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At least 1,225 records · Page 68

High energy efficient solid state laser sources

Recent progress in the development of highly efficient coherent optical sources is reviewed. This work focusses on nonlinear frequency conversion of the highly coherent output of the Non-Planar Ring Laser Oscillators developed earlier in the program, and includes high efficiency second harmonic generation and the operation of optical parametric oscillators for wavelength diversity and tunability.

Byer, Robert L.↗

High energy efficient solid state laser sources

Recent progress in the development of highly efficient coherent optical sources was reviewed. This work has focused on nonlinear frequency conversion of the highly coherent output of the non-planar ring laser oscillators developed earlier in the program, and includes high efficiency second harmonic generation and the operation of optical parametric oscillators for wavelength diversity and tunability.

Byer, Robert L.↗

Investigation of glass-ceramic lithium thiophosphate solid electrolytes using NMR and neutron scattering

Solid-state Li batteries require solid electrolytes which have high Li+ conductivity and good chemical/mechanical compatibility with Li metal anodes and high energy cathodes. Structure/function correlations which relate local bonding to macroscopic properties are needed to guide development of new solid electrolyte materials. This study combines diffraction measurements with solid-state nuclear magnetic resonance spectroscopy (ssNMR) and neutron pair distribution function (nPDF) analysis to probe the short-range vs. long-range structure of glass-ceramic Li 3 PS 4 -based solid electrolytes. Here, we demonstrate how different synthesis conditions (e.g., solvent selection and thermal processing) affect the resulting polyanionic network. More specifically, structures with high P coordination numbers (e.g., PS 4 3– and P 2 S 7 4– ) correlate with higher Li + mobility compared to other polyanions (e.g., (PS 3 ) n n– chains and P 2 S 6 4– ). Overall, this work demonstrates how ssNMR and nPDF can be used to draw key structure/function correlations for solid-state superionic conductors.

36 MATERIALS SCIENCE↗

Implementation of a Model Predictive Control Strategy to Regulate Temperature Inside Plug-Flow Solar Reactor With Countercurrent Flow

Abstract Solar-driven thermochemical energy storage systems are proven to be promising energy carriers (solar fuels) to utilize solar energy by using reactive solid-state pellets. However, the production of solar fuel requires a quasi-steady-state process temperature, which represents the main challenge due to the transient nature of solar power. In this work, an adaptive model predictive controller (MPC) is presented to regulate the temperature inside a tubular solar reactor to produce solid-state solar fuel for long-term thermal storage systems. The solar reactor system consists of a vertical tube heated circumferentially over a segment of its length by concentrated solar power, and the reactive pellets (MgMn2O4) are fed from the top end and flow downwards through the heated tube. A countercurrent flowing gas supplied from the lower end interacts with flowing pellets to reduce it thermochemically at a temperature range of 1000—1500 °C. A low-order physical model was developed to simulate the dynamics of the solar reactor including the reaction kinetics, and the proposed model was validated numerically by using a 7-kW electric furnace. The numerical model then was utilized to design the MPC controller, where the control system consists of an MPC code linked to an adaptive system identification code that updates system parameters online to ensure system robustness against external disturbances (sudden change in the flow inside the reactor), model mismatches, and uncertainty. The MPC controller parameters are tuned to enhance the system performance with minimum steady-state error and overshoot. The controller is tested to track different temperature ranges between 500 °C and 1400 °C with different particles/gas mass flowrates and ramping temperature profiles. Results show that the MPC controller successfully regulated the reactor temperature within ± 1 °C of its setpoint and maintained robust performance with minimum input effort when subjected to sudden changes in the amount of flowing media and the presence of chemical reaction.

