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At least 667 records · Page 37

Computational Materials Techniques for Thermal Protection Solutions: Materials and Process Design

Integrated computational materials techniques that span the atomistic and continuum scales have the potential to aid the design and manufacturing of thermal protection materials. Two cases demonstrating the practical application of these methods are discussed. Case one examines the selection of a high temperature coating for carbon/carbon, with the target application being a solar thermal propulsion heat exchanger. The performance of various refractory metal and metal-carbide coatings is characterized considering extreme thermal (3500 K) and chemical (hydrogen flows) conditions. The recession rate, hydrogen leakage, and likelihood of mechanical failure are characterized and provide directions for further experimental investigation. Case two examines the process optimization of a heat shield material composed of a woven silica fiber preform and cyanate ester resin. Frequently, internal voids were found to be present in this composite after the resin infusion and curing stages of manufacturing. Using the manufacturing conditions, computations indicate that both water adsorption and resin cure shrinkage are contributing factors to void formation. The results suggest an alternative process configuration for curing that would mitigate voids.

Haskins, Justin↗

Molecular Dynamics Investigation of the Structural and Mechanical Properties of Off-Stoichiometric Epoxy Resins

Molecular dynamic (MD) simulations were performed to compute the mechanical properties of off-stoichiometric epoxy resins as a function of hardener/epoxy mixture ratio (r). Properties were characterized in relation to their microscopic structures. Such resins have been used recently for adhesive-free bonding of large-scale composite structures using the co-curing-ply method. In this process, two partially precured composite panels with hardener-poor (HP) off-stoichiometric resins are coupled with ply(ies) of complementary hardener-rich (HR) formulations and then cured simultaneously. This bonding process has the potential to produce reliable and certifiable composite joints without the need for additional fasteners, which are often required for many conventional bonding methods because even small amounts of contamination can cause a weak bond. The reflow and mixing of the HP/HR resin in this bonding process result in a joint with no discernable interface that should not be susceptible to surface contamination. However, incomplete mixing of the two offset resins may result in chemical heterogeneity of the cured polymeric joint. Thus, different r values may be obtained across the joint. Classical MD simulations were performed to compute the Young’s modulus of polymers with different r values and correlate their properties to network structures. High stiffness was associated with molecular packing due to chemical crosslinking, leading to a single network structure. Moreover, the networks became denser as the ratio approached the stoichiometric value r = 1. Thus, the r = 1 systems were single clusters, with high stiffness, high molecular weight, and a high degree of crosslinking. Structural properties such as radius of gyration and mean square displacement were determined to investigate the variation in the stiffness with respect to r. This MD simulation study was validated with experimental measurements.

Chang Woon Jang↗

Solid-State Ultracapacitor Polymer Composite

An ultracapacitor made from a polymer loaded with ceramic powder would have several advantages over current ultracapacitors and batteries. First is the possibility of it being printable, which would allow for printing the energy storage device along with the circuit instead of having to find a way to add one later without damaging the rest of the components. When not printed in a specific design for use on a printed wiring board, this type of ultracapacitor could still be cured via a mold to a shape suitable to specific applications. Many polymers maintain some flexibility even after curing, such as the silicone used in this study. The manufacturing process would also be far simpler than that of conventional ultracapacitors.In this work, solid-state ultracapacitors were made by adding the dielectric powder to a two-part polymer (resin and hardener) at the same time. The mixture was then cured in the desired shape at a low temperature until completely set. The addition of the powder to the polymer increased its dielectric properties while leaving most of its physical properties unaltered. At higher powder loading percentages, there were some physical changes as the maximum loading point was approached. To determine the efficiency of these solid-state ultracapacitors, their capacitances were tested, and their dielectric constants (DCs) were measured and compared.

