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RAPID Manufacturing Institute Final Report

The Rapid Advancement of Process Intensification Deployment (RAPID) Manufacturing Institute, founded in 2017, is a public/private partnership between the U.S. Department of Energy and the American Institute of Chemical Engineers (AIChE). RAPID promotes the development, deployment and commercialization of Process Intensification (PI) and Modular Chemical Process Intensification (MCPI) technologies, enabling U.S. manufacturing to reduce energy consumption, improve process efficiencies and lower investment and operating costs. This mission was carried out through parallel work breakdown structure elements including the establishment of committees to guide the operations and technical direction of RAPID, the establishment of management practices and institute processes, education and workforce development (EWD), and six technical focus areas for the development of technologies to advance PI and MCPI. Throughout the initial six-year cooperative agreement, RAPID worked to meet performance metrics which focused on the operation and sustainment of the institute, education and workforce development and the development of PI and MCPI for the advancement of U.S. manufacturing. All these metrics were successfully met through a total of 43 projects which leveraged $\$$70M Federal with $\$$90M cost share. As a result of these efforts, 84 private and public organizations were brought together by RAPID as members to co-invest in R&D, commercialization and deployment of innovative technologies. In the research portfolio, 82% of the 38 projects achieved > 20% energy efficiency improvement. A RAPID Test Network was developed with 51 testbed facilities to enable access to resources, facilities, tools, and expertise. Eight EWD programs were also developed with over 13,000 impressions. RAPID’s efforts to research, develop, demonstrate, and deploy high-impact PI and modular process technology solutions have enabled reduced energy use, increased sustainability, and improved profitability for U.S. manufacturing.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Rapidly ramp cryogenic air separation unit without loss of O2 product purity—application for low-carbon fossil-fuel plants

The rapid integration of intermittent renewable sources into the electricity grid is driving the need for low-carbon, fossil-fuel power plant capable of rapid ramping. Therefore, a cryogenic air separation unit (ASU) as part of low-carbon, fossil-fuel power plant should be capable of rapid ramping. However, highly integrated and nonlinear processes of the ASU would significantly restrict this rapid ramping. To overcome this fundamental issue, we study the basic dynamic process of a state-of-the-art double-column ASU. A flow-driven dynamic model was established in Aspen Plus Dynamics, assuming perfect flow controls, to capture the basic dynamics of ramping ASU. We find the vapor-liquid counter-current flow structure in the low-pressure column is critical to the air separation when rapidly ramping the ASU. This flow structure is established based on a complicated heat integration process. It is simplified as an apparent counter-current heat transfer process in this work, which greatly reduces the complexity for studying the dynamics of ASU. For keeping this basic flow structure, the heat integration is maintained as its heat duty follows the ASU load, through several basic feed-forward and feed-back controllers on the critical stream flowrates. Moreover, we find a fundamental issue of mismatched dynamics in the low-pressure column, resulting in a significant loss of O2 product purity when rapidly ramping down the ASU and an obvious fluctuation of O2 product purity. Based on these explorations, we propose a basic control method for rapidly ramping the ASU without loss of O2 product purity. Results show the ASU basic dynamic process successfully ramps at a rate up to 10%/min (40-100% load) while maintaining the O2 product purity within 95.2-95.6 mol%.

Cheng, Mao↗

Energy dependence of \(\phi \) meson production at forward rapidity in pp collisions at the LHC

The production of Φ mesons has been studied in pp collisions at LHC energies with the ALICE detector via the dimuon decay channel in the rapidity region 2.5 < y < 4. Measurements of the differential cross section d 2 σ / dydpT are presented as a function of the transverse momentum (p T ) at the center-of-mass energies √s = 5.02, 8 and 13 TeV and compared with the ALICE results at midrapidity. The differential cross sections at √s = 5.02 and 13 TeV are also studied in several rapidity intervals as a function of p T , and as a function of rapidity in three p T intervals. A hardening of the p T -differential cross section with the collision energy is observed, while, for a given energy, p T spectra soften with increasing rapidity and, conversely, rapidity distributions get slightly narrower at increasing p T . The new results, complementing the published measurements at √s = 2.76 and 7 TeV, allow one to establish the energy dependence of Φ meson production and to compare the measured cross sections with phenomenological models. None of the considered models manages to describe the evolution of the cross section with p T and rapidity at all the energies.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