Engineering↗

Operando X-Ray Tomography Imaging of Solid-State Electrolyte Response to Li Evolution under Realistic Operating Conditions

Solid-state Li-ion conductors are a next-generation battery technology that are particularly promising for electric vehicles, offering the capacitive benefits of Li metal anodes with nonflammable electrolytes. Microstructural evolution in these solid-state batteries, especially the Li anode, requires deeper understanding of the conditions under which certain undesired behaviors are more likely to occur. This study utilizes operando X-ray computed tomography to visualize the behavior of lithium in response to device operation, considering variables that are relevant to a realistic battery: stack pressure, microscale defects such as pores, and temperature. This work demonstrates that experimental and operational conditions, especially temperature, affect the fundamental driving forces of realistic solid electrolyte systems and provides visual insight into possible mechanisms of Li migration. In particular, the effect of these variables on Li propagation from the anode through pre-existing defects and Li nucleation within the imperfectly electron-insulating electrolyte is highlighted.

battery↗

Time-Accurate Computational Fluid Dynamics Simulation of a Pair of Moving Solid Rocket Boosters

Since the Columbia accident, the threat to the Shuttle launch vehicle from debris during the liftoff timeframe has been assessed by the Liftoff Debris Team at NASA/MSFC. In addition to engineering methods of analysis, CFD-generated flow fields during the liftoff timeframe have been used in conjunction with 3-DOF debris transport methods to predict the motion of liftoff debris. Early models made use of a quasi-steady flow field approximation with the vehicle positioned at a fixed location relative to the ground; however, a moving overset mesh capability has recently been developed for the Loci/CHEM CFD software which enables higher-fidelity simulation of the Shuttle transient plume startup and liftoff environment. The present work details the simulation of the launch pad and mobile launch platform (MLP) with truncated solid rocket boosters (SRBs) moving in a prescribed liftoff trajectory derived from Shuttle flight measurements. Using Loci/CHEM, time-accurate RANS and hybrid RANS/LES simulations were performed for the timeframe T0+0 to T0+3.5 seconds, which consists of SRB startup to a vehicle altitude of approximately 90 feet above the MLP. Analysis of the transient flowfield focuses on the evolution of the SRB plumes in the MLP plume holes and the flame trench, impingement on the flame deflector, and especially impingment on the MLP deck resulting in upward flow which is a transport mechanism for debris. The results show excellent qualitative agreement with the visual record from past Shuttle flights, and comparisons to pressure measurements in the flame trench and on the MLP provide confidence in these simulation capabilities.

Strutzenberg, Louise L.↗

Chemical Heterogeneity in PAN/LLZTO Composite Electrolytes by Synchrotron Imaging

Solid polymer/ceramic composite electrolytes are promising for batteries due to their attractive thermal stability and mechanical properties. Chemical heterogeneity in solid composite electrolytes, such as the inhomogeneity in the ceramic phase and salt distribution at the polymer/ceramic interface, is critical to the performance of solid composite electrolytes. However, such heterogeneity has not been well understood yet. In this work, we use Synchrotron-based X-ray fluorescence imaging (XRF) and Transmission X-ray Microscope (TXM) to image nanoscale chemical heterogeneity in polyacrylamide/Li 7+x La 3 Zr 2–x Ta x O 12 (LLZTO) composite electrolytes and investigate the effects of lithium salt, salt concentration, and plasticizer. We find that LLZTO particles show strong inter- and intra-particles chemical heterogeneities, and the off-stoichiometry of Zr in an LLZTO particle is unlikely to be only balanced by Ta substitution. Moreover, statistical analysis suggests that LiI tends to accumulate at the ceramic/polymer interface at a low concentration of 5 wt%, but no such tendency was observed in samples with 10 wt% LiI. However, composite electrolytes with LiTFSI show interfacial accumulation at both 5 wt% and 10 wt%. Furthermore, this report provides insight into element distributions in solid composite electrolytes, and we hope further researches can shed light on the connections between chemical heterogeneity and ionic transport pathway inside.

36 MATERIALS SCIENCE↗

Supercritical Fluid Adsorption to Weakly Attractive Solids: Universal Scaling Laws

