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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 37 records · Page 2

Light $$Z^\prime $$ and Dirac fermion dark matter in the $$B-L$$ model

Abstract We consider a $$U(1)_{B-L}$$ U ( 1 ) B - L model with a $$Z^\prime $$ Z ′ portal Dirac fermion dark matter (DM) $$\chi $$ χ of low mass which couples very weakly to the $$B - L$$ B - L gauge boson $$Z^\prime $$ Z ′ . An arbitrary $$B-L$$ B - L charge $$Q\ne \pm 1, \pm 3$$ Q ≠ ± 1 , ± 3 of the DM $$\chi $$ χ ensures its stability. Motivated by the sensitivity reach of forthcoming “Lifetime Frontier” experiments, we focus on the $$Z^\prime $$ Z ′ mass, $$m_{Z^\prime }$$ m Z ′ , in the sub-GeV to few GeV range. To evaluate the DM relic abundance, we examine both the freeze-out and freeze-in DM scenarios. For the freeze-out scenario, we show that the observed DM abundance is reproduced near the $$Z^\prime $$ Z ′ resonance, $$m_\chi \simeq m_{Z^\prime }/2$$ m χ ≃ m Z ′ / 2 , where $$m_\chi $$ m χ is the DM mass. For the freeze-in scenario, we focus on $$m_\chi \ll m_{Z^\prime }$$ m χ ≪ m Z ′ . We show that for a fixed value of $$m_{Z^\prime }$$ m Z ′ , $$g_{BL}$$ g BL values roughly scale as 1/ Q to reproduce the observed DM abundance. For various Q values in the range between $$10^{-6}$$ 10 - 6 and $$10^2$$ 10 2 , we show that the gauge coupling values $$g_{BL}$$ g BL needed to reproduce the observed DM abundance lie in the search reach of future planned and/or proposed experiments such as FASER, Belle-II, LDMX, and SHiP. In the freeze-in case, the Q values to realize observable $$g_{BL}$$ g BL values are found to be much smaller than that in the freeze-out case.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Morphological changes of gamma prime precipitates in nickel-base superalloy single crystals

Changes in the morphology of the gamma prime precipitate were examined during tensile creep at temperatures between 927 and 1038 C in 001-oriented single crystals of a Ni-Al-Mo-Ta superalloy. In this alloy, which has a large negative misfit of -0.80%, the gamma prime particles link together during creep to form platelets, or rafts, which are aligned with their broad faces perpendicular to the applied tensile axis. The dimensions of the gamma and gamma prime phases were measured as directional coarsening developed in an attempt to trace the changing morphology under various stress levels. In addition, the effects of initial microstructure, as well as slight compositional variations, were related to raft development and creep properties. The results showed that directional coarsening of gamma prime began during primary creep, and under certain conditions, continued to develop after the onset of steady-state creep. The length of the rafts increased linearly with time up to a plateau region. The thickness of the rafts, however, remained equal to the initial gamma prime size at least up through the onset of tertiary creep; this is a clear indication of the stability of the finely-spaced gamma-gamma prime lamellar structure. It was found that the single crystals with the finest gamma prime size exhibited the longest creep lives, because the resultant rafted structure had a larger number of gamma-gamma prime interfaces per unit volume of material.

Mackay, R. A.↗

FPP: A Modeling Language for F Prime

We present F Prime Prime (FPP), a new open-source modeling language for F Prime. F Prime is an open-source flight software framework developed at JPL and deployed, among other places, on the Mars helicopter Ingenuity. FPP provides a convenient way to model the architectural elements of an F Prime application, e.g., components, ports, and their connections. It has a succinct and readable syntax, a well- defined semantics, and robust error checking and reporting. The FPP tool suite, written in Scala, analyzes FPP models, reports errors, and translates correct FPP models to a combination of XML and C++. Existing F Prime tools translate the XML to a partial implementation in C++, to be completed by the developers. The model elements have clean interfaces and are highly reusable. An accompanying visualization tool constructs diagrams of components and connections that FSW developers can use to understand and communicate their designs, for ex- ample at reviews. We discuss the design and implementation of FPP and the integration of FPP into F Prime. We also discuss our experience using FPP to construct F Prime models. Finally, we discuss our plans for future work, including improved code generation, improved visualization, and more advanced analysis capabilities.

