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At least 397 records · Page 22

Heterobimetallic zeolite, InV-ZSM-5, enables efficient conversion of biomass derived ethanol to renewable hydrocarbons

Here, direct catalytic conversion of ethanol to hydrocarbon blend-stock can increase biofuels use in current vehicles beyond the ethanol blend-wall of 10–15%. Literature reports describe quantitative conversion of ethanol over zeolite catalysts but high C 2 hydrocarbon formation renders this approach unsuitable for commercialization. Furthermore, the prior mechanistic studies suggested that ethanol conversion involves endothermic dehydration step. Here, we report the complete conversion of ethanol to hydrocarbons over InV-ZSM-5 without added hydrogen and which produces lower C 2 (<13%) as compared to that over H-ZSM-5. Experiments with C 2 H 5 OD and in situ DRIFT suggest that most of the products come from the hydrocarbon pool type mechanism and dehydration step is not necessary. Thus, our method of direct conversion of ethanol offers a pathway to produce suitable hydrocarbon blend-stock that may be blended at a refinery to produce fuels such as gasoline, diesel, JP-8, and jet fuel, or produce commodity chemicals such as BTX.

09 BIOMASS FUELS↗

Effect of alkali metal addition on catalytic performance of Ag/ZrO 2 /SBA-16 catalyst for single-step conversion of ethanol to butadiene

Here, we describe how adding Na and K to a 4Ag/4ZrO 2 /SBA-16 catalyst enhances catalytic performance for single-bed conversion of ethanol to butadiene. While adding Na and K leads to a slight decrease in conversion (i.e., ~10% loss), the production of desired butadiene is significantly increased with up to 50% improvement in productivity for the 4Ag/4ZrO 2 /SBA-16 catalyst promoted with 0.5% Na. The reasons for this improvement are a beneficial decrease in Lewis acid site concentration and higher Ag dispersion when Na or K are added, which results in decreased activity involving ethanol dehydration to ethylene and diethyl ether. A remarkable butadiene selectivity of 75% was achieved while maintaining high conversion (i.e., 90%) with 0.5Na/4Ag/4ZrO 2 /SBA-16 catalyst. A 72-hour catalyst lifetime study shows that because of higher coke formation from polymerization of desired butadiene, catalyst deactivation occurs more rapidly with the 0.5Na/4Ag/4ZrO 2 /SBA-16 (55% loss in conversion) than with 4Ag/4ZrO 2 /SBA-16 (45% loss in conversion). However, this does not alter the advantageous effect of Na addition because the butadiene yield remained higher throughout the study period for 0.5Na/4Ag/4ZrO 2 /SBA-16. A key finding is that during the reaction, Na limits sintering of Ag particles and promotes selective coking of the acid sites responsible for ethylene and diethyl ether formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanistic insights into the conversion of polyalcohols over Brønsted acid sites

Multi-layered plastic (MLP) films provide excellent properties for food packaging; however, because of the complicated chemistry of the hydrophobic substrates and tightly laminated hydrophilic layers, it is challenging to recycle the MLP films. The selective conversion of polar functional groups in hydrophilic layers with a minimal destruction of the carbon backbone of constituted polymers is considered a promising approach to improve the recyclability of MLP films. Here, in this study, we combine computational and experimental studies to investigate the acid-catalyzed conversion of functional groups in polyalcohols, through which we report potential reaction pathways involved in the conversion of ethylene vinyl alcohol (EVOH), a common copolymer used in MLP films as an oxygen barrier. Using 2,4-pentanediol as a model compound, we show that its conversion proceeds primarily through the dehydration of a hydroxyl group via either a stepwise or a concerted mechanism to form an unsaturated alcohol that can be further converted into a conjugated diene or a saturated ketone; this secondary reaction determines the product selectivity. The rate determining intermediates and transition states are identified, and the activation barriers are calculated, in agreement with experimentally observed product selectivities. This study thus provides insights for the selective conversion of EVOH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

X-ray induced Sm{sup 3+} to Sm{sup 2+} conversion in fluorophosphate and fluoroaluminate glasses for the monitoring of high-doses in microbeam radiation therapy