In this study, adsorption of light hydrocarbons (C1–C3) confined in the pores of silica aerogel (nominal density 0.2 g/cm 3 ) was studied experimentally and by computer simulation. Five isotherms of ethane (25.0, 32.0, 32.3, 33.0, and 35.0 °C) were obtained over a temperature range including the critical temperature of the bulk fluid (T c = 32.18 °C) to ~220 bar by the vibrating tube densimetry (VTD) method, which yields unique information impossible to obtain by excess sorption measurements. Two isotherms (35 and 50 °C) of methane adsorption in SiO 2 aerogel were measured far above its critical temperature, T c = -82.59 °C, at 0–150 bar using a gravimetric method. The experimental pore fluid properties of methane, ethane, propane, and CO 2 (obtained earlier by VTD for the same SiO 2 aerogel sample) show behavior conforming to the principle of corresponding states over the entire covered reduced temperature ranges from T r = 0.976 to T r = 1.696. The magnitudes of the excess adsorption maxima and the reduced fluid densities where the maxima occur for C1–C3 hydrocarbons and CO 2 are similar functions of the reduced temperature. This behavior indicates that, at least under the conditions covered in this work, the differences in molecular size and shape have only minor impacts on the solid–fluid interactions underlying the adsorption behavior. Lastly, these findings are supported by large-scale GCMC simulations of a lattice gas confined in the pores of a computer representation of the SiO 2 aerogel framework, yielding excess adsorption isotherms in good agreement with experimental measurements, as well as the underlying microstructures of the adsorbed fluids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Center for Energy Efficient Materials (CEEM) (Final Technical Report)

The mission of the Center for Energy Efficient Materials (CEEM) was to serve the Department of Energy and the nation as a center of excellence dedicated to advancing basic research in nano-structured materials and devices for applications to solar electricity, thermoelectric conversion of waste heat to electricity, and solidstate lighting. The foundation of CEEM was based on the unique capabilities of UCSB and its partner institutions to control, synthesize, characterize, model, and apply materials at the nanoscale for more efficient sustainable energy resources. This unique expertise was a key source of the synergy that unified the research of the Center. Although the Center’s focus was basic research, It’s longer-term objective has been to transfer new materials and devices into the commercial sector where they will have a substantial impact on the nation’s need for efficient sustainable energy resources. As one measure of the impact of the Center, two start-up companies were formed based on its research. In addition, Center participants published a total of 210 archival journal articles, of which 51 were exclusively sponsored by the DOE grant. The work of the Center was structured around four specific tasks: Organic Solar Cells, Solid-State Lighting, Thermoelectrics, and High Efficiency Multi-junction Photovoltaic devices. A brief summary of each follows – detailed descriptions are in Sections 4 & 5 of this report. Research supported through CEEM led to an important shift with respect to the choice of materials used for the fabrication of solution deposited organic solar cells. Solution deposition opens the opportunity to manufacture solar cells via economically-viable high throughput tools, such as roll to roll printing. Prior to CEEM, most organic semiconductors utilized for this purpose involved polymeric materials, which, although they can form thin films reliably, suffer from batch to batch variations due to the statistical nature of the chemical reactions that produce them. In response, the CEEM team developed well-defined molecular semiconductors that produce active layers with very high power conversion efficiencies, in other words they can convert a very high fraction of sunlight into useful electrical power. The fact that the semiconductor is formed from molecular species provides the basis for circumventing the unreliability of polymer counterparts and, as an additional bonus, allows one to attain much grater insight into the structure of the active layer. The latter is particularly important because efficient conversion is the result of a complex arrangement of two semiconductors that need to phase separate in a way akin to oil and water, but with domains that are described by nanoscale dimensions. CEEM was therefore able to provide deep insight into the influence of nanostructure, through the application of structural characterization tools and theoretical methods that describe how electrical charges migrate through the organic layer. Our research in light emitting diode (LED)-based solid state lighting (SSL) was directed at improving efficiency and reducing costs to enable the widespread deployment of economically-viable replacements for inefficient incandescent, halogen, and fluorescent-based lighting. Our specific focus was to advance the fundamental science and technology of light emitting diodes to both understand factors that limit efficiencies and to provide innovative and viable solutions to the current impediments. One of the main challenges we faced is the decrease in efficiency when LEDs are driven harder to increase light output---the so called “droop” effect. It requires large emitting surfaces to reach a desired optical output, and necessitates the use of costly heat sinks, both of which increase the cost. We successfully reduced droop by growing LED crystals having non-conventional orientations. As recognized by the award of the 2014 Nobel prize to the inventors of the nitride LEDs (one of whom was a member of CEEM), LEDs already have a large societal impact in both developed (leading to large energy savings) and developing countries (bringing light where there is no electrical grid). The improvements in efficiency sought after in the CEEM project are key to a further impact of solid state lighting by LEDs with a projected doubling in efficiency by year 2020. Direct generation of electricity from heat has enormous promise for beneficial use of waste heat. But practical power generation directly from heat requires understanding and development of new and improved materials that will be more efficient and rugged than today’s thermoelectric materials. To accomplish this goal CEEM has synthesized five distinct and promising new classes of thermoelectric materials: (a) nanoparticle arrays that are effective in maximizing electric power generation and reducing detrimental loss of heat; (b) nitride and (c) oxide thermal electric materials that are effective at high temperatures where much beneficial heat is available; (d) arrays of silicon nano-wires that integrate thermal electricity generation into silicon-based electronics and materials; and (e) chemically synthesized nanostructured compounds that are cost effective, earth abundant, and environmentally friendly. The further development of these thermoelectric sources of electricity could have revolutionary impact for society in the recovery of waste heat from sources such as power plants and automobile exhaust, where there could be significant associated energy saving. It could even, in the future, provide disruptive alternatives and replacements for today’s internal combustion engines and could enable improved all-electric propulsion by the heat from shipboard nuclear reactors. The High Efficiency Multi-junction Photovoltaics task was a UCSB/NREL collaboration which bonded sub-cells from two different compound semiconductors material systems to make high efficiency multijunction solar cells for concentrating photovoltaic applications thathave substantially higher efficiency than single substrate cells made of elemental semiconductors such as silicon. This task required the development of new cell bonding methods with excellent coupling of both photons and electrons between the sub-cells. To accomplish this, we developed (1) GaInN solar cells with enhanced performance by using quantum-well absorbers and front-surface optical texturing, (2) a hybrid "pillar-array" bond which uses an array of metal pillars for electrical coupling, and (3) a "hybrid moth-eye" optical coating which combines the benefits of nano-imprinted moth-eye coatings and traditional multilayer coatings. The technical effectiveness was assessed by measurement of the photovoltaic efficiency of solar cells made using these techniques; the ultrahigh efficiencies targeted by this work are of compelling economic value for concentrating photovoltaics.

