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Open access publications by faculty, postdocs, and graduate students in the Department of Materials Science and Engineering
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Item Tracking Chain Populations and Branching Structure during Polyethylene Deconstruction Processes(ACS Central Science, 2024-08-21) Balzer, Alex H.; Hinton, Zachary R.; Vance, Brandon C.; Vlachos, Dionisios G.; Korley, LaShanda T. J.; Epps, Thomas H., IIICatalytic deconstruction has emerged as a promising solution to valorize polyethylene (PE) waste into valuable products, such as oils, fuels, surfactants, and lubricants. Unfortunately, commercialization has been hampered by inadequate optimization of PE deconstruction due to an inability to either truly characterize the polymer transformations or adjust catalytic conditions to match the ever-evolving product distribution and associated property changes. To address these challenges, a detailed analysis of molar mass distributions and thermal characterization was developed herein and applied to low-density polyethylene (LDPE) deconstruction to enable more thorough identification of polymer chain characteristics within the solids (e.g., changes in molar mass or branching structure). For example, LDPE hydrocracking exhibited comparable rates of polymer chain isomerization and C–C bond scission, and the solids generated possessed a broadened molar mass distribution with a disappearance of a significant fraction of highly linear segments, indicating polymer-structure-dependent interactions with the catalyst. Solids analysis from pyrolysis yielded starkly different results, as the resulting solids were devoid of unreacted polymer chains and had a narrowed molar mass distribution even at short times (e.g., 0.2 h). By tracking the polymeric deconstruction behavior as a function of reaction type, time, and catalyst design, we mapped critical pathways toward PE valorization. Synopsis A comprehensive approach to track polymer chain evolution during deconstruction was developed and revealed the influence of deconstruction method and polymer architecture on product distributions.Item Tuning the thermal response of 3D-printed bilayer hydrogels via architectural control using binary ethanol–water solvent systems(RSC Applied Polymers, 2024-08-14) Klincewicz, Francis; Kalidindi, Subhash; Korley, LaShanda T. J.While stimuli-responsive materials can be prepared via many established procedures, digital light processing (DLP) 3D printing offers a simple and robust technique for the fabrication of hydrogels, including spatially-defined bilayer hydrogels. The use of synthesis solvent mixtures has recently gained attention as a facile alternative to more complicated chemical modifications to tune hydrogel morphology by exploiting solvent-monomer interactions and cononsolvency which, by extension, modulates stimuli-response time and magnitude. In this work, we utilized a binary solvent system consisting of ethanol and water to induce morphological changes within a thermally-responsive poly(N-isopropyl acrylamide) (pNIPAAm) hydrogel during polymerization. By varying the ratio of ethanol to water, we demonstrated that hydrogel properties, such as crosslink density, pore morphology, and thermal response, can be tuned and correlated. While mass expulsion was fastest in gels prepared in 100% ethanol, we found that gels prepared in 75%–25% ethanol–water and 50%–50% ethanol–water maintained mechanical integrity at high temperatures, allowing expulsion of water mass without large amounts of contraction. We utilized the experimental findings from the monolayer hydrogel studies and investigated the response of bilayer structures comprised of pNIPAAm hydrogel layer and a non-responsive poly(2-hydroxyethyl acrylate) (pHEA) hydrogel layer and applied a mathematical model to better understand the fundamental kinematics of these bilayer systems in response to temperature. We also demonstrated the utility of these bilayer hydrogels for use in soft robotics applications. Overall, this work highlights that modulation of binary solvent mixture ratios is a strategy that enables control of morphological and mechanical features of stimuli-responsive hydrogels via 3D printing.Item Tuning Excitonic Properties of Monochalcogenides via Design of Janus Structures(Journal of Physical Chemistry C, 2024-07-25) Querne, Mateus B. P.; Dias, Alexandre C.; Janotti, Anderson; Da Silva, Juarez L. F.; Lima, Matheus P.Two-dimensional (2D) Janus structures offer a unique range of properties as a result of their symmetry breaking, resulting from the distinct chemical composition on each side of the monolayers. Here, we report a theoretical investigation of 2D Janus Q′A′AQ P3m1 monochalcogenides from group IV (A and A′ = Ge and Sn; Q, Q′ = S and Se) and 2D non-Janus QAAQ P3̅m1 counterparts. Our theoretical framework is based on density functional theory calculations combined with maximally localized Wannier functions and tight-binding parametrization to evaluate