energy storage↗

Manufacturing of Thermoset Polyimide Composites by Laser Sintering

Selective Laser Sintering (SLS) is an additive manufacturing technique that builds 3D models layer by layer using a laser to selectively melt cross sections in powdered polymeric materials, following sequential slices of the computer-aided design (CAD) model. SLS generally uses thermoplastic polymeric powders such as polyamides. The resultant 3D-printed objects are often weaker in their strength compared to traditionally processed materials, due to their higher porosity. This paper described the process development of using melt-processable imide oligomers terminated with reactive 4-phenylethynylphthalic anhydride (4-PEPA) to conduct laser sintering (LS). The first successful 3D-printing of high temperature RTM370 thermoset polyimide carbon fiber composites were further post-cured to promote additional crosslinking for achieving higher temperature (T g = 370°C) capability. Another novel imide oligomer, RTM385-SLS, formulated with a complex melt viscosity [ƞ*] of ~104-105 poise is also suitable for LS. RTM385-SLS resin powder was mixed with 20-25% of hexagonal boron nitride (h-BN) and subjected to LS to print out “Green” specimens which could be further post-cured to afford a thermally conductive but electrically insulating composites with high T g of 385 °C. The cured composite specimens were then subjected to mechanical testing, thermal conductivity and porosity measurements as well as SEM characterization.

additive Manufacturing↗

TuFF internal WRAP for Rapid Pipeline Repair (TuFF iWRAP)

The goal of “TuFF internal WRAP for Rapid Pipeline Repair” (TuFF iWRAP) program was to develop a novel material system and placement process to fabricate structural pipe within the existing deteriorated pipelines without disruption of gas delivery. The team (University of Delaware – Center for Composite Materials (UD-CCM) and Plitzie Inc.) addressed this challenge by developing a new material feedstock and pipe in pipe (PIP) repair strategy. This allows the potential for significant cost reduction and has minimum operational impact on gas customers. The new robotic based placement design allows discontinuous placement of pipe sections creating a stand-alone structural liner within the legacy pipeline without the need for pipe shutdown. Here, the material is supplied using a tethered material feeding system and is placed and UV cured with the internal Wound Rapid Automated Placement (iWRAP) system. This provides maximum placement efficiency capable of traversing 90 angle bends in 12-inch pipe and overall design customization to meet pipe repair requirements (e.g., variable wall thickness, bridging gaps, etc.). UV-curable fiber reinforced composite material has been optimized to meet structural performance and placement/cure times. Superior strength and fatigue life has been demonstrated by improving fiber-matrix adhesion using new fiber sizing for UV resins. Rapid cure approaches using new liner and resins have been evaluated with industry. The appropriate design of the section joints has been developed and tested. We estimate coating time to be ~100 hours per mile enabling typical pipe repair within 1 week.

03 NATURAL GAS↗

Soil metagenomics umbrella narrative

Implementing accessible, authentic research experiences in introductory courses is challenging, particularly at institutions serving diverse student populations. To address this gap, we developed and deployed a Course-based Undergraduate Research Experience (CURE) focused on plant-microbe interactions in General Biology II at Northeastern Illinois University (NEIU), a minority-serving institution with a diverse student body. Students grew sugar beets (Beta vulgaris), extracted DNA from the rhizoplane, and used the Department of Energy Systems Biology Knowledgebase (KBase) for bioinformatic analysis to compare microbial relative abundance in fertilized versus unfertilized soil. Over five semesters, the CURE engaged 103 students and leveraged the intuitive KBase platform to make complex sequencing data accessible. Pre/post-course survey data revealed significant increases in student self-assessed research skills, including the ability to explain results and determine the types of data to collect. Furthermore, students reported significant gains in confidence related to experimental design and hypothesis development, alongside a strong increase in familiarity with KBase. Informal faculty feedback indicated high student engagement and appreciation for the real-world connections (e.g. food systems, agriculture, and health). This scalable, low-cost model effectively integrates data science tools into the foundational curriculum, demonstrating a potent strategy for boosting research skills and broadening participation in authentic scientific inquiry among diverse undergraduate students.

59 BASIC BIOLOGICAL SCIENCES↗

Fabricating Silver Nanowire–IZO Composite Transparent Conducting Electrodes at Roll-to-Roll Speed for Perovskite Solar Cells