Starch, Michael D.↗

Differential localization patterns of pyruvate kinase isoforms in murine naïve, formative, and primed pluripotent states

Highlights: • PKM1/2 protein abundance is greater in formative mEpiLCs compared to naïve mESCs or primed mEpiSCs. The ratio of PKM1/2 is maintained. • PKM1/2 are localized in both nuclear and cytoplasmic regions relative to GAPDH and OCT4 across the pluripotent continuum. • PKM1 localization is strongly correlated to OCT4 localization, and moderately to GAPDH in formative mEpiLCs. • PKM1/2 localization is moderately correlated to OCT4 and GAPDH localization in naïve mESCs. • PKM1/2 localization are moderately correlated to GAPDH localization in primed mEpiSCs. Mouse embryonic stem cells (mESCs) and mouse epiblast stem cells (mEpiSCs) represent opposite ends of the pluripotency continuum, referred to as naïve and primed pluripotent states, respectively. These divergent pluripotent states differ in several ways, including growth factor requirements, transcription factor expression, DNA methylation patterns, and metabolic profiles. Naïve cells employ both glycolysis and oxidative phosphorylation (OXPHOS), whereas primed cells preferentially utilize aerobic glycolysis, a trait shared with cancer cells referred to as the Warburg Effect. Until recently, metabolism has been regarded as a by-product of cell fate, however, evidence now supports metabolism as being a driver of stem cell state and fate decisions. Pyruvate kinase muscle isoforms (PKM1 and PKM2) are important for generating and maintaining pluripotent stem cells (PSCs) and mediating the Warburg Effect. Both isoforms catalyze the final, rate limiting step of glycolysis, generating adenosine triphosphate and pyruvate, however, the precise role(s) of PKM1/2 in naïve and primed pluripotency is not well understood. The primary objective of this study was to characterize the cellular expression and localization patterns of PKM1 and PKM2 in mESCs, chemically transitioned epiblast-like cells (mEpiLCs) representing formative pluripotency, and mEpiSCs using immunoblotting and confocal microscopy. The results indicate that PKM1 and PKM2 are not only localized to the cytoplasm, but also accumulate in differential subnuclear regions of mESC, mEpiLCs, and mEpiSCs as determined by a quantitative confocal microscopy employing orthogonal projections and airyscan processing. Importantly, we discovered that the subnuclear localization of PKM1/2 changes during the transition from mESCs, mEpiLCs, and mEpiSCs. Finally, we have comprehensively validated the appropriateness and power of the Pearson's correlation coefficient and Manders's overlap coefficient for assessing nuclear and cytoplasmic protein colocalization in PSCs by immunofluorescence confocal microscopy. We propose that nuclear PKM1/2 may assist with distinct pluripotency state maintenance and lineage priming by non-canonical mechanisms. These results advance our understanding of the overall mechanisms controlling naïve, formative, and primed pluripotency.

