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Creators/Authors contains: "Hart, A."

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  1. Free, publicly-accessible full text available September 2, 2025
  2. In supramolecular materials, multiple weak binding groups can act as a single collective unit when confined to a localized volume, thereby producing strong but dynamic bonds between material building blocks. This principle of multivalency provides a versatile means of controlling material assembly, as both the number and the type of supramolecular moieties become design handles to modulate the strength of intermolecular interactions. However, in materials with building blocks significantly larger than individual supramolecular moieties (e.g., polymer or nanoparticle scaffolds), the degree of multivalency is difficult to predict or control, as sufficiently large scaffolds inherently preclude separated supramolecular moieties from interacting. Because molecular models commonly used to examine supramolecular interactions are intrinsically unable to examine any trends or emergent behaviors that arise due to nanoscale scaffold geometry, our understanding of the thermodynamics of these massively multivalent systems remains limited. Here we address this challenge via the coassembly of polymer-grafted nanoparticles and multivalent polymers, systematically examining how multivalent scaffold size, shape, and spacing affect their collective thermodynamics. Investigating the interplay of polymer structure and supramolecular group stoichiometry reveals complicated but rationally describable trends that demonstrate how the supramolecular scaffold design can modulate the strength of multivalent interactions. This approach to self-assembled supramolecular materials thus allows for the manipulation of polymer−nanoparticle composites with controlled thermal stability, nanoparticle organization, and tailored meso- to microscopic structures. The sophisticated control of multivalent thermodynamics through precise modulation of the nanoscale scaffold geometry represents a significant advance in the ability to rationally design complex hierarchically structured materials via self-assembly. 
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  3. Ultraviolet (UV) printing of photopolymers is a widely adopted manufacturing method because of its high resolution and throughput. However, available printable photopolymers are typically thermosets, resulting in challenges in postprocessing and recycling of printed structures. Here, we present a new process called interfacial photopolymerization (IPP) which enables photopolymerization printing of linear chain polymers. In IPP, a polymer film is formed at the interface between two immiscible liquids, one containing a chain-growth monomer and the other containing a photoinitiator. We demonstrate the integration of IPP in a proof-of-concept projection system for printing of polyacrylonitrile (PAN) films and rudimentary multi-layer shapes . IPP shows in-plane and out-of-plane resolutions comparable to conventional photoprinting methods. Cohesive PAN films with number-average molecular weights greater than 15 kg mol–1 are obtained, and to our knowledge this is the first report of photopolymerization printing of PAN. A macrokinetics model of IPP is developed to elucidate the transport and reaction rates involved and evaluate how reaction parameters affect film thickness and print speed. Last, demonstration of IPP in a multilayer scheme suggests its suitabiliy for three-dimensional printing of linear-chain polymers. 
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  4. To help straddle the breadth of research on doctoral student stress, our team sought to explore the landscape of doctoral student stressors by interviewing an intentionally stratified sample of doctoral students four times during the course of an academic year. We present an overview of our research process and the top 10 most reported stressors from analysis of our interview data. Further, we report on the most frequent coping strategies used by students in our sample, contributing additional coping strategies used by engineering doctoral students. Understanding the most common factors which contribute to the stresses experienced by doctoral students and these students' effective coping strategies can support students, advisors, and departments to develop proactive interventions and strategies that support well-being and retention. 
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  5. Accelerator based neutrino oscillation experiments seek to measure the relative number of electron and muon (anti)neutrinos at different L / E values. However high statistics studies of neutrino interactions are almost exclusively measured using muon (anti)neutrinos since the dominant flavor of neutrinos produced by accelerator based beams are of the muon type. This work reports new measurements of electron (anti)neutrinos interactions in hydrocarbon, obtained by strongly suppressing backgrounds initiated by muon flavor (anti)neutrinos. Double differential cross sections as a function of visible energy transfer, E avail , and transverse momentum transfer, p T , or three momentum transfer, q 3 are presented. Published by the American Physical Society2024 
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  6. Neutron production in antineutrino interactions can lead to bias in energy reconstruction in neutrino oscillation experiments, but these interactions have rarely been studied. MINERvA previously studied neutron production at an average antineutrino energy of ∼3 GeV in 2016 and found deficiencies in leading models. In this paper, the MINERvA 6 GeV average antineutrino energy dataset is shown to have similar disagreements. A measurement of the cross section for an antineutrino to produce two or more neutrons and have low visible energy is presented as an experiment-independent way to explore neutron production modeling. This cross section disagrees with several leading models’ predictions. Neutron modeling techniques from nuclear physics are used to quantify neutron detection uncertainties on this result. 
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