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At least 379 records · Page 21

Effect of Proximity of Features on the Damage Threshold During Submicron Additive Manufacturing Via Two-Photon Polymerization

Two-photon polymerization (TPP) is a laser writing process that enables fabrication of millimeter scale three-dimensional (3D) structures with submicron features. In TPP, writing is achieved via nonlinear two-photon absorption that occurs at high laser intensities. Thus, it is essential to carefully select the incident power to prevent laser damage during polymerization. Currently, the feasible range of laser power is identified by writing small test patterns at varying power levels. Here in this paper, we demonstrate that the results of these tests cannot be generalized, because the damage threshold power depends on the proximity of features and reduces by as much as 47% for overlapping features. We have identified that this reduction occurs primarily due to an increase in the single-photon absorptivity of the resin after curing. We have captured the damage from proximity effects via X-ray 3D computed tomography (CT) images of a non-homogenous part that has varying feature density. Part damage manifests as internal spherical voids that arise due to boiling of the resist. We have empirically quantified this proximity effect by identifying the damage threshold power at different writing speeds and feature overlap spacings. In addition, we present a first-order analytical model that captures the scaling of this proximity effect. Based on this model and the experiments, we have identified that the proximity effect is more significant at high writing speeds; therefore, it adversely affects the scalability of manufacturing. The scaling laws and the empirical data generated here can be used to select the appropriate TPP writing parameters.

36 MATERIALS SCIENCE↗

Pseudoplasticity and Dynamic Interfacial Tension Relaxation Effects on Nucleate Pool Boiling in Aqueous Polymeric Liquids

Nucleate pool boiling heat transfer and its ebullient dynamics in polymeric solutions at atmospheric pressure saturated conditions are experimentally investigated. Three grades of hydroxyethyl cellulose (HEC) are used, which have intrinsic viscosity in the range 5.29 ≤ [ η ] ≤ 10.31 [dl/g]. Their aqueous solutions in different concentrations, with zero-shear viscosity in the range 0.0021 ≤ η 0 ≤ 0.0118 [N∙s/m 2 ], exhibit shear-thinning rheology in varying degrees, as well as gas–liquid interfacial tension relaxation and wetting. Boiling heat transfer in solutions with constant molar concentrations of each additive, which are greater than their respective critical polymer concentration C * , is seen to have anomalous characteristics. There is degradation in the heat transfer at low heat fluxes, relative to that in the solvent, where the postnucleation bubble dynamics in the partial boiling regime is dominated by viscous resistance of the polymeric solutions. At higher heat fluxes, however, there is enhancement of boiling heat transfer due to a complex interplay of pseudoplasticity and dynamic surface tension effects. The higher frequency vapor bubbling train with high interfacial shear rates in this fully developed boiling regime tends to be influenced by increasing shear-thinning and time-dependent differential interfacial tension relaxation at the dynamic gas–liquid interfaces.

Engineering↗

Feasibility and Reliability of a Single Layer Polymeric PV Backsheet in White, Transparent, or Luminescent Concentrator Options

A single layer polymeric backsheet material has been evaluated for use in silicon PV modules and as a luminescent solar collector. Physical and optical properties of the backsheet have been examined after damp heat, thermal cycling, and UV exposure for two different polymeric grades and three different pigment options including white, transparent, and photo-luminescent. As the importance of developing a white backsheet that is cost-effective, recyclable, and reliable is evident, the increased availability and use of bifacial cells is bound to increase the demand for transparent backsheets as well. In today's market, the cost of a clear backsheet is significantly higher than a white backsheet which is motivation for research and development of new material options in this field. Results from these extensive tests reveal the need for continued research in white pigments and positive results in transparent and luminescent backsheet options.

14 SOLAR ENERGY↗

All-polymeric control of nanoferronics

In the search for light and flexible nanoferronics, significant research effort is geared toward discovering the coexisting magnetic and electric orders in crystalline charge-transfer complexes. We report the first example of multiferroicity in centimeter-sized crystalline polymeric charge-transfer superstructures that grow at the liquid-air interface and are controlled by the regioregularity of the polymeric chain. The charge order–driven ferroic mechanism reveals spontaneous and hysteretic polarization and magnetization at the donor-acceptor interface. The charge transfer and ordering in the ferroic assemblies depend critically on the self-organizing and molecular packing of electron donors and acceptors. The invention described here not only represents a new coupling mechanism of magnetic and electric ordering but also creates a new class of emerging all-organic nanoferronics.

