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Oakdale, James S.

Publications and source records attributed to Oakdale, James S..

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Refractive index matching base resin for extremely fine three-dimensional ceramic structures

An optically clear resin for additive manufacturing includes an optically clear ceramic precursor having a pre-defined refractive index. Each molecule of the ceramic precursor has at least two photopolymerizable functional groups, at least one of the photopolymerizable functional groups being functionalized with a refractive index-tuning group thereby causing the ceramic precursor to have the pre-defined refractive index.

Mettry, Magi↗
DOE OSTI2024

Ultraviolet-Activated Solid-State Nitrene Cross-Linking: A Scalable Pathway to Prolonged Lifespan in Anion Exchange Membranes

Anion exchange membranes (AEMs) offer a cost-effective alternative to proton exchange membranes as alkaline fuel cells and electrolyzers permit the use of non-platinum group electrodes and components. Despite continued progress, the operational lifetime and stability of these membranes limit the widespread adoption of AEM-based electrochemical technologies. This study presents a flexible and easily implemented ultraviolet (UV)-initiated nitrene-based cross-linking method which uses a small, facile organic azide precursor. As a proof of concept, we demonstrate this approach on the well-studied poly(2,6-dimethyl-1,4-phenylene oxide) quaternary ammonium AEM (QPPO) polyelectrolyte. Further, a survey of cross-linker density (2.5–10 mol %) found that the addition of 10 mol % results in a 59% reduction in water uptake, a 58.8% decrease in the swell ratio, and a 31% increase in tensile strength vs the un-cross-linked material. Nitrene cross-linking also enhanced the membrane’s durability, enabling 1000 h of stable performance under electrochemical load. This UV-initiated cross-linking method may be easily integrated into production processes, allowing chemical cross-linking at any stage, including posthydration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Fabricating structured particles through rapid hardening and tailored collection methods

Fabrication of functional polymer-based particles by crosslinking UV-curable polymer drops in mid-air and collecting crosslinked particles in a solid container, a liquid suspension, or an air flow. The particles can contain different phases in the form or layered structures that contain one to multiple cores, or structures that are blended with dissolved or emulsified smaller domains. A curing system produces ultraviolet rays that are directed onto the particles in the jet stream from one side. A reflector positioned on other side of the jet stream reflects the ultraviolet rays back onto the particles in the jet stream.

Ye, Congwang↗
DOE OSTI2023

Tuning Alkaline Anion Exchange Membranes through Crosslinking: A Review of Synthetic Strategies and Property Relationships

Alkaline anion exchange membranes (AAEMs) are an enabling component for next-generation electrochemical devices, including alkaline fuel cells, water and CO2 electrolyzers, and flow batteries. While commercial systems, notably fuel cells, have traditionally relied on proton-exchange membranes, hydroxide-ion conducting AAEMs hold promise as a method to reduce cost-per-device by enabling the use of non-platinum group electrodes and cell components. AAEMs have undergone significant material development over the past two decades; however, challenges remain in the areas of durability, water management, high temperature performance, and selectivity. In this review, we survey crosslinking as a tool capable of tuning AAEM properties. While crosslinking implementations vary, they generally result in reduced water uptake and increased transport selectivity and alkaline stability. We survey synthetic methodologies for incorporating crosslinks during AAEM fabrication and highlight necessary precautions for each approach.

08 HYDROGEN↗
DOE OSTI2023

Post-Hydration Crosslinking of Ion Exchange Membranes to Control Water Content

The utilization of crosslinking as a technique to limit excess water uptake in ion exchange membranes is a well-established approach. However, traditional methods involve performing the crosslinking reaction before the membrane self-segregates into hydrophilic and hydrophobic domains upon exposure to water. In this study, we employ numerical and molecular simulations to explore the potential of post-hydration crosslinking of the polymer at subsaturated conditions. This process allows for the development of a nanosegregated morphology, which establishes well-connected but narrow water channels, while limiting additional sorption of water. The significant reduction in membrane swelling observed in our study indicates that post-hydration crosslinking could be a promising approach to regulate water uptake in ion exchange membranes. Here based on our analyses, we propose chemical crosslinking strategies that may yield high membrane gel fractions.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Tailoring of pores in aerogels using 3D printed structures

In one embodiment, a method includes acquiring a three-dimensional printed template created using an additive manufacturing technique, infilling the template with an aerogel precursor solution, allowing formation of a sol-gel, and converting the sol-gel to an aerogel. In another embodiment, a product includes an aerogel having inner channels corresponding to outer walls of a three-dimensional printed template around which the aerogel was formed.