A precise measurement of the Z -boson double-differential transverse momentum and rapidity distributions in the full phase space of the decay leptons with the ATLAS experiment at $\sqrt{s}=8$ TeV

This paper presents for the first time a precise measurement of the production properties of the Z boson in the full phase space of the decay leptons. This is in contrast to the many previous precise unfolded measurements per formed in the fiducial phase space of the decay leptons. The measurement is obtained from proton–proton collision data collected by the ATLAS experiment in 2012 at $\sqrt{s}$ = 8 TeV at the LHC and corresponding to an integrated luminosity of 20.2 fb -1 . The results, based on a total of 15.3 million Z boson decays to electron and muon pairs, extend and improve a previous measurement of the full set of angular coefficients describing Z-boson decay. The double-differential cross section distributions in Z-boson transverse momentum pT and rapidity y are measured in the pole region, defined as 80 < m ℓℓ < 100 GeV, over the range |y| < 3.6. The total uncertainty of the normalised cross-section measurements in the peak region of the pT distribution is dominated by statistical uncertainties over the full range and increases as a function of rapidity from 0.5–1.0% for |y| < 2.0 to 2 - 7% at higher rapidities. The results for the rapidity-dependent transverse momentum distributions are compared to state of-the-art QCD predictions, which combine in the best cases approximate N 4 LL resummation with N 3 LO fixed-order per turbative calculations. The differential rapidity distributions integrated over pT are even more precise, with accuracies from 0.2–0.3% for |y| < 2.0 to 0.4–0.9% at higher rapidities, and are compared to fixed-order QCD predictions using the most recent parton distribution functions. The agreement between data and predictions is quite good in most cases.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Rapid tempering to enhance dynamic performance of high and ultra-high strength steels

This study employed rapid, short-time duration (1 s) tempering to improve the dynamic performance of high-strength steel (HSS) and ultra-high-strength steel (UHSS), compared to quenched and conventionally (1800 s) tempered microstructures. Rapid tempering significantly improved the Charpy toughness of both steels compared to the conventionally tempered condition at an equivalent tempering parameter (TP) or hardness level. For conventionally tempered conditions, tempered martensite embrittlement was observed within the tempering temperature range of 200–400 °C, whereas rapid tempering exhibited increased Charpy toughness with increasing tempering temperature across all tempering conditions. Dynamic compression experiments indicated that rapid tempering led to improved ductility compared to the conventionally tempered condition at an equivalent TP. This work shows that the same rapid tempering strategy used for HSS is directly transferable to a higher-carbon UHSS and provides the first systematic evidence of improved strength-ductility combinations and cracking resistance under dynamic compression, supported by Kolsky bar experiments.

36 MATERIALS SCIENCE↗

Rapid Quenching of Molten Salts as an Approach for the Coordination Characterization of Corrosion Products

A new apparatus was built to rapidly cool molten salts in liquid argon to prevent contamination during quenching and enable new insight into the structure in the liquid state. To test the applicability of the apparatus, several industrially relevant chloride salt compositions were first melted, rapidly solidified, and then characterized. The design proved applicable for the rapid quenching of molten salt. Furthermore, the structure of the apparatus prevented exposure of the rapidly quenched salt to impurities (humidity, oxygen, etc.). X-ray diffraction of salt specimens cooled with and without liquid argon showed differences including a structure further from the expected stoichiometric equilibrium with rapid cooling. Of particular interest is the chemical state of metallic impurities, and this may be probed using electron paramagnetic resonance.