Fluorophosphate and fluoroaluminate glasses doped with trivalent samarium were evaluated as sensors of x-ray radiation for microbeam radiation therapy at the Canadian Light Source using the conversion of trivalent Sm{sup 3+} to the divalent form Sm{sup 2+}. Both types of glasses show similar conversion rates and may be used as a linear sensor up to {approx}150 Gy and as a nonlinear sensor up to {approx}2400 Gy, where saturation is reached. Experiments with a multi-slit collimator show high spatial resolution of the conversion pattern; the pattern was acquired by a confocal fluorescence microscopy technique. The effects of previous x-ray exposure may be erased by annealing at temperatures exceeding the glass transition temperature T{sub g} while annealing at T{sub A} < T{sub g} enhances the Sm conversion. This enhancement is explained by a thermally stimulated relaxation of host glass ionic matrix surrounding x-ray induced Sm{sup 2+} ions. In addition, some of the Sm{sup 3+}-doped glasses were codoped with Eu{sup 2+}-ions but the results show that there is no marked improvement in the conversion efficiency by the introduction of Eu{sup 2+}.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

O–X mode conversion in a non-symmetric torus at electron cyclotron frequencies

Previous work on this topic, [Weitzner, Phys. Plasmas 11, 866 (2004)], applicable in a system with toroidal symmetry, is here extended to the case of a non-symmetric background equilibrium state. Maxwell's equations with the cold plasma dielectric tensor are used to represent the plasma-electromagnetic wave interaction. Away from the mode conversion region, geometrical optics adequately characterizes the wave propagation. A new, simpler derivation of the wave equations in the mode conversion region is given. Aside from one very special case in which a general plasma equilibrium behaves like a stratified medium, the previous results apply and highly effective mode conversion is found. The matching of the mode conversion solution to the geometrical optics solution, not previously examined, is discussed. A relatively weak condition on the perpendicular wave number near the resonance layer is found. Provided that the perpendicular wave number is small, it tends to zero at the mode conversion layer and the solutions match effectively.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Three-dimensional core-collapse supernova models with phenomenological treatment of neutrino flavor conversions

Abstract We perform three-dimensional supernova simulations with a phenomenological treatment of neutrino flavor conversions. We show that the explosion energy can increase to as high as $\sim 10^{51}$ erg depending on the critical density for the onset of flavor conversions, due to a significant enhancement of the mean energy of electron antineutrinos. Our results confirm previous studies showing such energetic explosions, but for the first time in three-dimensional configurations. In addition, we predict neutrino and gravitational wave (GW) signals from a nearby supernova explosion aided by flavor conversions. We find that the neutrino event number decreases because of the reduced flux of heavy-lepton neutrinos. In order to detect GWs, next-generation GW telescopes such as Cosmic Explorer and the Einstein Telescope are needed even if the supernova event is located at the Galactic Center. These findings show that the neutrino flavor conversions can significantly change supernova dynamics and highlight the importance of further studies on the quantum kinetic equations to determine the conditions of the conversions and their asymptotic states.

Mori, Kanji↗

Photon Frequency Conversion in High-Q Superconducting Resonators: Axion Electrodynamics, QED, and Nonlinear Meissner Radiation

High-Q superconducting resonators have been proposed and developed as detectors of light-by-light scattering mediated by the hypothesized axion or virtual electron–positron pairs in quantum electrodynamics: the Euler–Heisenberg (EH) interaction. Photon frequency and mode conversion is central to the scheme for detecting such rare events. Superconducting resonators are nonlinear devices. The Meissner screening currents that confine the electromagnetic fields to the vacuum region of a superconducting RF cavity are nonlinear functions of the EM field at the vacuum–superconducting interface, and as a result can generate source currents and frequency conversion of microwave photons in the cavity. In this report we consider photon frequency and mode conversion in superconducting resonators with high quality factors from Meissner currents in single- and dual-cavity setups proposed for axion and QED searches based on light-by-light scattering. In a single cavity with two pump modes, photon frequency conversion by the Meissner screening current dominates photon generation by the EH interaction for cavities with Q≲1012⁠. The Meissner currents also generate background photons that limit the operation of the resonator for axion detection in three-mode, single-cavity setups. We also consider the leakage of photons from pump modes into the signal mode for both axion- and EH-mediated light-by-light scattering. Photon frequency conversion by the EH interaction can compete with Meissner and leakage radiation in ultra-high-Q cavities that are beyond the current state of the art. Meissner radiation and leakage backgrounds can be suppressed in dual-cavity setups with appropriate choices for pump and spectator modes, as well as the single-cavity setup proposed for heterodyne detection of galactic axion dark matter.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Raman Wavelength Conversion in Ionic Liquids