36 MATERIALS SCIENCE↗

Designing polymeric membranes with coordination chemistry for high-precision ion separations

State-of-the-art polymeric membranes are unable to perform the high-precision ion separations needed for technologies essential to a circular economy and clean energy future. Coordinative interactions are a mechanism to increase sorption of a target species into a membrane, but the effects of these interactions on membrane permeability and selectivity are poorly understood. We use a multilayered polymer membrane to assess how ion-membrane binding energies affect membrane permeability of similarly sized cations: Cu 2+ , Ni 2+ , Zn 2+ , Co 2+ , and Mg 2+ . We report that metals with higher binding energy to iminodiacetate groups of the polymer more selectively permeate through the membrane in multisalt solutions than single-salt solutions. In contrast, weaker binding species are precluded from diffusing into the polymer membrane, which leads to passage proportional to binding energy and independent of membrane thickness. Our findings demonstrate that selectivity of polymeric membranes can markedly increase by tailoring ion-membrane binding energy and minimizing membrane thickness.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemically recyclable thermoplastics from reversible-deactivation polymerization of cyclic acetals

Identifying plastics capable of chemical recycling to monomer (CRM) is the foremost challenge in creating a sustainable circular plastic economy. Polyacetals are promising candidates for CRM but lack useful tensile strengths owing to the low molecular weights produced using current uncontrolled cationic ring-opening polymerization (CROP) methods. Here, we present reversible-deactivation CROP of cyclic acetals using a commercial halomethyl ether initiator and an indium(III) bromide catalyst. Using this method, we synthesize poly(1,3-dioxolane) (PDXL), which demonstrates tensile strength comparable to some commodity polyolefins. Depolymerization of PDXL using strong acid catalysts returns monomer in near-quantitative yield and even proceeds from a commodity plastic waste mixture. Our efficient polymerization method affords a tough thermoplastic that can undergo selective depolymerization to monomer.

Abel, Brooks A.↗

Electronic, Ionic, and Mixed Conduction in Polymeric Systems

Polymers that simultaneously transport electrons and ions are paramount to drive the technological advances necessary for next-generation electrochemical devices, including energy storage devices and bioelectronics. However, efforts to describe the motion of ions or electrons separately within polymeric systems become inaccurate when both species are present. In this paper, we highlight the basic transport equations necessary to rationalize mixed transport and the multiscale materials properties that influence their transport coefficients. Potential figures of merit that enable a suitable performance benchmark in mixed conducting systems independent of end application are discussed. Practical design and implementation of mixed conducting polymers require an understanding of the evolving nature of structure and transport with ionic and electronic carrier density to capture the dynamic disorder inherent in polymeric materials.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Post-print UV curing method for improving the mechanical properties of prototypes derived from two-photon lithography [A post-print UV curing method for improving the mechanical properties of prototypes derived from two-photon polymerization]

Here, two photon polymerization (TPP) is a precise, reliable, and increasingly popular technique for rapid prototyping of micro-scale parts with sub-micron resolution. The materials of choice underlying this process are predominately acrylic resins cross-linked via free-radical polymerization. Due to the nature of the printing process, the derived parts are only partially cured and the corresponding mechanical properties, i.e. modulus and ultimate strength, are lower than if the material were cross-linked to the maximum extent. Herein, post-print curing via UV-driven radical generation, is demonstrated to increase the overall degree of cross-linking of low density, TPP-derived structures.

36 MATERIALS SCIENCE↗

Hyperbranched PDMAEMA-functionalized SiO 2 microparticles: ATRP polymerization and grafting in a continuous flow reactor

Flow chemistry offers high reaction yield, kinetic control, improved safety, reliability, scalability, and greater degree of process control. Herein, hyperbranched polymer-grafted silica microparticles (HP-SMPs) are synthesized in a commercially available flow reactor through atom transfer radical polymerization. Initiator-anchored silica microparticles are obtained by in situ silanization in the flow reactor. Hyperbranched poly[2-(dimethylamino)ethylmethacrylate] chains are grafted onto the initiator-anchored SMPs through inimer–monomer ratio control. To demonstrate the efficiency and universality of this approach in grafting polymers onto SMPs, multiple hyperbranched polymeric structures are obtained by varying the inimer concentration. Dye absorption test is conducted to demonstrate the potential applications of HP-SMPs.