the excitonic properties. The phonon band structures exhibit exclusively real (nonimaginary) branches for all materials. Particularly, SeGeSnS has greater energetic stability than its non-Janus counterparts, representing an outstanding energetic stability among the investigated materials. However, SGeSnS and SGeSnSe have higher formation energies than the already synthesized MoSSe, making them more challenging to grow than the other investigated structures. The electronic structure analysis demonstrates that materials with Janus structures exhibit band gaps wider than those of their non-Janus counterparts, with the absolute value of the band gap predominantly determined by the core rather than the surface composition. Moreover, exciton binding energies range from 0.20 to 0.37 eV, reducing band gap values in the range of 21% to 32%. Thus, excitonic effects influence the optoelectronic properties more than the point-inversion symmetry breaking inherent in the Janus structures; however, both features are necessary to enhance the interaction between the materials and sunlight. We also found anisotropic behavior of the absorption coefficient, which was attributed to the inherent structural asymmetry of the Janus materials.Item Engineering lignin-derivable diacrylate networks with tunable architecture and mechanics(Materials Advances, 2024-07-03) Wong, Yu-Tai; Korley, LaShanda T. J.Network engineering strategies offer a promising pathway toward tunable thermomechanical properties of bio-derivable, aromatic (meth)acrylate thermosets to expand their application library. In this work, a series of acrylate thermosets, synthesized from lignin-derivable vanillyl alcohol/bisguaiacol F diacrylates (VDA/BGFDA) and a bio-based n-butyl acrylate (BA), were designed as a sustainable platform to explore structure-architecture-property relationships. Using this approach, we examined a series of processable, fully bio-derivable acrylates. Increasing the diacrylate content across all networks improved storage moduli at 25 °C (E′25) by up to 2 GPa (1.1 GPa for VDA/BA-25/75 vs. 3.1 GPa for VDA/BA-75/25, and 1.5 GPa for BGFDA/BA-25/75 vs. 1.7 GPa for BGFDA/BA-50/50), and led to a more inhomogeneous network as evidenced by lower acrylate group conversion and a broader tan δ peak, indicating heterogeneous relaxation modes. Modifying the aromatic content of the starting diacrylate impacted the final inhomogeneity of the network, with increasing inhomogeneity observed for the bis-aromatic BGFDA relative to the mono-aromatic VDA. Similarly, combining the mono- and bis-aromatic diacrylates generated a network with a biphasic-like thermal relaxation mode. By correlating network architecture and material performance, the increasing architectural complexity suggested a more convoluted thermal relaxation mode while the enhancement of thermomechanical properties could still be achieved for potential application as damping materials. Overall, we presented a design strategy utilizing bio-derivable acrylates to expand the suite of renewable material platforms from a network engineering perspective.Item Supramolecular Gelation of Cadmium Oleate in the Synthesis of Nanocrystals for Applications in Photonics and Optoelectronics(ACS Applied Nano Materials, 2024-05-22) Welsch, Tory A.; Cleveland, Jill M.; Thomas, Jessica A.; Schyns, Zoé Odile Georgette; Korley, LaShanda T. J.; Doty, Matthew F.Cadmium oleate is widely used as a cation precursor in the synthesis of cadmium chalcogenide nanocrystal quantum dots (QDs) for a broad range of photonic and optoelectronic applications. Cd oleate can noncovalently assemble to form a supramolecular coordination gel, or metallogel, in solvents commonly used to disperse oleate-capped QDs. The gelation severely impedes the purification of oleate-capped QDs from excess Cd oleate, resulting in a gelled product that cannot be reliably characterized or used in further synthesis reactions. Here, we investigate the Cd oleate gel to gain insights into its viscoelastic properties and behavior under conditions relevant to QD synthesis, purification, and storage. We then examine how to effectively mitigate gelation by adding oleylamine as an additional ligand to disrupt noncovalent assembly. We synthesize PbS/CdS core/shell QDs via cation exchange as a case study to illustrate gelation of the reaction product and further demonstrate how this issue can be resolved through a better understanding of the supramolecular gel.Item Imidazolium-Based Sulfonating Agent to Control the Degree of Sulfonation of Aromatic Polymers and Enable Plastics-to-Electronics Upgrading(JACS Au, 2024-07-03) Lo, Chun-Yuan; Koutsoukos, Kelsey P.; Nguyen, Dan My; Wu, Yuhang; Angel Trujillo, David Alejandro; Miller, Tabitha; Shrestha, Tulaja; Mackey, Ethan; Damani, Vidhika S.; Kanbur, Uddhav; Opila, Robert; Martin, David C.; Kaphan, David; Kayser, Laure V.The accumulation of plastic waste in the environment is a growing environmental, economic, and societal challenge. Plastic upgrading, the conversion of low-value