was accordingly monitored throughout the study. The materials range in hardness with the polyurethane adhesive being the hardest and acting plastically, followed by an acrylic which exhibits greater hardening with time, a polyurethane sealant, which behaves in an elastomeric manner, and a silicon sealant, which is the softest of the set. Samples were prepared and subjected to UV radiation at three different temperatures namely 45, 60 and 80°C, for different aging periods ranging from 1 day for higher temperatures to 150 days for lower ones. The samples were then subjected to the Fourier transform Infrared spectroscopy (FTIR) test to monitor the change in the chemical composition of the materials along the aging durations and conditions. The materials were then subjected to mechanical testing along two modes of mechanical loading, which are a simple tension until failure and a double-cyclic test with progressively increasing strain limits after every two successful cycles until the sample reaches failure. The samples are loaded at constant strain rates throughout both tests. These tests revealed the change of behavior of our materials along the aging periods and conditions. The changes in mechanical behavior vary across each individual material depending on the aging temperature and period, with the changes ranging from hardening to softening, embrittlement or an increase in the maximum strain the material can endure before failure. A general trend would be that most materials become harder after photo-oxidation, however due to the range of temperatures in the aging conditions, thermo-oxidation, which causes softening in some of the polymers, has an increasingly notable effect at higher temperatures. A visible correlation can be noted between the change in mechanical behavior and a change in absorbance of Infrared Radiation (IR) in the FTIR spectrum, as the greater the crosslinking throughout the polymer matrix, the lower the absorbance of IR radiation due to the increased stiffness of the overall macro-molecular structure.
Korayem, Abd-Elrahman↗
Analyzing Next-Generation Supply Chains Using the Materials Flows through Industry Tool
The Materials Flows through Industry (MFI) tool is a supply chain modeling tool developed at the National Renewable Energy Laboratory (NREL) with funding from the Department of Energy's Advanced Manufacturing Office. MFI was created to identify and analyze opportunities to reduce the energy and carbon intensities of the U.S. industrial sector (Hanes and Carpenter 2017). In this work, we present an overview of the MFI tool's structure and capabilities, as well as the results of using MFI to analyze a novel NREL-developed process to 'upcycle' PET plastic into higher-value composite materials (Rorrer et al. 2019). This process combines recycled PET (rPET) plastic with inputs that can be derived from biomass, including muconic acid, acrylic acid, and ethylene glycol, to chemically break down the plastic back to its monomers in a process called glycolization. Then, repolymerization and the application of fiberglass yields the valuable glass fiber reinforced plastic (GFRP) composite, a performance material used in the manufacture of wind turbine blades, boat hulls, and other applications. This rPET-derived GFRP was found to have superior strength and fiberglass adhesion compared to conventional GFRP formulations. Our findings indicate that this GFRP production process, were it to be widely commercialized beyond its current lab-scale, could potentially reduce the fossil energy intensity of the GFRP supply chain by between 37% and 58% compared to the conventional method of GFRP manufacture from fossil-derived inputs. We also estimate potential supply chain greenhouse gas (GHG) emissions reductions between 30% and 40% from this process. Scaling these GHG offset estimates up to annual GFRP production in the U.S. would be roughly equivalent to removing between 150,000 and 200,000 vehicles from U.S. roads. These ranges of impact estimates represent the range of differences associated with the various economic allocation methods we have assumed for the intensity contributions from the first life of the PET plastic. Following Shen et al. (2010), we derive economic allocation factors from the current price ratios of clear- and green-colored recycled PET plastic to virgin PET resin ('waste-valuation' approach) or assume them to be zero in a more simplistic allocation ('cutoff' approach). Future work involving the MFI modeling tool will also be discussed, including preliminary results comparing the energy intensity of conventional and bio-based nylons manufacturing. Attendees will also be encouraged to conduct MFI supply chain modeling of their own by requesting a user account on the MFI web application, which is freely available to the public at the following address: https://mfitool.nrel.gov.