60 APPLIED LIFE SCIENCES↗

Factors which influence directional coarsening of Gamma prime during creep in nickel-base superalloy single crystals

Changes in the morphology of the gamma prime precipitate were examined as a function of time during creep at 982 C in 001 oriented single crystals of a Ni-Al-Mo-Ta superalloy. In this alloy, which has a large negative misfit of -0.80 pct., the gamma prime particles link together during creep to form platelets, or rafts, which are aligned with their broad faces perpendicular to the applied tensile axis. The effects of initial microstructure and alloy composition of raft development and creep properties were investigated. Directional coarsening of gamma prime begins during primary creep and continues well after the onset of second state creep. The thickness of the rafts remains constant up through the onset of tertiary creep a clear indication of the stability of the finely-spaced gamma/gamma prime lamellar structure. The thickness of the rafts which formed was equal to the initial gamma prime size which was present prior to testing. The single crystals with the finest gamma prime size exhibited the longest creep lives, because the resultant rafted structure had a larger number of gamma/gamma prime interfaces per unit volume of material. Reducing the Mo content by only 0.73 wt. pct. increased the creep life by a factor of three, because the precipitation of a third phase was eliminated.

Mackay, R. A.↗

Factors which influence directional coarsening of gamma-prime during creep in nickel-base superalloy single crystals

Changes in the morphology of the gamma prime precipitate were examined as a function of the time during creep at 982 C in 001 oriented single crystals of a Ni-Al-Mo-Ta superalloy. In this alloy, which has a large negative misfit of -0.80 pct., the gamma prime particles link together during creep to form platelets, or rafts, which are aligned with their broad faces perpendicular to the applied tensile axis. The effects of initial microstructure and alloy composition of raft development and creep properties were investigated. Directional coarsening of gamma prime begins during primary creep and continues well after the onset of second state creep. The thickness of the rafts remains constant up through the onset of tertiary creep, a clear indication of the stability of the finely-spaced gamma/gamma prime lamellar structure. The thickness of the rafts which formed was equal to the initial gamma prime size which was present prior to testing. The single crystals with the finest gamma prime size exhibited the longest creep lives, because the resultant rafted structure had a larger number of gamma/gamma prime interfaces per unit volume of material. Reducing the Mo content by only 0.73 wt. pct. increased the creep life by a factor of three, because the precipitation of a third phase was eliminated.

Mackay, R. A.↗

Re-naming D Double Prime

"Knowledge about the dynamics of the D double prime region is a key to unlock some fundamental mysteries of the Earth heat engine which governs a wide range of global geophysical processes from tectonics to geodynamo." This benign sentence makes complete sense to many geophysicists. But for many others, it makes sense all except the odd nomenclature "D double prime". One knows about the crust, upper and lower mantle, outer and inner core, but where is the D double prime region? What meaning does it try to convey? Where is D prime region, or D, or A, B, C regions for that matter, and are there higher-order primes? How does such an odd name come about anyway? D double prime, or more "simply" D", is a generic designation given to the thin shell, about 200 km thick, of the lowermost mantle just above the core-mantle boundary inside the Earth. Incidentally, whether D" is "simpler" than "D double prime" depends on whether you are pronouncing it or writing/typing it; and D" can be confusing to readers in distinguishing quotation marks (such as in the above sentences) and second derivatives, and to word processors in spelling check and indexing.

Chao, Benjamin F.↗

Experimental warming accelerates positive soil priming in a temperate grassland ecosystem

Abstract Unravelling biosphere feedback mechanisms is crucial for predicting the impacts of global warming. Soil priming, an effect of fresh plant-derived carbon (C) on native soil organic carbon (SOC) decomposition, is a key feedback mechanism that could release large amounts of soil C into the atmosphere. However, the impacts of climate warming on soil priming remain elusive. Here, we show that experimental warming accelerates soil priming by 12.7% in a temperate grassland. Warming alters bacterial communities, with 38% of unique active phylotypes detected under warming. The functional genes essential for soil C decomposition are also stimulated, which could be linked to priming effects. We incorporate lab-derived information into an ecosystem model showing that model parameter uncertainty can be reduced by 32–37%. Model simulations from 2010 to 2016 indicate an increase in soil C decomposition under warming, with a 9.1% rise in priming-induced CO 2 emissions. If our findings can be generalized to other ecosystems over an extended period of time, soil priming could play an important role in terrestrial C cycle feedbacks and climate change.