polymers to high-value materials, could address this challenge. Among upgrading strategies, the sulfonation of aromatic polymers is a powerful approach to access high-value materials for a range of applications, such as ion-exchange resins and membranes, electronic materials, and pharmaceuticals. While many sulfonation methods have been reported, achieving high degrees of sulfonation while minimizing side reactions that lead to defects in the polymer chains remains challenging. Additionally, sulfonating agents are most often used in large excess, which prevents precise control over the degree of sulfonation of aromatic polymers and their functionality. Herein, we address these challenges using 1,3-disulfonic acid imidazolium chloride ([Dsim]Cl), a sulfonic acid-based ionic liquid, to sulfonate aromatic polymers and upgrade plastic waste to electronic materials. We show that stoichiometric [Dsim]Cl can effectively sulfonate model polystyrene up to 92% in high yields, with minimal defects and high regioselectivity for the para position. Owing to its high reactivity, the use of substoichiometric [Dsim]Cl uniquely allows for precise control over the degree of sulfonation of polystyrene. This approach is also applicable to a wide range of aromatic polymers, including waste plastic. To prove the utility of our approach, samples of poly(styrene sulfonate) (PSS), obtained from either partially sulfonated polystyrene or expanded polystyrene waste, are used as scaffolds for poly(3,4-ethylenedioxythiophene) (PEDOT) to form the ubiquitous conductive material PEDOT:PSS. PEDOT:PSS from plastic waste is subsequently integrated into organic electrochemical transistors (OECTs) or as a hole transport layer (HTL) in a hybrid solar cell and shows the same performance as commercial PEDOT:PSS. This imidazolium-mediated approach to precisely sulfonating aromatic polymers provides a pathway toward upgrading postconsumer plastic waste to high-value electronic materials.Item Dynamic reporters for probing real-time activation of human fibroblasts from single cells to populations(APL Bioengineering, 2024-06-24) Cassel, Samantha E.; Huntington, Breanna M.; Chen, Wilfred; Lei, Pedro; Andreadis, Stelios T.; Kloxin, April M.Activation of fibroblasts is pivotal for wound healing; however, persistent activation leads to maladaptive processes and is a hallmark of fibrosis, where disease mechanisms are only partially understood. Human in vitro model systems complement in vivo animal models for both hypothesis testing and drug evaluation to improve the identification of therapeutics relevant to human disease. Despite advances, a challenge remains in understanding the dynamics of human fibroblast responses to complex microenvironment stimuli, motivating the need for more advanced tools to investigate fibrotic mechanisms. This work established approaches for assessing the temporal dynamics of these responses using genetically encoded fluorescent reporters of alpha smooth muscle actin expression, an indicator of fibroblast activation. Specifically, we created a toolset of human lung fibroblast reporter cell lines from different origins (male, female; healthy, idiopathic pulmonary fibrosis) and used three different versions of the reporter with the fluorescent protein modified to exhibit different temporal stabilities, providing temporal resolution of protein expression processes over a range of timescales. Using this toolset, we demonstrated that reporters provide insight into population shifts in response to both mechanical and biochemical cues that are not detectable by traditional end point assessments with differential responses based on cell origin. Furthermore, individual cells can also be tracked over time, with opportunities for comparison to complementary end point measurements. The establishment of this reporter toolset enables dynamic cell investigations that can be translated into more complex synthetic culture environments for elucidating disease mechanisms and evaluating therapeutics for lung fibrosis and other complex biological processes more broadly.Item Large Rashba spin splittings in bulk and monolayer of BiAs(Physical Review Materials, 2024-05-20) Zubair, Muhammad; Evangelista, Igor; Khalid, Shoaib; Medasani, Bharat; Janotti, AndersonThere is great interest in developing new materials with Rashba split bands near the Fermi level for spintronics. Using first-principles calculations, we predict BiAs as a semiconductor with large Rashba splitting in bulk and monolayer forms. Bulk BiAs has a layered crystal structure with two atoms in a rhombohedral primitive cell, derived from the structure of the parent Bi and As elemental phases. It is a narrow band gap semiconductor, and it shows a combination of Rashba and Dresselhaus spin splitting with a characteristic spin texture around the L point in the Brillouin zone of the hexagonal conventional unit cell. It has sizable Rashba energies and Rashba coupling constants in the valence and conduction bands at the band edges. The 2D monolayer of BiAs has a