36 MATERIALS SCIENCE↗

Rapid in situ nutrient element distribution in plants and soils using laser-induced breakdown spectroscopy ($\mathrm{LIBS}$)

The aim of this study is to develop and test the applicability of a rapid in situ plant chemistry profiling technique to determine elemental composition of small-volume plant and soil samples obtained from a woody bioenergy crop species, Populus trichocarpa. Expanding the research tools available to characterize the nutrient element correlations among plant tissue types and soil depths is a critical need in the path of understanding productivity and adaptation of plants to variations in external abiotic and biotic factors and developing sustainable perennial bioenergy crops that are co-optimized for biomass valorization aboveground and carbon sequestration belowground. Several plant root, stem, and soil samples were tested using laser-induced breakdown spectroscopy (LIBS) to evaluate the presence and distribution of nutrient elements. Samples were tested as collected and after being dried and cross sectioned to evaluate the effectiveness of using LIBS for in situ analysis on plant samples. The collected LIBS spectra show the elemental peaks were the same in both the as collected and prepared samples for roots and stems. Qualitative amounts of elements such as H, C, N, O, Li, Na, Mg, K, Ca, Fe, Al, and Si were able to be identified rapidly in raw samples. Here in this report we demonstrate suitability of LIBS in obtaining rapid, in situ, elemental distribution in plant and soil samples, utilizing only small sample volumes and minimal sample preparation. This demonstration opens up a new rapid phenotyping avenue necessary to fill the asymmetrical knowledge gaps in belowground performance of plant systems.

59 BASIC BIOLOGICAL SCIENCES↗

Interface morphology and dislocation-mediated processes during rapid solidification of thin films

Rapid solidification experiments have, in recent years, revealed a wealth of new microstructural phenomena that suggest a strong connection between the kinetics of solidification and the crystalline structures that emerge as a result. In this work, we investigate the interplay between interface morphology and defect-mediated processes during rapid solidification conditions using a Phase Field Crystal (PFC) model, enabling us to simultaneously and efficiently explore the physics of solidification and elasto-plasticity in the formalism of a single-field theory. We predict that there are two mechanisms by which dislocations emitted directly from the solid–liquid interface induce orientation gradients as well as the formation of subgrain boundaries within a single solidifying cell. We relate these mechanisms to the morphology of the moving solid–liquid interface and identify a suitable control parameter in the PFC model with which we can go between said morphologies by effectively changing the relative strength of the capillary length and kinetic coefficients of the solid–liquid interface. Thus, we are able to provide mechanistic explanations for several microstructural features (with an emphasis on orientation gradients and subgrain boundaries) observed during the rapid solidification of pure materials. We also provide a simple explanation for the formation of “jagged” subgrain boundaries, which is consistent with our experimental observations in rapidly solidified samples of Aluminum, whose mechanisms have thus far been unknown.

Interface morphology↗

Microstructure development during rapid alloy solidification

Abstract Solidification processing of structural alloys can take place over an extremely wide range of solid–liquid interface velocities spanning six orders of magnitude, from the low-velocity constitutional supercooling limit of microns/s to the high-velocity absolute stability limit of m/s. In between these two limits, the solid–liquid interface is morphologically unstable and typically forms cellular-dendritic microstructures, but also other microstructures that remain elusive. Rapid developments in additive manufacturing have renewed the interest in modeling the high-velocity range, where approximate analytical theories provide limited predictions. In this article, we discuss recent advances in phase-field modeling of rapid solidification of metallic alloys, including a brief description of state-of-the-art experiments used for model validation. We describe how phase-field models can cope with the dual challenge of carrying out simulations on experimentally relevant length- and time scales and incorporating nonequilibrium effects at the solid–liquid interface that become dominant at rapid rates. We present selected results, illustrating how phase-field simulations have yielded unprecedented insights into high-velocity interface dynamics, shedding new light on both the absolute stability limit and the formation of banded microstructures that are a hallmark of rapid alloy solidification near this limit. We also discuss state-of-the-art experiments used to validate those insights. Graphical abstract

36 MATERIALS SCIENCE↗

The Role of Retained Austenite in Tempered Martensite Embrittlement of 4340 and 300-M Steels Investigated through Rapid Tempering

Tempered martensite embrittlement (TME) is investigated in two medium carbon, high strength steels, 4340 (low silicon) and 300-M (high silicon), via rapid (1, 10, or 100 s) and conventional (3600 s) tempering. Rapid tempering of 4340 diminishes the depth of the TME toughness trough, where improvements in impact toughness correspond to the suppression of retained austenite decomposition. In 300-M, retained austenite decomposition is suppressed to an even greater extent by rapid tempering. While toughness improves overall after rapid tempering, TME severity remains consistent in 300-M across the tempering conditions examined. Through interrupted tensile tests, it was found that the 300-M conditions that exhibit TME are associated with mechanically unstable retained austenite. Unstable retained austenite is shown to mechanically transform early in the deformation process, presumably resulting in fresh martensite adjacent to interlath cementite that ultimately contributes to TME. The present results emphasize the role of both the thermal decomposition and mechanical transformation of retained austenite in the manifestation of TME.