36 MATERIALS SCIENCE↗

Scaling the polymerization of polyaldehydes through continuous flow synthesis

Abstract A plug flow reactor was constructed to scale the synthesis of metastable, phthalaldehyde-based polymers to achieve production rates of 1–2 kg per day. The flow-induced mixing and in-line polymerization quench and precipitation sequences resulted in improved polymer purity and long-term stability compared to the same materials made from a conventional batch process. Cryogenic rheology was used to probe the complex fluid dynamics encountered during the polymerization of PPA homopolymers. It is envisioned that this continuous flow manufacturing approach could be extended to other low ceiling temperature or aldehyde monomer systems to help implement and support a plastic circular economy. Graphical abstract

Schwartz, Jared M.↗

Final Technical Report - Polymeric Multilayer Infrared Reflecting Mirrors

The goal of this project was to develop a clear, polymeric, multilayer film with an expanded infrared (IR) reflection band which would allow improved rejection of incident IR energy. The IR reflection band is covering the region from about 850 nm to 1830 nm. This film is essentially clear and colorless in the visible portion of the electromagnetic spectra (visible light transmission of about 89%) while reflecting 90-95% of the IR energy over the portion of the spectra indicated above. This film has a nominal thickness of 3 mils, is polymeric in nature (contains no metals, metal oxides, or other material types) and is essentially clear in appearance This film can then be used as a component of other products such as a solar window film, an IR reflecting interlayer for laminated glass, a heat rejecting skylight film, a base film for daylight redirecting products, a greenhouse film, and many more applications. One of the main strengths of this product is that because it is a standalone IR rejecting film, it can be incorporated and retrofitted into many applications that desire or require the transmission of visible light, but want to block other portions of the solar spectra, especially the IR portion. Many of the applications exist in the window glazing product area where this film can provide for substantial energy improvements in applications where visible light is desired.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Investigations Into the Reusability of Amidoxime-Based Polymeric Uranium Adsorbents

Significant advancements in amidoxime-based polymeric adsorbents to extract uranium from seawater are achieved in recent years. The success of uranium adsorbent development can help provide a sustainable supply of fuel for nuclear reactors. To bring down the production cost of this new technology, in addition to the development of novel adsorbents with high uranium capacity and manufacture cost, the development of adsorbent re-using technique is critical because it can further reduce the cost of the adsorbent manufacture. In our last report, the use of high concentrations of bicarbonate solution (3M KHCO3) was identified as a cost-effective, environmental friendly method to strip uranium from amidoxime-based polymeric adsorbents. This study aims to further improve the method for high recovery of uranium capacity in re-uses and to evaluate the performance of adsorbents after multiple re-use cycles. Adsorption of dissolved organic matter (DOM) on the uranium adsorbents during seawater exposure can hinder the uranium adsorption and slow down the adsorption rate. An additional NaOH rinse (0.5 M NaOH, room temperature) was applied after the 3 M KHCO3 elution to remove natural organic matter from adsorbents. The combination of 3 M KHCO3 elution and 0.5 M NaOH rinse significantly improves the recovery of uranium adsorption capacity in the re-used adsorbents. In the first re-use, most ORNL adsorbents tested achieve ~100% recovery by using 3 M KHCO3 elution + 0.5 M NaOH rinse approach, in comparison to 54% recovery when only 3 M KHCO3 elution was applied. A significant drop in capacity was observed when the adsorbents went through more than one re-use. FTIR spectra revealed that degradation of amidoxime ligands occurs during seawater exposure, and is more significant the longer the exposure time. Significantly elevated ratios of Ca/U and Mg/U in re-used adsorbents support the decrease in abundance of amidoxime ligands and increase carboxylate group from FT-IR analysis. The impact of the length of seawater exposure cycle in adsorbent re-use was evaluated by comparing the adsorption capacity for a common adsorbent formulation (ORNL AI8 formulation) under different exposure cycle (28 days and 42 days). Adsorbents with a 28 days seawater exposure cycle had higher recovery of uranium capacity than adsorbent with 42 days of seawater exposure. Under different cumulative seawater exposure time, the adsorbent with 28 days seawater exposure cycle also had less amidoxime ligands degradation than the adsorbent with 42 days seawater exposure cycle. These observations support the negative impact of prolonged seawater exposure on amidoxime ligands stability. Recovery of uranium capacity in re-uses also varies across different adsorbent formulations. Among three different ORNL adsorbents tested (AI8, AF8, AF1-DMSO), AI8 had the best recovery in each re-use, followed by AF8 and then AF1-DMSO. This demonstrates that continuing efforts on developing new adsorbents with high capacity and stability is critical. The overall performance of adsorbents in multiple re-use cycles can be evaluated by calculation total harvestable uranium, the summation of adsorbed uranium from each seawater exposure cycle. In this assessment, the ORNL AI8 braid with 28 days seawater exposure cycle can reach total harvestable uranium 10g Uranium/kg adsorbent in ~140 days; while the same type of braid but with 42 days seawater exposure cycle reach the same level in ~170 days. Notably, the performance of total harvestable uranium also varies among different adsorbent formulations (AI8 > AF1-DMSO > AF8). Short seawater exposure cycle is associated with high re-use frequency. The development of low-cost offshore adsorbent deployment/extraction is essential for high frequency reuse operation. This study also highlights the importance to examine the re-use performance of newly developed uranium adsorbents for selection of optimal adsorbents for ocean deployment.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Improved Structural Design and CO 2 Capture of Porous Hydroxy-Rich Polymeric Organic Frameworks