much larger band gap at Γ, with a circular spin texture characteristic of a pure Rashba effect. The Rashba energy and Rashba coupling constant of monolayer BiAs are large compared to other known 2D materials and rapidly increase under biaxial tensile strain.Item Gallium-incorporated TiO2 thin films by atomic layer deposition for future electronic devices(Frontiers in Materials, 2024-06-13) Sun, Qingxuan; Lin, Yingzhen; Han, Chaoya; Yang, Ze; Li, Ying; Zeng, Yuping; Yang, Weifeng; Zhang, JieTitanium dioxide (TiO2) with advantages including abundance in earth, non-toxicity, high chemical stability, surface hydrophobicity in dark, and extremely high permittivity could be highly promising for advanced electronics. However, the thermal stability and low bandgap (Eg) of TiO2 pose a big challenge for TiO2 to be used as dielectric, which could be resolved by doping with other metal cations. In this work, we studied the impact of gallium incorporation on electrical and material characteristics of TiO2 thin films. These TiO2 and TiXGaO films with thickness of 15 nm were derived by atomic layer deposition (ALD) and then annealed in O2 ambient at 500°C, where the levels of Ga incorporation were tuned by the cycle ratio (X) of TiO2 to that of Ga2O3 during ALD growth. Both thin film transistors (TFTs) using TiXGaO (TiO2) thin films as the channel and metal-oxide semiconductor capacitors (MOSCAPs) using TiXGaO (TiO2) thin films as the dielectric were fabricated to unravel the impact of Ga incorporation on electrical properties of TiO2 thin films. It is found that the Ga incorporation reduces the conductivity of TiO2 thin films significantly. Pure TiO2 thin films could be the ideal channel material for TFTs with excellent switching behaviors whereas Ga-incorporated TiO2 thin films could be the dielectric material for MOSCAPs with good insulating properties. The leakage current and dielectric constant (k) value are also found to be decreased with the increased Ga content in TiXGaO/Si MOSCAPs. Additionally, the density of interface trap (Dit) between TiXGaO and Si were extracted by multi-frequency conductance method, where a “U-shape” trap profile with similar level of Dit values can be observed for TiXGaO MOSCAPs with varying Ga contents. Material characterizations show that the Ga incorporation destabilizes the crystallization and enlarges the bandgap (Eg) of TiO2 while maintaining a smooth surface. Interestingly, Ga incorporation is found to decrease the overall oxygen content and introduce more oxygen-related defects in the film. As a result, the reduction of leakage current upon Ga incorporation in MOSCAPs could be explained by amorphization of the film and enlarged band offset to Si rather than oxygen defect passivation. These Ga-incorporated TiO2 films may found promising usage in future electronic device applications such as trench capacitors in dynamic random-access memory, where the emerging high-k dielectrics with low leakage currents and high thermal stability are demanded.Item MEMS-actuated terahertz metamaterials driven by phase-transition materials(Frontiers of Optoelectronics, 2024-05-27) Huang, Zhixiang; Wu, Weipeng; Herrmann, Eric; Ma, Ke; Chase, Zizwe A.; Searles, Thomas A.; Jungfleisch, M. Benjamin; Wang, XiThe non-ionizing and penetrative characteristics of terahertz (THz) radiation have recently led to its adoption across a variety of applications. To effectively utilize THz radiation, modulators with precise control are imperative. While most recent THz modulators manipulate the amplitude, frequency, or phase of incident THz radiation, considerably less progress has been made toward THz polarization modulation. Conventional methods for polarization control suffer from high driving voltages, restricted modulation depth, and narrow band capabilities, which hinder device performance and broader applications. Consequently, an ideal THz modulator that offers high modulation depth along with ease of processing and operation is required. In this paper, we propose and realize a THz metamaterial comprised of microelectromechanical systems (MEMS) actuated by the phase-transition material vanadium dioxide (VO2). Simulation and experimental results of the three-dimensional metamaterials show that by leveraging the unique phase-transition attributes of VO2, our THz polarization modulator offers notable advancements over existing designs, including broad operation spectrum, high modulation depth, ease of fabrication, ease of operation condition, and continuous modulation capabilities. These enhanced features make the system a viable candidate for a range of THz applications, including telecommunications, imaging, and radar systems. Graphical Abstract available at: https://doi.org/10.1007/s12200-024-00116-4Item Antibody and siRNA Nanocarriers to Suppress Wnt Signaling, Tumor Growth, and Lung Metastasis in Triple-Negative Breast Cancer(Advanced Therapeutics, 2024-04-26) Dang, Megan N.; Suri, Sejal; Li, Kejian; Gomez Casas, Carolina; Stigliano, Gianna; Riley, Rachel S.; Scully, Mackenzie