14 SOLAR ENERGY↗

Room-temperature solid state synthesis of ZnO/Bi{sub 2}O{sub 3} heterojunction and their solar light photocatalytic performance

Highlights: • ZnO/Bi{sub 2}O{sub 3} hierarchical nanostructures were synthesized via a solid-state reaction. • The amount of Bi{sub 2}O{sub 3} plays an important role in controlling the morphology. • The amount of Bi{sub 2}O{sub 3} plays an important role in controlling the photocatalysis. - Abstract: ZnO/Bi{sub 2}O{sub 3} heterojunction was prepared by solid state reaction method at room temperature. The as-prepared nanostructures were characterized as the assembled nanosheets of ZnO on which Bi{sub 2}O{sub 3} nanoparticles were well dispersed. Further studies revealed that the morphology and photocatalytic property could be regulated by tuning the amount of Bi{sub 2}O{sub 3}. The introduction of Bi{sub 2}O{sub 3} can lead to the enhancement of solar light absorption, and the 5% ZnO/Bi{sub 2}O{sub 3} samples exhibited the best photocatalytic activity under the solar light irradiation. The excellent photocatalytic performances could be ascribed to the synergistic effects of the hierarchical nanostructures and the effective separation of photogenerated carriers. Moreover, the hydroxyl radicals (·OH) are found to be the main active species generated in the oxidation reaction of RhB over ZnO/Bi{sub 2}O{sub 3} photocatalyst. Therefore, our work demonstrated a facile way to prepare hierarchical nanostructures with excellent photocatalytic performance using solid state method at room temperature.

36 MATERIALS SCIENCE↗

Guanidinium-Assisted Surface Matrix Engineering for Highly Efficient Perovskite Quantum Dot Photovoltaics