Chandrasekaran, Swetha↗
DOE OSTI2023

Isolating Chemical Reaction Mechanism as a Variable with Reactive Coarse-Grained Molecular Dynamics: Step-Growth versus Chain-Growth Polymerization

Here we present a general approach to isolate chemical reaction mechanism as an independently controllable variable across chemically distinct systems. Modern approaches to reduce the computational expense of molecular dynamics simulations often group multiple atoms into a single “coarse-grained” interaction site, which leads to a loss of chemical resolution. In this work we convert this shortcoming into a feature and use identical coarse-grained models to represent molecules that share nonreactive characteristics but react by different mechanisms. As a proof of concept, we use this approach to simulate and investigate distinct, yet similar, trifunctional isocyanurate resin formulations that polymerize by either chain- or step-growth. Because the underlying molecular mechanics of these models are identical, all emergent differences are a function of the reaction mechanism only. We find that the microscopic morphologies resemble related all-atom simulations and that simulated mechanical testing reasonably agrees with experiment.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Aging of UV curable PDMS developed for large-scale, high viscosity stereolithography

Polydimethylsiloxane (PDMS) elastomers are silicone rubbers that find widespread application in both academic and industrial settings. This study investigates the use of photosensitive platinum catalysts for UV-activated hydrosilylation of PDMS, which enables the additive manufacturing of PDMS objects through techniques such as stereolithography. Specifically, this study focuses on understanding the aging behavior of Pt-catalyzed, UV-curable PDMS samples, including their mechanical behavior under thermal and UV-accelerated aging conditions. The results show that the Pt-catalyzed, UV-curable PDMS introduced in this research is ‘under-cured’ after being printed and will slowly evolve over time resulting in increased stiffness and decreased elongation, likely due to the formation of additional crosslinks. FTIR spectroscopy indicates that no new chemical bonds or functional groups are generated through the aging process, suggesting that no thermal degradation or polymer chain scissions occur in the polymer matrix. Overall, this PDMS formulation exhibits greater mechanical strength and significantly less reduction in strength with aging, compared with the commonly used, UV-curable thiol-ene PDMS.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Exponential Water Uptake in Ionomer Membranes Results from Polymer Plasticization

Water content is the most influential factor in the performance of ion-exchange membranes (IEMs), controlling their mechanical rigidity, ionic conductivity, and degradation rates. Membranes absorb water exponentially at high water activity (a w ), making that region of the sorption isotherm the most influential on membrane properties. Plasticization of the polymer by water has been proposed to cause this exponential uptake at high a w . However, an integrated microscopic picture of the structure, thermodynamic, and mechanical properties of IEMs as a function of a w has remained elusive. In this work, we use large-scale molecular simulations validated with experimental measurements to compute the sorption isotherms, Young’s modulus, polymer dynamics, and structure of IEMs. The simulations unveil that the exponential increase in water uptake (WU) coincides in all cases with the glass to rubber transition of the membrane, as measured through its Young’s modulus and segmental polymer dynamics. Functionalization of the polymer with alkyl groups further contributes to its plasticization, increasing the WU at a given a w and ion-exchange capacity (IEC). The alkyl chains act synergistically with water to plasticize the polymer matrix and allow water penetration in the membrane. The simulations reveal that the width of the water channels depends on the ratio λ of water to ions in the polymer but is independent of its IEC. We conclude that differences in the polymer matrix–not the water channels–are responsible for the distinct uptake response of IEMs to the thermodynamic driving force of water activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

System and method for liquid crystal display system incorporating wire grid polarizers for large scale and large volume stereolithography

The present disclosure relates to a liquid crystal display (LCD) system. The system in one example has a light source for generating unpolarized light, and an LCD screen arranged in a path of transmittance of the unpolarized light. First and second wire grid polarizers are arranged adjacent to the LCD screen and each have a plurality of nano-scale wires, with the first and second wire grid polarizers have differing polarizations. A pitch of each of the nano-scale wires is no larger than one-third a wavelength of the unpolarized light from the light source. The wire grid polarizers create, in connection with operation of the LCD screen, a 2D light mask suitable for initiating the polymerization of an optically curable material.

Duoss, Eric B.↗
DOE OSTI2022

Use of wire grid polarizers with liquid crystal display for large-volume stereolithography

Spatial light modulators that use liquid crystal devices (LCDs) to pattern ultraviolet light for vat polymerization suffer from a few limitations: limited range of wavelengths that can be patterned, low damage threshold for incoming light, and low efficiency of light transmission. A monochrome LCD can more efficiently transmit useful wavelengths of light for stereolithography (365–405 nm) than a color LCD, but it still contains two absorptive film polarizers that suffer from the aforementioned limitations. Wire grid polarizers reflect rather than absorb the blocked polarizations of light, resulting in a higher intensity damage threshold. They can also polarize lower wavelength light that is limited only by the wire pitch. In this work, this research investigates the effects of replacing an LCD’s film polarizers with wire grid polarizers to enable polarization and patterning of high intensity UV light, resulting in shorter curing times and the ability to print a wider range of stereolithography feedstocks.

42 ENGINEERING↗
DOE OSTI2021

Fabricating structured particles through rapid hardening and tailored collection methods

Fabrication of functional polymer-based particles by crosslinking UV-curable polymer drops in mid-air and collecting crosslinked particles in a solid container, a liquid suspension, or an air flow. The particles can contain different phases in the form or layered structures that contain one to multiple cores, or structures that are blended with dissolved or emulsified smaller domains. A curing system produces ultraviolet rays that are directed onto the particles in the jet stream from one side. A reflector positioned on other side of the jet stream reflects the ultraviolet rays back onto the particles in the jet stream.