A.; Hoover, Elise C.; Aboeleneen, Sara B.; Kramarenko, George C.; Day, Emily S.The paucity of targeted therapies for triple-negative breast cancer (TNBC) causes patients with this aggressive disease to suffer a poor clinical prognosis. A promising target for therapeutic intervention is the Wnt signaling pathway, which is activated in TNBC cells when extracellular Wnt ligands bind overexpressed Frizzled7 (FZD7) transmembrane receptors. This stabilizes intracellular β-catenin proteins that in turn promote transcription of oncogenes that drive tumor growth and metastasis. To suppress Wnt signaling in TNBC cells, this work develops therapeutic nanoparticles (NPs) functionalized with FZD7 antibodies and β-catenin small interfering RNAs (siRNAs). The antibodies enable TNBC cell specific binding and inhibit Wnt signaling by locking FZD7 receptors in a ligand unresponsive state, while the siRNAs suppress β-catenin through RNA interference. Compared to NPs coated with antibodies or siRNAs individually, NPs coated with both agents more potently reduce the expression of several Wnt related genes in TNBC cells, leading to greater inhibition of cell proliferation, migration, and spheroid formation. In two murine models of metastatic TNBC, the dual antibody/siRNA nanocarriers outperformed controls in terms of inhibiting tumor growth, metastasis, and recurrence. These findings demonstrate suppressing Wnt signaling at both the receptor and mRNA levels via antibody/siRNA nanocarriers is a promising approach to combat TNBC.Item Lignin-derivable, thermoplastic, non-isocyanate polyurethanes with increased hydrogen-bonding content and toughness vs. petroleum-derived analogues(Materials Advances, 2024-04-02) Mahajan, Jignesh S.; Hinton, Zachary R.; Nombera Bueno, Eduardo; Epps, Thomas H. III; Korley, LaShanda T. J.The functionality inherent in lignin-derivable bisguaiacols/bissyringols can improve the processability and performance of the resulting polymers. Herein, non-isocyanate polyurethanes (NIPUs) were synthesized from bisguaiacols/bissyringols with varying degrees of methoxy substitution and differing bridging groups. Notably, the presence of increasing numbers of methoxy groups (0, 2, and 4) in bisphenol F (BPF)-, bisguaiacol F (BGF)-, and bissyringol F (BSF)-NIPUs led to higher percentages of hydrogen-bonded –OH/–NH groups (i.e., ∼65%, ∼85%, ∼95%, respectively). Increased hydrogen bonding between chains improved the elongation-at-break (εbreak) and toughness of lignin-derivable NIPUs over their petroleum counterparts without a reduction in Young's moduli and tensile strengths. For example, BSF-NIPU exhibited the highest εbreak ∼210% and toughness ∼62 MJ m−3, followed by BGF-NIPU (εbreak ∼185% and toughness ∼58 MJ m−3), and then BPF-NIPU (εbreak ∼140% and toughness ∼42 MJ m−3). Similar trends were found in the dimethyl-substituted analogues, particularly for the bisphenol A-NIPU and bisguaiacol A-NIPU. Importantly, the melt rheology of the lignin-derivable NIPUs was comparable to that of the petroleum-derived analogues, with a slightly lower viscosity (i.e., improved melt flow) for the bio-derivable NIPUs. These findings suggested that the added functionalities (methoxy groups) derived from lignin precursors improved thermomechanical stability while also offering increased processability. Altogether, the structure–property-processing relationships described in this work can help facilitate the development of sustainable, performance-advantaged polymers.Item Macrophage variance: investigating how macrophage origin influences responses to soluble and physical cues with immortalized vs. primary cells in 2D and 3D culture(Frontiers in Biomaterials Science, 2024-05-22) Graf, Jodi; Bomb, Kartik; Trautmann-Rodriguez, Michael; Jarai, Bader M.; Gill, Nicole; Kloxin, April M.; Fromen, Catherine A.Macrophages are phagocytic innate immune cells capable of phenotypical switching in response to the local microenvironment. Studies often use either primary macrophages or immortalized cell lines for hypothesis testing, therapeutic assessment, and biomaterial evaluation without carefully considering the potential effects of cell source and tissue of origin, which strongly influence macrophage response. Surprisingly, limited information is available about how, under similar stimuli, immortalized cell lines and primary cells respond in both phenotypical and functional changes. To address this need, in this work, we cultured immortalized macrophage cell lines derived from different origins (i.e., blood, lung, peritoneal) to understand and compare macrophage phenotypical responses, including polarization and plasticity, morphological changes, and phagocytic functionalities, as well as compared primary macrophages extracted from peritoneal and bone marrow to their immortalized cell line counterparts. We found significant differences in baseline expression of different markers (e.g., CD86, MHCII, CD206, and EGR2) amongst different cell lines, which further influence both polarization and repolarization