36 MATERIALS SCIENCE↗

Fast redox switches lead to rapid transformation of goethite in humid tropical soils: A Mössbauer spectroscopy study

Abstract Humid tropical forest soils experience frequent rainfall, which limits oxygen diffusion and creates redox heterogeneity in upland soils. In this study we gauged the effect of short‐term anoxic conditions on Fe mineralogy of relatively Fe‐ and C‐rich surface soils (C/Fe mole ratio ∼5) from a humid tropical forest in Puerto Rico. Soils subjected to 4‐d oxic/anoxic oscillation were characterized by selective chemical extractions, Mössbauer spectroscopy (MBS), and X‐ray diffraction. Chemical extraction data suggested that rapidly switching redox conditions had subtle effects on bulk Fe mineralogy. Mössbauer, on the other hand, indicated that (a) the soil Fe is a mixture of goethites of varying characteristics with minor contributions from ferrihydrite (<5%) and Fe(III)‐organic matter (OM) phases (∼10%), and (b) anoxic conditions rapidly transformed all forms of goethite to relatively stable Fe oxides. Such fast changes in goethite features could be due to rapid depletion and sorption of bio‐released structural Al or sorbed OM onto residual soil components. The rapid temporal changes in MBS parameters and corresponding pore water nominal oxidation state of C values suggest that Fe‐C transformations in these upland tropical soils are complex and intricately coupled. A comprehensive understanding of the fate of Fe, Al, and OM (Fe‐organic moieties) during redox switches and concurrent changes in pore water chemistry is critical for development of robust transport models in humid tropical soils, which are subject to episodic low‐redox events.

54 ENVIRONMENTAL SCIENCES↗

Rapid Load Transition for Integrated Solid Oxide Fuel Cell - Gas Turbine (SOFC-GT) Energy Systems: A Demonstration of the Potential for Grid Response

Rapid load transition is an essential requirement for integrated energy systems to maintain grid resilience as more renewable resources are added to the grid. Integrated solid oxide fuel cell - gas turbine (SOFC-GT) systems can provide high efficiency and low carbon emissions over a broad range of turndown. These hybrids also have the potential to enable rapid grid response. The challenge has been to demonstrate effective control strategies to manage load transitions. In the present study, a load transition of ~50% was achieved in 10 s using a novel but simple strategy. Power demand on the SOFC and the GT were ramped down concurrently. During this transition, the SOFC anode fuel was manipulated to maintain SOFC fuel utilization while the cathode inlet air flow and temperature were also manipulated to thermally protect the SOFC. This study was conducted using the Hybrid Performance (Hyper) facility at the National Energy Technology Laboratory (NETL) in a co-simulation environment with the Idaho National Laboratory (INL)'s grid-simulation. The load ramping strategy was tested using a hardware-based cyber-physical simulation methodology. The results demonstrate a high-fidelity representation of SOFC-GT hybrid dynamics and validation of the control strategy. Thermal and electrochemical transients indicated that the SOFC was well protected during rapid load turndown without violating operability constraints. This demonstration revealed the non-linear nature of tightly coupled SOFC-GT system components, especially the non-linear response of SOFC cathode air flow and inlet temperature controls. These results highlight the needs and challenges in developing adaptive automatic controls for autonomous rapid load transitions. This work demonstrates that SOFC-GT hybrids are a viable option to provide the fast-ramping characteristics essential to accommodate high levels of variable renewable power while maintaining grid resilience, reliability, and environmental performance. The results also demonstrate the utility of co-simulation in advancing the tightly-coupled integrated energy systems needed to meet goals for zero-carbon power generation.