Here, we explore the use of room-temperature ionic liquids (ILs) as Raman wavelength converters. ILs provide an engineerable framework to design suitable liquids for wavelength conversion over a broad spectral range, through careful selection of the molecular structures of the IL anions and cations so that specific characteristics can be obtained, such as a desirable Raman shift, low Brillouin scattering, and good optical transmission in the pump and Stokes wavelengths. Applying such criteria, we demonstrate that 1-ethyl-3-methylimidazolium dicyanamide (EMIM DCA) is an effective medium for conversion of 532-nm pulses from a Q-switched Nd :YAG laser to 603 nm. This corresponds to an approximate 2200 cm –1 shift, which can be used to generate mid-infrared radiation through subsequent difference frequency generation for optical pumping of CO 2 lasers. Threefold-higher Raman conversion efficiency is obtained in EMIM DCA compared with water under identical conditions in a proof-of-principle single-pass conversion setup, resulting in an efficient generation of multimillijoule, <6 ns duration, high-quality orange laser pulses in a wavelength region that is difficult to access at high energies. Consequently, we examine ILs representing two other classes of Raman-active functional groups and obtain conversion up to the fifth-order Stokes shift and first anti-Stokes shift. Through the tunable selection of their components and their useful dynamical properties, ILs provide a platform for efficient, simple, and alignment-tolerant high-energy Raman shifting with numerous industrial and technological applications.

74 ATOMIC AND MOLECULAR PHYSICS↗

Two first-order phase transitions in hybrid compact stars: Higher-order multiplet stars, reaction modes, and intermediate conversion speeds

We study compact stars with hybrid equations of state consisting of a nuclear outer region and two nested quark phases, each separated from the lower density phase by a strong first-order phase transition. The stability of these models is determined by calculating their radial oscillation modes with different conversion rates between adjacent phases and hence junction conditions for the modes at the phase separation interface between them. In the case when the timescale of transition is faster than the period of oscillations, we recover the traditional stability criterion implying that ∂M/∂ρ c > 0 on the stable branch(es), where M is the mass and ρ c is the central density. In the opposite limit of slow conversion, we find stable stellar multiplets beyond triplets consisting of stars that are stable by the usual criterion plus slow-conversion (denoted by s) hybrid stars with ∂M/∂ρ c < 0 that are stabilized due to an alternative junction condition on the fluid displacement field at the interface reflecting the slow rate of conversion. We also study the properties of the reaction mode, the radial mode that only exists for stars with rapid (abbreviated by r) phase transitions, in stars with either two rapid phase transitions or alternating rapid and slow phase transitions for the first time. Here, the implications of alternative junction conditions are also examined, with these conditions generally being found to provide stability properties similar to those for a slow conversion rate.

79 ASTRONOMY AND ASTROPHYSICS↗

Distinguishing Charged Lepton Flavor Violation Scenarios with Inelastic 𝜇 → 𝑒 Conversion

The Mu2e and COMET experiments are expected to improve existing limits on charged lepton flavor violation (CLFV) by roughly 4 orders of magnitude. 𝜇 → 𝑒 conversion experiments are typically optimized for electrons produced without nuclear excitation, as this maximizes the electron energy and minimizes backgrounds from the free decay of the muon. Here we argue that Mu2e and COMET will be able to extract additional constraints on CLFV from inelastic 𝜇 → 𝑒 conversion, given the 27 Al target they have chosen and backgrounds they anticipate. We describe CLFV scenarios in which inelastic CLFV can induce measurable distortions in the near-endpoint spectrum of conversion electrons, including cases where certain contributing operators cannot be probed in elastic 𝜇 → 𝑒 conversion. We extend the nonrelativistic EFT treatment of elastic 𝜇 → 𝑒 conversion to include the new nuclear operators needed for the inelastic process, evaluate the associated nuclear response functions, and describe several new-physics scenarios where the inelastic process can provide additional information on CLFV.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