Polymeric organic frameworks (POFs) are tunable and robust porous materials with potential applications for gas capture, catalysis, and separations technologies. A series of new porous POFs have been synthesized from the reaction of phloroglucinol or resorcinol derivatives with aryl aldehyde precursors. The monomers have various molecular shapes including linear, bent, trigonal, and tetrahedral geometries. Depending on the size and geometric matching of the monomers, the polymers are dominantly microporous with some mesoporous character or they are non-porous. In addition to standard spectroscopic and surface characterization, the materials were screened as adsorbents for carbon dioxide capture at low pressure (0-1 bar). The best performing material (POF 1D) has a CO 2 capture capacity of 9.0 wt. % (2.04 mmol g -1 ) at 298 K and 1 bar which is comparable to other polymeric organic frameworks. Isosteric heats of adsorption for POF 1A, POF 2A, and POF 2B were found to be dependent on the weight percent of CO 2 adsorbed: this suggests there are both chemisorptive and physisorptive components of CO 2 capture by the POFs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Improving the Thermomechanical Stability of High Efficiency Perovskite Solar Cells via Polymeric Nanofiber Reinforcement

We show that the mechanical stability of perovskite thin films can be increased by an order of magnitude by nanocompositing with polymeric nanofibers using a scalable method. We discuss the increase in fracture resistance energy, Gc, in the nanocomposite samples with respect to nanofiber orientation. We demonstrate this platform with commodity polymeric nanofibers including nylon-6,6 and polyvinyl alcohol. The fiber network reduces the mechanical fragility of the PSCs by increasing their fracture energy several-fold, while maintaining comparable morphology, chemical composition, and device efficiencies to pristine perovskite. Improved power conversion efficiency stability of the nanocomposites under accelerated aging conditions is demonstrated. This platform is a promising advance toward the commercial viability of PSCs.