This study addresses the challenges of efficient, large-scale production of flexible transparent conducting electrodes (TCEs). We fabricate TCEs on polyethylene terephthalate (PET) substrates using a high-speed roll-to-roll (R2R) compatible method that combines gravure printing and photonic curing. The hybrid TCEs consist of Ag metal bus lines (Ag MBLs) coated with silver nanowires (AgNWs) and indium zinc oxide (IZO) layers. All materials are solutions deposited at speeds exceeding 10 m/min using gravure printing. We conduct a systematic study to optimize coating parameters and tune solvent composition to achieve a uniform AgNW network. The entire stack undergoes photonic curing, a low-energy annealing method that can be completed at high speeds and will not damage the plastic substrates. The resulting hybrid TCEs exhibit a transmittance of 92% averaged from 400 nm to 1100 nm and a sheet resistance of 11 Ω/sq. Mechanical durability is tested by bending the hybrid TCEs to a strain of 1% for 2000 cycles. The results show a minimal increase (<5%) in resistance. The high-throughput potential is established by showing that each hybrid TCE fabrication step can be completed at 30 m/min. We further fabricate methylammonium lead iodide solar cells to demonstrate the practical use of these TCEs, achieving an average power conversion efficiency (PCE) of 13%. The high-performance hybrid TCEs produced using R2R-compatible processes show potential as a viable choice for replacing vacuum-deposited indium tin oxide films on PET.

14 SOLAR ENERGY↗

Effect of Boundary Conditions on Process-Induced Stresses in a Plain Weave Unit Cell

Woven polymer matrix composites (PMCs) are leveraged in aerospace applications for their desirable specific properties, yet they are vulnerable to high residual stresses during manufacturing and their complex geometry makes experimental results difficult to observe. Process modeling is needed to characterize the effects of the curing and predict end stress states. Finite element software can be used to model woven architectures, however accurate representation of processing conditions remains a challenge when it comes to selecting boundary conditions. The effect of BCs on process-induced stress within woven PMCs is studied. The commercial Finite Element Analysis (FEA) software Abaqus is coupled with user-written subroutines in a process modeling framework. A two-dimensionally (2D) woven PMC repeating unit cell (RUC) is modeled with TexGen and Abaqus. Virtual curing is imposed on the bulk matrix. The BC study is conducted with Free, Periodic, Flat, and Flat-Free configurations. Results show that the end stress state is sensitive to the boundary condition assumptions. Flat BC results show great agreement with Periodic BCs. Residual stress results from process modeling are then compared with a linear-elastic thermal cooldown analysis in Abaqus. Cooldown results indicate an overestimation in matrix stresses compared with process modeling.

micromechanics↗

Triplet Fusion Upconversion for Photocuring 3D-Printed Particle-Reinforced Composite Networks

High energy photons (λ < 400 nm) are frequently used to initiate free radical polymerizations to form polymer networks, but are only effective for transparent objects. This phenomenon poses a major challenge to additive manufacturing of particle-reinforced composite networks since deep light penetration of short-wavelength photons limits the homogeneous modification of physicochemical and mechanical properties. Herein, the unconventional, yet versatile, multiexciton process of triplet–triplet annihilation upconversion (TTA-UC) is employed for curing opaque hydrogel composites created by direct-ink-write (DIW) 3D printing. TTA-UC converts low energy red light (λ max = 660 nm) for deep penetration into higher-energy blue light to initiate free radical polymerizations within opaque objects. Further, as proof-of-principle, hydrogels containing up to 15 wt.% TiO 2 filler particles and doped with TTA-UC chromophores are readily cured with red light, while composites without the chromophores and TiO 2 loadings as little as 1–2 wt.% remain uncured. Importantly, this method has wide potential to modify the chemical and mechanical properties of complex DIW 3D-printed composite polymer networks.

36 MATERIALS SCIENCE↗

Multimaterial 3D Printing in Activating Bath Enables In Situ Polymerization of Thermosets with Intricate Geometries and Diverse Elastic Behaviors

Polydicyclopentadiene, p(DCPD), is a high‐performance thermoset valued for its exceptional toughness, strength, and stiffness. When copolymerized with 1,5‐cyclooctadiene (COD), its mechanical properties can be tuned from glassy to rubbery at room temperature. While frontal polymerization enables a rapid and energy‐efficient route to 3D print DCPD‐based materials, challenges such as ink shelf life and gravitational distortion, especially in direct ink writing of soft COD‐rich formulations, must be considered. Here, a complementary chemical strategy is presented, embedded 3D printing, that enables localized in situ polymerization of printed DCPD/COD inks within a reactive support matrix. The matrix provides both physical support and a reservoir of chemical activator, which diffuses into the ink, activates a latent bis(N‐heterocyclic carbene) Ru precatalyst, and initiates ring‐opening metathesis polymerization. Curing begins at the ink–matrix interface and propagates inward via diffusion, stabilizing the interface and preventing capillary‐driven deformation regardless of the matrix yield stress. This approach eliminates the need for cold storage, external curing, or photoinitiation, significantly expanding the processing window. Using this method, diverse thermosetting and elastomeric architectures are fabricated with features as small as 5 µm and aspect ratios of 100, including interlinked chains, shallow spherical shells exhibiting snap‐through buckling, and hair‐like fin arrays inaccessible through traditional techniques.