TU-EF-304-06: A Comparison of CT Number to Relative Linear Stopping Power Conversion Curves Used by Proton Therapy Centers

Purpose: To compare the CT Number (CTN) to Relative Linear Stopping Power (RLSP) conversion curves used by 14 proton institutions in their dose calculations. Methods: The proton institution’s CTN to RLSP conversion curves were collected by the Imaging and Radiation Oncology Core (IROC) Houston QA Center during its on-site dosimetry review audits. The CTN values were converted to scaled CT Numbers. The scaling assigns a CTN of 0 to air and 1000 to water to allow intercomparison. The conversion curves were compared and the mean curve was calculated based on institutions’ predicted RLSP values for air (CTN 0), lung (CTN 250), fat (CTN 950), water (1000), liver (CTN 1050), and bone (CTN 2000) points. Results: One institution’s curve was found to have a unique curve shape between the scaled CTN of 1025 to 1225. This institution modified its curve based on the findings. Another institution had higher RLSP values than expected for both low and high CTNs. This institution recalibrated their two CT scanners and the new data placed their curve closer to the mean of all institutions. After corrections were made to several conversion curves, four institutions still fall outside 2 standard deviations at very low CTNs (100–200), and two institutions fall outside between CTN 850–900. The largest percent difference in RLSP values between institutions for the specific tissues reviewed was 22% for the lung point. Conclusion: The review and comparison of CTN to RLSP conversion curves allows IROC Houston to identify any outliers and make recommendations for improvement. Several institutions improved their clinical dose calculation accuracy as a Result of this review. There is still area for improvement, particularly in the lung area of the curve. The IROC Houston QA Center is supported by NCI grant CA180803.

60 APPLIED LIFE SCIENCES↗

Low-Enriched Uranium Fuel Conversion Activities for the High Flux Isotope Reactor, Annual Report for FY 2011

This report describes progress made during FY11 in ORNL activities to support converting the High Flux Isotope Reactor (HFIR) from high-enriched uranium (HEU) fuel to low-enriched uranium (LEU) fuel. Conversion from HEU to LEU will require a change in fuel form from uranium oxide to a uranium-molybdenum (UMo) alloy. With both radial and axial contouring of the fuel foil and an increase in reactor power to 100 MW, calculations indicate that the HFIR can be operated with LEU fuel with no degradation in performance to users from the current levels achieved with HEU fuel. Studies are continuing to demonstrate that the fuel thermal safety margins can be preserved following conversion. Studies are also continuing to update other aspects of the reactor steady state operation and accident response for the effects of fuel conversion. Technical input has been provided to Oregon State University in support of their hydraulic testing program. The HFIR conversion schedule was revised and provided to the GTRI program. In addition to HFIR conversion activities, technical support was provided directly to the Fuel Fabrication Capability program manager.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Catalytic Conversion of Biomass to Fuels and Chemicals Using Ionic Liquids

This project provides critical innovations and fundamental understandings that enable development of an economically-viable process for catalytic conversion of biomass (sugar) to 5-hydroxymethylfurfural (HMF). A low-cost ionic liquid (Cyphos 106) is discovered for fast conversion of fructose into HMF under moderate reaction conditions without any catalyst. HMF yield from fructose is almost 100% on the carbon molar basis. Adsorbent materials and adsorption process are invented and demonstrated for separation of 99% pure HMF product and recovery of the ionic liquid from the reaction mixtures. The adsorbent material appears very stable in repeated adsorption/regeneration cycles. Novel membrane-coated adsorbent particles are made and demonstrated to achieve excellent adsorption separation performances at low pressure drops. This is very important for a practical adsorption process because ionic liquids are known of high viscosity. Nearly 100% conversion (or dissolution) of cellulose in the catalytic ionic liquid into small molecules was observed. It is promising to produce HMF, sugars and other fermentable species directly from cellulose feedstock. However, several gaps were identified and could not be resolved in this project. Reaction and separation tests at larger scales are needed to minimize impacts of incidental errors on the mass balance and to show 99.9% ionic liquid recovery. The cellulose reaction tests were troubled with poor reproducibility. Further studies on cellulose conversion in ionic liquids under better controlled conditions are necessary to delineate reaction products, dissolution kinetics, effects of mass and heat transfer in the reactor on conversion, and separation of final reaction mixtures.