DIRECT ENERGY CONVERSION,POWER TRANSMISSION AND DI↗

Measurements of inclusive J/ψ production at midrapidity and forward rapidity in Pb–Pb collisions at $\sqrt{s_{NN}}$ = 5.02 TeV

The measurements of the inclusive J/ψ yield at midrapidity (|y| < 0.9) and forward rapidity (2.5 < y < 4) in Pb–Pb collisions at $\sqrt{s_{NN}}$ = 5.02 TeV with the ALICE detector at the LHC are reported. The inclusive J/ψ production yields and nuclear modification factors, R AA , are measured as a function of the collision centrality, J/ψ transverse momentum (p T ), and rapidity. The J/ψ average transverse momentum and squared transverse momentum ($\langle$p T $\rangle$ and $\langle$$p^{2}_{T}$$\rangle$) are evaluated as a function of the centrality at midrapidity. Compared to the previous ALICE publications, here the entire Pb–Pb collisions dataset collected during the LHC Run 2 is used, which improves the precision of the measurements and extends the p T coverage. The p T -integrated R AA shows a hint of an increasing trend towards unity from semicentral to central collisions at midrapidity, while it is flat at forward rapidity. The p T -differential R AA shows a strong suppression at high p T with less suppression at low p T where it reaches a larger value at midrapidity compared to forward rapidity. The ratio of the p T -integrated yields of J/ψ to those of D 0 mesons is reported for the first time for the central and semicentral event classes at midrapidity. Model calculations implementing charmonium production via the coalescence of charm quarks and antiquarks during the fireball evolution (transport models) or in a statistical approach with thermal weights are in good agreement with the data at low p T . At higher p T , the data are well described by transport models and a model based on energy loss in the strongly-interacting medium produced in nuclear collisions at the LHC.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Rapidity dependence of antideuteron coalescence in pp collisions at $\sqrt{s}$ = 13 TeV with ALICE

The production yields of antideuterons and antiprotons are measured in pp collisions at a center-of-mass energy of $\sqrt{s}$ = 13 TeV, as a function of transverse momentum ( p T ) and rapidity ( y ), for the first time rapidity-differentially up to | y | = 0.7. The measured spectra are used to study the p T and rapidity dependence of the coalescence parameter B 2 , which quantifies the coalescence probability of antideuterons. The p T and rapidity dependence of the obtained B 2 is extrapolated for p T > 1.7 GeV/ c and | y | = 0.7 using the phenomenological antideuteron production model implemented in Pythia 8.3 as well as a baryon coalescence afterburner model based on EPOS 3. Such measurements are of interest to the astrophysics community, since they can be used for the calculation of the flux of antinuclei from cosmic rays, in combination with coalescence models.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Evaporation of a Reactive Nanofluid Sessile Drop: Capturing Rapid Emergence of Surface Crystals with In Situ Synchrotron X-ray Diffraction

Mechanisms for surface pattern formation from evaporation of a reactive nanofluid sessile drop are not well understood. In contrast to the coffee-ring effect from inert particles, rapid chemical and morphological transformation of reactive nanoparticles upon rapid evaporative drying are challenging to probe experimentally. Here, using grazing-incidence X-ray surface scattering, the nanostructure of nascent surface patterns has been probed as a ZnO nanofluid sessile drop rapidly dries. The high temporal resolution enabled by the high flux of synchrotron X-rays allows the observation of the emergence of Zn(OH) 2 surface crystals from the onset of evaporation and their rapid evolution into the final residual surface pattern, via transient layered complexes evident from the temporary appearance of X-ray diffraction peaks preceding Zn(OH) 2 formation. The results offer mechanistic insights of morphogenesis of surface patterns from evaporation-induced self-assembly and self-organization of reactive nanofluids, previously untenable using other experimental methods.