54 ENVIRONMENTAL SCIENCES↗

Phenolic acid-degrading Paraburkholderia prime decomposition in forest soil

Abstract Plant-derived phenolic acids are catabolized by soil microorganisms whose activity may enhance the decomposition of soil organic carbon (SOC). We characterized whether phenolic acid-degrading bacteria enhance SOC mineralization in forest soils when primed with 13C-labeled p-hydroxybenzoic acid (pHB). We further tested whether pHB-induced priming could explain differences in SOC content among mono-specific tree plantations in a 70-year-old common garden experiment. pHB addition primed significant losses of SOC (3–13 µmols C g−1 dry wt soil over 7 days) compared to glucose, which reduced mineralization (-3 to -8 µmols C g−1 dry wt soil over 7 days). The principal degraders of pHB were Paraburkholderia and Caballeronia in all plantations regardless of tree species or soil type, with one predominant phylotype (RP11ASV) enriched 23-fold following peak pHB respiration. We isolated and confirmed the phenolic degrading activity of a strain matching this phylotype (RP11T), which encoded numerous oxidative enzymes, including secretion signal-bearing laccase, Dyp-type peroxidase and aryl-alcohol oxidase. Increased relative abundance of RP11ASV corresponded with higher pHB respiration and expression of pHB monooxygenase (pobA), which was inversely proportional to SOC content among plantations. pobA expression proved a responsive measure of priming activity. We found that stimulating phenolic-acid degrading bacteria can prime decomposition and that this activity, corresponding with differences in tree species, is a potential mechanism in SOC cycling in forests. Overall, this study highlights the ecology and function of Paraburkholderia whose associations with plant roots and capacity to degrade phenolics suggest a role for specialized bacteria in the priming effect.

54 ENVIRONMENTAL SCIENCES↗

The development of gamma-gamma-prime lamellar structures in a nickel-base superalloy during elevated temperature mechanical testing

The kinetics of the formation and subsequent development of the directional coarsening of the gamma-prime precipitate in model Ni-Al-Mo-Ta superalloy single crystals are examined during tensile creep under various stress levels at 982 and 1038 C. Special attention is given to the gamma and gamma-prime relation to creep time and strain in order to trace the changing gamma-gamma-prime morphology. Directional coarsening of gamma-prime is found to begin during primary creep and its rate is shown to increase with an increase in temperature or stress level. The length of gamma-prime thickness increased linearly with time up to a plateau reached after the onset of steady state creep. The raft thickness, equal to the gamma-prime size, remained constant at this initial value up through the onset of the tertiary creep. The interlaminar spacing indicates the stability of directionally coarsened structure.

Mackay, R. A.↗

Effect of initial gamma prime size on the elevated temperature creep properties of single crystal nickel base superalloys

The influence of initial gamma-prime size and shape on the high-temperature creep properties of two single-crystal Ni-base superalloys was investigated. The two alloys were chosen to represent different magnitudes of gamma/gamma-prime lattice mismatch. A range of initial microstructures was produced by various quenching and aging treatments. Creep-rupture testing at 1000 C was performed under stresses where gamma-prime directionally coarsens to form gamma/gamma-prime lamellae in the early portion of the creep life. Both alloys exhibited a peak in creep resistance as a function of initial gamma-prime size. The peak corresponded to an initial microstructure consisting of cuboidal precipitates aligned along 001 line directions. These aligned cuboidal gamma-prime particles directionally coarsened into a relatively perfect lamellar gamma/gamma-prime structure in the early stages of creep, whereas the more irregularly shaped and distributed gamma-prime particles in both under- and overaged material formed more irregular lamellae with more imperfections. The alloy with a lower magnitude of mismatch was less sensitive to initial gamma-prime size and shape.