09 BIOMASS FUELS↗

Irradiation Experiment Conceptual Design Parameters for MURR LEU U-Mo Fuel Conversion Revision

This report contains the results of reactor design and performance calculations for conversion of the University of Missouri Research Reactor (MURR) from the use of highly-enriched uranium (HEU) fuel to the use of low-enriched uranium (LEU) fuel. The analyses were performed by staff members of the Global Threat Reduction Initiative (GTRI) Reactor Conversion Program at the Argonne National Laboratory (ANL) and the MURR Facility. The core conversion to LEU is being performed with financial support from the U. S. government. In the framework of its non-proliferation policies, the international community presently aims to minimize the amount of nuclear material available that could be used for nuclear weapons. In this geopolitical context most research and test reactors, both domestic and international, have started a program of conversion to the use of LEU fuel. A new type of LEU fuel based on an alloy of uranium and molybdenum (U-Mo) is expected to allow the conversion of U.S. domestic high performance reactors like MURR. This report presents the nominal steady-state irradiation conditions of a key set of plates containing peak irradiation parameters found in MURR cores fueled with the LEU monolithic U-Mo alloy fuel with 10 wt% Mo. Manufacturing tolerances and other uncertainties in reactor geometry and materials are also presented and used to estimate the uncertainties in these irradiation parameters above nominal steady-state conditions.

Stillman, J.↗

Irradiation Experiment Conceptual Design Parameters for MITR LEU U-Mo Fuel Conversion

This report contains the results of reactor design and performance calculations for conversion of the Massachusetts Institute of Technology Reactor (MITR) from the use of highly-enriched uranium (HEU) fuel to the use of low-enriched uranium (LEU) fuel. The analyses were performed by staff members of the Global Threat Reduction Initiative (GTRI) Reactor Conversion Program at the Argonne National Laboratory (ANL) and the MITR Facility. The core conversion to LEU is being performed with financial support from the U. S. government. In the framework of its non-proliferation policies, the international community presently aims to minimize the amount of nuclear material available that could be used for nuclear weapons. In this geopolitical context most research and test reactors, both domestic and international, have started a program of conversion to the use of LEU fuel. A new type of LEU fuel based on an alloy of uranium and molybdenum (U-Mo) is expected to allow the conversion of U.S. domestic high performance reactors like MITR. This report presents the nominal steady-state irradiation conditions of plates containing peak irradiation parameters found in MITR cores fueled with the LEU monolithic U-Mo alloy fuel with 10 wt% Mo. Manufacturing tolerances and other uncertainties in reactor geometry and materials are also presented and used to estimate the uncertainties in these irradiation parameters above nominal steady-state conditions.

Wilson, Erik H.↗

Planning Document for an NBSR Conversion Safety Analysis Report

The NIST Center for Neutron Research (NCNR) is a reactor-laboratory complex providing the National Institute of Standards and Technology (NIST) and the nation with a world-class facility for the performance of neutron-based research. The heart of this facility is the National Bureau of Standards Reactor (NBSR). The NBSR is a heavy water moderated and cooled reactor operating at 20 MW. It is fueled with high-enriched uranium (HEU) fuel elements. A Global Threat Reduction Initiative (GTRI) program is underway to convert the reactor to low-enriched uranium (LEU) fuel. This program includes the qualification of the proposed fuel, uranium and molybdenum alloy foil clad in an aluminum alloy, and the development of the fabrication techniques. This report is a planning document for the conversion Safety Analysis Report (SAR) that would be submitted to, and approved by, the Nuclear Regulatory Commission (NRC) before the reactor could be converted. This report follows the recommended format and content from the NRC codified in NUREG-1537, “Guidelines for Preparing and Reviewing Applications for the Licensing of Non-power Reactors,” Chapter 18, “Highly Enriched to Low-Enriched Uranium Conversions.” The emphasis herein is on the SAR chapters that require significant changes as a result of conversion, primarily Chapter 4, Reactor Description, and Chapter 13, Safety Analysis. The document provides information on the proposed design for the LEU fuel elements and identifies what information is still missing. This document is intended to assist ongoing fuel development efforts, and to provide a platform for the development of the final conversion SAR. This report contributes directly to the reactor conversion pillar of the GTRI program, but also acts as a boundary condition for the fuel development and fuel fabrication pillars.