36 MATERIALS SCIENCE↗

Rapid Allylic 1,6 H-Atom Transfer in an Unsaturated Criegee Intermediate

Here, a novel allylic 1,6 hydrogen-atom-transfer mechanism is established through infrared activation of the 2-butenal oxide Criegee intermediate, resulting in very rapid unimolecular decay to hydroxyl (OH) radical products. A new precursor, Z/E -1,3-diiodobut-1-ene, is synthesized and photolyzed in the presence of oxygen to generate anew four-carbon Criegee intermediate with extended conjugation across the vinyl and carbonyl oxide groups that facilitates rapid allylic 1,6 H-atom transfer. A low-energy reaction pathway involving isomerization of 2-butenal oxide from a lower-energy ( tZZ ) conformer to a higher-energy ( cZZ ) conformer followed by 1,6 hydrogen transfer via a seven-membered ring transition state is predicted theoretically and shown experimentally to yield OH products. The low-lying ( tZZ ) conformer of 2-butenaloxide is identified based on computed an harmonic frequencies and intensities of its conformers. Experimental IR action spectra recorded in the fundamental CH stretch region with OH product detection by UV laser-induced fluorescence reveal a distinctive IR transition of the low-lying ( tZZ ) conformer at 2996 cm -1 that results in rapid unimolecular decay to OH products. Statistical RRKM calculations involving a combination of conformational isomerization and unimolecular decay via 1,6 H-transfer yield an effective decay rate k eff ( E ) on the order of 10 8 s -1 at ca. 3000 cm -1 in good accord with the experiment. Unimolecular decay proceeds with significant enhancement due to quantum mechanical tunneling. A rapid thermal decay rate of ca. 10 6 s -1 is predicted by master-equation modeling of 2-butenal oxide at 298 K, 1 bar. This novel unimolecular decay pathway is expected to increase the nonphotolytic production of OH radicals upon alkene ozonolysis in the troposphere.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tripogon loliiformis tolerates rapid desiccation after metabolic and transcriptional priming during initial drying

Abstract Crop plants and undomesticated resilient species employ different strategies to regulate their energy resources and growth. Most crop species are sensitive to stress and prioritise rapid growth to maximise yield or biomass production. In contrast, resilient plants grow slowly, are small, and allocate their resources for survival in challenging environments. One small group of plants, termed resurrection plants, survive desiccation of their vegetative tissue and regain full metabolic activity upon watering. However, the precise molecular mechanisms underlying this extreme tolerance remain unknown. In this study, we employed a transcriptomics and metabolomics approach, to investigate the mechanisms of desiccation tolerance in Tripogon loliiformis , a modified desiccation-tolerant plant, that survives gradual but not rapid drying. We show that T. loliiformis can survive rapid desiccation if it is gradually dried to 60% relative water content (RWC). Furthermore, the gene expression data showed that T. loliiformis is genetically predisposed for desiccation in the hydrated state, as evidenced by the accumulation of MYB, NAC, bZIP, WRKY transcription factors along with the phytohormones, abscisic acid, salicylic acid, amino acids (e.g., proline) and TCA cycle sugars during initial drying. Through network analysis of co-expressed genes, we observed differential responses to desiccation between T. loliiformis shoots and roots. Dehydrating shoots displayed global transcriptional changes across broad functional categories, although no enrichment was observed during drying. In contrast, dehydrating roots showed distinct network changes with the most significant differences occurring at 40% RWC. The cumulative effects of the early stress responses may indicate the minimum requirements of desiccation tolerance and enable T. loliiformis to survive rapid drying. These findings potentially hold promise for identifying biotechnological solutions aimed at developing drought-tolerant crops without growth and yield penalties.

59 BASIC BIOLOGICAL SCIENCES↗

Probing initial baryon stopping and equation of state with rapidity-dependent directed flow of identified particles

In this work, using a (3 + 1)-dimensional hybrid framework with parametric initial conditions, we study the rapidity-dependent directed flow $v_1 (y)$ of identified particles, including pions, kaons, protons, and lambdas in heavy-ion collisions. Cases involving Au + Au collisions are considered, performed at $\sqrt {^SNN}$ ranging from 7.7 to 200 GeV. The dynamics in the beam direction is constrained using the measured pseudo-rapidity distribution of charged particles and the net proton rapidity distribution. Within this framework, the directed flow of mesons is driven by the sideward pressure gradient from the tilted source, and that of baryons mainly due to the initial asymmetric baryon distribution with respect to the beam axis driven by the transverse expansion. Our approach successfully reproduces the rapidity- and beam energy-dependence of $v_1$ for both mesons and baryons. We find that the $v_1 (y)$ of baryons has strong constraining power on the initial baryon stopping, and together with that of mesons, the directed flow probes the equation of state of the dense nuclear matter at finite chemical potentials.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