36 MATERIALS SCIENCE↗
Melt-Spun PAN Precursor for Cost-Effective Carbon Fibers in High Pressure Compressed Gas Tankage
The objective of this program was to synthesize melt-spinnable polyacrylonitrile (PAN) precursor that will lead to carbon fiber 25% less expensive than carbon fiber produced from conventional PAN precursor when produced in large volumes. The carbon fiber produced from this precursor needs to achieve ≥ 700 ksi tensile strength with this cost reduction to replace the incumbent fiber. In this program, the technology for producing precursor and then converted carbon fiber (CF) capable of meeting the 700 ksi target was to be demonstrated at a small scale in tows, containing ≥ 100 filaments. If this program moved on to a “Phase 2”, the processes would be scaled up to produce and test Type IV compressed gas storage tanks capable of meeting the 700-bar ultimate targeted FOA performance level. Precursor fiber production typically contributes a large fraction (~50%) to finished CF manufactured cost. Presently, all high strength CFs are manufactured from solution spun PAN precursor, accomplished at low temperatures using large amounts of environmentally unfriendly solvents that impart major impact to line speed and costs involved with handling and reclaiming the solvents and associated “waste streams” required in spinning and extracting those solvents. PAN melt spinning was demonstrated by the company BASF in CF precursor production and used in production of some other acrylic fibers, but significant production challenges remain for meeting the established CF metrics. Melt spinning requires use of plasticizers to suppress the melt temperature of the predominantly PAN formulation to a point sufficiently below the temperature of significant cross-linking. Fortunately, BASF and this team’s earlier work had demonstrated acrylic formulations melt spun with combinations of plasticizing solvents at much lower solvent levels. This project team made significant progress in understanding technical issues and identifying formulation pathways in earlier work in this area where >250ksi strength was achieved. The goal of this program was to pursue a more comprehensive approach with a larger, more diverse team having greater equipment design and overall production capabilities to push rapidly beyond the science to resolve remaining “engineering” issues associated with establishing stable, continuous processes for precursor fiber leading to enhanced, cost-effective CF and composite tank production.
36 MATERIALS SCIENCE↗
Tunable Conversion of Poly(Acrylic Acid) to Vinyl Methyl Ether Copolymers via Electrochemical Decarboxylation
Recognizing the potential of polymer-to-polymer transformations for plastics valorization, a new electrochemical strategy for the decarboxylative functionalization of polyacrylates has been developed. In contrast to most electrochemical approaches to plastic waste valorization that use small-molecule mediators or only form deconstruction products, this report describes one of the first direct electrochemical redox upconversions of a commodity polymer and involves activation of poly(acrylic acid), a material commonly found in disposable diapers and other personal hygiene products. Via electrochemical decarboxylation, poly(acrylic acid) is converted to methyl ether-containing copolymers. Although methods to prepare the 1:1 regularly alternating poly(vinyl methyl ether-alt-maleic anhydride) are known, routes to generate copolymers with variable levels of vinyl methyl ether and acrylate moieties are unknown, but such polymers may have utility in similar applications, such as dentifrices. Tunable conversions with up to 62 mol% vinyl methyl ether content were achieved via controlled-current electrolyses at >100 mA. This approach enables efficient access to copolymers with broad range of comonomer content from a common waste polymer starting material.
Dauzvardis, Fabian [University of Delaware, Newark↗
Plasticizer-Free Gradient-Crosslinked Polyurethane Electrolyte for Room-Temperature Solid-State Lithium Batteries
Polymer-based solid-state electrolytes are promising for next-generation lithium metal batteries, yet their limited ionic conductivity and mechanical stability at ambient conditions remain key challenges. Herein, we report a novel gradient crosslinked polymer electrolyte (PU/PUA/PU) synthesized via a sequential in situ UV-curing process that integrates a mechanically robust polyurethane acrylate (PUA) core with soft linear polyurethane (PU) interfaces. This all-solid membrane operates without any liquid plasticizer and the interfacial PU layers ensure low interfacial resistance and intimate electrode contact, while the PUA core provides enhanced dimensional stability and dendrite suppression. As a result, the gradient electrolyte delivers an impressive ∼2.6 × 10 −4 S cm −1 ionic conductivity at 25 °C (two orders of magnitude higher than conventional PEO) and remains electrochemically stable >5 V (vs Li + /Li). Structural analysis confirms the formation of a well-defined crosslinked network with suppressed crystallinity and expanded interchain spacing. Electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV) further validate these properties. When applied in a Li||NMC811 cell, the PU/PUA/PU electrolyte delivers stable cycling with high capacity at both 60 °C and 25 °C, demonstrating its potential for room-temperature solid-state battery applications without reliance on plasticizers or heating. In conclusion, this gradient design offers a practical path toward ambient-condition operation of solid-state lithium batteries, providing a paradigm for overcoming the traditional trade-off between ionic conductivity and mechanical robustness.