42 ENGINEERING↗

Highly Efficient Non-Oxidative Methane Conversion with Continuous Hydrogen Removal

A non-oxidative methane conversion catalytic system has been successfully developed. Ball-milling and annealing above 1973 K are necessary in order to synthesize the unique methane activation catalyst. Characterization and evaluation of catalysts shows that the surface area should be carefully controlled to minimize coke deposition. The influence of temperature, pressure, space velocity and hydrogen concentration on catalytic process was systematically studied. The reaction conditions were optimized to a combination of 1323 K, ambient pressure and a space velocity of 4900 ml/g·h. A process, using 0.5% Fe/SiO 2 catalyst under these conditions, yield a methane conversion of 15.62%, with product distribution of 40.05% C 2 , 26.48% BTX and 10.7% naphthalene and demonstrated stable operation of at least 50 hours. This result meets the milestone in the phase I proposal. A non-oxidative methane catalyst-integrated SOFC reactor was accomplished, using nickel-free cells of both ScSZ oxygen-ion conductor and BZY proton conductor. With in-situ hydrogen removal enabled by SOFC, hydrogen concentration in the reactor was effectively reduced, shifting reaction equilibrium and boosting methane conversion. However, due to the high temperature requirement of this reaction, most available proton-conducting SOFCs become oxygen-ion conducting, leading to side reactions and counteracting the benefits from hydrogen removal. To take advantage of the enhanced oxygen-ion conductance of SOFC at high temperatures, we have also paired the nickel-free SOFCs with high-performance oxidative coupling of methane (OCM) catalysts. The SOFC-OCM tubular membrane reactor, employing a Mn-Ce-Na 2 WO 4 /SiO 2 -based catalyst, demonstrates a remarkable performance of 60.7% methane conversion with 41.6% C 2 + selectivity, 5.8 ethylene-to-ethane ratio and 19.4% ethylene yield. The use of integrated SOFC-OCM reactor enables better hydrocarbon selectivity and higher ethylene-to-ethane ratio, eliminating the need of an expensive air separation unit and preventing the direct co-feed of explosive methane-oxygen mixture. We believe this presents a great promise towards commercialization as an advanced methane conversion technology.

02 PETROLEUM↗

Strategies for Achieving the DOE Hydrogen Shot Goal: Thermal Conversion Approaches

In July 2021 the United States (U.S.) Department of Energy (DOE) launched the first of a series of Department-wide Energy Earthshot goals designed to accelerate breakthroughs of more abundant, affordable, and reliable clean energy solutions within the decade. The Hydrogen Shot goal seeks to reduce the cost of clean hydrogen to $\$$1 per 1 kilogram in 1 decade ("1 1 1"). Today, thermal conversion of fossil fuels represents the predominant, lowest cost method of hydrogen production. In 2020 approximately 75 percent of global, dedicated hydrogen production was produced via fossil fuels using thermal conversion approaches such as steam reforming and gasification. However, carbon management techniques such as CO 2 capture and sequestration (CCS) and pyrolysis are not widely represented in the current fossil-based hydrogen production fleet. Lowering the cost of clean hydrogen production from commercial and advanced thermal conversion-based technologies is critical for successfully achieving the Hydrogen Shot goal. This report presents the findings from an initial screening analysis of several scenarios that explore cost drivers related to clean hydrogen production. The screening encompasses commercially available and developing thermal conversion technology alternatives as well as factors exogenous to the plant such as feedstock/byproduct pricing, CO 2 pipeline and storage infrastructure costs, and scale to assess potential pathways towards meeting the Hydrogen Shot goal. Additionally, this report presents initial Research and Development (R&D) strategies to advance thermal conversion technology towards meeting the Hydrogen Shot goal.

08 HYDROGEN↗