of the cells, in addition to their phagocytic functionality. Additionally, we observed that, while RAW 264.7 cells behave similarly to the primary bone marrow-derived macrophages, there are noticeable phenotypical and functional differences in cell line (IC-21) and primary peritoneal macrophages, highlighting tissue-specific differences in macrophage response amongst cell lines and primary cells. Moving to three-dimensional (3D) culture in well-defined biomaterials, blood-derived primary and cell line macrophages were encapsulated within hydrogel-based synthetic extracellular matrices and their polarization profiles and cell morphologies were compared. Macrophages exhibited less pronounced polarization during 3D culture in these compliant, soft materials compared to two-dimensional (2D) culture on rigid, tissue culture plastic plates. Overall, our findings highlight origin-specific differences in macrophage response, and therefore, careful considerations must be made to identify the appropriate cell source for the application of interest.Item Theoretical insights into the adsorption and gas sensing performance of Fe/Cu-adsorbed graphene(Physical Chemistry Chemical Physics, 2024-04-17) Nguyen, Darien K.; Ho, Dai Q.; Trung, Nguyen TienThe binding mechanism of gas molecules on material surfaces is essential for understanding adsorption and sensing performance. In the present study, we examine the interaction of some volatile organic compounds (VOCs), including HCHO, C2H5OH, and CH3COCH3, on pristine graphene and its Fe/Cu-adsorbed surfaces using first-principles calculations. The results indicate that the adsorption of these molecules on graphene is regarded as physisorption, while chemisorption is observed for Fe/Cu attached surfaces. The binding of sites on molecules and surfaces primarily involves hydrogen bonds for the pure form of graphene. In contrast, stable interactions occur at functional groups such as >C[double bond, length as m-dash]O, –OH with Fe/Cu atoms, as well as C[double bond, length as m-dash]C bonds of π-rings on modified structures of graphene. It is noticeable that stronger adsorption is observed in the case of Fe addition (Gr-Fe) compared to Cu (Gr-Cu), enhancing the gas adsorption and sensing performance on graphene. Remarkably, the graphene surfaces supported by Fe and Cu improved selectivity in detecting VOC molecules, particularly C2H5OH and CH3COCH3 for Gr-Fe, and HCHO for Gr-Cu. Quantum chemical analyses reveal that the Fe/Cu⋯O/C contacts are covalent interactions, contributing significantly to the stability of configurations and sensing properties of Fe/Cu-adsorbed graphene. In summary, the observed improvements in selectivity, enhanced adsorption strength, and the identification of crucial interactions at the surface offer valuable insights into designing highly efficient gas sensors and developing advanced sensing materials.Item Bioderived silicon nano-quills: synthesis, structure and performance in lithium-ion battery anodes(Green Chemistry, 2024-03-12) Chen, Nancy; Sabet, Morteza; Sapkota, Nawraj; Parekh, Mihir; Chiluwal, Shailendra; Koehler, Kelliann; Clemons, Craig M.; Ding, Yi; Rao, Apparao M.; Pilla, SrikanthCellulose nanocrystals (CNCs) are bioderived one-dimensional species with versatile surface chemistry and unique self-assembling behavior in aqueous solutions. This work presents a scientific approach to leverage these characteristics for creating CNC network templates and processing them to engineer a novel silicon (Si)-based material called silicon nano-quill (SiNQ) for energy storage applications. The SiNQ structure possesses a porous, tubular morphology with a substantial ability to store lithium ions while maintaining its structural integrity. The presence of Si suboxides in the SiNQ structure is demonstrated to be crucial for realizing a stable cycling performance. One of the defining attributes of SiNQ is its water dispersibility due to Si–H surface bonds, promoting water-based Si-graphite electrode manufacturing with environmental and economic benefits. The incorporation of only 17 wt% SiNQ enhances the capacity of graphitic anodes by ∼2.5 times. An initial coulombic efficiency of 97.5% is achieved by employing a versatile pre-lithiation. The SiNQ-graphite anodes with high active loading, when subjected to accelerated charging/discharging conditions at 5.4 mA cm−2, exhibit stable cycling stability up to 500 cycles and average coulombic efficiency of >99%. A generalized physics-based cyclic voltammetry model is presented to explain the remarkable behavior of SiNQs under fast-charging conditions.Item Band Engineering of ErAs:InGaAlBiAs Nanocomposite Materials for Terahertz Photoconductive Switches Pumped at 1550 nm(Advanced Functional Materials, 2024-04-18) Acuna, Wilder; Wu, Weipeng; Bork, James; Doty, Mathew F.; Jungfleisch, M. Benjamin; Gundlach, Lars; Zide, Joshua M. O.Terahertz technology has the potential to have a large impact in myriad fields, such as biomedical science, spectroscopy, and communications. Making these