25 ENERGY STORAGE↗
Material Extrusion Printing of Poly(Acrylonitrile‐Styrene‐Acrylate) and Poly(Acrylonitrile‐Butadiene‐Styrene) Structures Reinforced with Poly(Phenylene Oxide) Additives for Improved Thermomechanical Properties and their Surface Analysis by Time‐of‐Flight Secondary Ion Mass Spectrometry
Fused filament fabrication offers the ability to 3D print complex geometries made from plastic filament materials; however, these parts are mechanically outperformed by parts created by traditional fabrication methods. To overcome this challenge, a high-performance polymer poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) is incorporated as an additive into two common engineering thermoplastics, poly(acrylonitrile-styrene-acrylate) (ASA) and poly(acrylonitrile-butadiene-styrene) (ABS). Structures printed from these polymer blends are more mechanically robust compared to those prepared from the parent polymers, with low loading levels (1–5 wt%) of PPO improving the elastic strength by up to ≈30% relative to the parent terpolymers. Even at higher loading levels (10 and 20 wt% PPO), there is no evidence of additive aggregation in the model thin films, which is supported by compositional analysis of the copolymers and chemical analysis via time-of-flight secondary ion mass spectrometry. The enhancements in mechanical properties of ASA and ABS blends appear to be a consequence of homogeneous incorporation of the PPO additive. In conclusion, this work explores expanding materials-property space using miscible blends of engineering thermoplastics to improve mechanical performance as a general approach to overcoming challenges with parts created by melt-based material extrusion printing.
additive manufacturing↗
High-resolution fiber imaging for pulsed power experiments
This work presents a novel approach for imaging the visible emissions from plasmas in pulsed power experiments using high-resolution plastic optical fibers. The diagnostic consists of a 2 mm diameter core commercial cable constructed of 13 000 individual acrylic fibers. The fibers are fused together to create a single high-resolution bundle. Different designs were investigated to cover a wide range of resolutions and fields of view (3–700 µm and 0.05–45 mm, respectively). The system was tested on the 1-MA Mykonos accelerator at Sandia National Laboratories and successfully imaged visible emission from a hybrid x-pinch target. Diagnostic development and preliminary results are presented.
Fulford, K. W. (ORCID:0000000309691832)↗
Understanding the Elastic, Plastic, and Damage Features in Fracturing of Self-reinforced Thermoplastic Composites via Non-destructive Digital Imaging Correlation
This work demonstrated the utilization of non-destructive Digital Imaging Correlation (DIC) method to characterize the elastic, plastic, and damage features during the Mode I intra-laminar fracturing process of self-reinforced thermoplastic composites by using a self-reinforced polypropylene (PP) composite as an example. The DIC results clearly showed the development of huge plastic zone (PZ) and non-negligible Fracture Process Zone (FPZ) in front of the notch tip during the fracturing process, and the geometries and sizes of the foregoing zones at the peak load were further quantified. Such an interesting fracturing behavior of self-reinforced thermoplastic composites is way different from brittle materials (e.g., glass, acrylic, etc.), ductile materials (e.g., aluminum, steel, etc.), and even quasi-brittle materials (e.g., concrete, nanoparticle-reinforced composites, tough ceramics, wood, cement, carbon/glass fiber-reinforced polymers, etc.). Thus, understanding the elastic, plastic, and damage features is the first step before better characterizing the material fracture properties of self-reinforced thermoplastic composites through new analytical methods and computational modeling. These efforts are of utmost importance for wide applications of self-reinforced thermoplastic composites in various engineering fields in the future.
Lightweight Composites, Self-reinforced Thermoplas↗
Pixelated plastic scintillator array manufacturing using fast-, photo-curable resin
Pixelated plastic scintillator arrays can serve as high efficiency and high resolution neutron imaging detectors. Manufacturing these arrays is intensive in both time and labor. This article presents a fabrication method based on additive manufacturing for two-dimensional plastic organic scintillator arrays using a custom-built automated assembly machine and a custom photocurable resin that has significant non-aromatic acrylate oligomer content. The process involves two main stages: fully autonomous production of one-dimensional layered arrays, followed by semi-autonomous cutting and stacking to form two-dimensional pixel arrays. One-dimensional arrays were manufactured at a rate of around 4 layers per hour with minimal defects and tight dimensional tolerances, while two-dimensional arrays up to 7 x 7 pixels and 70 mm in length were completed in approximately 3.5 hours. Final arrays exhibited dimensional deviations of less than 0.5 mm. Two-dimensional arrays read out by a multi-anode photomultiplier tube demonstrated per-pixel position resolution and pulse-shape discrimination, enabling gamma–neutron interaction separation in mixed radiation environments.