chemical activation↗

Latent Catalysis as a Platform for Accessing Diverse Material Properties in Vat Photopolymerization 3D Printing

Vat photopolymerization (VP) 3D printing is an attractive strategy to manufacture customized polymer parts. The properties of printed materials are limited by the need to employ a low viscosity liquid resin and achieve rapid polymerization kinetics. To circumvent this limitation, dual‐cure methods have been developed using reagents embedded in the liquid resin formulation; however, the reagent‐based approach requires the discovery and optimization of new chemistry for each desired material. Here, in this work, we demonstrate a catalytic, dual‐cure platform that enables access to both Nylon‐6 and polyester interpenetrating networks through VP 3D printing under a universal approach. Structure–reactivity relationships of the latent NHC catalysts led to the identification of a magnesium chloride–NHC adduct as a latent catalyst that is orthogonal to radical polymerization and can be unmasked at elevated temperatures post‐printing to initiate ring‐opening polymerization of lactones and lactams. This strategy results in access to semicrystalline materials, which are a challenging morphology to access via VP 3D printing, that have attractive mechanical properties and can be printed at high resolution. This work represents the first photochemical‐based 3D printing of Nylon‐based materials and demonstrates the value of catalytic approaches to access new material properties in VP 3D printing.

Colliver, Cali N. [University of North Carolina, C↗

Tuning the Mechanical Properties of Crosslinked Copolymers via Sequence and Solvent‐Selective Swelling for Vat Photopolymerization

Block copolymers (BCPs) offer distinct advantages for vat photopolymerization by enabling mechanically programmable network structures through microphase-separated morphologies that can be kinetically trapped during curing, yielding properties unattainable in homogeneous resins. However, the respective roles of repeat-unit sequence and solvent environment, together with their interplay in directing network formation and mechanical performance, remain unclear. Here, we synthesize a series of CO 2 -based polycarbonate copolymers comprising a crosslinkable glassy poly(vinyl cyclohexene carbonate) (PVCHC, A block) and a non-crosslinkable soft poly(propylene carbonate) (PPC, B block). The polymer sequence is systematically varied (ABA, BAB, and statistical), and solvent choice controls block-selective swelling to jointly control gelation behavior, microphase morphology, and mechanical response through changes in the accessibility and local environment of photocrosslinkable vinyl groups during network formation, as revealed by photorheology and small angle x-ray scattering. By tuning polymer sequence and curing solvent, we transform nominally identical formulations from brittle to highly ductile materials, achieving a three-orders-of-magnitude range in toughness (0.003 to 9.1 MJ m −3 ). These results establish clear structure–processing–property relationships and identify polymer sequence and selective solvation as powerful strategies for programming both printability and performance of block copolymer resins for additive manufacturing.

additive manufacturing↗

Fluorine-Free Superhydrophobic Coatings: Rapid Fabrication and Highly Efficient Oil/Water Separation

In this work, a rapid method is demonstrated to obtain a fluorine-free superhydrophobic/superoleophilic coating by a simple two-step method: dip-coating and oven curing. The chemical structure of the coating is based on the crosslinking reaction of an alkyl methacrylate, a dimethacrylate (crosslinker) and a silane (adhesive), using AIBN as initiator, toluene as solvent, and silica nanoparticles to enhance surface roughness. Chemorheology results show that the coating is fully cured even in 20 min at 100 °C, exhibiting a water contact angle (CA) of 162 ± 2°, sliding angle (SA) of 4 ± 1°, nanometrical structures throughout the surface, and excellent adhesion properties for the mesh screen. The coating exhibits outstanding oil/water separation efficiency (96–99%) for seven different types of oil (gasoline, diesel, petroleum ether, hexane, toluene, chloroform, and dichloromethane), and in addition presents high recyclability. Based on nonisothermal TGA, the activation energy of degradation, calculated using the Kissinger and Ozawa models, is 113.5 and 114 kJ mol -1 , respectively. Finally, the coating is thermally aged at 150 °C: the CA exhibits a smooth decrease up to 129 ± 1° at 120 min, and FTIR analysis shows structural changes possibly related to the generation of thermal oxidation products.