Nathal, M. V.↗

Word-identification priming for ignored and attended words

Three experiments examined contributions of study phase awareness of word identity to subsequent word-identification priming by manipulating visual attention to words at study. In Experiment 1, word-identification priming was reduced for ignored relative to attended words, even though ignored words were identified sufficiently to produce negative priming in the study phase. Word-identification priming was also reduced after color naming relative to emotional valence rating (Experiment 2) or word reading (Experiment 3), even though an effect of emotional valence upon color naming (Experiment 2) indicated that words were identified at study. Thus, word-identification priming was reduced even when word identification occurred at study. Word-identification priming may depend on awareness of word identity at the time of study.

Mental Recall↗

The importance of nutrients for microbial priming in a bog rhizosphere

Wetlands host anaerobic microbes which convert organic carbon into methane (CH 4 ), a powerful greenhouse gas. Wetland plants can influence which carbon compounds are available for microbial processing by exuding freshly fixed carbon from their roots. Notably, exudation of carbon from plant roots can trigger microbial priming: the process of new carbon stimulating the microbial community into processing more soil carbon than they otherwise would have. This study utilized high resolution Fourier transform ion cyclotron mass spectrometry (FT-ICR-MS) analysis to probe the chemical composition of soil organic compounds from the rhizosphere of Carex aquatillis, a common wetland sedge, which is known to have stimulated microbial priming within a peat soil. The goal was to identify what types of molecules are created or lost during microbial priming in the wetland rhizosphere and thus advance mechanistic understanding of the process. FT-ICR-MS analysis demonstrated that more microbial transformations of carbon occurred among water-soluble compounds than among hydrophobic compounds, but that some hydrophobic compounds were processed as well. Crucially for understanding microbial priming, the root exudates triggered increased processing of high molecular weight molecules regardless of nutrient content but processed low molecular weight compounds only if they contained essential nutrients. Furthermore, the pattern of which molecules are processed and which are not is evidence for a selective priming effect in which some types of carbon compounds are used at an increased rate, while others are not.

59 BASIC BIOLOGICAL SCIENCES↗

Arbuscular mycorrhizal trees cause a higher carbon to nitrogen ratio of soil organic matter decomposition via rhizosphere priming than ectomycorrhizal trees

Tree roots and their associated microbes can significantly influence soil organic matter (SOM) decomposition, i.e., the rhizosphere priming effect. This effect is expected to be greater in trees associated with arbuscular mycorrhizal (AM) fungi, which produce higher extracellular enzymes especially surrounding hyphae, than in trees associated with ectomycorrhizal (ECM) fungi. In this work, we selected five tree species associated with AM (Juglans mandshurica Maxim. and Cunninghamia lanceolata (Lamb.) Hook.) or ECM (Picea koraiensis Nakai, Quercus mongolica Fischer ex Turcz. and Larix kaempferi (Lamb.) Carriere). We grew tree seedlings inside of cores lined with different mesh sizes to investigate how roots, hyphae and exudates influence soil carbon (C) and nitrogen (N) mineralization via the rhizosphere priming effect, using a 13 C natural abundance approach and a 15 N pool dilution method, concurrently. We found that tree seedlings significantly accelerated soil C decomposition by on average 78%, i.e., positive priming, compared to unplanted control pots. AM-associated trees induced 2.1 times greater soil C decomposition than ECM-associated trees across all mesh sizes. In contrast, gross N mineralization did not differ between tree-mycorrhizal associations. Compared to ECM counterparts, AM-associated trees had higher C- and lower N-degrading enzyme activities. Consequently, AM-associated trees induced a significantly higher C:N ratio of SOM decomposition than their ECM counterparts, which could be associated with the differences in soil enzyme activities for C and N degradation. Further, for both AM- and ECM-associated trees, we found no significant influences of mesh size on soil C decomposition, suggesting that the rhizosphere priming effect of mycorrhizal symbiosis was predominantly driven by root exudates. We conclude that SOM decomposition caused by AM-associated trees may have a higher C:N ratio than that by ECM-associated trees mainly due to differences in microbial enzyme investment. Our findings imply that tree-mycorrhizal associations are capable of modulating soil biogeochemical cycling via the rhizosphere priming effect.