Metal halide perovskite quantum dots (Pe-QDs) are of great interest in new-generation photovoltaics (PVs). However, it remains challenging in the construction of conductive and intact Pe-QD films to maximize their functionality. Herein, a ligand-assisted surface matrix strategy to engineer the surface and packing states of Pe-QD solids is demonstrated by a mild thermal annealing treatment after ligand exchange processing (referred to as “LE-TA”) triggered by guanidinium thiocyanate. The “LE-TA” method induces the formation of surface matrix on CsPbI 3 QDs, which is dominated by the cationic guanidinium (GA+) rather than the SCN-, maintaining the intact cubic structure and facilitating interparticle electrical interaction of QD solids. Consequently, the GA-matrix-confined CsPbI 3 QDs exhibit remarkably enhanced charge mobility and carrier diffusion length compared to control ones, leading to a champion power conversion efficiency of 15.21% when assembled in PVs, which is one of the highest among all Pe-QD solar cells. Additionally, the “LE-TA” method shows similar effects when applied to other Pe-QD PV systems like CsPbBr 3 and FAPbI 3 (FA = formamidinium), indicating its versatility in regulating the surfaces of various Pe-QDs. This work may afford new guidelines to construct electrically conductive and structurally intact Pe-QD solids for efficient optoelectronic devices.

36 MATERIALS SCIENCE↗

Direct observation of defect-aided structural evolution in Ni-rich layered cathode

Ni-rich LiNi 1-x-y Mn x Co y O 2 (NMC) layered compounds have become the dominated cathode for lithium ion batteries. The role of crystallographic defects on their structure evolution and consequent performance degradation during electrochemical cycling is not yet fully understood. In this work, we investigated the structural evolution of Ni-rich NMC cathode in a solid-state cell via in-situ transmission electron microscopy. We identified antiphase boundary (APB) and twin boundary (TB) separating layered phases played an important role on phase change. Upon the lithium depletion, the APB extends across the layered structure, while Li/transition metal (TM) ion mixing in the layered phases is detected to induce the rock-salt phase formation along the coherent TB. According to DFT calculations, Li/TM mixing and phase transition are aided by the low diffusion barriers of TM ions at planar defects. Finally, this work reveals the dynamical scenario of secondary phase evolution, which helps to unveil the origin of performance fading in Ni-rich NMC.

25 ENERGY STORAGE↗

NMR Hydrogen Storage Systems: Ionic Hydrides and Mobile Species

We have used NMR to gain understanding of simple and complex (ionic-covalent) hydrogen storage solids. These are static, often in situ NMR measurements taken at the reaction conditions, typically involving high temperatures and high pressures. The work described here builds on our group's recent success with this technique in the discovery of a new mobile chemical species which evidently plays a key role in the dehydriding and rehydriding chemistry of NaAIH 4 , the archetype of complex hydrogen storage solids. Other hydrogen storage compounds have also been explored in depth, and some of the pertinent results will be mentioned, though here we focus principally on our work with NaAlH 4 .

08 HYDROGEN↗

Unit cell geometry of multiaxial preforms for structural composites

The objective of this study is to investigate the yarn geometry of multiaxial preforms. The importance of multiaxial preforms for structural composites is well recognized by the industry but, to exploit their full potential, engineering design rules must be established. This study is a step in that direction. In this work the preform geometry for knitted and braided preforms was studied by making a range of well designed samples and studying them by photo microscopy. The structural geometry of the preforms is related to the processing parameters. Based on solid modeling and B-spline methodology a software package is developed. This computer code enables real time structural representations of complex fiber architecture based on the rule of preform manufacturing. The code has the capability of zooming and section plotting. These capabilities provide a powerful means to study the effect of processing variables on the preform geometry. the code also can be extended to an auto mesh generator for downstream structural analysis using finite element method. This report is organized into six sections. In the first section the scope and background of this work is elaborated. In section two the unit cell geometries of braided and multi-axial warp knitted preforms is discussed. The theoretical frame work of yarn path modeling and solid modeling is presented in section three. The thin section microscopy carried out to observe the structural geometry of the preforms is the subject in section four. The structural geometry is related to the processing parameters in section five. Section six documents the implementation of the modeling techniques into the computer code MP-CAD. A user manual for the software is also presented here. The source codes and published papers are listed in the Appendices.