36 MATERIALS SCIENCE↗

Carbon Fiber Reinforced Epoxy Vitrimer: Robust Mechanical Performance and Facile Hydrothermal Decomposition in Pure Water

Conventional carbon fiber reinforced thermosetting polymers (CFRPs) are neither recyclable nor repairable due to their crosslinked network. The rapid growing CFRP market raises a serious concern of the waste management. In this work, a viable method to develop a readily recyclable CFRP based on epoxy vitrimer is introduced. First, a self-catalytic epoxy prepolymer with built-in hydroxy and tertiary amine groups is designed, which upon reaction with an anhydride formed a catalyst-free epoxy vitrimer. The epoxy prepolymer is synthesized from a diamine and an excess of bisphenol A epoxy resin. The hydroxyls and tertiary amines of the epoxy prepolymer efficiently catalyze both curing and the dynamic transesterification of the crosslinked polymer without the need of a catalyst. Then, the epoxy vitrimer is used as the matrix resin to prepare CFRP. The resulting CFRP exhibited a tensile strength as high as 356 MPa. More interestingly, the matrix of the CFRP is efficiently degraded in pure water at above 160 °C. This is because the built-in tertiary amines catalyze the hydrolysis of the ester bonds of the crosslinked network. The simple method developed in this work provides a framework for the development of recyclable CFRP.

Liu, Tuan↗

Effect of recycled fibers and shredded intermediates variation on the mechanical properties and energy absorption of fiber‐reinforced composite panels

Abstract The global composite industry generates large quantities of waste which mostly ends up in landfills due to a lack of established end‐use applications for multiple waste streams. The scrap from end‐of‐life (EoL) includes manufacturing waste such as dry chopped fiber tows, loose fibers, shredded fibers from fabric textile operations, cured/semi‐cured prepregs, and fully cured composite structure waste from aircraft, automobiles, wind blades, boats, and pressure vessels. In this work, different composite waste streams were reduced to shredded intermediates, followed by simple blending, and subjected to wet compression molding to produce composite panels. The panels/plaques were tested for mechanical properties (flexure and impact), fiber‐matrix wet‐out, and property bounds. It was found that wet‐compression molding was a viable and scale‐able approach to produce recycled panels from EoL composites shredded scrap. Furthermore, full‐scale size panels for use in truck bodies and intermodal shipping container flooring were manufactured and their impact resistance was tested using a drop weight impact test. They were tested both for high‐ and low‐velocity load. In the case of high‐velocity load, the average impact load was 14,673 N; the average absorbed energy was 101.6 J; the average elastic energy was 11.7 J and the impact resistance was 1065 J/m. In the case of the low‐velocity drop weight impact test, it was found that the average impact load was 7877.358 N; the average absorbed energy was 9.718 J; the average elastic energy was 9.14 J, and the impact resistance was 184.1 J/m. The shredded composite was shown to be a candidate material for the manufacture of truck bodies and intermodal containers’ flooring panels. Highlights By using shredded intermediates from different composite waste streams, it is possible to manufacture composite panels. Wet–compression process is an appropriate technique for manufacturing recycled fiber composite panels. Regardless of the source of scrap, the mechanical properties of the produced composite panels were improved. The recycling process technology can be transformed to commercial scale to produce full‐size transportation flooring panels. A product pathway is established in consideration of lower cost and improved recyclability.