Ye, Congwang↗
DOE OSTI2021

Degradation Studies of Silicone Rubbers in Direct Contact with Corrosive Solids Under Compression

Silicone elastomers are polymer materials widely used within the complex, serving as cushions, adhesives, binders, and potting compounds. Excellent high-temperature resistance combined with low-temperature flexibility, high resistance to chemicals and long-term age-related stability, make silicones first-choice materials in many application areas. However, the siloxane bonds comprising the backbone of silicone elastomers are susceptible to hydrolysis when catalytic amounts of acid or base are present. Hydrolysis is a form of degradation that results in chain-cleavage and rearrangement reactions, which can manifest in changes to the physical response and mechanical properties of the elastomer. This task aims to assess and quantify the extent of degradation and/or corrosion of silicone elastomer materials when placed in direct compressive contact with an Arrhenius base under varying environments (oxidative/nonoxidative, relative humidity, temperature, time, etc.).

36 MATERIALS SCIENCE↗
DOE OSTI2021

Chemical Modifications of Ag Catalyst Surfaces with Imidazolium Ionomers Modulate H 2 Evolution Rates during Electrochemical CO 2 Reduction

Bridging polymer design with catalyst surface science is a promising direction for tuning and optimizing electrochemical reactors that could impact long-term goals in energy and sustainability. Particularly, the interaction between inorganic catalyst surfaces and organic-based ionomers provides an avenue to both steer reaction selectivity and promote activity. In this work, we studied the role of imidazolium-based ionomers for electrocatalytic CO 2 reduction to CO (CO 2 R) on Ag surfaces and found that they produce no effect on CO 2 R activity yet strongly promote the competing hydrogen evolution reaction (HER). By examining the dependence of HER and CO 2 R rates on concentrations of CO 2 and HCO 3 –, we developed a kinetic model that attributes HER promotion to intrinsic promotion of HCO 3 – reduction by imidazolium ionomers. We also show that varying the ionomer structure by changing substituents on the imidazolium ring modulates the HER promotion. This ionomer-structure dependence was analyzed via Taft steric parameters and density functional theory calculations, which suggest that steric bulk from functionalities on the imidazolium ring reduces access of the ionomer to both HCO 3 – and the Ag surface, thus limiting the promotional effect. Our results help develop design rules for ionomer–catalyst interactions in CO 2 R and motivate further work into precisely uncovering the interplay between primary and secondary coordination in determining electrocatalytic behavior.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Click-chemistry compatible structures, click-chemistry functionalized structures, and materials and methods for making the same

According to several embodiments, a composition of matter includes: a three-dimensional structure comprising photo polymerized molecules. At least some of the photo polymerized molecules further comprise one or more protected click-chemistry compatible functional groups; and at least portions of one or more surfaces of the three-dimensional structure are functionalized with one or more of the protected click-chemistry compatible functional groups. An additive manufacturing resin suitable for fabricating a click-chemistry compatible composition of matter includes: a photo polymerizable compound; and a click-chemistry compatible compound. A method of forming an additive manufacturing resin suitable for fabricating a click-chemistry compatible composition of matter includes: reacting a compound comprising a terminal alkyne group or a terminal azide group with a protecting reagent to form a protected reactive diluent precursor, reacting the precursor with a compound to form a protected reactive diluent; and mixing the protected reactive diluent with a photo polymerizable compound.

Campbell, Patrick↗
DOE OSTI2021

3D Printing of High Viscosity Reinforced Silicone Elastomers

Recent advances in additive manufacturing, specifically direct ink writing (DIW) and ink-jetting, have enabled the production of elastomeric silicone parts with deterministic control over the structure, shape, and mechanical properties. These new technologies offer rapid prototyping advantages and find applications in various fields, including biomedical devices, prosthetics, metamaterials, and soft robotics. Stereolithography (SLA) is a complementary approach with the ability to print with finer features and potentially higher throughput. However, all high-performance silicone elastomers are composites of polysiloxane networks reinforced with particulate filler, and consequently, silicone resins tend to have high viscosities (gel- or paste-like), which complicates or completely inhibits the layer-by-layer recoating process central to most SLA technologies. Herein, the design and build of a digital light projection SLA printer suitable for handling high-viscosity resins is demonstrated. Further, a series of UV-curable silicone resins with thiol-ene crosslinking and reinforced by a combination of fumed silica and MQ resins are also described. The resulting silicone elastomers are shown to have tunable mechanical properties, with 100–350% elongation and ultimate tensile strength from 1 to 2.5 MPa. Three-dimensional printed features of 0.4 mm were achieved, and complexity is demonstrated by octet-truss lattices that display negative stiffness.

36 MATERIALS SCIENCE↗