54 ENVIRONMENTAL SCIENCES↗

Polar Resources Ice Mining Experiment-1 (PRIME-1) NASA’s First Polar Drilling and Volatiles Detection Mission

The US Administration announced in 2019 that NASA would return to the Moon where it would seek to establish a sustainable lunar presence. In Situ Resource Utilization (ISRU) is needed to sustain and grow hu-man surface exploration and it is therefore a vital part of ensuring this bold endeavor. ISRU requires ground-truth on physical, mineral, and volatile characteristics of the resources. Water, a key and game-changing resource, exists in the polar regions of the Moon. Learning to harvest and use this resource first requires understanding where the resource is abundantly located and on what scales. Harvested water, which is usable for life support and fuel, must be identified, quantified, and assessed for its mining feasibility. The project goal for PRIME-1 is to develop a flight-ready instrumentation package that can assess the volatiles at a polar lunar landing location. PRIME-1 is the combination of two instruments; Mass Spectrometer observing lunar operations (MSolo) and The Regolith and Ice Drill for Exploring New Terrain (TRIDENT). TRIDENT is an 1-meter augering drill capable of bringing incremental lunar regolith samples to the surface for volatile analysis. MSolo is a modified, commercial-off-the-shelf (COTS) mass spectrometer capable of qualifying and quantifying atomic species in the 1-100 amu range, including isotopic differentiation. These two lunar flight instruments operating together make up the PRIME-1 instrument suite. PRIME-1 intends to fly on and operate from a static lunar lander acquired by the NASA Commercial Lunar Payload Services (CLPS) acquisition process. The PRIME-1 payload suite was selected to fly on Intuitive Machines Nova-C lander, and is currently targeting a late Fall 2023 landing attempt.

MSolo↗

Polar Resources Ice Mining Experiment-1 (PRIME-1) NASA’s First Polar Drilling and Volatiles Detection Mission

The US Administration announced in 2019 that NASA would return to the Moon where it would seek to establish a sustainable lunar presence. In Situ Resource Utilization (ISRU) is needed to sustain and grow hu-man surface exploration and it is therefore a vital part of ensuring this bold endeavor. ISRU requires ground-truth on physical, mineral, and volatile characteristics of the resources. Water, a key and game-changing resource, exists in the polar regions of the Moon. Learning to harvest and use this resource first requires understanding where the resource is abundantly located and on what scales. Harvested water, which is usable for life support and fuel, must be identified, quantified, and assessed for its mining feasibility. The project goal for PRIME-1 is to develop a flight-ready instrumentation package that can assess the volatiles at a polar lunar landing location. PRIME-1 is the combination of two instruments; Mass Spectrometer observing lunar operations (MSolo) and The Regolith and Ice Drill for Exploring New Terrain (TRIDENT). TRIDENT is an 1-meter augering drill capable of bringing incremental lunar regolith samples to the surface for volatile analysis. MSolo is a modified, commercial-off-the-shelf (COTS) mass spectrometer capable of qualifying and quantifying atomic species in the 1-100 amu range, including isotopic differentiation. These two lunar flight instruments operating together make up the PRIME-1 instrument suite. PRIME-1 intends to fly on and operate from a static lunar lander acquired by the NASA Commercial Lunar Payload Services (CLPS) acquisition process. The PRIME-1 payload suite was selected to fly on Intuitive Machines Nova-C lander, and is currently targeting a late Fall 2023 landing attempt.