Vaidya, Uday↗

Acrylonitrile-butadiene-lignin thermoplastic rubber adhesive for enhanced metal-to-metal joining

With the growing requirement for lightweight structural materials in automotive, aerospace, and infrastructure applications, multi-material joints made with adhesive have attracted intense research interest. Commercial thermoset adhesives are one-time cures, and difficult to disassemble the bonded components for repair and recycling. Our prior work with a thermoplastic acrylonitrile-butadiene-lignin rubber (ABL) addresses this sustainability/recycling challenge, but the adhesive exhibits deficient joining strength compared to standard thermosets. Here, we modify the ABL matrix by loading particulate fillers to enhance its modulus and toughness. Further, the goal is to manufacture a cure-free thermoplastic adhesive system with a simple dispensing protocol and characteristic ductility combined with a high yield stress for improved shear strength of a bonded joint. Fumed silica (FS) and epoxidized glass spheres (EGS) were used as fillers in the ABL to promote the dispersion of lignin particles that tailored the functionalities and free energy components of the adhesive surface. With optimal loading of FS (5 wt%) and EGS (30 wt%) in the ABL adhesive matrix, the lap-shear strength of the bonded aluminum joint was elevated by 128%, compared to the neat ABL, reaching 21 MPa, which is 90% of the performance of a commercial epoxy-based adhesive.

36 MATERIALS SCIENCE↗

The Triple Catalytic Action of Tertiary Nitrogen Catalysts in Recyclable Epoxy-Anhydride Thermosets

The thermosetting polymer matrix in fiber reinforced composites is an important component for energy related applications, such as the lightweighting of vehicles or their use in wind and waterpower turbine blades, due to their ability to provide superior adhesion, stiffness, and applicability to a wide range of manufacturing processes. Despite these benefits, today's thermosets are widely considered to be unrecyclable; thus, there is a large interest in redesigning these materials to be inherently recyclable so that energy intensive production of fibers and monomers can be circumvented, bolstering composite manufacture supply chains. Polyester covalent adaptable networks (PECANs) are one such promising alternative to the incumbent, nonrecyclable epoxy-amine thermosets. PECANs can be formed from the ring-opening co-polymerization (ROCOP) of epoxy-anhydride monomer mixtures and subsequent curing at mild temperatures to exhibit similar performance to conventional epoxies while also possessing unique dynamic chemistries along the ester-hydroxyl backbone that are capable of transesterification and thus reprocessability. While significant advancements have been made in formulating these materials for improved mechanical properties or optimizing solvolysis and reprocessing strategies, less attention has been placed on the impact of the residing amine catalyst used to generate the polyester network. In this work, we evaluated the triple-catalytic efficacy of 12 tertiary amines that act as a curing (bulk ROCOP), a transesterification (internal bond exchange), and a deconstruction (methanolysis) catalyst for PECAN thermosets. Specifically, we first distinguish between chain-growth and step-growth polymerization mechanisms for epoxy-amine and epoxy-anhydride mechanisms. We also utilized density functional theory (DFT) to estimate the basicity (pKb) of each catalyst. Of the tested catalysts, the ROCOP of the studied PECAN network can be completed between 95 and 247 min (at 80 degrees C), with variable gelation phenomena. Additionally, the stress relaxation (transesterification metric) efficiency of the tested PECAN networks with alternative embedded catalysts ranged from 95% to 15% reduction in stress after 5 h at 200 degrees C, and the depolymerization efficacy ranged from 2.5% to 9.8% deconstruction after 36 h at 130 degrees C. Overall, the nitrogen-based moieties were demonstrated to influence polymerization kinetics, catalyze the dynamic transesterification exchange mechanism, and aid in the solvolysis of the thermosets at end-of-life.

36 MATERIALS SCIENCE↗

Shear and combustion characterization of printable ammonium perchlorate composite propellant formulations

Seven formulations of ammonium perchlorate composite propellant (APCP) are developed and their properties relevant for successful additive manufacture are characterized. Extrusion in a custom-built 3D printing system and spindle viscometry are used to collect viscosity measurements of curing primary and non-curing secondary versions of the formulations. The formulations that behave similarly to a Bingham plastic, with apparent viscosities between 4 and 8 thousand Pa*s at 30 minutes post-mix, are determined to be most suitable for printing applications. Measurements of one material show a yield stress of 1 kPa. Ambient pressure burn rates of 2.0–2.9 mm/s were measured for the compositions tested. All measured burn rates were comparable to the lower end of typical burn rates for APCP. In conclusion, the results of the characterization demonstrate a propellant suitable for use in a 3D printing system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