applications practical requires efficient, reliable, and low-cost devices. Photoconductive switches (PCS), devices capable of emitting and detecting terahertz pulses, are a technology that needs more efficiency when working at telecom wavelength excitation (1550 nm) to exploit the advantages this wavelength offers. ErAs:InGaAs is a semiconductor nanocomposite working at this energy; however, high dark resistivity is challenging due to a high electron concentration as the Fermi level lies in the conduction band. To increase dark resistivity, ErAs:InGaAlBiAs material is used as the active material in a PCS detecting Terahertz pulses. ErAs nanoparticles reduce the carrier lifetime to subpicosecond values required for short temporal resolution, while ErAs pins the effective Fermi level in the host material bandgap. Unlike InGaAs, InGaAlBiAs offers enough freedom for band engineering to have a material compatible with a 1550 nm pump and a Fermi level deep in the bandgap, meaning low carrier concentration and high dark resistivity. Band engineering is possible by incorporating aluminum to lift the conduction band edge to the Fermi level and bismuth to keep a bandgap compatible with 1550 nm excitation.Item A novel digital lifecycle for Material-Process-Microstructure-Performance relationships of thermoplastic olefins foams manufactured via supercritical fluid assisted foam injection molding(Polymer Engineering and Science, 2024-03-15) Pradeep, Sai Aditya; Deshpande, Amit M.; Lavertu, Pierre‐Yves; Zheng, Ting; Yerra, Veera Aditya; Shimabukuro, Yiro; Li, Gang; Pilla, SrikanthThis research significantly enhances the applicability of thermoplastic olefins (TPOs) in the automotive industry using supercritical N2 as a physical foaming agent, effectively addressing the limitations of traditional chemical agents. It merges experimental results with simulations to establish detailed material-process-microstructure-performance (MP2) relationships, targeting 5–20% weight reductions. This innovative approach labeled digital lifecycle (DLC) helps accurately predict tensile, flexural, and impact properties based on the foam microstructure, along with experimentally demonstrating improved paintability. The study combines process simulations with finite element models to develop a comprehensive digital model for accurately predicting mechanical properties. Our findings demonstrate a strong correlation between simulated and experimental data, with about a 5% error across various weight reduction targets, marking significant improvements over existing analytical models. This research highlights the efficacy of physical foaming agents in TPO enhancement and emphasizes the importance of integrating experimental and simulation methods to capture the underlying foaming mechanism to establish material-process-microstructure-performance (MP2) relationships. Highlights - Establishes a material-process-microstructure-performance (MP2) for TPO foams - Sustainably produces TPO foams using supercritical (ScF) N2 with 20% lightweighting - Shows enhanced paintability for TPO foam improved surface aesthetics - Digital lifecycle (DLC) that predicts both foam microstructure and properties - DLC maps process effects & microstructure onto FEA mesh for precise predictionItem Adhesion Characterization and Enhancement between Polyimide-Silica Composite and Nodulated Copper for Applications in Next-Generation Microelectronics(ACS Applied Materials & Interfaces, 2024-01-17) Doshi, Sagar M.; Barry, Alexander; Schneider, Alexander; Parambil, Nithin; Mulzer, Catherine; Yahyazadehfar, Mobin; Samadi-Dooki, Aref; Foltz, Benjamin; Warrington, Keith; Wessel, Richard; Zhang, Lei; Simone, Christopher; Blackman, Gregory S.; Lamontia, Mark A.; Gillespie, John W. Jr.As the need for high-speed electronics continues to rise rapidly, printed wiring board (PWB) requirements become ever-more demanding. A typical PWB is fabricated by bonding dielectric films such as polyimide to electrically conductive copper foil such as rolled annealed (RA) copper and is expected to become thinner, flexible, durable, and compatible with high-frequency 5G performance. Polyimide films inherently feature a higher coefficient of thermal expansion (CTE) than copper foils; this mismatch causes residual thermal stresses. To attenuate the mismatch, silica nanoparticles may be used to reduce the CTE of PI. A nodulated copper surface can be used to enhance the Cu/PI adhesion by additional bonding mechanisms that could include a type of mechanical bonding, which is a focus of this study. In this investigation, a 90° peel test was used to measure the peel strength in copper/polyimide/copper laminates containing nodulated copper and polyimide reinforced with 0, 20, and 40 wt % silica nanoparticles. The influence of silica nanoparticles on the peel strength was quantitatively evaluated. Laminates incorporating polyimide films lacking silica nanoparticles had a ∼3.75× higher peel strength compared with laminates reinforced with 40% silica. Their failure surfaces were