36 MATERIALS SCIENCE↗
Manufacturing and characterization of a boron-loaded fast-cured plastic organic scintillator
A novel fast-cured, boron-loaded, plastic organic scintillator was developed and characterized. A diisopropylnaphthalene-containing scintillator was manufactured in minutes with the addition of two commercially available fast-curing monomers, isobornyl acrylate (IBOA) and 1,6-Hexanediol dimethacrylate (HDDMA). Further, the light yield of the device was measured to be approximately 70% relative to a similarly sized, but several-year-aged, EJ-276 detector. Using a coincidence capture technique, the neutron capture light output was found to be 87.7 ± 4.2 keVee, which was 1.47 ± 0.07 greater than the light output from a 59.5 keV electron. Producing a viable fast-cured and thermal-neutron-sensitive detector enables the capability to pursue cost-effective 3D printed thermal neutron detectors in a timely manner.
46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
BOTTLE 2 - Analysis
The use of analysis is foundational to BOTTLE. In particular, we conduct techno-economic analysis (TEA), life cycle assessment (LCA), and supply chain modeling for each new BOTTLE innovation, spanning new deconstruction and upcycling technologies to redesigned polymers. These critical analysis tools are used in parallel with laboratory research to ensure that BOTTLE technologies can ultimately meet our key metrics. The BOTTLE team used analysis early in the current 3-year project cycle to identify research priorities from a scale, energy, and economics perspective (Nicholson et al., Joule 2021), and recently we presented a comprehensive framework for comparing new circularity-focused approaches to linear, incumbent practices (Nicholson et al., Ann. Rev. Chem. Biomolec. Eng. 2022). This presentation will also review case studies in analysis for closed-loop PET recycling across a range of recycling methods, baseline studies that we have conducted for plastics pyrolysis and gasification as another comparator for BOTTLE technologies, and a comprehensive study of existing closed-loop recycling technologies from a full suite of environmental impacts and feedstock quality metrics. We have undertaken studies of circular polymers being developed in the Redesign task, and we will present an exemplary case for a bio-based acrylic polymer that can replace polymethyl methacrylate. Overall, analysis is critical to enable the BOTTLE Consortium to focus on impactful, realistic technologies.
BIOMASS FUELS↗
Catalytic Chemical Recycling of Post-Consumer Polyethylene
Among commercial plastics, polyolefins are the most widely produced worldwide but have limited recyclability. Here, we report a chemical recycling route for the conversion of post-consumer high-density polyethylene (HDPE) into telechelic macromonomers suitable for circular reprocessing. Unsaturation was introduced into HDPE by catalytic dehydrogenation using an Ir-POCOP catalyst without an alkene acceptor. Cross-metathesis with 2-hydroxyethyl acrylate followed by hydrogenation transformed the partially unsaturated HDPE into telechelic macromonomers. The direct repolymerization of the macromonomers gave a brittle material due to the low overall weight-average molecular weight. Aminolysis of telechelic macromonomers with a small amount of diethanolamine increased the overall functionality. The resulting macromonomers were repolymerized through transesterification to generate a polymer with comparable mechanical properties to the starting post-consumer HDPE waste. Finally, depolymerization of the repolymerized material catalyzed by an organic base regenerated the telechelic macromonomers, thereby allowing waste polyethylene materials to enter a chemical recycling pathway.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Advances in catalytic production processes of biomass-derived vinyl monomers
Plastic industries currently source the majority of monomers from crude oil substances. Although we have witnessed a significant interest of companies in the utilization of sustainable feedstock materials for bio-based compound synthesis in the past decade, the transition to photosynthetic or chemosynthetic plant-based production in a circular carbon economy is largely slow due to complex biomass processing, costs and related reaction factors. The upgrade of the separated platform chemicals with a deeper supporting understanding of processes, models and a root–cause analysis about the underlying distribution challenges of engineered transformation mechanisms, catalyzed conversion pathways and selectivity would be beneficial to advance applied scientific development, bio-refining and manufacturing output amount. This review provides a summary, assessment and perspective for three important polymer-forming vinyl molecules, i.e. acrylic acid, methacrylic acid and styrene. These provide a backbone to produce acrylates, polystyrene, resins, rubbers, protective surface coatings, adhesives, textiles and other obtained copolymers. A succinct analytical overview on the thermo-catalytic intermediate routes for property-wise drop-in alternatives is presented. Sugars, acrolein, allyl alcohol, ethylbenzene, glycerol, 3-hydroxypropionic acid, isobutene, itaconic acid and lactic acid are considered as the main starting reactants. Catalysts span mixed metal oxides, silicates, native or impregnated zeolite frameworks (HBEA, HZSM, and MFI) and hetero-poly acids as well as homogeneous base hydroxides or platinum group metals, supported on carbon, alumina and sulfates. Finally, the article concludes with a brief state sum-up of the results, topics and opportunities for systematic future research or scaling.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