Ko, Frank↗

Activity and Stability of (Pr 1-x Nd x ) 2 NiO 4+δ as Cathodes for Oxide Fuel Cells: Part VI. The Role of Cu Dopant on the Structure and Electrochemical Properties

Phase instability in praseodymium nickelates is a major concern for the long-term operations of solid oxide fuel cells since it may lead to the performance degradation. In this work, praseodymium nickelates (ex. Pr 2 NiO 4+δ ) have been stabilized via substitution on both Pr- and Ni-sites. Systematic studies over a wide range of compositions were conducted via long-term thermal annealing studies (T ≤ 870°C) and electrochemical tests in full cells. Proposed (Pr 0.50 Nd 0.50 ) 2 Ni 1-y Cu y O 4+δ compositions (y = 0.05, 0.10, 0.20, and 0.30) showed the most promising results and serve as a comprehensive extension to our previous studies in this series of papers. A stable long-term performance was obtained for temperatures up to 790°C for 500 hours at 0.80 V with a minimal tradeoff between the activity (power density of 0.8–1.0 W cm -2 at 850°C) and performance stability. A preserved parent phase and suppressed performance degradation, when compared to Pr 2 NiO 4+δ , make newly developed electrodes attractive candidates for the state-of-the-art solid oxide fuel cell applications.

36 MATERIALS SCIENCE↗

Determining Flame Temperature By Broadband Two Color Pyrometry in A Flame Spreading Over A Thin Solid in Microgravity

Fire spread inside a spacecraft is a constant concern in space travel. Understanding how the fire grows and spreads, and how it can potentially be extinguished is critical for planning future missions. The conditions inside a spacecraft can greatly vary from those encountered on earth, including microgravity, low velocity flows, reduced ambient pressure and high oxygen, and thus affecting the combustion processes. In microgravity, the contributions of thermal radiation from gaseous species and soot can play a critical role in the spread of a flame and the problem has not been fully understood yet. The overall objective of this work is to address this by studying the soot temperature of microgravity flames spreading over a thin solid in microgravity. The experiments presented here were performed as part of the NASA project Saffire IV, conducted in orbit on board the Cygnus resupply vehicle before it re-entered the Earth’s atmosphere. The fuel considered is a thin fabric made of cotton and fiberglass (Sibal) exposed to a forced flow of 20 cm/s in a concurrent flow configuration. Reconstruction of the flame temperature fields is extracted from two color broadband emission pyrometry (B2CP) as the flame propagates over the solid fuel. A methodology, relevant assumptions and its applicability to other microgravity experiments are discussed here. The data obtained shows that the technique provides an acceptable average temperature around ~1300 K, which remains relatively constant during the spread with an error value smaller than 117 K. The data presented in this work provides a methodology that could be applied to other microgravity experiments to be performed by NASA. It is expected that the results will provide insight for what is to be expected in different conditions relevant for fire safety in future space facilities.

fire↗

Specific Impulse of Electric Solid Propellant in an Electrothermal Ablation-Fed Pulsed Plasma Thruster

Electric solid propellants are advanced solid chemical rocket propellants that can be controlled (ignited, throttled, and extinguished) through the application and removal of an electric current. Recent work has focused on application of this propellant in an electrothermal ablation-fed pulsed plasma thruster. In this paper, impulse bit measurements in such devices fed by either the electric solid propellant or a traditional state-of-the-art propellant, polytetrafluoroethylene, are expanded upon. It is demonstrated that a surface layer in the hygroscopic electric solid propellant is rapidly ablated over the first few discharges of the device, which correspondingly decreases specific impulse relative to the traditional polytetrafluoroethylene propellant. Correcting these data by subtracting the early discharge ablation mass loss measurements yields a corrected electric solid propellant specific impulse of approximately 300 s. As the test duration increases to a large number of discharges, and the initial mass loss is a reduced fraction of the total, the effect of absorbed water in the propellant is decreased and the specific impulse without any corrections approaches the corrected 300 s value.

Glascock, Matthew S.↗

Modelling K shell spectra from short pulse heated buried microdot targets

K shell X-ray emission measurements have been used to diagnose plasma conditions in short-pulse heated buried microdot targets on the Orion high power laser. These experiments have been used to validate simulations of short pulse laser-solid interaction that combine hybrid PIC modelling of the laser absorption with radiation-hydrodynamics simulations including an electron transport model. Comparison of these simulations with streaked K shell spectroscopy show the importance of including radial gradients in fitting the spectra. An example is presented of the emission of sulphur from a 50 µm diameter microdot sample buried in a plastic foil. Previously agreement between simulation and experiment was obtained only by treating the absorbed energy, electron temperature and beam divergence as fitting parameters. Overall, the good agreement obtained in this work used the measured laser energy and laser pulse length and calculated the laser-solid target interaction from first principles.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