MSolo↗

Data and scripts associated with a manuscript modeling microbial regulation of priming effects

This data package is associated with the publication “Modeling Microbial Regulatory Feedback in Organic Matter Decomposition Identifies Copiotrophic Traits as Key Drivers of Positive Priming” published as a preprint on BioRXiv by Ahamed et al. (2026); https://doi.org/10.1101/2024.08.11.607483. The package contains MATLAB scripts and saved simulation outputs used to implement a cybernetic model of microbial regulation during complex organic matter (OM) decomposition governing priming effects. It includes models of (i) single microbial functional groups (copiotrophic or oligotrophic degraders) and (ii) binary consortia composed of degraders and non-degraders with contrasting or common growth traits. Simulation results were generated using Monte Carlo analyses, with randomized key model parameters across a range of environmental mixing fractions of complex and labile OM. The dataset was created to provide a transparent and reusable computational framework for systematically exploring how microbial growth traits, metabolic regulation, and community composition influence OM decomposition dynamics and priming effects. For details on how to navigate data packages generated by this project, see https://data.ess-dive.lbl.gov/portals/PNNLRiverCorridorSFA/About. In addition to a readme, this data package also includes a file-level metadata (FLMD) file that describes each file and a data dictionary (DD) that describes the variable definitions. This package includes: (1) annotated MATLAB code implementing the system of ordinary differential equations and cybernetic control laws; (2) saved output files containing data (e.g., biomass, substrates, enzyme levels, priming metrics); and (3) scripts for processing saved outputs and regenerating figures. Specifically, the data package contains three main MATLAB scripts: runPrimingModel.m, runPlotData.m, and runPlotSuppFigS1.m, along with this readme and supporting documentation. Users should begin with runPrimingModel.m, which contains the annotated code implementing the system of ordinary differential equations and cybernetic control laws. This script runs the Monte Carlo simulations of microbial OM decomposition and allows users to modify microbial trait definitions, adjust parameter distributions, or define new community configurations. Simulation outputs are automatically saved as .mat files in the folder named SavedData, which stores all pre-generated results included in this package. The second script, runPlotData.m, reads files from the SavedData folder and processes them to regenerate the figures presented in the manuscript. The third script, runPlotSuppFigS1.m, specifically generates Figure S1 in the Supplementary Material of the manuscript. The package also includes the aforementioned files in non-proprietary .txt format. If users intend to use them, they should first save the files in their respective .m or .mat formats prior to execution in MATLAB.

Biomass concentration↗

Alumina Priming-Mediated Enhanced Binding of Diethylzinc with Carbonyl Groups in Poly(Methyl Methacrylate) during Vapor-Phase Infiltration

Vapor-phase infiltration (VPI) of inorganic materials in polymers is increasingly becoming popular for synthesizing various functional hybrid materials. While AlO x infiltration using trimethylaluminum (TMA) has been extensively studied, the mechanism of diethylzinc (DEZ)-based ZnO x infiltration, especially one that is initiated by AlO x priming, has not received much attention because highly reactive hydroxyl groups generated by AlO x -priming are expected to dominate the initial binding of DEZ, thus enabling the overall ZnO x VPI. Here, we interrogate the ZnO x infiltration mechanism in AlO x -primed poly(methyl methacrylate) (PMMA) in comparison to the control AlO x -only infiltration by utilizing a suite of complementary characterizations, including quartz crystal microbalance mass gain measurement, transmission electron microscopy, infrared reflection–absorption spectroscopy (IRRAS), and synchrotron X-ray absorption spectroscopy (XAS). The multivalent TMA precursor and associated hyperbranched AlO x network can quickly saturate the AlO x infiltration by clogging the polymer-free volume near the top. On the contrary, the ZnO x infiltration using divalent DEZ precursor, once activated via AlO x -priming, can lead to accelerated ZnOx infiltration. With the help of IRRAS, XAS, and density functional theory (DFT) simulations, we uncover that the AlO x -priming enhances the reactivity of neighboring carbonyl groups toward DEZ and opens up simultaneous reaction pathways, leading to accelerated high-fidelity infiltration of ZnO x .

36 MATERIALS SCIENCE↗