analyzed by using scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDX), and X-ray photoelectron spectroscopy to identify the mode of failure and to understand bonding mechanisms. The key bonding mechanism, mechanical interlocking, was achieved when the polyimide surrounded or engulfed the copper nodules when the laminate was created. Post-testing failure surface analysis revealed the presence of copper on the polyimide side and polyimide on the copper side, indicating mixed mode failure. An analytical model was developed to determine the impact of applied pressure, temperature, and time on the polyimide penetration and mechanical interlocking around the copper nodules. The model was validated by measuring the peel strength on another set of specimens fabricated using increased temperature and pressure that showed a 3× increase in peel strength compared to lower temperature/pressure processing conditions. This enhanced adhesion resulted from the lower polymer material viscosity at higher temperatures, which fosters deeper and more complete penetration around the copper nodules during processing at higher pressures for longer durations. The methodology of combining peel testing, viscosity and CTE measurement, SEM/EDX, surface chemical analysis, and penetration depth calculation developed herein enables the calculation of the desired processing parameters to enhance functionality and improve adhesion.Item Single-Mask Fabrication of Sharp SiOx Nanocones(IEEE Transactions on Semiconductor Manufacturing, 2023-11-28) Herrmann, Eric; Wang, XiThe patterning of silicon and silicon oxide nanocones onto the surfaces of devices introduces interesting phenomena such as anti-reflection and super-transmissivity. While silicon nanocone formation is well-documented, current techniques to fabricate silicon oxide nanocones either involve complex fabrication procedures, non-deterministic placement, or poor uniformity. Here, we introduce a single-mask dry etching procedure for the fabrication of sharp silicon oxide nanocones with smooth sidewalls and deterministic distribution using electron beam lithography. Silicon oxide films deposited using plasma-enhanced chemical vapor deposition are etched using a thin alumina hard mask of selectivity > 88, enabling high aspect ratio nanocones with smooth sidewalls and arbitrary distribution across the target substrate. We further introduce a novel multi-step dry etching technique to achieve ultra-sharp amorphous silicon oxide nanocones with tip diameters of ~10 nm. The processes presented in this work may have applications in the fabrication of amorphous nanocone arrays onto arbitrary substrates or as nanoscale probes.Item Growth factors and growth factor gene therapies for treating chronic wounds(Bioengineering and Translational Medicine, 2023-12-28) Mullin, James A.; Rahmani, Erfan; Kiick, Kristi L.; Sullivan, Millicent O.Chronic wounds are an unmet clinical need affecting millions of patients globally, and current standards of care fail to consistently promote complete wound closure and prevent recurrence. Disruptions in growth factor signaling, a hallmark of chronic wounds, have led researchers to pursue growth factor therapies as potential supplements to standards of care. Initial studies delivering growth factors in protein form showed promise, with a few formulations reaching clinical trials and one obtaining clinical approval. However, protein-form growth factors are limited by instability and off-target effects. Gene therapy offers an alternative approach to deliver growth factors to the chronic wound environment, but safety concerns surrounding gene therapy as well as efficacy challenges in the gene delivery process have prevented clinical translation. Current growth factor delivery and gene therapy approaches have primarily used single growth factor formulations, but recent efforts have aimed to develop multi-growth factor approaches that are better suited to address growth factor insufficiencies in the chronic wound environment, and these strategies have demonstrated improved efficacy in preclinical studies. This review provides an overview of chronic wound healing, emphasizing the need and potential for growth factor therapies. It includes a summary of current standards of care, recent advances in growth factor, cell-based, and gene therapy approaches, and future perspectives for multi-growth factor therapeutics. Translational Impact Statement Chronic wounds persist as a healthcare challenge despite extensive research on various treatments, including growth factors and gene therapies. Progress in translating these therapeutics to clinical use has been slow, with many growth factor approaches demonstrating promise in preclinical studies but providing limited benefits in clinical trials or clinical application. This review presents recent advances in growth factor therapies and growth factor gene therapies, discusses obstacles to regulatory approval, and offers perspectives on potential innovations for successful clinical translation.