Samoylov, Anton↗

Porous Polymeric Materials FY24 PDRD Final Report

Fillers and pore formers are used in many materials at Kansas City National Security Campus (KCNSC) to fine tune density and stiffness. Current off-the-shelf options such as urea and Expancel do not always provide the desired properties. This project investigated several methods for introducing porosity in rigid polymers such as epoxy and polyurethane. This work was done at partnering universities to identify a variety of methods to create porous polymeric materials. The University of Oklahoma (OU) investigated emulsion templating of epoxy, where the epoxy is mixed with a surfactant and water to form an emulsion. The emulsion is then molded and cured. During the cure process, water droplets evaporate to form porous structures. Total porosity can be tuned by changing the concentration of water added to the polymer. The University of Kansas (KU) investigated the synthesis of phenolic microballoons by spray drying, as well as methods of incorporating removable porogens into epoxy and polyurethane materials to create polymeric foams.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Water Sorption Study of Various Polymers and Polymeric Composites

In the formulations of many composite materials, polymeric materials are often used as binder materials to enhance processability, functionality, and safety during manufacturing. For instance, poly(ester urethane), such as Estane® 5703, is used in the formulation of PBX 9501, and vinyl copolymer elastomer (VCE) is used in the formulation of VCE/filler compos ites. The stability of these binders directly impacts the overall stability and performance of their composites. Estane and VCE are prone to hydrolytic degradation, with water sorption behavior playing a significant role in their long-term stability and aging behavior. Hence, it is critical to study their water sorption behavior under various humidity and tempera ture conditions. To improve the accuracy and reduce labor-intensive work involved in water sorption experiments, an automated Dynamic Vapor Sorption (DVS) system was employed, which can generate large datasets. To efficiently process and analyze these datasets, Python scripts were developed. These scripts not only streamlined data processing, but also accu rately derived the Arrhenius parameters related to water diffusion and sorption properties for the tested materials. This approach offers a robust framework for evaluating water trans port and sorption processes in polymeric materials and adds valuable capabilities to future water sorption testing efforts.

36 MATERIALS SCIENCE↗

Effects of Incorporating High-Volume Fly Ash into Tricalcium Silicate on the Degree of Silicate Polymerization and Aluminum Substitution for Silicon in Calcium Silicate Hydrate

This study assesses the quantitative effects of incorporating high-volume fly ash (HVFA) into tricalcium silicate (C 3 S) paste on the hydration, degree of silicate polymerization, and Al substitution for Si in calcium silicate hydrate (C–S–H). Thermogravimetric analysis and isothermal conduction calorimetry showed that, although the induction period of C 3 S hydration was significantly extended, the degree of hydration of C 3 S after the deceleration period increased due to HVFA incorporation. Synchrotron-sourced soft X-ray spectromicroscopy further showed that most of the C 3 S in the C 3 S-HVFA paste was fully hydrated after 28 days of hydration, while that in the pure C 3 S paste was not. The chemical shifts of the Si K edge peaks in the near-edge X-ray fine structure of C–S–H in the C 3 S-HVFA paste directly indicate that Al substitutes for Si in C–S–H and that the additional silicate provided by the HVFA induces an enhanced degree of silicate polymerization. This new spectromicroscopic approach, supplemented with 27 Al and 29 Si magic-angle spinning nuclear magnetic resonance spectroscopy and transmission electron microscopy, turned out to be a powerful characterization tool for studying a local atomic binding structure of C–S–H in C 3 S-HVFA system and presented results consistent with previous literature.

36 MATERIALS SCIENCE↗

Toward Thermally Stimuli-Responsive Polymeric Vesicles Fabricated by Block Copolymer Blends for Nanocarriers

Polymeric vesicles, characterized by enhanced colloidal stability, excellent mechanical properties, controllable surface functionality, and adjustable membrane thickness, are extremely useful in nano- and bio-technology for potential applications as nanosized carriers for drugs and enzymes. However, a few preparative steps are necessary to achieve a unilamellar vesicle with a narrow size distribution. Herein, we report the spontaneous formation of unilamellar polymeric vesicles with nanometer sizes (<50 nm), fabricated by simply mixing diblock copolymers (P(EO-AGE)(2K-2K) and P(EO-AGE)(0.75K-2K)) with differing hydrophilic mass fractions in aqueous solutions. Depending on the mixing ratio of block copolymers and the temperature, the block copolymer mixtures self-assemble into various nanostructures, such as spherical and cylindrical micelles, or vesicles. The self-assembled structures of the block copolymer mixtures were characterized by small-angle neutron scattering, resulting in a phase diagram drawn as a function of temperature and the mixing condition. Notably, the critical temperature for the micelle-to-vesicle phase transition can be easily controlled by altering the mixing conditions; it decreases with an increase in the concentration of one of the block copolymers.

block copolymers↗